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diff --git a/.gitattributes b/.gitattributes new file mode 100644 index 0000000..d7b82bc --- /dev/null +++ b/.gitattributes @@ -0,0 +1,4 @@ +*.txt text eol=lf +*.htm text eol=lf +*.html text eol=lf +*.md text eol=lf diff --git a/LICENSE.txt b/LICENSE.txt new file mode 100644 index 0000000..6312041 --- /dev/null +++ b/LICENSE.txt @@ -0,0 +1,11 @@ +This eBook, including all associated images, markup, improvements, +metadata, and any other content or labor, has been confirmed to be +in the PUBLIC DOMAIN IN THE UNITED STATES. + +Procedures for determining public domain status are described in +the "Copyright How-To" at https://www.gutenberg.org. + +No investigation has been made concerning possible copyrights in +jurisdictions other than the United States. Anyone seeking to utilize +this eBook outside of the United States should confirm copyright +status under the laws that apply to them. diff --git a/README.md b/README.md new file mode 100644 index 0000000..23f9ba2 --- /dev/null +++ b/README.md @@ -0,0 +1,2 @@ +Project Gutenberg (https://www.gutenberg.org) public repository for +eBook #67920 (https://www.gutenberg.org/ebooks/67920) diff --git a/old/67920-0.txt b/old/67920-0.txt deleted file mode 100644 index 0f868b4..0000000 --- a/old/67920-0.txt +++ /dev/null @@ -1,1893 +0,0 @@ -The Project Gutenberg eBook of A Further Investigation of the -Symmetrical Chloride of Paranitroorthosulphobenzoic Acid, by William E. -Henderson - -This eBook is for the use of anyone anywhere in the United States and -most other parts of the world at no cost and with almost no restrictions -whatsoever. You may copy it, give it away or re-use it under the terms -of the Project Gutenberg License included with this eBook or online at -www.gutenberg.org. If you are not located in the United States, you -will have to check the laws of the country where you are located before -using this eBook. - -Title: A Further Investigation of the Symmetrical Chloride of - Paranitroorthosulphobenzoic Acid - -Author: William E. Henderson - -Release Date: April 25, 2022 [eBook #67920] - -Language: English - -Produced by: The Online Distributed Proofreading Team at - https://www.pgdp.net (This file was produced from images - generously made available by The Internet Archive) - -*** START OF THE PROJECT GUTENBERG EBOOK A FURTHER INVESTIGATION OF -THE SYMMETRICAL CHLORIDE OF PARANITROORTHOSULPHOBENZOIC ACID *** - - - - - -Transcriber’s Notes: - - Typographical and punctuation errors have been silently corrected. - - - - - A Further Investigation of the - Symmetrical Chloride of - Paranitroorthosulphobenzoic Acid. - - Dissertation. - - Submitted to the Board of University - Studies of the Johns Hopkins University - for the Degree of Doctor of Philosophy. - - — by — - William E. Henderson. - - 1897 - - - - -Acknowledgment. - - -The author esteems it a privilege as well as a pleasure to give -expression to his sincere sense of gratitude to Prof. Remsen,under -whose guidance this work was carried on not only for instruction -received in the lecture room, but for his frequent suggestion, and his -constant and friendly interest in the work as it progressed. These have -at all times been an encouragement and an incentive. - -He wishes also to express his appreciation of the instruction and -kindly guidance in the laboratory, of Drs. Morse and Renouf, as well as -of Dr. Ames of the Physical Laboratory. - - - - -Contents. - - - I. Introduction. Page 1 - - II. Preparation of the Acid Potassium Salt - of Paranitroorthosulphobenzoic Acid. 6 - - III. Preparation of the Symmetrical Chloride - of Paranitroorthosulphobenzoic Acid. 12 - - IV. Properties of the Symmetrical Chloride - of Paranitroorthosulphobenzoic Acid. 19 - - V. The Action of Benzene and Aluminium - Chloride on the Symmetrical Chloride - of Paranitroorthosulphobenzoic Acid. 22 - - The Barium Salts of - Paranitroorthobenzoybbenzenesulphonic Acid. 24 - - VI. The Action of Alcohols on the Symmetrical Chloride - of Paranitroorthosulphobenzoic Acid. 30 - 1. Methyl Alcohol. 31 - 2. Ethyl Alcohol. 32 - Action of Ethyl Alcohol on the Unsymmetrical - Chloride. 36 - - VII. The Action of Phenols on the Symmetrical Chloride - of Paranitroorthosulphobenzoic Acid. 38 - 1. Phenol. 40 - 2. Orthocresol. 48 - 3. Paracresol. 51 - 4. Hydroquinone. 53 - 5. Resorcin. 56 - 6. Pyrogallol. 59 - 7. β-naphthol. 61 - - VIII. The Action of Aniline on the Symmetrical Chloride - of Paranitroorthosulphobenzoic Acid. 62 - - IX. The Action of Phosphorus Oxychloride on the Fusible - Anilid of Paranitroorthosulphobenzoic Acid. 71 - - X. The Action of Reagents on the Dianil of - Paranitroorthosulphobenzoic Acid. 77 - 1. Of Hydrochloric Acid. 77 - 2. Of Alcoholic Potash. 78 - 3. Of Glacial Acetic Acid. 79 - - XI. Conclusions. 82 - - Biographical. 85 - - - - -I. Introduction. - - -The sulphobenzoic acids have been the subject of investigation in this -laboratory for a number of years past. Among the many interesting -facts that have been brought to light in the course of this study, -perhaps no others have been attended with more interest than the -discovery of well characterized isomerism in the case of the chlorides -of orthosulphobenzoic acid, and its paranitro derivative; together -with the preparation of a series of isomeric derivatives of these -substances. The chlorides themselves have been isolated in the -crystalline condition, and have been found to differ markedly, not -only in chemical, but in physical properties as well. - -The first evidence that such isomerism existed, was obtained by Remsen -and Coates[1] who, in the course of an investigation of the action of -aniline upon the chloride of orthosulphobenzoic acid, obtained two -isomeric anilids quite different in properties, which they designated -as fusible and infusible respectively. The following year, Remsen and -Kohler[2] obtained one of the chlorides in crystalline form, together -with an oil which they did not succeed in crystallizing. - -This however was accomplished the succeeding year by Remsen and -Saunders[3], and a still more satisfactory result was obtained by -Remsen and McKee[4] in 1895. The chloride melting at 79° was found to -yield only the fusible anilid, together with an anil, while from the -lower melting chloride, in addition to these, the infusible anilid was -also formed. - -[1] Am. Chem. Journ. XVII, 311. - -[2] Ibid XVII, 230. - -[3] Ibid XVII, 354. - -[4] Ibid XVIII, 794. - -In 1895, Gray[5] isolated the two corresponding isomeric chlorides of -paranitroorthosulphobenzoic acid, the lower melting chloride being -obtained in small quantity only. The succeeding year Hollis[6] made a -more careful study of this lower melting chloride, and prepared it in -considerable quantity. - -From evidence drawn from the action of ammonia upon these chlorides, -taken in connection with a number of other facts, the higher melting -chloride is identified as the one possessing a symmetrical structure, -while the lower melting chloride possesses an unsymmetrical structure. -The first one, when treated with ammonia is slowly transformed into the -ammonium salt of paranitrobenzoic sulphinide: - -[5] Inaug. Diss. J. H. Univ. 1895. - -[6] Inaug. Diss. J. H. Univ. 1896. - - CO - / \ - COCl / N.NH₄ - / / / - C₆H₃——SO₂Cl + 4NH₃ = C₆H₃——SO₂ + 2NH₄Cl. - \ \ - NO₂ NO₂ - -while the lower melting chloride is quickly transformed into the -ammonium salt of paranitroorthocyanbenzenesulphonic acid: - - CCl₂ - / \ - / O CN - / / / - C₆H₃——SO₂ + 4NH₃ = C₆H₃——SO₂ONH₄ + 2NH₄Cl. - \ \ - NO₂ NO₂ - -Gray’s study of the symmetrical chloride was confined for the most part -to the preparation of a series of salts of this latter acid, and to -an investigation of the action of aniline upon the chloride itself. -It was thought to be of interest to extend this study to a wider -range of reactions, as well as to improve, if possible, the method of -preparing the chloride in pure condition. At the suggestion of Prof. -Remsen this work was accordingly undertaken. - - - - -II. Preparation of Material. - - -The method employed in the preparation of paranitroorthosulphobenzoic -acid was essentially that described by Hart,[7] Kastle,[8] Gray[9] -and Hollis.[10] The details of it are repeated here for the purpose of -calling attention to certain facts that came under the author’s notice. - -[7] Am. Chem. Journ. I, 350. - -[8] Ibid XI, 177. - -[9] Inaug. Diss. J. H. Univ. 1845. - -[10] Inaug. Diss. J. H. Univ. 1896. - -100 grams of paranitrotoluene are added to 400 grams of fuming sulfuric -acid, and the mixture heated in a balloon flask at 100° on a water -bath. The heating is continued until a few drops of the mixture, added -to cold water, dissolves completely to a clear solution. The time -required for this operation varies much with the conditions. Continued -stirring very considerably hastens the reaction, as paranitrotoluene -forms a layer on the acid, which presents a small surface to its -action. With constant stirring the reaction is complete in a few hours, -whereas if no stirring is resorted to, as much as several days may be -required, especially when large quantities are employed at one time. - -When the reaction is complete, the mixture is poured into a -large volume of water, and neutralized with calcium carbonate. -In the filtrate from calcium sulphate, the calcium salt of -paranitroorthotoluene sulphonic acid is found, and this is converted -into the potassium salt in the usual way. - -The oxidation of the potassium salt is effected as follows. 50 grams of -the salt are dissolved in 2½ litres of water, and to this is added a -solution of 15 grams of potassium hydroxide. The mixture is heated to -100° on a water-bath, and when this temperature is reached, 110 grams -of potassium permanganate are added. Heating is continued until the -solution is decolorized, care being taken to prevent the evolution of -free oxygen. - -The oxides of manganese are then filtered off, the filtrate neutralized -with hydrochloric acid, and evaporated to about one fifth of its -original volume. Strong hydrochloric acid is them added in excess, and -on cooling the acid potassium salt of paranitroorthosulphobenzoic acid -separates in very slender colorless needles completely filling the -liquid. - -For the success of this operation it is important that the potassium -salt of paranitroorthotoluenesulphonic acid and the potassium hydroxide -should both be perfectly dissolved before they are heated together. -If the two substances lie together in solid form at the bottom of the -flask, a very slight elevation of temperature leads to the formation -of an extremely troublesome red substance, which is very difficult -to remove. It is almost impossible to remove it from the oxidation -product by recrystallization, since any considerable amount of it has -a marked influence on the solubility of the salt, rendering it much -more soluble. It persists throughout all subsequent transformations of -paranitroorthosulphobenzoic acid, and should therefore be carefully -avoided. - -Otto Fischer[11] has shown that in concentrated solution, potassium -hydroxide acts on nitro derivatives of toluene, with the formation -of various colored substances derived from stilbene. In the case -of paranitroorthotoluenesulphonic acid, he describes the substance -formed as possessing a cherry red color. The reactions involved in its -formation are: - - CH₃ HC ============ CH - / / \ - 2C₆H₃——SO₂OK = C₆H₃——SO₂OK KO.O₂S——C₆H₃ + 2H₂O - \ \ / - NO₂ \ / - \ /-- O --\ / - N N - \-- O --/ - -By oxidation this passes to a nitro compound of the composition - - HC============ CH - / \ - C₆H₃——SO₂OK KOO₂S——C₆H₃ - \ / - NO₂ O₂N - -It was no doubt the formation of substances of this nature that -occasioned the color observed in some of the oxidations. - -[11] Ber. XXVI-2231; XXVIII-2281 - -The only effective method of separating this colored substance was -found to be to pass to the neutral salt of paranitroorthosulphobenzoic -acid, by making the solution slightly alkaline. The salt of this -colored substance is also formed and the two can be separated by a few -recrystallizations in a fairly satisfactory manner. - -The yield in both of the transformations involved in the preparation -of paranitroorthosulphobenzoic acid does not fall far short of the -theoretical. - - - - -III. Preparation of the Symmetrical Chloride of -Paranitroorthosulphobenzoic Acid. - - -This chloride was first separated from its unsymmetrical isomer -by Gray[12]. It was obtained by allowing a chloroform solution of -the mixed chlorides to evaporate until the chloroform had almost -entirely disappeared. In the thick liquid so obtained, crystals of the -symmetrical chloride were formed. It was also obtained by applying the -method devised by Bucher in connection with the corresponding chloride -of orthosulphobenzoic acid—i.e. by the action of dilute ammonia on the -mixed chlorides. Gray also found that the best conditions for securing -a relatively large proportion of the symmetrical chloride were, the -employment of as low a temperature as possible in the formation of the -chlorides, and of as small an excess of phosphorus pentachloride as -would suffice for the reaction. - -[12] Inaug. Diss. J. H. Univ. 1895. - -After many experiments, under widely differing conditions, the -following method of procedure, embodying the results of Gray’s work, -was adopted. - -Dehydrated acid potassium salt of paranitroorthosulphobenzoic acid, -and phosphorus pentachloride, in the ratio of 40: 55 grams, are -brought together in a mortar and intimately mixed. The mixture is -put into an evaporating dish, and placed on a sulphuric acid bath, -previously heated to 150°. As soon as the action has been well started, -the dish is removed, and the reaction allowed to proceed without -further heating. When it is complete, and the contents of the dish -has cooled down to the temperature of the room, the oily product is -poured slowly into a salts bottle containing ice water, the bottle -being frequently shaken during the process. The shaking is continued -with renewed portions of water, as long as the wash water is cloudy. -The water is then poured off, the brownish gummy chloride dissolved -in chloroform, and the solution placed in a good-sized separating -funnel. Ice water is then added, and the contents of the funnel treated -with successive portions of ammonia (desk ammonia diluted one half). -Shaking is continued after each addition until the odor of ammonia has -disappeared, and ice is added from time to time as may be required. - -When it is found that the odor of ammonia persists after several -minutes’ shaking, the chloroform layer, which is usually filled with a -solid substance that has separated during the process, is drawn off, -filtered, and dried with calcium chloride. - -By this process all of the unsymmetrical chloride is converted into the -ammonium salt of paranitroorthocyanbenzenesulphonic acid, according to -the equation: - - CCl₂ - / \ - / O CN - / / / - C₆H₃——SO₂ + 4NH₃ = C₆H₃——SO₃NH₄ + 2NH₄Cl. - \ \ - NO₂ NO₂ - -while the symmetrical chloride remains for the most part unchanged, -though some of it is converted into the ammonium salt of -paranitrobenzoic sulphinide: - - CO - / \ - COCl / N.NH₄ - / / / - C₆H₃——SO₂Cl + 4NH₃ = C₆H₃——SO₂ + 2NH₄Cl. - \ \ - NO₂ NO₂ - -It was found that working in this way the symmetrical chloride could -be prepared in pure condition, free from its isomer. The chloroform -completely evaporates in a short time leaving fine crystals of the -symmetrical chloride. In case the evaporation is slow and incomplete, -it may be concluded that not all of the unsymmetrical chloride has been -removed. The yield was uniformly about 40 per cent of the theoretical. - -From the water used to wash the chlorides a considerable amount of the -original salt can be recovered, as the reaction under the conditions -employed, is never complete. - -An examination was made of the substance mentioned as separating in -the chloroform solution of the chlorides, during the treatment with -ammonia, and it was found to possess the following properties. It -is insoluble in benzene, chloroform, acetone, ether and ligroin; -soluble in glacial acetic acid, from which it separates on cooling -in colorless, crystalline condition; insoluble in the cold in -water, alcohol and ammonia, but by boiling with these reagents, or -by long standing in the cold, it is dissolved with decomposition. -It was dissolved in hot water and the solution, which was acid -in reaction, was neutralized with potassium carbonate. On adding -an excess of hydrochloric acid to the solution, and allowing -it to cool, characteristic crystals of acid potassium salt of -paranitroorthosulphobenzoic acid separated. These properties identify -the substance as the anhydride of this acid. - -The formation of the corresponding anhydride of orthosulphobenzoic acid -by the action of phosphorus pentachloride upon its acid potassium salt -was observed by Sohon[13], who made use of the reaction to prepare this -anhydride in quantity. - -[13] Inaug. Diss. J. H. Univ. 1896. - - - - -IV. Properties of the Symmetrical Chloride of -Paranitroorthosulphobenzoic Acid. - - -As first obtained, the crystals of the symmetrical chloride resemble -irregularly shaped pieces of amber, both in color, and in lustre. -On recrystallization from chloroform or ether, they may be obtained -perfectly colorless, and are often of very simple crystallographic -form. The chloride crystallizes in the monoclinic system, and possesses -a very remarkable crystallizing power, in which respect it differs -noticeably form its isomer. Even in chloroform solution that is far -from dry, crystals appear with the greatest ease. - -The habit of the crystals differs very much according to the -conditions of crystallization. Not infrequently almost perfectly -formed crystals of the simplest form—the oblique octahedron—were -obtained though for the most part the form was much more complicated, -pinacoid and dome faces, together with basal planes being prominent. -As a rule, the crystals were not suitable for crystallographic work, -as the faces are usually uneven and the edges rounded. By proper -precautions however, good ones were obtained, and measurements of these -will be found in this dissertation when it appears in print. - -The size of some of the crystals obtained was unusual for substances -of this class. One crystal obtained with no special precautions, save -letting a solution of the chloride stand undisturbed for several days, -in a rather cool place measured 3 × 2.5 × 1.5 cm., and weighed 11.2 -grams. The crystals are quite compact, their density being abut 1.85. -They melt at 98° (uncorr.) The chloride is quite stable in crystalline -condition. Even in moist air the crystals were unchanged, and retained -their lustre as long as they were in my possession. - -An analysis for chlorine gave the following results. - - .2200 gram gave .2212 gram AgCl. - - COCl - / - Cal. for C₆H₃——SO₂Cl - \ - NO₂ - Found. - Cl = 24.94 24.83 - - - - -V. The Action of Benzene and Aluminium Chloride on the Symmetrical -Chloride of Paranitroorthosulphobenzoic Acid. - - -Hollis[14] in his study of the action of these reagents upon the -unsymmetrical chloride, tested their action upon one portion of the -symmetrical chloride, and found the products to be identical in the two -cases. A few experiments were made in confirmation of these results, -and the same products, in general, were obtained. It was observed -however that the reactions differ in the relative ease with which -they are brought about. In the case of the symmetrical chloride, the -reaction is a much more vigorous one. On adding aluminium chloride to -a solution of the symmetrical chloride, in benzene, action begins -at once the temperature of the hand, and very little external heat, -and that only in the latter stages of the operation, is needful for -the completion of the reaction. The application of much heat converts -all of the product into thick tarry substances from which nothing -satisfactory could be obtained. - -[14] Inaug. Diss. J. H. Univ. 1896. - -When the reaction was complete, the resulting product was isolated and -purified in accordance with the directions given by Hollis. Repeated -trials showed that, as in the case of the unsymmetrical chloride, only -one phenyl group could be introduced by this method. The resulting -compound, paranitroorthobenzoylbenzenesulphon chloride, was identical -with that derived from the unsymmetrical chloride. Owing, however, -to the fact that so much more decomposition occurs in the reaction -with the symmetrical chloride, in paranitroorthobenzoylbenzene sulphon -chloride could not be obtained in perfectly pure condition. In -appearance it agreed closely with that described by Hollis, forming -very characteristic greenish, rhombic crystals. These melted, not very -sharply, at 174° instead of 177° as observed by Hollis. - -Accordingly, to establish the identity of the two compounds beyond -any doubt, the material on hand was converted into the barium salt of -paranitroorthobenzoylbenzene sulphonic acid. This was done by boiling -the sulphon chloride with dilute hydrochloric acid until complete -solution had been effected; evaporating to dryness on a water-bath; -dissolving the residue in hot water, and neutralizing with barium -carbonate. On filtering the hot solution from the excess of carbonate, -and allowing it to cool, the barium salt separated. - -The solution was somewhat colored by impurities, and the long needles -in which the salt crystallized were also somewhat colored. They were -analysed with the expectation that they would prove to be specimens -of the salt described by Hollis as having three, or three and a half -molecules of water of crystallization, in as much as the conditions -under which they were formed were favorable to the formation of salts -with these ratios of water of crystallization. Hollis found that this -salt could be obtained with at least four different ratios of water -of crystallization viz. three, three and a half, six and seven -molecules respectively. The analysis was as follows, the amount of -barium being calculated on the basis of the anhydrous salt. - -0.3087 gram lost 0.064 gram at 210°, and gave 0.0759 gram BaSO₄. - - Cal. for (C₁₃H₈O₆NS)₂Ba + 11H₂O Found. - H₂O = 20.90 20.73 - Ba = 18.29 18.23 - -The mother-liquor, in which the crystals remaining from analysis were -redissolved, was warmed, but not boiled, with boneblack, to remove -impurities. When filtered, the solution was perfectly colorless, and -on standing for some time, well formed colorless, rhombic crystals -appeared. On analysis they gave results as follows. - -0.2804 gram lost 0.0405 gram at 210°, and gave 0.0759 gram BaSO₄. - - Cal. for (C₁₃H₈O₆NS)₂Ba + 7H₂O. Found. - H₂O = 14.40 14.44. - Ba = 18.29 18.03. - -In making a further supply of the salt it was found that if the -solution, after filtering from the barium carbonate, was diluted to -such an extent that no crystals separated on cooling, then on slow -evaporation under a bell-jar the first crystals to appear were very -long slender needles. As evaporation proceeded, these needles became -much thicker assuming prismatic proportions, and corresponded in -appearance to the salt described by Hollis as having six molecules of -crystal water. - -As growth proceeded, the crystals became dark in color, and the -mother-liquor correspondingly clearer, the crystals evidently absorbing -the impurity in their growth. - -When the solution had become quite colorless, rhombic crystals of the -salt containing seven molecules of water of crystallization appeared. -The larger prismatic crystals were carefully removed, and redissolved -in water in order to see if the same phenomena would repeat themselves. -This in fact was the case, crystals of both types appearing in the -same way as described. Without separating the crystals in this second -experiment, water was added, and the crystals dissolved. The solution -was then warmed briskly with boneblack, and filtered. From the -filtrate, which was colorless, nothing but rhombic crystals having -seven molecules of water of crystallization could be obtained, -although a great many variations in the conditions were tried. Analysis -of these last crystals was as follows: - -0.2400 gram lost 0.035 gram at 210°, and gave 0.0637 gram BaSO₄. - - Cal. for (C₁₃H₈O₆NS)₂Ba + 7H₂O. Found. - H₂O = 14.40 14.58 - Ba = 18.29 18.27 - -Hollis states that treatment with boneblack decomposes this salt, -and hence he did not purify it prior to crystallization. From the -experiments just described it seems probable that the impurities -present affect the crystalline habit, and the degree of hydration of -this salt in a very striking manner. By careful warming with boneblack -no decomposition was observed, and the crystals so obtained have -constantly seven molecules of crystal water. - - - - -VI. The Action of Alcohols upon the Symmetrical Chloride of -Paranitroorthosulphobenzoic Acid. - - -Kastle[15] found that when the chlorides of paranitroorthosulphobenzoic -acid (which he supposed to be an individual) were dissolved in alcohol, -and the solution boiled for some time, the acid etherial salt of -paranitroorthosulphobenzoic acid was the final product. The reactions -were shown to be: - - COCl COOC₂H₅ - / / - I. C₆H₃——SO₂Cl + C₂H₅OH = C₆H₃——SO₂Cl + HCl. - \ \ - NO₂ NO₂ - - COOC₂H₅ COOC₂H₅ - / / - II. C₆H₃——SO₂Cl + C₂H₅OH = C₆H₃——SO₂OC₂H₅ + HCl - \ \ - NO₂ NO₂ - - COOC₂H₅ COOC₂H₅ - / / - III. C₆H₃——SO₂OC₂H₅ + C₂H₅OH = C₆H₃——SO₂OH + (C₂H₅)₂O - \ \ - NO₂ NO₂ - -[15] Am. Ch. Journ. XI--281. - -Kastle, it will be observed, gave the symmetrical formula to this -mixture of chlorides. Several acid etherial salts were made, and a -series of the neutral salts of various metals described by him. - -The action of pure symmetrical chloride was studied in the same general -manner to see if the resulting products would be the same as those -formed from the mixed chlorides. - - -1. Action of Methyl Alcohol upon the Symmetrical chloride. - -A portion of the chloride was dissolved in methyl alcohol, and the -solution boiled until a drop added to cold water gave no precipitate, -of unchanged chloride. The alcohol was then distilled off, and the -thick syrup remaining, diluted with water. This solution was -neutralized with barium carbonate and filtered. On cooling, the barium -salt crystallized in shining mica-like plates, or in yellowish needles -corresponding accurately with those described by Kastle. They gave the -following analytical results. - -0.2664 gram lost 0.0211 gram at 150°, and gave 0.0870 gram BaSO₄. - - [ COOCH₃ ] - [ / ] - Cal. for [C₆H₃——SO₂O ] Ba + 3H₂O - [ \ ] - [ NO₂ ]2 - Found - H₂O = 7.79 7.88 - [anhydrous salt] Ba = 20.85 20.85 - - -2. In like manner the barium ethyl salt was made. It also agreed -perfectly with Kastle’s description, crystallizing in fine, colorless -needles, forming in tufts from a not too concentrated solution. In case -it is necessary to concentrate these solutions, it is of advantage -to add a small quantity of alcohol to the solution as this prevents -any great amount of saponification, which otherwise takes place to a -noticeable extent. - -Analysis. - - I. 0.2824 gram lost 0.0276 gram at 180°, and gave 0.0860 gram BaSO₄. - - II. 0.2655 gram lost 0.0262 gram at 190°, and gave 0.0815 gram BaSO₄. - - [ COOC₂H₃ ] - [ / ] - Cal. for [C₆H₃——SO₂O ] Ba + 4H₂O. - [ \ ] - [ NO₂ ]2 - Found. - I II - H₂O = 9.51 9.77 9.86 - Ba = 20.00 19.84 20.02 - -Kastle also found that by dissolving the mixed chlorides in alcohol -in the cold, and allowing the solution to evaporate, there separated -after a time, crystals of the chloride of the acid etherial salt of -paranitroorthosulphobenzoic acid whose formation and composition are -represented in equation I. - -This same product was sought for when pure symmetrical chloride was -employed, but without success. In every case, crystals of unchanged -chloride separated, or else it was found that it had been completely -converted into the acid etherial salt. In another trial cold water -was carefully added in small portions, since Kastle found that such -treatment facilitated the separation of the substance; the chloride -alone appeared. Still other attempts were made to obtain the substance -by adding a large amount of water to the solution of the chloride -in alcohol, after it had stood for some time. In this way, quite a -precipitate was thrown down, and this was filtered off and crystallized -from ether. It always proved to be the symmetrical chloride, and none -of the other substance was obtained. - -Karslake[16] in working with the symmetrical chloride of -orthosulphobenzoic acid, was unable to isolate the analogous compound, -although from the mixed chlorides, by the action of alcohols, Remsen -and Dohme[17] had obtained chloro-etherial salts. - -[16] Inaug. Diss. J. H. Univ. 1895. - -[17] Am. Ch. Journ. XI, 341. - -In as much as the pure symmetrical chloride is relatively stable in -cold alcohol (it can be crystallized from warm alcohol with very -little loss), it is possible that it is more stable than the chloro -etherial salt, and that in consequence the latter, when formed, yields -more readily to the further action of alcohol than does the unacted -on chloride. Hence when the action begins, it at once proceeds to the -limit. The fact that the symmetrical chloride is rather sparingly -soluble in cold alcohol, making the use of concentrated solutions -impossible, may also be a factor in the case. Whatever may be the -cause, this substance could not be obtained under any conditions that -were devised. - -Having in my possession a very small specimen of crystallized -unsymmetrical chloride, it was submitted to the action of ethyl -alcohol, under as nearly as possible the conditions employed by Kastle. -Crystals of a colorless substance were obtained, which in every respect -agreed with Kastle’s description of the chloride of the acid ethyl -etherial salt of paranitroorthosulphobenzoic acid. Crystallized from -ether they melted at 68°. - -The conditions employed by Kastle in preparing the chloride would -undoubtedly lead to a relatively large proportion of unsymmetrical -chloride, and it is to this chloride that the formation of the chloro -etherial salt is apparently due. - - - - -VII. The Action of Phenols upon the Symmetrical Chloride of -Paranitroorthosulphobenzoic Acid. - - -Remsen and Saunders[18] in their investigation of the chlorides of -orthosulphobenzoic acid, studied the action of phenol upon these -substances, and from both the symmetrical chloride and the mixed -chlorides, they obtained a normal diphenyl ether together with a -red substance which was not further studied. It was formed in small -quantity and was probably the corresponding sulphonphthalein. Later -McKee[19] obtained these same substances from both the symmetrical -and the unsymmetrical chlorides. R. Meyer[20] obtained analogous -substances by the action of various phenols upon phthalyl -chloride. It seemed probable, therefore, that the chlorides of -paranitroorthosulphobenzoic acid would yield similar derivatives, -and a study was accordingly made of the reaction of the symmetrical -chloride with a series of phenols. The products in some instances were -exceedingly difficult to deal with, possessing properties that made it -impossible to prepare them for analysis, but even in such cases there -could be little doubt as to the general nature of the reactions which -had occurred. - -[18] Am. Chem. Journ. XVII, 347. - -[19] Ibid. XVIII, 798. - -[20] Ber. XXVI, 204. - - -1. The Action of Phenol upon the Symmetrical Chloride of -Paranitroorthosulphobenzoic Acid. - -A portion of the symmetrical chloride was brought together with -somewhat more than double the molecular amount of phenol. The mixture -was placed in a good-sized test-tube and the temperature gradually -raised by means of a sulphuric acid bath. - -As soon as the phenol melts, some slight action occurs, as is indicated -by the fact that the mixture assumes a bright red color. No appreciable -amount of hydrochloric acid gas is evolved however, until the liquid -mixture has reached a temperature of about 115°. At this point the -gas is freely evolved, and the action is complete at a temperature -of 125°. The temperature observations were made by means of a -thermometer used as a stirring rod in the mixture. During the heating, -the color of the liquid becomes a much more intense red, growing darker -in shade, and the liquid itself becomes somewhat viscous but does not -solidify while hot. - -When cool, the melt was repeatedly extracted with boiling water, -the aqueous solution being very deep purple in color. The colored -matter was removed very slowly in this manner, and so the process -was continued with dilute alkali. A solid insoluble residue was thus -obtained, of a light-brownish color. This was dissolved in alcohol, -boiled with boneblack and filtered. On cooling, needles of a straw -yellow color were deposited from the alcoholic solution. - -This proved to be the normal diphenyl etherial salt of -paranitroorthosulphobenzoic acid, the formation of this substance being -expressed by the equation: - - COCl COOC₆H₅ - / / - C₆H₃——SO₂Cl + 2C₆H₅OH = C₆H₃——SO₂OC₆H₅ + 2HCl. - \ \ - NO₂ NO₂ - -Analysis of the substance gave the following results: - - I. 0.1627 gram gave 0.3398 gram CO₂ and 0.0510 gram H₂O. - - II. 0.1999 gram gave 0.4180 gram CO₂ and 0.0600 gram H₂O. - - III. 0.2649 gram gave 0.1561 gram BaSO₄. - - COOC₆H₅ - / - Cal. for C₆H₃——SO₂OC₆H₅ - \ - NO₂ Found. - I II III - - C = 57.14 56.97 57.03 —— - H = 3.26 3.47 3.33 —— - S = 8.02 —— —— 8.09 - -This substance melts at 119° (uncorr). - -It possesses properties similar to those of the diphenyl etherial -salt of orthosulphobenzoic acid described by Saunders. It is -insoluble in water, and is unaffected by hydrochloric acid or aqueous -alkali. On heating for a short time with alcoholic potash, the -needles were transformed into a voluminous precipitate. This was -filtered off, dissolved in water, and hydrochloric acid was added. -On cooling, characteristic crystals of the acid potassium salt of -paranitroorthosulphobenzoic separated. - -Analysis. - -0.1392 gram lost 0.009 gram at 150° and gave 0.0385 gram K₂SO₄. - - COOH - / - Cal. for C₆H₃——SO₂OK + H₂O - \ - NO₂ - Found. - H₂O = 5.95 H₂O = 6.51 - K = 13.65 K = 13.35 - -No attempt was made to isolate the corresponding intermediate -chlor-etherial salt of the composition - - COOC₆H₅ - / - C₆H₃——SO₂Cl - \ - NO₂ - -or its acid as was done by McKee[21] in his work on the analogous -etherial salt of orthosulphobenzoic acid. - -[21] Am. Ch. Journ. XVIII-799 - -On evaporating the aqueous extract from the original melt almost to -dryness on the water-bath, there was a deposit on the sides of thedish -of scales possessing a beautiful bronze-green metallic lustre They -formed a deep purple solution in alkalis, or magenta, if the solution -was very dilute, and orange-yellow in acids. On acidifying the alkaline -extract with hydrochloric acid, this same substance was precipitated -as a brownish flocculent precipitate. It was, however, found to be -impossible to obtain this substance in pure condition. The amount -formed in the reaction is small, and its properties were such as to -render work with it very difficult. The method of precipitation is not -satisfactory because, owing to the fact that the substance is soluble -in acid solutions to an unusual extent for substances of this class, -the solution had to be concentrated to such a degree as to render the -precipitated substance very impure from acids and alkali salts. These -could not be removed by washing, obviously, without again dissolving -the substance. From its properties however, and its color reactions, -there can be little doubt that the substance is a sulphonphthaleïn, -and that it is always formed in considerable quantities in the -reaction of phenol upon the symmetrical chloride. - -It was noticed that the aqueous extract of the mass left after fusion -was almost always decidedly acid in reaction, and it was thought that -this might be due to the formation of an acid etherial salt, whose -formation would be expressed by the equations: - - COCl COOC₆H₅ - / / - C₆H₃——SO₂Cl + C₆H₅OH = C₆H₃——SO₂Cl + HCl. - \ \ - NO₂ NO₂ - - COOC₆H₅ COOC₆H₅ - / / - C₆H₃——SO₂Cl + H₂O = C₆H₃——SO₂OH + HCl. - \ \ - NO₂ NO₂ - -Accordingly, the solution was saturated with barium carbonate, the -excess of carbonate removed by filtration, the filtrate concentrated, -and allowed to cool. Crystals in the form of pearly scales separated, -which upon analysis proved to be the neutral barium salt of -paranitroorthosulphobenzoic acid. - -0.2291 gram anhydrous salt gave 0.1386 gram BaSO₄. - - COO - / \ - / Ba - / / - Cal. for C₆H₃——SO₂O - \ - NO₂ - Found - Ba = 35.85 35.57 - -This would seen to indicate that the reaction is an incomplete one even -in the presence of excess of phenol. No indications of the formation of -an acid etherial salt was observed. - - -2. The Action of Orthocresol upon the Symmetrical Chloride of -Paranitroorthosulphobenzoic Acid. - -With orthocresol the reaction proceeds with more difficulty. A higher -temperature was required (135°-145°), and quite an amount of tarry -material was obtained from which very little could be extracted. The -product was warmed repeatedly with dilute alkali, the solution so -obtained neutralized with hydrochloric acid, and distilled with steam -for several hours to free it from cresol. The resulting solution was -then evaporated to small volume, and acidified with hydrochloric acid. -A considerable precipitate was thrown down, which was easily filtered -off and dried. In this condition it is a dark purple-red powder, lumps -of which possessed a yellowish-bronze metallic lustre. In dilute -alkaline solution it forms a deep-bluish purple solution, while in -acids it is crimson, or light yellow if the solution is dilute. It is a -excellent indicator, especially with ammonia. - -In the insoluble tarry substance the etherial salt was sought for -and obtained in small quantity only. As this substance is soluble in -alcohol, and separates again on cooling in much the same condition, -the etherial salt could not be isolated be crystallization from this -solvent. By boiling the substance with benzene, purifying the filtrate -with boneblack, and allowing the benzene to evaporate, an almost -colorless gummy substance was obtained, which when dissolved in -alcohol, crystallizes in small colorless needles which melt at 89°-90°. -They were not obtained in quantity sufficient for analysis, but there -was little doubt that they were crystals of the diorthocresol etherial -salt. - -Apparently much more decomposition occurred in this reaction than -when paracresol was employed, probably in consequence of the higher -temperature required for the reaction. - - -3. The Action of Paracresol upon the Symmetrical Chloride of -Paranitroorthosulphobenzoic Acid. - -This reaction was conducted in the same manner as with phenol. No -hydrochloric acid was evolved until a temperature of about 110° was -reached, although after melting, the solution had steadily darkened to -a deep reddish-brown color. At 130°, after heating for several hours, -hydrochloric acid ceased to be evolved. The product was treated as in -the last experiment. The alkaline extract did not exhibit any marked -color reactions, such as were observed in most of these experiments, -being dull reddish-brown in both acid and alkaline solution. - -The insoluble residue crystallized from alcohol in light brown -transparent crystals, which did not lose their color by repeated -crystallization, and boiling with boneblack, and melted sharply at -117°. From benzene they crystallized in colorless needles or flat, -narrow plates. These become opaque on exposure to the air, apparently -through loss of benzene of crystallization. - -Analysis of the needles from alcohol gave the following results: - - I. 0.2372 gram of substance gave 0.5137 gram CO₂ and - 0.0965 gram H₂O. - - II. 0.2223 gram gave 0.1203 gram BaSO₄. - - COOC₆H₄.CH₃ - / - Cal. for C₆H₃——SO₂OC₆H₄.CH₃ - \ - NO₂ - Found. - I II - C = 59.08 59.06 - H = 3.98 4.52 - S = 7.49 7.43 - - -4. The Action of Hydroquinone upon the Symmetrical Chloride of -Paranitroorthosulphobenzoic Acid. - -Action with hydroquinone occurs at 120°-135°, the mixture at the same -time becoming dark colored and viscous. - -On cooling, the product was powdered and treated with dilute alkali. -It readily dissolved, without residue, forming a dark red solution. -In concentrated solution the addition of acid produces a voluminous -precipitate, dark brown in color, which when washed, and dried in paper -forms an almost black powder. A dilute solution of this powder is dark -red when alkaline, orange-yellow when acid. - -From the way in which this powder was obtained, and owing to the fact -that its solubility prevented repeated washing, it was evident that it -would not give close analytical results for a calculated formula. It -was thought, however, that analysis would give a general idea of the -composition. - -Analysis of different specimens gave results for sulphur which averaged -about 5.5%. The percentage required for the formula - - C[C₆H₃(OH)₂]₂ - / \ - / O - / / - C₆H₃——SO₂ - \ - NO₂ - -which represents the simplest sulphonfluoresceïn, is 7.43. - -The compound could hardly have been so far from pure as to occasion -such a discrepancy in results as this. It would appear, therefore, that -more than two molecules of hydroquinone enter into the reaction with -one molecule of the chloride. Should four molecules be involved in the -reaction, leading to a compound of some such formula as - - C[C₆H₃(OH)₂] - / \ - / O - / / - C₆H₃——SO[C₆H₃(OH)₂]₂ - \ - NO₂ - -the theoretical percentage of sulphur would be 6.00 which corresponds -much more closely with the results obtained. - -This is in accord with the observations of a number of workers in -this laboratory—Lyman, Gilpin, Linn and others—who have worked on -various sulphonfluoresceïns, and have found that in many cases four, -six and even eight phenol residues condense with one molecule of the -anhydrous acid. Lyman[22] especially describes a tetra hydroquinone -sulphonfluoresceïn derived from orthosulphoparatoluic acid. No etherial -salt was observed. - -[22] Am. Chem. Journ. XVI-525 - -5. The Action of Resorcin upon the Symmetrical Chloride of -Paranitroorthosulphobenzoic Acid. - -The reaction of resorcin with the chloride is a much cleaner one -and proceeds more easily than in the case just described, leading -apparently to an individual compound which is well characterized. - -During the reaction, which is complete at 125°, the mixture becomes -almost perfectly solid, and when cool, it is quite brittle. It was -reduced to a reddish powder in a mortar and dissolved in sodium -hydroxide, there being no insoluble residue. By the addition of -hydrochloric acid, the sulphonfluoresceïn was thrown down as a -chocolate-brown precipitate, which was filtered off, washed to -neutral reaction on a filter, and dried on paper. In this condition -it is a light chocolate-brown powder. In dilute alkaline solution it -possesses a slight fluorescence being pink by transmitted and yellow be -reflected light, suggesting eosin in a general way. It is interesting -to note that the sulphonfluoresceïn of orthosulphobenzoic acid -possesses a fluorescence that can hardly be distinguished from ordinary -fluoresceïn and that the introduction of a nitro group into the acid -residue produces much of the same effect as do the four bromine atoms -in eosin. In acid solution the color is reddish-orange. - -Analysis of the compound, prepared as above described, gave the -following results. - - I. 0.1745 gram gave 0.3339 gram of CO₂ and - 0.059 gram H₂O. - - II. 0.1467 gram gave 0.2820 gram CO₂ and - 0.0432 gram H₂O. - - III. 0.1732 gram gave 0.3345 gram CO₂ and - 0.0571 gram H₂O. - - IV. 0.2000 gram gave 0.1104 gram BaSO₄. - - V. 0.1505 gram gave 0.0820 gram BaSO₄. - - OH ] - / ] - C[C₆H₃ ] - / \ \ ] - / O OH ]2 - / / - Cal. for C₆H₃——SO₂ - \ - NO₂ - Found - I II III IV V - C = 52.66 52.18 52.42 52.67 —— —— - H = 3.46 3.76 3.27 3.66 —— —— - S = 7.39 —— —— —— 7.57 7.48 - -An effort to obtain the anhydride was unsuccessful. Some loss of weight -was observed, but the compound underwent decomposition before this loss -amounted to much. - - -6. The Action of Pyrogallol upon the Symmetrical Chloride of -Paranitroorthosulphobenzoic Acid. - -The product of this action dissolves readily in dilute sodium hydroxide -without residue, producing a very deep purple-black color when -concentrated, passing to grayish-violet as the solution is diluted. On -adding hydrochloric acid, precipitation occurs, as in most of these -reactions. On attempting to filter off this precipitate, it forms a -sticky, black mass on the filter with which little can be done. It is -best to evaporate to dryness before filtration and powder the residue. -This powder can then be washed fairly clean from alkali salts and -acid. - -Nothing to suggest the formation of an etherial salt was observed. - -Analysis of this product for sulphur showed that in this galleïn, as -in the case of the hydroquinone phthaleïn more than two pyrogallol -residues had entered the acid residue. The indications were that -six had entered into one of the chloride. This also agrees with the -observation of Lyman[23], who describes a hexapyrogallol galleïn of -orthosulphoparatoluic acid. - -Probably a mixture of varying composition was obtained, and little -importance was attached to the results save as they showed that no -etherial salt is formed in the reaction. - -[23] Am. Ch. Journ. XVI-527. - - -7. The Action of β-Naphthol upon the Symmetrical Chloride of -Paranitroorthosulphobenzoic Acid. - -It was hoped that here, as in the case of the monohydroxy phenols an -etherial salt would be obtained. It was found, however, that very -little action occurred, save such as was indicated by the development -of a bright carmine color in the melted mixture, until a temperature of -about 160° was reached. At this point hydrochloric acid was evolved, -but the chloride itself undergoes decomposition. Nothing definite could -be isolated among the reaction products, save unchanged β-Naphthol. - - - - -VIII. The Action of Aniline upon the Symmetrical Chloride of -Paranitroorthosulphobenzoic Acid. - - -As has been pointed out in the Introduction, it was in connection -with the aniline derivatives of orthosulphobenzoic acid, that the -isomerism of the chlorides was first noticed, two anilids being -obtained. Accordingly, when Gray began his study of the chlorides -of paranitroorthosulphobenzoic acid, his first effort was to obtain -evidence of the existence of two anilids. These were not obtained, -however, until after the chlorides themselves had been isolated, as -their properties made their isolation and preparation a matter of -difficulty. - -Some points still remained in doubt after Gray’s study, and a further -investigation was thought to be desirable to clear these up. - -Some time was spent in an endeavor to obtain a method by which a good -yield of fusible, or symmetrical, anilid could be obtained. The yield -in all cases tried, is not a good one. The presence of the nitro group -appears to complicate the reaction, leading to secondary reactions -whose course could not be followed. Upon bringing aniline and the -chloride together, a very vivid red color was always observed, and the -same was true when it was necessary to employ alkali. The fact that -such colors develop when nitro compounds are treated with alkali has -been noticed in many instances and some progress has been made in the -study of these compounds. Jackson and Ittner[24] have lately reviewed -this subject. - -If a solution of the symmetrical chloride in ether is slowly added to a -similar solution of aniline, no appreciable amount of heat is evolved. -If the resulting solution is allowed to stand at ordinary temperatures, -action proceeds very slowly, aniline hydrochloride being precipitated -as the reaction proceeds. This can be filtered off from time to time -and the rate of action so observed. In such a way it was found that -five grams of chloride required about fifty hours time to react -completely with an excess of aniline. Similar results were obtained -with chloroform as the solvent. By boiling the solution for an hour or -more the reaction is complete. - -[24] Am. Chem. Journ. XIX-199 - -The method employed was to bring the chloride and an excess of -aniline—somewhat more than four molecules—together in chloroform -solution. The flask was then boiled for about an hour, when the -chloroform was distilled off. During the boiling as well as the -distillation more or less bumping occurs in consequence of the aniline -hydrochloride which separates, and constant shaking of the flask is -sometimes necessary. The residue which is in a thick, gummy condition -in consequence of the presence of an excess of aniline, was digested -with water acidulated with hydrochloric acid. The excess of aniline -is thus removed, and the reaction product obtained as a reddish-brown -solid substance. This was treated with dilute sodium hydroxide, all -lumps being broken up with a stirring rod. The undissolved substance -is largely anil, which was filtered off. The anilid was then regained -by acidifying the alkaline solution, in which it was dissolved. It -separates immediately as a curdy colorless precipitate, though it is -frequently colored pink by impurity. It was found that this color could -be removed, in case not much was present, by redissolving the anilid in -alkali, and slowly pouring the solution into an excess of dilute acid. - -In all cases a considerable amount of anil was obtained, even when the -substances were employed in the molecular ratios of 1:10. The reactions -involved, so far as the formation of anilid and anil are concerned are, - - COCl CO.NH.C₆H₅ - / / - C₆H₃——SO₂Cl + 4C₆H₅NH₂ = C₆H₃——SO₂.NH.C₆H₅ + C₆H₅NH₃Cl - \ \ - NO₂ NO₂ - - CO - / \ - COCl / N.C₆H₅ - / / / - C₆H₃——SO₂Cl + 3C₆H₅NH₂ = C₆H₃——SO₂ + 2C₆H₅NH₃Cl - \ \ - NO₂ NO₂ - -On the whole the reaction seemed to be the most satisfactory in -chloroform solution, the main objection being, that, owing to the -simultaneous presence of chloroform, alkali, an a trace of aniline, -phenyl isocyanide is always formed, and renders the work more or less -unpleasant. - -A number of experiments were also made to see if the yield could -be increased be employing a modification of the “Schotten-Baumann -Reaction”[25] for the formation of anilids. For this purpose an etherial -solution of the chloride was added to a like solution of aniline in -which was suspended finely powdered anhydrous potassium carbonate. The -proportions of the substances were those demanded by the equation - - COCl CO.NH.C₆H₅ - / / - C₆H₃——SO₂Cl + 2C₆H₅NH₂ + 2K₂Cl₃ = C₆H₃——SO₂NH.C₆H₅ + 2KCl + 2KHCO₃ - \ \ - NO₂ NO₂ - -Very little anilid was, however obtained, but in its place a -substance soluble in water, of acid reaction capable of forming salts -and yielding several well characterized derivatives. I hope to -investigate this reaction more fully at some future time. - -[25] Ber. XVII-2545; XXIII, 3430. - - * * * * * - -The anilid is rather sparingly soluble in alcohol, from which it is -deposited on cooling in very small needles. These melt, as stated by -Gray, at 222°. It is also soluble in chloroform and glacial acetic -acid, but does not form well defined crystals from any solvent. It -dissolves in dilute alkali from which solution acids precipitate it -unchanged. - - * * * * * - -The anil is also soluble in alcohol, glacial acetic acid etc. It -crystallizes in much better-formed crystals than does the anilid. These -melt at 188°. - -On boiling the anil with aniline for a time, it is converted into the -anilid - - CO - / \ - / N.C₆H₅ CO.NH.C₆H₅ - / / / - C₆H₃——SO₂ + C₆H₅NH₂ = C₆H₃——SO₂NH.C₆H₅ - \ \ - NO₂ NO₂ - -In none of these reactions was any infusible anilid observed. - - - - -IX. The Action of Phosphorus Oxychloride upon the Fusible Anilid. - - -Hunter[26] found that when either of the anilids of orthosulphobenzoic -acid were treated with phosphorus oxychloride, or similar dehydrating -agents, a molecule of water was abstracted with the formation of a new -substance. A careful study of the compound led to the belief that it -was a dianil, and that its formation and structure could be represented -by the equation - - C=N.C₆H₅ - / \ - CO.NH.C₆H₅ / \ - / / .N.C₆H₅ - C₆H₄ = C₆H₄ / + H₂O. - \ \ / - SO₂NH.C₆H₅ SO₂ - -A corresponding study of the fusible anilid of -paranitroorthosulphobenzoic acid was undertaken. - -The method employed in this study was as follows. A tubulated retort -of convenient size was fused onto the inner tube of a small condenser. -This was done to avoid connections, which are nearly always attacked by -the oxychloride. Another satisfactory plan is to have the neck of the -retort of the same size as the inner tube of the condenser. The ends -are placed in contact, and the tubes bound in position by wrapping with -asbestos paper. Over the joint so made, a tight rubber tube is drawn. - -[26] Am. Ch. Journ. XVIII-810. - -A convenient amount of phosphorus oxychloride (50 c.c.) was placed -in the retort and the anilid (5 gr.) added through the tubulus. On -boiling, with the condenser inverted, the anilid soon dissolved, -with evolution of hydrochloric acid gas, and the solution became -bright yellow in color, sometimes inclining to orange. The boiling was -continued as long as hydrochloric acid was given off. The oxychloride -was then distilled off under diminished pressure, care being taken to -shake the retort constantly during the distillation as violent bumping -is almost sure to occur especially towards the end of the operation. -The product remaining, spattered over the walls of the retort, was a -greenish yellow solid. - -Water was then added, and the whole allowed to stand for an hour or -so to thoroughly dissolve the phosphoric acid formed in the reaction. - -In case the anilid is not perfectly dry, a much more energetic reaction -occurs, and on distilling off the oxychloride, the product remains as a -dark, gummy mass. This should be spread out on the sides of the retort -while still liquid. On cooling and adding water, this gum gradually -disappears, and in its place is found the yellow solid product just -described. The gum appears to be a solution of this substance in -phosphoric acid. - -After the substance is filtered off and dried, it can be crystallized -from acetone, benzene, glacial acetic acid or alcohol. From these -solvents it crystallizes in small yellow needles resembling quinone in -appearance. - -The crystals obtained form acetone are rather larger than those from -the other solvents, and are more nearly orange in color, apparently -because of their greater compactness. When glacial acetic acid is used, -care must be taken to avoid any unnecessary heating, as continued -heating produces a change that will presently be described. The -substance melts at 208°. - -Analysis of the substance resulted as follows: - - I. 0.3822 gram gave 0.8334 gram CO₂ and 0.1272 gram H₂O. - - II. 0.2645 gram gave 0.5812 gram CO₂ and 0.0910 gram H₂O. - - III. 0.2023 gram gave 0.1283 gram BaSO₄. - - IV. 0.2061 gram gave 0.1280 gram BaSO₄. - - V. 0.1853 gram gave 16.73 C.C.N (Standard). - - C=N.C₆H₅ - / \ - / .N.C₆H₅ - / / - Cal. for C₆H₃——SO₂ - \ - NO₂ - Found. - I II III IV V - C = 60.11 59.47 59.93 —— —— —— - H = 3.44 3.69 3.82 —— —— —— - S = 8.45 —— —— 8.70 8.52 —— - N = 11.08 —— —— —— —— 11.35 - -For analyses I & II I am indebted to Mr. Nakaseko, who kindly made them -for me. - - - - -X. The Action of Reagents upon the Dianil of -Paranitroorthosulphobenzoic Acid. - - -1. The Action of Hydrochloric Acid on the Dianil - -When the dianil is boiled for some time with concentrated hydrochloric -acid, the yellow color of the substance disappears, and the dianil is -converted into a colorless substance without, however, passing into -solution. The substance so obtained was filtered off, and crystallized -from alcohol. It crystallized in small colorless needles, which melted -at 183°, and possessed all the properties of the anil, which, in fact, -it proved to be. The reaction was therefore - - C=N.C₆H₅ CO - / \ / \ - / N.C₆H₅ / N.C₆H₅ - / / / / - C₆H₃——SO₂ + HCl + H₂O = C₆H₃——SO₂ + C₆H₅NH₃Cl - \ \ - NO₂ NO₂ - -This reaction also explains the fact that some anil was always obtained -in making the dianil from the anilid. Hydrochloric acid is formed -in the reaction, and in turn acts on the dianil in the sense of the -equation just given. - - -2. The Action of Alcoholic Potash on the Dianil. - -On boiling the dianil with alcoholic potash for a time, the solution -turned red, and nothing but tarry products were obtained. In this -respect the dianil differs from the dianil of orthosulphobenzoic acid, -which under similar conditions, is transformed into infusible anilid. -This observation is, however, in keeping with the fact that the nitro -derivative, is in general much less stable in the presence of alkali. - - -3. The Action of Glacial Acetic Acid on the Dianil. - -When the dianil is boiled with glacial acetic acid for some time, the -color of the solution changes to a much lighter shade of yellow, or -becomes colorless. On evaporating the solution to small volume, and -allowing it to cool, a colorless substance separates. This is infusible -anilid. It could not be obtained in crystals from any solvent, but -always separated in flakes. It does not melt or undergo change at 340°. - -Like the fusible anilid it dissolves in dilute alkali, but on -acidifying the solution it does not immediately reappear. After -standing for some time, however, it gradually separates in perfectly -pure form. In this particular my observation differs from that of -Gray,[27] who states that this anilid is decomposed by solution in -alkali. - -[27] Inaug. Diss. J. H. Unis. 1895. - -A specimen that had been repeatedly precipitated gave the following -results on analysis. - - I. 0.1607 gram gave 13.88 C.C.N. (standard). - - II. 0.2195 gram gave 0.1285 gram BaSO₄. - - III. 0.1357 gram gave 0.0807 gram BaSO₄. - - C[NH.C₆H₅]₂ - / \ - / O - / / - Cal. for C₆H₃——SO₂ - \ - NO₂ - Found. - I. II. III. - - N = 10.58 10.85 —— —— - S = 8.06 —— 8.00 8.16 - -By this series of transformations it is possible to pass from one -anilid to the other, the steps being: - - CO.NH.C₆H₅ C=N.C₆H₅ C[NH.C₆H₅]₂ - / / \ / \ - / / N.C₆H₅ / O - / / / / / - C₆H₃——SO₂NH.C₆H₅ ➡ C₆H₃——SO₂ ➡ C₆H₃——SO₂ - \ \ \ - NO₂ NO₂ NO₂ - -This is of special interest as affording a means of passing from a -derivative of one of the chlorides, to a substance derived from the -other, by steps that can be clearly followed. - - - - -Conclusions. - - -In the course of this investigation several facts have been established. - -1. By the methods described, the symmetrical chloride of -paranitroorthosulphobenzoic acid can be obtained in fine crystalline -form, perfectly free from its isomer, with an average yield of forty -percent. - -2. By treatment of the chloride with benzene and aluminium chloride, -only one chlorine atom can be replaced by a phenyl group. - -3. The barium salt of paranitroorthobenzoyl benzenesulphonic acid, when -perfectly pure, crystallizes constantly with seven molecules of water -of crystallization. - -4. With alcohols, the symmetrical chloride yields directly the acid -etherial salt of paranitroorthosulphobenzoic acid, no evidence -having been obtained of an intermediate chloro-etherial salt. The -unsymmetrical chloride on the other hand yields the intermediate -product. - -5. With phenols, two series of derivatives are obtained. - - (1) With monohydroxy phenols, both etherial salts and - sulphonphthaleïns are formed, the former predominating. - - (2) With polyhydroxy phenols no etherial salts were obtained, - but compounds of the unsymmetrical type, usually containing - more than two phenol residues. - -6. With aniline an anil and an anilid of symmetrical constitution are -formed. - -7. With phosphorus oxychloride, the anilid, by loss of water, forms a -dianil. - -8. This dianil undergoes transformation with - - (1) Glacial acetic acid, forming an anilid of unsymmetrical - constitution. - - (2) Hydrochloric acid forming the anil. - - (3) Alcoholic potash, with the formation of colored decomposition - products. - - - - -Biographical. - - -The author of the foregoing dissertation was born at Wilkinsburg, Pa., -Jan. 29., 1870. Owing to prolonged sickness in childhood his education, -prior to entering college, was much interrupted, and was largely -confined to instruction received at home. - -In the fall of 1887 he entered Wooster University (Ohio), from which -institution he received the degree of Bachelor of Arts in 1891. The two -following years were spent as a teacher of Sciences in the College of -Emporia (Kansas). In 1893 he entered the Johns Hopkins University where -he has since been a student of chemistry, with physics and mathematics -as subordinate studies. - -In 1895 he was appointed University Scholar in Chemistry. During 1895-6 -he served as lecture assistant to Prof. Remsen and Dr. Renouf in the -undergraduate courses. In the spring of 1896 he was appointed Fellow -for the present year. - -*** END OF THE PROJECT GUTENBERG EBOOK A FURTHER INVESTIGATION OF THE -SYMMETRICAL CHLORIDE OF PARANITROORTHOSULPHOBENZOIC ACID *** - -Updated editions will replace the previous one--the old editions will -be renamed. - -Creating the works from print editions not protected by U.S. copyright -law means that no one owns a United States copyright in these works, -so the Foundation (and you!) can copy and distribute it in the -United States without permission and without paying copyright -royalties. Special rules, set forth in the General Terms of Use part -of this license, apply to copying and distributing Project -Gutenberg-tm electronic works to protect the PROJECT GUTENBERG-tm -concept and trademark. 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margin-left: 0em; padding-left: 10em;} -.ws11 {display: inline; margin-left: 0em; padding-left: 11em;} -.ws11-5 {display: inline; margin-left: 0em; padding-left: 11.5em;} -.ws12 {display: inline; margin-left: 0em; padding-left: 12em;} -.ws12-5 {display: inline; margin-left: 0em; padding-left: 12.5em;} -.ws13 {display: inline; margin-left: 0em; padding-left: 13em;} -.ws13-5 {display: inline; margin-left: 0em; padding-left: 13.5em;} -.ws14 {display: inline; margin-left: 0em; padding-left: 14em;} -.ws14-5 {display: inline; margin-left: 0em; padding-left: 14.5em;} -.ws15-5 {display: inline; margin-left: 0em; padding-left: 15.5em;} -.ws16 {display: inline; margin-left: 0em; padding-left: 16em;} -.ws17 {display: inline; margin-left: 0em; padding-left: 17em;} - </style> - </head> -<body> -<p style='text-align:center; font-size:1.2em; font-weight:bold'>The Project Gutenberg eBook of A Further Investigation of the Symmetrical Chloride of Paranitroorthosulphobenzoic Acid, by William E. Henderson</p> -<div style='display:block; margin:1em 0'> -This eBook is for the use of anyone anywhere in the United States and -most other parts of the world at no cost and with almost no restrictions -whatsoever. You may copy it, give it away or re-use it under the terms -of the Project Gutenberg License included with this eBook or online -at <a href="https://www.gutenberg.org">www.gutenberg.org</a>. If you -are not located in the United States, you will have to check the laws of the -country where you are located before using this eBook. -</div> - -<p style='display:block; margin-top:1em; margin-bottom:1em; margin-left:2em; text-indent:-2em'>Title: A Further Investigation of the Symmetrical Chloride of Paranitroorthosulphobenzoic Acid</p> -<p style='display:block; margin-top:1em; margin-bottom:0; margin-left:2em; text-indent:-2em'>Author: William E. Henderson</p> -<p style='display:block; text-indent:0; margin:1em 0'>Release Date: April 25, 2022 [eBook #67920]</p> -<p style='display:block; text-indent:0; margin:1em 0'>Language: English</p> - <p style='display:block; margin-top:1em; margin-bottom:0; margin-left:2em; text-indent:-2em; text-align:left'>Produced by: The Online Distributed Proofreading Team at https://www.pgdp.net (This file was produced from images generously made available by The Internet Archive)</p> -<div style='margin-top:2em; margin-bottom:4em'>*** START OF THE PROJECT GUTENBERG EBOOK A FURTHER INVESTIGATION OF THE SYMMETRICAL CHLORIDE OF PARANITROORTHOSULPHOBENZOIC ACID ***</div> - -<hr class="chap x-ebookmaker-drop" /> - -<h1>A Further Investigation of the<br />Symmetrical Chloride of<br /> -Paranitroorthosulphobenzoic Acid.</h1> - -<hr class="chap x-ebookmaker-drop" /> - -<p class="f150 space-below1">Dissertation.</p> - -<p class="f120">Submitted to the Board of University<br /> -Studies of the Johns Hopkins University<br /> -for the Degree of Doctor of Philosophy.</p> - -<p class="center space-above2">— by —</p> -<p class="f150">William E. Henderson.</p> - -<p class="center space-above2">1897</p> - -<hr class="chap x-ebookmaker-drop" /> - -<div class="chapter"> -<h2 class="nobreak">Acknowledgment.</h2> -</div> -<div class="blockquot"> -<p>The author esteems it a privilege as well as a pleasure to give -expression to his sincere sense of gratitude to Prof. Remsen,under -whose guidance this work was carried on not only for instruction -received in the lecture room, but for his frequent suggestion, and his -constant and friendly interest in the work as it progressed. These have -at all times been an encouragement and an incentive.</p> - -<p>He wishes also to express his appreciation of the instruction and -kindly guidance in the laboratory, of Drs. Morse and Renouf, as well as -of Dr. Ames of the Physical Laboratory.</p> -</div> - -<hr class="chap x-ebookmaker-drop" /> - -<div class="chapter"> -<h2 class="nobreak">Contents.</h2> -</div> - -<table class="fontsize_120" border="0" cellspacing="0" summary="TOC" cellpadding="0" > - <tbody><tr> - <td class="tdr">I.</td> - <td class="tdl_ws1">Introduction.</td> - <td class="tdr"><a href="#Page_1">Page 1</a></td> - </tr><tr> - <td class="tdr">II.</td> - <td class="tdl_ws1">Preparation of the Acid Potassium Salt</td> - <td class="tdr"> </td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdl_ws2">of Paranitroorthosulphobenzoic Acid.</td> - <td class="tdr"><a href="#Page_6"> 6</a></td> - </tr><tr> - <td class="tdr">III.</td> - <td class="tdl_ws1">Preparation of the Symmetrical Chloride</td> - <td class="tdr"> </td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdl_ws2">of Paranitroorthosulphobenzoic Acid.</td> - <td class="tdr"><a href="#Page_12">12</a></td> - </tr><tr> - <td class="tdr">IV.</td> - <td class="tdl_ws1">Properties of the Symmetrical Chloride</td> - <td class="tdr"> </td> - </tr><tr> - <td class="tdr bb"> </td> - <td class="tdl_ws2 bb">of Paranitroorthosulphobenzoic Acid.</td> - <td class="tdr bb"><a href="#Page_19">19</a></td> - </tr><tr> - <td class="tdr">V.</td> - <td class="tdl_ws1">The Action of Benzene and Aluminium</td> - <td class="tdr"> </td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdl_ws2">Chloride on the Symmetrical Chloride</td> - <td class="tdr"> </td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdl_ws2">of Paranitroorthosulphobenzoic Acid.</td> - <td class="tdr"><a href="#Page_22">22</a></td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdl_ws1">The Barium Salts of</td> - <td class="tdr"> </td> - </tr><tr> - <td class="tdr bb"> </td> - <td class="tdl_ws2 bb">Paranitroorthobenzoybbenzenesulphonic Acid.</td> - <td class="tdr bb"><a href="#Page_24">24</a></td> - </tr><tr> - <td class="tdr">VI.</td> - <td class="tdl_ws1">The Action of Alcohols on the Symmetrical Chloride</td> - <td class="tdr"> </td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdl_ws2">of Paranitroorthosulphobenzoic Acid.</td> - <td class="tdr"><a href="#Page_30">30</a></td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdl_ws3">1. Methyl Alcohol.</td> - <td class="tdr"><a href="#VI_1">31</a></td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdl_ws3">2. Ethyl Alcohol.</td> - <td class="tdr"><a href="#VI_2">32</a></td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdl_ws3">Action of Ethyl Alcohol on the Unsymmetrical</td> - <td class="tdr"> </td> - </tr><tr> - <td class="tdr bb"> </td> - <td class="tdl_ws3 bb"> Chloride.</td> - <td class="tdr bb"><a href="#VI_3">36</a></td> - </tr><tr> - <td class="tdr">VII.</td> - <td class="tdl_ws1">The Action of Phenols on the Symmetrical Chloride</td> - <td class="tdr"> </td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdl_ws2">of Paranitroorthosulphobenzoic Acid.</td> - <td class="tdr"><a href="#Page_38">38</a></td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdl_ws3">1. Phenol.</td> - <td class="tdr"><a href="#VII_1">40</a></td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdl_ws3">2. Orthocresol.</td> - <td class="tdr"><a href="#VII_2">48</a></td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdl_ws3">3. Paracresol.</td> - <td class="tdr"><a href="#VII_3">51</a></td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdl_ws3">4. Hydroquinone.</td> - <td class="tdr"><a href="#VII_4">53</a></td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdl_ws3">5. Resorcin.</td> - <td class="tdr"><a href="#VII_5">56</a></td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdl_ws3">6. Pyrogallol.</td> - <td class="tdr"><a href="#VII_6">59</a></td> - </tr><tr> - <td class="tdr bb"> </td> - <td class="tdl_ws3 bb">7. β-naphthol.</td> - <td class="tdr bb"><a href="#VII_7">61</a></td> - </tr><tr> - <td class="tdr">VIII.</td> - <td class="tdl_ws1">The Action of Aniline on the Symmetrical Chloride</td> - <td class="tdr"> </td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdl_ws2">of Paranitroorthosulphobenzoic Acid.</td> - <td class="tdr"><a href="#Page_62">62</a></td> - </tr><tr> - <td class="tdr">IX.</td> - <td class="tdl_ws1">The Action of Phosphorus Oxychloride on the Fusible</td> - <td class="tdr"> </td> - </tr><tr> - <td class="tdr bb"> </td> - <td class="tdl_ws2 bb">Anilid of Paranitroorthosulphobenzoic Acid.</td> - <td class="tdr bb"><a href="#Page_71">71</a></td> - </tr><tr> - <td class="tdr">X.</td> - <td class="tdl_ws1">The Action of Reagents on the Dianil of</td> - <td class="tdr"> </td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdl_ws2">Paranitroorthosulphobenzoic Acid.</td> - <td class="tdr"><a href="#Page_77">77</a></td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdl_ws3">1. Of Hydrochloric Acid.</td> - <td class="tdr"><a href="#X_1">77</a></td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdl_ws3">2. Of Alcoholic Potash.</td> - <td class="tdr"><a href="#X_2">78</a></td> - </tr><tr> - <td class="tdr bb"> </td> - <td class="tdl_ws3 bb">3. Of Glacial Acetic Acid.</td> - <td class="tdr bb"><a href="#X_3">79</a></td> - </tr><tr> - <td class="tdr">XI.</td> - <td class="tdl_ws1">Conclusions.</td> - <td class="tdr"><a href="#Page_82">82</a></td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdl_ws1">Biographical.</td> - <td class="tdr"><a href="#Page_85">85</a></td> - </tr> - </tbody> -</table> - -<hr class="chap x-ebookmaker-drop" /> - -<div class="chapter"> -<p><span class="pagenum" id="Page_1">[Pg 1]</span></p> -<h2 class="nobreak">I. Introduction.</h2> -</div> - -<p>The sulphobenzoic acids have been the subject of investigation in this -laboratory for a number of years past. Among the many interesting -facts that have been brought to light in the course of this study, -perhaps no others have been attended with more interest than the -discovery of well characterized isomerism in the case of the chlorides -of orthosulphobenzoic acid, and its paranitro derivative; together -with the preparation of a series of isomeric derivatives of these -substances. The chlorides themselves have been isolated in the -crystalline condition, and have been found to differ markedly, not only -<span class="pagenum" id="Page_2">[Pg 2]</span> -in chemical, but in physical properties as well.</p> - -<p>The first evidence that such isomerism existed, was obtained by Remsen -and Coates<a id="FNanchor_1" href="#Footnote_1" class="fnanchor">[1]</a> - who, in the course of an investigation of the action of -aniline upon the chloride of orthosulphobenzoic acid, obtained two -isomeric anilids quite different in properties, which they designated -as fusible and infusible respectively. The following year, Remsen and -Kohler<a id="FNanchor_2" href="#Footnote_2" class="fnanchor">[2]</a> -obtained one of the chlorides in crystalline form, together -with an oil which they did not succeed in crystallizing.</p> - -<p>This however was accomplished the succeeding year by Remsen and -Saunders<a id="FNanchor_3" href="#Footnote_3" class="fnanchor">[3]</a>, -and a still more satisfactory result was obtained by -<span class="pagenum" id="Page_3">[Pg 3]</span> -Remsen and McKee<a id="FNanchor_4" href="#Footnote_4" class="fnanchor">[4]</a> -in 1895. The chloride melting at 79° was found to yield only the -fusible anilid, together with an anil, while from the lower melting -chloride, in addition to these, the infusible anilid was also formed.</p> - -<p>In 1895, Gray<a id="FNanchor_5" href="#Footnote_5" class="fnanchor">[5]</a> -isolated the two corresponding isomeric chlorides of -paranitroorthosulphobenzoic acid, the lower melting chloride being -obtained in small quantity only. The succeeding year -Hollis<a id="FNanchor_6" href="#Footnote_6" class="fnanchor">[6]</a> -made a more careful study of this lower melting chloride, and prepared -it in considerable quantity.</p> - -<p>From evidence drawn from the action of ammonia upon these chlorides, -taken in connection with a number of other facts, the higher melting -chloride is identified as the one possessing a symmetrical structure, -<span class="pagenum" id="Page_4">[Pg 4]</span> -while the lower melting chloride possesses an unsymmetrical structure. -The first one, when treated with ammonia is slowly transformed into the -ammonium salt of paranitrobenzoic sulphinide:</p> - -<p class="left120 no-wrap"><b> -<span class="ws12">CO</span><br /> -<span class="ws14-5">/</span><span class="ws2">\</span><br /> -<span class="ws4">COCl</span> <span class="ws7-5">/</span><span class="ws2">N.NH₄</span><br /> -<span class="ws3-5">/</span><span class="ws10">/</span><span class="ws2-5">/</span><br /> -<span class="ws2">C₆H₃—SO₂Cl + 4NH₃ = C₆H₃—SO₂ + 2NH₄Cl.</span><br /> -<span class="ws3-5">\</span><span class="ws10">\</span><br /> -<span class="ws4">NO₂</span><span class="ws8">NO₂</span><br /> -</b></p> - -<p class="no-indent">while the lower melting chloride is quickly transformed -into the ammonium salt of paranitroorthocyanbenzenesulphonic acid:</p> - -<p class="left120 no-wrap"><b> -<span class="ws2">CCl₂</span><br /> -<span class="ws4-5">/</span>   \<br /> -<span class="ws4">/</span><span class="ws2-5">O</span><span class="ws5-5">CN</span><br /> -<span class="ws3-5">/</span><span class="ws2-5">/</span><span class="ws6-5">/</span><br /> -<span class="ws2">C₆H₃—SO₂ + 4NH₃ = C₆H₃—SO₂ONH₄ + 2NH₄Cl.</span><br /> -<span class="ws3-5">\</span><span class="ws9">\</span><br /> -<span class="ws4">NO₂</span><span class="ws7">NO₂</span><br /> -</b></p> - -<p>Gray’s study of the symmetrical chloride was confined for the most part -to the preparation of a series of salts of this latter acid, and to an -<span class="pagenum" id="Page_5">[Pg 5]</span> -investigation of the action of aniline upon the chloride itself. It -was thought to be of interest to extend this study to a wider range of -reactions, as well as to improve, if possible, the method of preparing -the chloride in pure condition. At the suggestion of Prof. Remsen this -work was accordingly undertaken.</p> -<hr class="chap x-ebookmaker-drop" /> - -<div class="chapter"> -<p><span class="pagenum" id="Page_6">[Pg 6]</span></p> -<h2 class="nobreak">II. Preparation of Material.</h2> -</div> - -<p>The method employed in the preparation of paranitroorthosulphobenzoic -acid was essentially that described by -Hart,<a id="FNanchor_7" href="#Footnote_7" class="fnanchor">[7]</a> -Kastle,<a id="FNanchor_8" href="#Footnote_8" class="fnanchor">[8]</a> -Gray<a id="FNanchor_9" href="#Footnote_9" class="fnanchor">[9]</a> -and Hollis.<a id="FNanchor_10" href="#Footnote_10" class="fnanchor">[10]</a> -The details of it are repeated here for the purpose of calling -attention to certain facts that came under the author’s notice.</p> - -<p>100 grams of paranitrotoluene are added to 400 grams of fuming sulfuric -acid, and the mixture heated in a balloon flask at 100° on a water -bath. The heating is continued until a few drops of the mixture, added -to cold water, dissolves completely to a clear solution. The time -<span class="pagenum" id="Page_7">[Pg 7]</span> -required for this operation varies much with the conditions. Continued -stirring very considerably hastens the reaction, as paranitrotoluene -forms a layer on the acid, which presents a small surface to its -action. With constant stirring the reaction is complete in a few hours, -whereas if no stirring is resorted to, as much as several days may be -required, especially when large quantities are employed at one time.</p> - -<p>When the reaction is complete, the mixture is poured into a -large volume of water, and neutralized with calcium carbonate. -In the filtrate from calcium sulphate, the calcium salt of -paranitroorthotoluene sulphonic acid is found, and this is converted -into the potassium salt in the usual way. -<span class="pagenum" id="Page_8">[Pg 8]</span></p> - -<p>The oxidation of the potassium salt is effected as follows. 50 grams of -the salt are dissolved in 2½ litres of water, and to this is added a -solution of 15 grams of potassium hydroxide. The mixture is heated to -100° on a water-bath, and when this temperature is reached, 110 grams -of potassium permanganate are added. Heating is continued until the -solution is decolorized, care being taken to prevent the evolution of -free oxygen.</p> - -<p>The oxides of manganese are then filtered off, the filtrate neutralized -with hydrochloric acid, and evaporated to about one fifth of its -original volume. Strong hydrochloric acid is them added in excess, and -on cooling the acid potassium salt of paranitroorthosulphobenzoic acid -separates in very slender colorless needles completely filling the liquid. -<span class="pagenum" id="Page_9">[Pg 9]</span></p> - -<p>For the success of this operation it is important that the potassium -salt of paranitroorthotoluenesulphonic acid and the potassium hydroxide -should both be perfectly dissolved before they are heated together. -If the two substances lie together in solid form at the bottom of the -flask, a very slight elevation of temperature leads to the formation -of an extremely troublesome red substance, which is very difficult -to remove. It is almost impossible to remove it from the oxidation -product by recrystallization, since any considerable amount of it has -a marked influence on the solubility of the salt, rendering it much -more soluble. It persists throughout all subsequent transformations of -paranitroorthosulphobenzoic acid, and should therefore be carefully avoided. -<span class="pagenum" id="Page_10">[Pg 10]</span></p> - -<p>Otto Fischer<a id="FNanchor_11" href="#Footnote_11" class="fnanchor">[11]</a> -has shown that in concentrated solution, potassium hydroxide -acts on nitro derivatives of toluene, with the formation of -various colored substances derived from stilbene. In the case of -paranitroorthotoluenesulphonic acid, he describes the substance formed -as possessing a cherry red color. The reactions involved in its -formation are:</p> - -<p class="left120 no-wrap"><b> - CH₃<span class="ws5">HC ============== CH</span><br /> -<span class="ws4">/</span><span class="ws7">/</span><span class="ws10">\</span><br /> -<span class="ws2">2C₆H₃—SO₂OK = C₆H₃—SO₂OK KO.O₂S—C₆H₃ + 2H₂O</span><br /> -<span class="ws4">\</span><span class="ws7">\</span><span class="ws10">/</span><br /> -<span class="ws4">NO₂</span><span class="ws6">\</span><span class="ws8-5">/</span><br /> -<span class="ws12-5">\</span><span class="ws1"> /</span>— O — \<span class="ws1-5">/</span><br /> -<span class="ws13">N</span><span class="ws4-5">N</span><br /> -<span class="ws13-5"> \</span>— O — /<br /> -</b></p> - -<p>By oxidation this passes to a nitro compound of the composition</p> - -<p class="left120 no-wrap"><b> - HC ============= CH<br /> -<span class="ws4">/</span><span class="ws9">\</span><br /> -<span class="ws2">C₆H₃—SO₂OK KOO₂S—C₆H₃</span><br /> -<span class="ws4">\</span><span class="ws9">/</span><br /> -<span class="ws4">NO₂</span><span class="ws6">O₂N</span><br /> -</b></p> - -<p>It was no doubt the formation of substances of this nature that -occasioned the color observed in some of the oxidations. -<span class="pagenum" id="Page_11">[Pg 11]</span></p> - -<p>The only effective method of separating this colored substance was -found to be to pass to the neutral salt of paranitroorthosulphobenzoic -acid, by making the solution slightly alkaline. The salt of this -colored substance is also formed and the two can be separated by a few -recrystallizations in a fairly satisfactory manner.</p> - -<p>The yield in both of the transformations involved in the preparation -of paranitroorthosulphobenzoic acid does not fall far short of the theoretical.</p> - -<hr class="chap x-ebookmaker-drop" /> - -<div class="chapter"> -<p><span class="pagenum" id="Page_12">[Pg 12]</span></p> -<h2 class="nobreak">III. Preparation of the<br />Symmetrical Chloride of<br /> -Paranitroorthosulphobenzoic Acid.</h2> -</div> - -<p>This chloride was first separated from its unsymmetrical isomer -by Gray<a id="FNanchor_12" href="#Footnote_12" class="fnanchor">[12]</a>. -It was obtained by allowing a chloroform solution of -the mixed chlorides to evaporate until the chloroform had almost -entirely disappeared. In the thick liquid so obtained, crystals of the -symmetrical chloride were formed. It was also obtained by applying the -method devised by Bucher in connection with the corresponding chloride -of orthosulphobenzoic acid—i.e. by the action of dilute ammonia on the -mixed chlorides. Gray also found that the best conditions for securing -a relatively large proportion of the symmetrical chloride were, the -<span class="pagenum" id="Page_13">[Pg 13]</span> -employment of as low a temperature as possible in the formation of the -chlorides, and of as small an excess of phosphorus pentachloride as -would suffice for the reaction.</p> - -<p>After many experiments, under widely differing conditions, the -following method of procedure, embodying the results of Gray’s work, -was adopted.</p> - -<p>Dehydrated acid potassium salt of paranitroorthosulphobenzoic acid, and -phosphorus pentachloride, in the ratio of 40: 55 grams, are brought -together in a mortar and intimately mixed. The mixture is put into -an evaporating dish, and placed on a sulphuric acid bath, previously -heated to 150°. As soon as the action has been well started, the -dish is removed, and the reaction allowed to proceed without further -<span class="pagenum" id="Page_14">[Pg 14]</span> -heating. When it is complete, and the contents of the dish has cooled -down to the temperature of the room, the oily product is poured -slowly into a salts bottle containing ice water, the bottle being -frequently shaken during the process. The shaking is continued with -renewed portions of water, as long as the wash water is cloudy. The -water is then poured off, the brownish gummy chloride dissolved in -chloroform, and the solution placed in a good-sized separating funnel. -Ice water is then added, and the contents of the funnel treated with -successive portions of ammonia (desk ammonia diluted one half). -Shaking is continued after each addition until the odor of ammonia has -disappeared, and ice is added from time to time as may be required. -<span class="pagenum" id="Page_15">[Pg 15]</span></p> - -<p>When it is found that the odor of ammonia persists after several -minutes’ shaking, the chloroform layer, which is usually filled with a -solid substance that has separated during the process, is drawn off, -filtered, and dried with calcium chloride.</p> - -<p>By this process all of the unsymmetrical chloride is converted into the -ammonium salt of paranitroorthocyanbenzenesulphonic acid, according to -the equation:</p> - -<p class="left120 no-wrap"><b> -<span class="ws2">CCl₂</span><br /> -<span class="ws4-5">/</span><span class="ws1">\</span><br /> -<span class="ws4">/</span><span class="ws2">O</span><span class="ws5">CN</span><br /> -<span class="ws3-5">/</span><span class="ws2">/</span><span class="ws6">/</span><br /> -<span class="ws2">C₆H₃—SO₂ + 4NH₃ = C₆H₃—SO₃NH₄ + 2NH₄Cl.</span><br /> -<span class="ws3-5">\</span><span class="ws8">\</span><br /> -<span class="ws4">NO₂</span><span class="ws6-5">NO₂</span><br /> -</b></p> - -<p class="no-indent">while the symmetrical chloride remains for the -most part unchanged, though some of it is converted into the ammonium -salt of paranitrobenzoic sulphinide:</p> - -<p class="left120 no-wrap"><b> -<span class="ws12">CO</span><br /> -<span class="ws14-5">/</span><span class="ws1">\</span><br /> -<span class="ws4">COCl</span><span class="ws7-5">/</span><span class="ws2">N.NH₄</span><br /> -<span class="ws3-5">/</span><span class="ws9-5">/</span><span class="ws2-5">/</span><br /> -<span class="ws2">C₆H₃—SO₂Cl + 4NH₃ = C₆H₃—SO₂ + 2NH₄Cl.</span><br /> -<span class="ws3-5">\</span><span class="ws9-5">\</span><br /> -<span class="ws4">NO₂</span><span class="ws8">NO₂</span><br /> -</b></p> - -<p><span class="pagenum" id="Page_16">[Pg 16]</span> -It was found that working in this way the symmetrical chloride could -be prepared in pure condition, free from its isomer. The chloroform -completely evaporates in a short time leaving fine crystals of the -symmetrical chloride. In case the evaporation is slow and incomplete, -it may be concluded that not all of the unsymmetrical chloride has been -removed. The yield was uniformly about 40 per cent of the theoretical.</p> - -<p>From the water used to wash the chlorides a considerable amount of the -original salt can be recovered, as the reaction under the conditions -employed, is never complete.</p> - -<p>An examination was made of the substance mentioned as separating in -the chloroform solution of the chlorides, during the treatment with -<span class="pagenum" id="Page_17">[Pg 17]</span> -ammonia, and it was found to possess the following properties. It -is insoluble in benzene, chloroform, acetone, ether and ligroin; -soluble in glacial acetic acid, from which it separates on cooling -in colorless, crystalline condition; insoluble in the cold in -water, alcohol and ammonia, but by boiling with these reagents, or -by long standing in the cold, it is dissolved with decomposition. -It was dissolved in hot water and the solution, which was acid -in reaction, was neutralized with potassium carbonate. On adding -an excess of hydrochloric acid to the solution, and allowing -it to cool, characteristic crystals of acid potassium salt of -paranitroorthosulphobenzoic acid separated. These properties identify -the substance as the anhydride of this acid. -<span class="pagenum" id="Page_18">[Pg 18]</span></p> - -<p>The formation of the corresponding anhydride of orthosulphobenzoic acid -by the action of phosphorus pentachloride upon its acid potassium salt -was observed by Sohon<a id="FNanchor_13" href="#Footnote_13" class="fnanchor">[13]</a>, -who made use of the reaction to prepare this anhydride in quantity.</p> - -<hr class="chap x-ebookmaker-drop" /> - -<div class="chapter"> -<p><span class="pagenum" id="Page_19">[Pg 19]</span></p> - -<h2 class="nobreak">IV. Properties of the Symmetrical Chloride<br /> - of Paranitroorthosulphobenzoic Acid.</h2> -</div> - -<p>As first obtained, the crystals of the symmetrical chloride resemble -irregularly shaped pieces of amber, both in color, and in lustre. -On recrystallization from chloroform or ether, they may be obtained -perfectly colorless, and are often of very simple crystallographic -form. The chloride crystallizes in the monoclinic system, and possesses -a very remarkable crystallizing power, in which respect it differs -noticeably form its isomer. Even in chloroform solution that is far -from dry, crystals appear with the greatest ease.</p> - -<p>The habit of the crystals differs very much according to the conditions -<span class="pagenum" id="Page_20">[Pg 20]</span> -of crystallization. Not infrequently almost perfectly formed crystals -of the simplest form—the oblique octahedron—were obtained though -for the most part the form was much more complicated, pinacoid and -dome faces, together with basal planes being prominent. As a rule, the -crystals were not suitable for crystallographic work, as the faces are -usually uneven and the edges rounded. By proper precautions however, -good ones were obtained, and measurements of these will be found in -this dissertation when it appears in print.</p> - -<p>The size of some of the crystals obtained was unusual for substances -of this class. One crystal obtained with no special precautions, save -letting a solution of the chloride stand undisturbed for several days, -in a rather cool place measured 3 × 2.5 × 1.5 cm., and weighed 11.2 -<span class="pagenum" id="Page_21">[Pg 21]</span> -grams. The crystals are quite compact, their density being abut 1.85. -They melt at 98° (uncorr.) The chloride is quite stable in crystalline -condition. Even in moist air the crystals were unchanged, and retained -their lustre as long as they were in my possession.</p> - -<p>An analysis for chlorine gave the following results.</p> - -<table class="fontsize_120" border="0" cellspacing="0" summary=" " cellpadding="0" > - <tbody><tr> - <td class="tdc">.2200 gram gave</td> - <td class="tdc">.2212 gram AgCl.</td> - </tr><tr> - <td class="tdc" colspan="2"> </td> - </tr><tr> - <td class="tdc"><b> - <span class="ws4-5">COCl</span><br /> - <span class="ws1-5">/</span><br /> - Cal. for C₆H₃—SO₂Cl<br /> - <span class="ws1-5">\</span><br /> - <span class="ws4">NO₂</span></b> -</td> - <td class="tdc_bott"><b>Found.</b></td> - </tr><tr> - <td class="tdc">Cl = 24.94</td> - <td class="tdc">24.83</td> - </tr> - </tbody> -</table> - -<hr class="chap x-ebookmaker-drop" /> -<p><span class="pagenum" id="Page_22">[Pg 22]</span></p> -<div class="chapter"> -<h2 class="nobreak">V. The Action of Benzene and Aluminium Chloride<br /> - on the Symmetrical Chloride of<br /> - Paranitroorthosulphobenzoic Acid.</h2> -</div> - -<p>Hollis<a id="FNanchor_14" href="#Footnote_14" class="fnanchor">[14]</a> -in his study of the action of these reagents upon the -unsymmetrical chloride, tested their action upon one portion of the -symmetrical chloride, and found the products to be identical in the two -cases. A few experiments were made in confirmation of these results, -and the same products, in general, were obtained. It was observed -however that the reactions differ in the relative ease with which -they are brought about. In the case of the symmetrical chloride, the -reaction is a much more vigorous one. On adding aluminium chloride to -<span class="pagenum" id="Page_23">[Pg 23]</span> -a solution of the symmetrical chloride, in benzene, action begins at -once the temperature of the hand, and very little external heat, and -that only in the latter stages of the operation, is needful for the -completion of the reaction. The application of much heat converts -all of the product into thick tarry substances from which nothing -satisfactory could be obtained.</p> - -<p>When the reaction was complete, the resulting product was isolated and -purified in accordance with the directions given by Hollis. Repeated -trials showed that, as in the case of the unsymmetrical chloride, only -one phenyl group could be introduced by this method. The resulting -compound, paranitroorthobenzoylbenzenesulphon chloride, was identical -with that derived from the unsymmetrical chloride. Owing, however, to -<span class="pagenum" id="Page_24">[Pg 24]</span> -the fact that so much more decomposition occurs in the reaction with -the symmetrical chloride, in paranitroorthobenzoylbenzene sulphon -chloride could not be obtained in perfectly pure condition. In -appearance it agreed closely with that described by Hollis, forming -very characteristic greenish, rhombic crystals. These melted, not very -sharply, at 174° instead of 177° as observed by Hollis.</p> - -<p>Accordingly, to establish the identity of the two compounds beyond -any doubt, the material on hand was converted into the barium salt of -paranitroorthobenzoylbenzene sulphonic acid. This was done by boiling -the sulphon chloride with dilute hydrochloric acid until complete -solution had been effected; evaporating to dryness on a water-bath; -<span class="pagenum" id="Page_25">[Pg 25]</span> -dissolving the residue in hot water, and neutralizing with barium -carbonate. On filtering the hot solution from the excess of carbonate, -and allowing it to cool, the barium salt separated.</p> - -<p>The solution was somewhat colored by impurities, and the long needles -in which the salt crystallized were also somewhat colored. They were -analysed with the expectation that they would prove to be specimens -of the salt described by Hollis as having three, or three and a half -molecules of water of crystallization, in as much as the conditions -under which they were formed were favorable to the formation of salts -with these ratios of water of crystallization. Hollis found that this -salt could be obtained with at least four different ratios of water of -<span class="pagenum" id="Page_26">[Pg 26]</span> -crystallization viz. three, three and a half, six and seven molecules -respectively. The analysis was as follows, the amount of barium being -calculated on the basis of the anhydrous salt.</p> - -<table class="fontsize_120" border="0" cellspacing="0" summary=" " cellpadding="0" > - <tbody><tr> - <td class="tdc">0.3087 gram lost 0.064 gram at 210°,</td> - <td class="tdc"> </td> - </tr><tr> - <td class="tdc"> </td> - <td class="tdc">and gave 0.0759 gram BaSO₄.</td> - </tr><tr> - <td class="tdc" colspan="2"> </td> - </tr><tr> - <td class="tdc"><b>Cal. for<br /> (C₁₃H₈O₆NS)₂Ba + 11H₂O</b></td> - <td class="tdc_bott"><b>Found.</b></td> - </tr><tr> - <td class="tdc">H₂O = 20.90</td> - <td class="tdc">20.73</td> - </tr><tr> - <td class="tdc"> Ba = 18.29</td> - <td class="tdc">18.23</td> - </tr> - </tbody> -</table> - -<p>The mother-liquor, in which the crystals remaining from analysis were -redissolved, was warmed, but not boiled, with boneblack, to remove -impurities. When filtered, the solution was perfectly colorless, and -on standing for some time, well formed colorless, rhombic crystals -appeared. On analysis they gave results as follows. -<span class="pagenum" id="Page_27">[Pg 27]</span></p> - -<table class="fontsize_120" border="0" cellspacing="0" summary=" " cellpadding="0" > - <tbody><tr> - <td class="tdc">0.2804 gram lost 0.0405 gram at 210°,</td> - <td class="tdc"> </td> - </tr><tr> - <td class="tdc"> </td> - <td class="tdc">and gave 0.0759 gram BaSO₄.</td> - </tr><tr> - <td class="tdc" colspan="2"> </td> - </tr><tr> - <td class="tdc"><b>Cal. for<br /> (C₁₃H₈O₆NS)₂Ba + 7H₂O.</b></td> - <td class="tdc_bott"><b>Found.</b></td> - </tr><tr> - <td class="tdc">H₂O = 14.40</td> - <td class="tdc">14.44.</td> - </tr><tr> - <td class="tdc"> Ba = 18.29</td> - <td class="tdc">18.03.</td> - </tr> - </tbody> -</table> - -<p>In making a further supply of the salt it was found that if the -solution, after filtering from the barium carbonate, was diluted to -such an extent that no crystals separated on cooling, then on slow -evaporation under a bell-jar the first crystals to appear were very -long slender needles. As evaporation proceeded, these needles became -much thicker assuming prismatic proportions, and corresponded in -appearance to the salt described by Hollis as having six molecules of -crystal water.</p> - -<p>As growth proceeded, the crystals became dark in color, and the -mother-liquor correspondingly clearer, the crystals evidently absorbing -the impurity in their growth. -<span class="pagenum" id="Page_28">[Pg 28]</span></p> - -<p>When the solution had become quite colorless, rhombic crystals of the -salt containing seven molecules of water of crystallization appeared. -The larger prismatic crystals were carefully removed, and redissolved -in water in order to see if the same phenomena would repeat themselves. -This in fact was the case, crystals of both types appearing in the -same way as described. Without separating the crystals in this second -experiment, water was added, and the crystals dissolved. The solution -was then warmed briskly with boneblack, and filtered. From the filtrate, -which was colorless, nothing but rhombic crystals having seven -<span class="pagenum" id="Page_29">[Pg 29]</span> -molecules of water of crystallization could be obtained, although a -great many variations in the conditions were tried. Analysis of these -last crystals was as follows:</p> - -<table class="fontsize_120" border="0" cellspacing="0" summary=" " cellpadding="0" > - <tbody><tr> - <td class="tdc">0.2400 gram lost 0.035 gram at 210°,</td> - <td class="tdc"> </td> - </tr><tr> - <td class="tdc"> </td> - <td class="tdc">and gave 0.0637 gram BaSO₄.</td> - </tr><tr> - <td class="tdc" colspan="2"> </td> - </tr><tr> - <td class="tdc"><b>Cal. for<br /> (C₁₃H₈O₆NS)₂Ba + 7H₂O.</b></td> - <td class="tdc_bott"><b>Found.</b></td> - </tr><tr> - <td class="tdc">H₂O = 14.40</td> - <td class="tdc">14.58</td> - </tr><tr> - <td class="tdc"> Ba = 18.29</td> - <td class="tdc">18.27</td> - </tr> - </tbody> -</table> - -<p>Hollis states that treatment with boneblack decomposes this salt, -and hence he did not purify it prior to crystallization. From the -experiments just described it seems probable that the impurities -present affect the crystalline habit, and the degree of hydration of -this salt in a very striking manner. By careful warming with boneblack -no decomposition was observed, and the crystals so obtained have -constantly seven molecules of crystal water.</p> - -<hr class="chap x-ebookmaker-drop" /> -<p><span class="pagenum" id="Page_30">[Pg 30]</span></p> -<div class="chapter"> -<h2 class="nobreak">VI. The Action of Alcohols<br /> upon the Symmetrical Chloride<br /> - of Paranitroorthosulphobenzoic Acid.</h2> -</div> - -<p>Kastle<a id="FNanchor_15" href="#Footnote_15" class="fnanchor">[15]</a> -found that when the chlorides of paranitroorthosulphobenzoic -acid (which he supposed to be an individual) were dissolved in alcohol, -and the solution boiled for some time, the acid etherial salt of -paranitroorthosulphobenzoic acid was the final product. The reactions -were shown to be:</p> - -<p class="left120 space-below2 no-wrap"><b> -<span class="ws2">COCl</span><span class="ws9">COOC₂H₅</span><br /> -<span class="ws5">/</span><span class="ws11">/</span><br /> -<span class="ws2-5">I. C₆H₃—SO₂Cl + C₂H₅OH = C₆H₃—SO₂Cl + HCl.</span><br /> -<span class="ws5">\</span><span class="ws11">\</span><br /> -<span class="ws5">NO₂</span><span class="ws10">NO₂</span><br /> -</b></p> - -<p class="left120 space-below2 no-wrap"><b> -<span class="ws2">COOC₂H₅</span><span class="ws7">COOC₂H₅</span><br /> -<span class="ws5">/</span><span class="ws11">/</span><br /> -<span class="ws2">II. C₆H₃—SO₂Cl + C₂H₅OH = C₆H₃—SO₂OC₂H₅ + HCl</span><br /> -<span class="ws5">\</span><span class="ws11">\</span><br /> -<span class="ws5">NO₂</span><span class="ws10">NO₂</span><br /> -</b></p> - -<p class="left120 no-wrap"><b> -<span class="ws2">COOC₂H₅</span><span class="ws9">COOC₂H₅</span><br /> -<span class="ws5">/</span><span class="ws13">/</span><br /> -<span class="ws1-5">III. C₆H₃—SO₂OC₂H₅ + C₂H₅OH = C₆H₃—SO₂OH + (C₂H₅)₂O</span><br /> -<span class="ws5">\</span><span class="ws13">\</span><br /> -<span class="ws5">NO₂</span><span class="ws12">NO₂</span><br /> -</b></p> - -<p><span class="pagenum" id="Page_31">[Pg 31]</span> -Kastle, it will be observed, gave the symmetrical formula to this -mixture of chlorides. Several acid etherial salts were made, and a -series of the neutral salts of various metals described by him.</p> - -<p>The action of pure symmetrical chloride was studied in the same general -manner to see if the resulting products would be the same as those -formed from the mixed chlorides.</p> - -<p id="VI_1"><span class="fontsize_120 space-above1"><b>1.</b></span> -Action of Methyl Alcohol upon the Symmetrical chloride.</p> - -<p>A portion of the chloride was dissolved in methyl alcohol, and the -solution boiled until a drop added to cold water gave no precipitate, -of unchanged chloride. The alcohol was then distilled off, and -the thick syrup remaining, diluted with water. This solution was -<span class="pagenum" id="Page_32">[Pg 32]</span> -neutralized with barium carbonate and filtered. On cooling, the barium -salt crystallized in shining mica-like plates, or in yellowish needles -corresponding accurately with those described by Kastle. They gave the -following analytical results.</p> - -<table class="fontsize_120" border="0" cellspacing="0" summary=" " cellpadding="0" > - <tbody><tr> - <td class="tdc" colspan="4">0.2664 gram lost 0.0211 gram at 150°,</td> - <td class="tdc" colspan="3"> </td> - </tr><tr> - <td class="tdc" colspan="4"> </td> - <td class="tdc" colspan="3">and gave 0.0870 gram BaSO₄.</td> - </tr><tr> - <td class="tdc" colspan="7"> </td> - </tr><tr> - <td class="tdc"><b>Cal. for</b></td> - <td class="tdc"><b><span class="fontsize_400">[</span></b></td> - <td class="tdl"><b><span class="ws1-5">COOCH₃</span><br /> - <span class="ws1-5">/</span><br /> - C₆H₃—SO₂O<br /> - <span class="ws1-5">\</span><br /> - <span class="ws1-5">NO₂</span></b></td> - <td class="tdl"><b><span class="fontsize_400">]</span></b></td> - <td class="tdc_bott"><b><span class="fontsize_150">2</span></b></td> - <td class="tdl"><b>Ba + 3H₂O</b></td> - <td class="tdr_bott"><b>Found.</b></td> - </tr><tr> - <td class="tdc" colspan="7"> </td> - </tr><tr> - <td class="tdr" colspan="6">H₂O = 7.79</td> - <td class="tdr">7.88</td> - </tr><tr> - <td class="tdr" colspan="6">[anhydrous salt] Ba = 20.85</td> - <td class="tdr">20.85</td> - </tr> - </tbody> -</table> - -<p id="VI_2"><span class="fontsize_120 space-above1"><b>2.</b></span> In like manner the -barium ethyl salt was made. It also agreed perfectly with Kastle’s -description, crystallizing in fine, colorless needles, forming in -tufts from a not too concentrated solution. In case it is necessary -to concentrate these solutions, it is of advantage to add a small -<span class="pagenum" id="Page_33">[Pg 33]</span> -quantity of alcohol to the solution as this prevents any great amount -of saponification, which otherwise takes place to a noticeable extent.</p> - -<p class="fontsize_120"><b>Analysis.</b></p> - -<table class="fontsize_120" border="0" cellspacing="0" summary=" " cellpadding="0" > - <tbody><tr> - <td class="tdl" colspan="7"> I. 0.2824 gram lost 0.0276 gram at 180°,</td> - </tr><tr> - <td class="tdl" colspan="7"><span class="ws3">and gave 0.0860 gram BaSO₄.</span></td> - </tr><tr> - <td class="tdc" colspan="7"> </td> - </tr><tr> - <td class="tdl" colspan="7">II. 0.2655 gram lost 0.0262 gram at 190°,</td> - </tr><tr> - <td class="tdl" colspan="7"><span class="ws3">and gave 0.0815 gram BaSO₄.</span></td> - </tr><tr> - <td class="tdc" colspan="7"> </td> - </tr><tr> - <td class="tdc"><b>Cal. for</b></td> - <td class="tdc"><b><span class="fontsize_400">[</span></b></td> - <td class="tdl"><b><span class="ws1-5">COOC₂H₃</span><br /> - <span class="ws1-5">/</span><br /> - C₆H₃—SO₂O<br /> - <span class="ws1-5">\</span><br /> - <span class="ws1-5">NO₂</span></b></td> - <td class="tdl"><b><span class="fontsize_400">]</span></b></td> - <td class="tdc_bott"><b><span class="fontsize_150">2</span></b></td> - <td class="tdl"><b>Ba + 4H₂O.</b></td> - <td class="tdr_bott"><b>Found. </b></td> - </tr><tr> - <td class="tdr" colspan="5"> </td> - <td class="tdr">I </td> - <td class="tdr">II </td> - </tr><tr> - <td class="tdr" colspan="5">H₂O = 9.51</td> - <td class="tdr">9.77</td> - <td class="tdr">9.86</td> - </tr><tr> - <td class="tdr" colspan="5">Ba = 20.00</td> - <td class="tdr">19.84</td> - <td class="tdr">20.02</td> - </tr> - </tbody> -</table> - -<p>Kastle also found that by dissolving the mixed chlorides in alcohol in -the cold, and allowing the solution to evaporate, there separated after -<span class="pagenum" id="Page_34">[Pg 34]</span> -a time, crystals of the chloride of the acid etherial salt of -paranitroorthosulphobenzoic acid whose formation and composition are -represented in equation I.</p> - -<p>This same product was sought for when pure symmetrical chloride was -employed, but without success. In every case, crystals of unchanged -chloride separated, or else it was found that it had been completely -converted into the acid etherial salt. In another trial cold water -was carefully added in small portions, since Kastle found that such -treatment facilitated the separation of the substance; the chloride -alone appeared. Still other attempts were made to obtain the substance -by adding a large amount of water to the solution of the chloride in -<span class="pagenum" id="Page_35">[Pg 35]</span> -alcohol, after it had stood for some time. In this way, quite a -precipitate was thrown down, and this was filtered off and crystallized -from ether. It always proved to be the symmetrical chloride, and none -of the other substance was obtained.</p> - -<p>Karslake<a id="FNanchor_16" href="#Footnote_16" class="fnanchor">[16]</a> -in working with the symmetrical chloride of -orthosulphobenzoic acid, was unable to isolate the analogous compound, -although from the mixed chlorides, by the action of alcohols, Remsen -and Dohme<a id="FNanchor_17" href="#Footnote_17" class="fnanchor">[17]</a> -had obtained chloro-etherial salts.</p> - -<p>In as much as the pure symmetrical chloride is relatively stable in -<span class="pagenum" id="Page_36">[Pg 36]</span> -cold alcohol (it can be crystallized from warm alcohol with very -little loss), it is possible that it is more stable than the chloro -etherial salt, and that in consequence the latter, when formed, yields -more readily to the further action of alcohol than does the unacted -on chloride. Hence when the action begins, it at once proceeds to the -limit. The fact that the symmetrical chloride is rather sparingly -soluble in cold alcohol, making the use of concentrated solutions -impossible, may also be a factor in the case. Whatever may be the -cause, this substance could not be obtained under any conditions that -were devised.</p> - -<p id="VI_3">Having in my possession a very small specimen of crystallized -unsymmetrical chloride, it was submitted to the action of ethyl -alcohol, under as nearly as possible the conditions employed by Kastle. -<span class="pagenum" id="Page_37">[Pg 37]</span> -Crystals of a colorless substance were obtained, which in every respect -agreed with Kastle’s description of the chloride of the acid ethyl -etherial salt of paranitroorthosulphobenzoic acid. Crystallized from -ether they melted at 68°.</p> - -<p>The conditions employed by Kastle in preparing the chloride would -undoubtedly lead to a relatively large proportion of unsymmetrical -chloride, and it is to this chloride that the formation of the chloro -etherial salt is apparently due.</p> -<hr class="chap x-ebookmaker-drop" /> - -<div class="chapter"> -<p><span class="pagenum" id="Page_38">[Pg 38]</span></p> -<h2 class="nobreak">VII. The Action of Phenols upon the Symmetrical Chloride<br /> - of Paranitroorthosulphobenzoic Acid.</h2> -</div> - -<p>Remsen and Saunders<a id="FNanchor_18" href="#Footnote_18" class="fnanchor">[18]</a> -in their investigation of the chlorides of -orthosulphobenzoic acid, studied the action of phenol upon these -substances, and from both the symmetrical chloride and the mixed -chlorides, they obtained a normal diphenyl ether together with a -red substance which was not further studied. It was formed in small -quantity and was probably the corresponding sulphonphthalein. Later -McKee<a id="FNanchor_19" href="#Footnote_19" class="fnanchor">[19]</a> -obtained these same substances from both the symmetrical -and the unsymmetrical chlorides. R. Meyer<a id="FNanchor_20" href="#Footnote_20" class="fnanchor">[20]</a> -obtained analogous substances by the action of various phenols upon phthalyl chloride. -<span class="pagenum" id="Page_39">[Pg 39]</span> -It seemed probable, therefore, that the chlorides of -paranitroorthosulphobenzoic acid would yield similar derivatives, -and a study was accordingly made of the reaction of the symmetrical -chloride with a series of phenols. The products in some instances were -exceedingly difficult to deal with, possessing properties that made it -impossible to prepare them for analysis, but even in such cases there could -be little doubt as to the general nature of the reactions which had occurred. -<span class="pagenum" id="Page_40">[Pg 40]</span></p> - -<p id="VII_1"><span class="fontsize_120 space-above1"><b>1.</b></span>The Action of -Phenol upon the Symmetrical Chloride of Paranitroorthosulphobenzoic Acid.</p> - -<p>A portion of the symmetrical chloride was brought together with -somewhat more than double the molecular amount of phenol. The mixture -was placed in a good-sized test-tube and the temperature gradually -raised by means of a sulphuric acid bath.</p> - -<p>As soon as the phenol melts, some slight action occurs, as is indicated -by the fact that the mixture assumes a bright red color. No appreciable -amount of hydrochloric acid gas is evolved however, until the liquid -mixture has reached a temperature of about 115°. At this point the gas -is freely evolved, and the action is complete at a temperature of 125°. -<span class="pagenum" id="Page_41">[Pg 41]</span> -The temperature observations were made by means of a thermometer used -as a stirring rod in the mixture. During the heating, the color of the -liquid becomes a much more intense red, growing darker in shade, and the -liquid itself becomes somewhat viscous but does not solidify while hot.</p> - -<p>When cool, the melt was repeatedly extracted with boiling water, -the aqueous solution being very deep purple in color. The colored -matter was removed very slowly in this manner, and so the process -was continued with dilute alkali. A solid insoluble residue was thus -obtained, of a light-brownish color. This was dissolved in alcohol, -boiled with boneblack and filtered. On cooling, needles of a straw -yellow color were deposited from the alcoholic solution. -<span class="pagenum" id="Page_42">[Pg 42]</span></p> - -<p>This proved to be the normal diphenyl etherial salt of -paranitroorthosulphobenzoic acid, the formation of this substance being -expressed by the equation:</p> - -<p class="left120 space-below2 no-wrap"><b> -<span class="ws1">COCl</span><span class="ws10">COOC₆H₅</span><br /> -<span class="ws4">/</span><span class="ws12">/</span><br /> -<span class="ws2-5">C₆H₃—SO₂Cl + 2C₆H₅OH = C₆H₃—SO₂OC₆H₅ + 2HCl.</span><br /> -<span class="ws4">\</span><span class="ws12">\</span><br /> -<span class="ws4">NO₂</span><span class="ws11">NO₂</span><br /> -</b></p> - -<p class="fontsize_120"><b>Analysis of the substance gave the following results:</b></p> - -<table class="fontsize_120" border="0" cellspacing="0" summary=" " cellpadding="0" > - <tbody><tr> - <td class="tdl" colspan="4"> I. 0.1627 gram gave 0.3398 gram CO₂ and 0.0510 gram H₂O.</td> - </tr><tr> - <td class="tdc" colspan="4"> </td> - </tr><tr> - <td class="tdl" colspan="4"> II. 0.1999 gram gave 0.4180 gram CO₂ and 0.0600 gram H₂O.</td> - </tr><tr> - <td class="tdc" colspan="4"> </td> - </tr><tr> - <td class="tdl" colspan="4">III. 0.2649 gram gave 0.1561 gram BaSO₄.</td> - </tr><tr> - <td class="tdc" colspan="4"> </td> - </tr><tr> - <td class="tdc"><b>Cal. for</b></td> - <td class="tdl"><b><span class="ws1-5">COOC₆H₅</span><br /> - <span class="ws1-5">/</span><br /> - C₆H₃—SO₂OC₆H₅<br /> - <span class="ws1-5">\</span><br /> - <span class="ws1-5">NO₂</span></b></td> - <td class="tdc_bott" colspan="2"><b>Found.   </b></td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdr"><b>I</b> </td> - <td class="tdr"><b>II</b> </td> - <td class="tdr"><b>III</b> </td> - </tr><tr> - <td class="tdr">C =57.14</td> - <td class="tdr">56.97</td> - <td class="tdr">57.03</td> - <td class="tdr">——</td> - </tr><tr> - <td class="tdr">H = 3.26</td> - <td class="tdr">3.47</td> - <td class="tdr">3.33</td> - <td class="tdr">——</td> - </tr><tr> - <td class="tdr">S = 8.02</td> - <td class="tdr">——</td> - <td class="tdr">——</td> - <td class="tdr">8.09</td> - </tr> - </tbody> -</table> - -<p class="space-below1">This substance melts at 119° (uncorr).</p> - -<p><span class="pagenum" id="Page_43">[Pg 43]</span> -It possesses properties similar to those of the diphenyl etherial -salt of orthosulphobenzoic acid described by Saunders. It is -insoluble in water, and is unaffected by hydrochloric acid or aqueous -alkali. On heating for a short time with alcoholic potash, the -needles were transformed into a voluminous precipitate. This was -filtered off, dissolved in water, and hydrochloric acid was added. -On cooling, characteristic crystals of the acid potassium salt of -paranitroorthosulphobenzoic separated.</p> - -<p class="fontsize_120"><b>Analysis.</b></p> - -<table class="fontsize_120" border="0" cellspacing="0" summary=" " cellpadding="0" > - <tbody><tr> - <td class="tdc" colspan="2">0.1392 gram lost 0.009 gram at 150° and gave 0.0385 gram K₂SO₄.</td> - </tr><tr> - <td class="tdc"><b> - <span class="ws4-5">COOH</span><br /> - <span class="ws1-5">/</span><br /> - Cal. for C₆H₃—SO₂OK + H₂O<br /> - <span class="ws1-5">\</span><br /> - <span class="ws4">NO₂</span></b></td> - <td class="tdc_bott"><b>Found.</b></td> - </tr><tr> - <td class="tdc">H₂O = 5.95</td> - <td class="tdc">H₂O = 6.51</td> - </tr><tr> - <td class="tdc"><span class="ws1">K = 13.65</span></td> - <td class="tdc"><span class="ws1">K = 13.35</span></td> - </tr> - </tbody> -</table> - -<p><span class="pagenum" id="Page_44">[Pg 44]</span> -No attempt was made to isolate the corresponding intermediate -chlor-etherial salt of the composition</p> - -<table class="fontsize_120" border="0" cellspacing="0" summary=" " cellpadding="0" > - <tbody><tr> - <td class="tdc"><b> - <span class="ws6">COOC₆H₅</span><br /> - <span class="ws1-5">/</span><br /> - C₆H₃—SO₂Cl<br /> - <span class="ws1-5">\</span><br /> - <span class="ws4">NO₂</span></b></td> - </tr> - </tbody> -</table> - -<p class="no-indent">or its acid as was done by -McKee<a id="FNanchor_21" href="#Footnote_21" class="fnanchor">[21]</a> -in his work on the analogous etherial salt of orthosulphobenzoic acid.</p> - -<p>On evaporating the aqueous extract from the original melt almost to -dryness on the water-bath, there was a deposit on the sides of thedish -of scales possessing a beautiful bronze-green metallic lustre They -formed a deep purple solution in alkalis, or magenta, if the solution -was very dilute, and orange-yellow in acids. On acidifying the alkaline -extract with hydrochloric acid, this same substance was precipitated as -a brownish flocculent precipitate. It was, however, found to be -<span class="pagenum" id="Page_45">[Pg 45]</span> -impossible to obtain this substance in pure condition. The amount -formed in the reaction is small, and its properties were such as to -render work with it very difficult. The method of precipitation is not -satisfactory because, owing to the fact that the substance is soluble -in acid solutions to an unusual extent for substances of this class, -the solution had to be concentrated to such a degree as to render the -precipitated substance very impure from acids and alkali salts. These -could not be removed by washing, obviously, without again dissolving -the substance. From its properties however, and its color reactions, -there can be little doubt that the substance is a sulphonphthaleïn, and -<span class="pagenum" id="Page_46">[Pg 46]</span> -that it is always formed in considerable quantities in the reaction of -phenol upon the symmetrical chloride.</p> - -<p>It was noticed that the aqueous extract of the mass left after fusion -was almost always decidedly acid in reaction, and it was thought that -this might be due to the formation of an acid etherial salt, whose -formation would be expressed by the equations:</p> - -<p class="left120 space-below2 no-wrap"><b> -<span class="ws2">COCl</span><span class="ws9">COOC₆H₅</span><br /> -<span class="ws5">/</span><span class="ws11">/</span><br /> -<span class="ws3-5">C₆H₃—SO₂Cl + C₆H₅OH = C₆H₃—SO₂Cl + HCl.</span><br /> -<span class="ws5">\</span><span class="ws11">\</span><br /> -<span class="ws5">NO₂</span><span class="ws10">NO₂</span><br /> -</b></p> - -<p class="left120 no-wrap"><b> -<span class="ws2">COOC₆H₅</span><span class="ws6">COOC₆H₅</span><br /> -<span class="ws5">/</span><span class="ws10">/</span><br /> -<span class="ws3-5">C₆H₃—SO₂Cl + H₂O = C₆H₃—SO₂OH + HCl.</span><br /> -<span class="ws5">\</span><span class="ws10">\</span><br /> -<span class="ws5">NO₂</span><span class="ws9">NO₂</span><br /> -</b></p> - -<p class="space-below1">Accordingly, the solution was saturated with -barium carbonate, the excess of carbonate removed by filtration, the -filtrate concentrated, and allowed to cool. Crystals in the form of -<span class="pagenum" id="Page_47">[Pg 47]</span> -pearly scales separated, which upon analysis proved to be the neutral -barium salt of paranitroorthosulphobenzoic acid.</p> - -<table class="fontsize_120" border="0" cellspacing="0" summary=" " cellpadding="0" > - <tbody><tr> - <td class="tdc" colspan="2">0.2291 gram anhydrous salt gave 0.1386 gram BaSO₄.</td> - </tr><tr> - <td class="tdc" colspan="2"> </td> - </tr><tr> - <td class="tdc"><b> - <span class="ws5">COO</span><br /> - <span class="ws3-5">/</span> \<br /> - <span class="ws4-5">/</span><span class="ws1">Ba</span><br /> - <span class="ws3-5">/</span><span class="ws1-5">/</span><br /> - Cal. for C₆H₃—SO₂O<br /> - <span class="ws1-5">\</span><br /> - <span class="ws4">NO₂</span></b></td> - <td class="tdc_bott"><b>Found.</b></td> - </tr><tr> - <td class="tdc">Ba = 35.85</td> - <td class="tdc">35.57</td> - </tr> - </tbody> -</table> - -<p>This would seen to indicate that the reaction is an incomplete one even -in the presence of excess of phenol. No indications of the formation of -an acid etherial salt was observed. -<span class="pagenum" id="Page_48">[Pg 48]</span></p> - -<p id="VII_2"><span class="fontsize_120 space-above1"><b>2.</b></span> -The Action of Orthocresol upon the Symmetrical Chloride of -Paranitroorthosulphobenzoic Acid.</p> - -<p>With orthocresol the reaction proceeds with more difficulty. A higher -temperature was required (135°-145°), and quite an amount of tarry -material was obtained from which very little could be extracted. The -product was warmed repeatedly with dilute alkali, the solution so -obtained neutralized with hydrochloric acid, and distilled with steam -for several hours to free it from cresol. The resulting solution was -then evaporated to small volume, and acidified with hydrochloric acid. -A considerable precipitate was thrown down, which was easily filtered -<span class="pagenum" id="Page_49">[Pg 49]</span> -off and dried. In this condition it is a dark purple-red powder, lumps -of which possessed a yellowish-bronze metallic lustre. In dilute -alkaline solution it forms a deep-bluish purple solution, while in -acids it is crimson, or light yellow if the solution is dilute. It is a -excellent indicator, especially with ammonia.</p> - -<p>In the insoluble tarry substance the etherial salt was sought for -and obtained in small quantity only. As this substance is soluble in -alcohol, and separates again on cooling in much the same condition, -the etherial salt could not be isolated be crystallization from this -solvent. By boiling the substance with benzene, purifying the filtrate -with boneblack, and allowing the benzene to evaporate, an almost -<span class="pagenum" id="Page_50">[Pg 50]</span> -colorless gummy substance was obtained, which when dissolved in -alcohol, crystallizes in small colorless needles which melt at 89°-90°. -They were not obtained in quantity sufficient for analysis, but there -was little doubt that they were crystals of the diorthocresol etherial salt.</p> - -<p>Apparently much more decomposition occurred in this reaction than -when paracresol was employed, probably in consequence of the higher -temperature required for the reaction. -<span class="pagenum" id="Page_51">[Pg 51]</span></p> - -<p id="VII_3"><span class="fontsize_120 space-above1"><b>3.</b></span> -The Action of Paracresol upon the Symmetrical Chloride of -Paranitroorthosulphobenzoic Acid.</p> - -<p>This reaction was conducted in the same manner as with phenol. No -hydrochloric acid was evolved until a temperature of about 110° was -reached, although after melting, the solution had steadily darkened to -a deep reddish-brown color. At 130°, after heating for several hours, -hydrochloric acid ceased to be evolved. The product was treated as in -the last experiment. The alkaline extract did not exhibit any marked -color reactions, such as were observed in most of these experiments, -being dull reddish-brown in both acid and alkaline solution. -<span class="pagenum" id="Page_52">[Pg 52]</span></p> - -<p>The insoluble residue crystallized from alcohol in light brown -transparent crystals, which did not lose their color by repeated -crystallization, and boiling with boneblack, and melted sharply at -117°. From benzene they crystallized in colorless needles or flat, -narrow plates. These become opaque on exposure to the air, apparently -through loss of benzene of crystallization.</p> - -<p class="fontsize_120"><b>Analysis of the needles from alcohol gave -the following results:</b></p> - -<table class="fontsize_120" border="0" cellspacing="0" summary=" " cellpadding="0" > - <tbody><tr> - <td class="tdl" colspan="3"> I. 0.2372 gram of substance gave 0.5137 gram CO₂ and 0.0965 gram H₂O.</td> - </tr><tr> - <td class="tdc" colspan="3"> </td> - </tr><tr> - <td class="tdl" colspan="3">II. 0.2223 gram gave 0.1203 gram BaSO₄.</td> - </tr><tr> - <td class="tdc" colspan="3"> </td> - </tr><tr> - <td class="tdc"><b>Cal. for</b></td> - <td class="tdl"><b><span class="ws1-5">COOC₆H₄.CH₃</span><br /> - <span class="ws1-5">/</span><br /> - C₆H₃—SO₂OC₆H₄.CH₃<br /> - <span class="ws1-5">\</span><br /> - <span class="ws1-5">NO₂</span></b></td> - <td class="tdc_bott" colspan="2"><b>Found.   </b></td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdr"><b>I</b> </td> - <td class="tdr"><b>II</b> </td> - </tr><tr> - <td class="tdr"><span class="ws3">C = 59.08</span></td> - <td class="tdr">59.06</td> - <td class="tdr"> </td> - </tr><tr> - <td class="tdr">H = 3.98</td> - <td class="tdr">4.52</td> - <td class="tdr"> </td> - </tr><tr> - <td class="tdr">S = 7.49</td> - <td class="tdr"> </td> - <td class="tdr">7.43</td> - </tr> - </tbody> -</table> - -<p><span class="pagenum" id="Page_53">[Pg 53]</span></p> - -<p id="VII_4"><span class="fontsize_120 space-above1"><b>4.</b></span> -The Action of Hydroquinone upon the Symmetrical Chloride of -Paranitroorthosulphobenzoic Acid.</p> - -<p>Action with hydroquinone occurs at 120°-135°, the mixture at the same -time becoming dark colored and viscous.</p> - -<p>On cooling, the product was powdered and treated with dilute alkali. -It readily dissolved, without residue, forming a dark red solution. -In concentrated solution the addition of acid produces a voluminous -precipitate, dark brown in color, which when washed, and dried in paper -forms an almost black powder. A dilute solution of this powder is dark -red when alkaline, orange-yellow when acid. -<span class="pagenum" id="Page_54">[Pg 54]</span></p> - -<p>From the way in which this powder was obtained, and owing to the fact -that its solubility prevented repeated washing, it was evident that it -would not give close analytical results for a calculated formula. It was -thought, however, that analysis would give a general idea of the composition.</p> - -<p>Analysis of different specimens gave results for sulphur which averaged -about 5.5%. The percentage required for the formula</p> - -<table class="fontsize_120" border="0" cellspacing="0" summary=" " cellpadding="0" > - <tbody><tr> - <td class="tdc"><b> - <span class="ws8-5">C<big>[</big>C₆H₃(OH)₂<big>]₂</big></span><br /> - <span class="ws2-5">/</span><span class="ws1">\</span><br /> - <span class="ws2-5">/</span><span class="ws1-5">O</span><br /> - <span class="ws1-5">/</span><span class="ws2">/</span><br /> - C₆H₃—SO₂<br />\<br /> - <span class="ws1-5">NO₂</span></b></td> - </tr> - </tbody> -</table> - -<p class="no-indent">which represents the simplest sulphonfluoresceïn, -is 7.43.</p> - -<p>The compound could hardly have been so far from pure as to occasion -such a discrepancy in results as this. It would appear, therefore, that -more than two molecules of hydroquinone enter into the reaction with -<span class="pagenum" id="Page_55">[Pg 55]</span> -one molecule of the chloride. Should four molecules be involved in the -reaction, leading to a compound of some such formula as</p> - -<table class="fontsize_120" border="0" cellspacing="0" summary=" " cellpadding="0" > - <tbody><tr> - <td class="tdc"><b> - <span class="ws7">C<big>[</big>C₆H₃(OH)₂<big>]</big></span><br /> - <span class="ws1-5">/</span><span class="ws1">\</span><br /> - <span class="ws1-5">/</span><span class="ws1-5">O</span><br /> - /<span class="ws2">/</span><br /> - <span class="ws4">C₆H₃—SO<big>[</big>C₆H₃(OH)₂<big>]₂</big></span><br /> - \<span class="ws2-5"> </span><br />NO₂</b></td> - </tr> - </tbody> -</table> - -<p class="no-indent">the theoretical percentage of sulphur would be 6.00 -which corresponds much more closely with the results obtained.</p> - -<p>This is in accord with the observations of a number of workers in -this laboratory—Lyman, Gilpin, Linn and others—who have worked on -various sulphonfluoresceïns, and have found that in many cases four, -six and even eight phenol residues condense with one molecule of the -anhydrous acid. Lyman<a id="FNanchor_22" href="#Footnote_22" class="fnanchor">[22]</a> -especially describes a tetra hydroquinone sulphonfluoresceïn derived -from orthosulphoparatoluic acid. No etherial salt was observed. -<span class="pagenum" id="Page_56">[Pg 56]</span></p> - -<p id="VII_5"><span class="fontsize_120 space-above1"><b>5.</b></span> -The Action of Resorcin upon the Symmetrical Chloride of -Paranitroorthosulphobenzoic Acid.</p> - -<p>The reaction of resorcin with the chloride is a much cleaner one -and proceeds more easily than in the case just described, leading -apparently to an individual compound which is well characterized.</p> - -<p>During the reaction, which is complete at 125°, the mixture becomes -almost perfectly solid, and when cool, it is quite brittle. It was -reduced to a reddish powder in a mortar and dissolved in sodium -hydroxide, there being no insoluble residue. By the addition of -hydrochloric acid, the sulphonfluoresceïn was thrown down as a -chocolate-brown precipitate, which was filtered off, washed to neutral -<span class="pagenum" id="Page_57">[Pg 57]</span> -reaction on a filter, and dried on paper. In this condition it is a -light chocolate-brown powder. In dilute alkaline solution it possesses -a slight fluorescence being pink by transmitted and yellow be reflected -light, suggesting eosin in a general way. It is interesting to note -that the sulphonfluoresceïn of orthosulphobenzoic acid possesses a -fluorescence that can hardly be distinguished from ordinary fluoresceïn -and that the introduction of a nitro group into the acid residue -produces much of the same effect as do the four bromine atoms in eosin. -In acid solution the color is reddish-orange.</p> - -<p><b><span class="fontsize_120">Analysis of the compound,</span></b> prepared as above -described, gave the following results. -<span class="pagenum" id="Page_58">[Pg 58]</span></p> - -<p class="left120 space-below2 no-wrap"><b> -<span class="ws1">COCl</span><span class="ws10">COOC₆H₅</span><br /> -<span class="ws4">/</span><span class="ws12">/</span><br /> -<span class="ws2-5">C₆H₃—SO₂Cl + 2C₆H₅OH = C₆H₃—SO₂OC₆H₅ + 2HCl.</span><br /> -<span class="ws4">\</span><span class="ws12">\</span><br /> -<span class="ws4">NO₂</span><span class="ws11">NO₂</span><br /> -</b></p> - -<p class="fontsize_120"><b>Analysis of the substance gave the following results:</b></p> - -<table class="fontsize_120" border="0" cellspacing="0" summary=" " cellpadding="0" > - <tbody><tr> - <td class="tdl" colspan="6"> I. 0.1745 gram gave 0.3339 gram of CO₂ and 0.059 gram H₂O.</td> - </tr><tr> - <td class="tdc" colspan="6"> </td> - </tr><tr> - <td class="tdl" colspan="6"> II. 0.1467 gram gave 0.2820 gram CO₂ and 0.0432 gram H₂O.</td> - </tr><tr> - <td class="tdc" colspan="6"> </td> - </tr><tr> - <td class="tdl" colspan="6">III. 0.1732 gram gave 0.3345 gram CO₂ and 0.0571 gram H₂O.</td> - </tr><tr> - <td class="tdc" colspan="6"> </td> - </tr><tr> - <td class="tdl" colspan="6"> IV. 0.2000 gram gave 0.1104 gram BaSO₄.</td> - </tr><tr> - <td class="tdc" colspan="6"> </td> - </tr><tr> - <td class="tdl" colspan="6"> V. 0.1505 gram gave 0.0820 gram BaSO₄.</td> - </tr><tr> - <td class="tdc" colspan="6"> </td> - </tr><tr> - <td class="tdc"><br /> <br /><b>Cal. for</b></td> - <td class="tdl"><b><span class="ws6">OH</span><br /> - <span class="ws5-5">/</span><br /> - <span class="ws3">C[C₆H₃ <span class="fontsize_120 ws1">]</span></span><br /> - <span class="ws2-5">/</span><span class="ws1">\</span><span class="ws1-5">\</span><span class="fontsize_120 ws2">2</span><br /> - <span class="ws2">/</span><span class="ws2">O</span><span class="ws1">OH</span><br /> - <span class="ws1-5">/</span><span class="ws2-5">/</span><br /> - C₆H₃—SO₂<br /> - <span class="ws1-5">\</span><br /> - <span class="ws1-5">NO₂</span></b></td> - <td class="tdc_bott" colspan="4"><span class="fontsize_120"><b>Found.   </b></span></td> - </tr><tr> - <td class="tdr bb"> </td> - <td class="tdr bb"><b>I</b> </td> - <td class="tdr bb"><b>II</b> </td> - <td class="tdr bb"><b>III</b> </td> - <td class="tdr bb"><b>IV</b> </td> - <td class="tdr bb"><b>V</b> </td> - </tr><tr> - <td class="tdr">C = 52.66</td> - <td class="tdr br">52.18 </td> - <td class="tdr br">52.42 </td> - <td class="tdr br">52.67 </td> - <td class="tdr br">—— </td> - <td class="tdr">——</td> - </tr><tr> - <td class="tdr">H = 3.46</td> - <td class="tdr br">3.76 </td> - <td class="tdr br">3.27 </td> - <td class="tdr br">3.66 </td> - <td class="tdr br">—— </td> - <td class="tdr">——</td> - </tr><tr> - <td class="tdr">S = 7.39</td> - <td class="tdr br">—— </td> - <td class="tdr br">—— </td> - <td class="tdr br">—— </td> - <td class="tdr br">7.57 </td> - <td class="tdr">7.48</td> - </tr><tr> - <td class="tdc bt" colspan="6"> </td> - </tr> - </tbody> -</table> - -<p>An effort to obtain the anhydride was unsuccessful. Some loss of weight -was observed, but the compound underwent decomposition before this loss -amounted to much. -<span class="pagenum" id="Page_59">[Pg 59]</span></p> - -<p id="VII_6"><span class="fontsize_120 space-above1"><b>6.</b></span> -The Action of Pyrogallol upon the Symmetrical Chloride of -Paranitroorthosulphobenzoic Acid.</p> - -<p>The product of this action dissolves readily in dilute sodium -hydroxide without residue, producing a very deep purple-black color -when concentrated, passing to grayish-violet as the solution is -diluted. On adding hydrochloric acid, precipitation occurs, as in most -of these reactions. On attempting to filter off this precipitate, it -forms a sticky, black mass on the filter with which little can be done. -It is best to evaporate to dryness before filtration and powder the residue. -This powder can then be washed fairly clean from alkali salts and acid. -<span class="pagenum" id="Page_60">[Pg 60]</span></p> - -<p>Nothing to suggest the formation of an etherial salt was observed.</p> - -<p>Analysis of this product for sulphur showed that in this galleïn, as -in the case of the hydroquinone phthaleïn more than two pyrogallol -residues had entered the acid residue. The indications were that -six had entered into one of the chloride. This also agrees with the -observation of Lyman<a id="FNanchor_23" href="#Footnote_23" class="fnanchor">[23]</a>, -who describes a hexapyrogallol galleïn of orthosulphoparatoluic acid.</p> - -<p>Probably a mixture of varying composition was obtained, and little -importance was attached to the results save as they showed that no -etherial salt is formed in the reaction. -<span class="pagenum" id="Page_61">[Pg 61]</span></p> - -<p id="VII_7"><span class="fontsize_120 space-above1"><b>7.</b></span> -The Action of β-Naphthol upon the Symmetrical Chloride of -Paranitroorthosulphobenzoic Acid.</p> - -<p>It was hoped that here, as in the case of the monohydroxy phenols an -etherial salt would be obtained. It was found, however, that very -little action occurred, save such as was indicated by the development -of a bright carmine color in the melted mixture, until a temperature of -about 160° was reached. At this point hydrochloric acid was evolved, -but the chloride itself undergoes decomposition. Nothing definite could -be isolated among the reaction products, save unchanged β-Naphthol.</p> -<hr class="chap x-ebookmaker-drop" /> - -<div class="chapter"> -<p><span class="pagenum" id="Page_62">[Pg 62]</span></p> - -<h2 class="nobreak">VIII. The Action of Aniline upon<br /> the Symmetrical -Chloride<br /> of Paranitroorthosulphobenzoic Acid.</h2> -</div> - -<p>As has been pointed out in the Introduction, it was in connection -with the aniline derivatives of orthosulphobenzoic acid, that the -isomerism of the chlorides was first noticed, two anilids being -obtained. Accordingly, when Gray began his study of the chlorides -of paranitroorthosulphobenzoic acid, his first effort was to obtain -evidence of the existence of two anilids. These were not obtained, -however, until after the chlorides themselves had been isolated, as their -properties made their isolation and preparation a matter of difficulty. -<span class="pagenum" id="Page_63">[Pg 63]</span></p> - -<p>Some points still remained in doubt after Gray’s study, and a further -investigation was thought to be desirable to clear these up.</p> - -<p>Some time was spent in an endeavor to obtain a method by which a good -yield of fusible, or symmetrical, anilid could be obtained. The yield -in all cases tried, is not a good one. The presence of the nitro group -appears to complicate the reaction, leading to secondary reactions -whose course could not be followed. Upon bringing aniline and the -chloride together, a very vivid red color was always observed, and the -same was true when it was necessary to employ alkali. The fact that -such colors develop when nitro compounds are treated with alkali has -<span class="pagenum" id="Page_64">[Pg 64]</span> -been noticed in many instances and some progress has been made in the -study of these compounds. Jackson and Ittner<a id="FNanchor_24" href="#Footnote_24" class="fnanchor">[24]</a> -have lately reviewed this subject.</p> - -<p>If a solution of the symmetrical chloride in ether is slowly added to a -similar solution of aniline, no appreciable amount of heat is evolved. -If the resulting solution is allowed to stand at ordinary temperatures, -action proceeds very slowly, aniline hydrochloride being precipitated -as the reaction proceeds. This can be filtered off from time to time -and the rate of action so observed. In such a way it was found that -five grams of chloride required about fifty hours time to react -completely with an excess of aniline. Similar results were obtained -<span class="pagenum" id="Page_65">[Pg 65]</span> -with chloroform as the solvent. By boiling the solution for an hour or -more the reaction is complete.</p> - -<p>The method employed was to bring the chloride and an excess of -aniline—somewhat more than four molecules—together in chloroform -solution. The flask was then boiled for about an hour, when the -chloroform was distilled off. During the boiling as well as the -distillation more or less bumping occurs in consequence of the aniline -hydrochloride which separates, and constant shaking of the flask is -sometimes necessary. The residue which is in a thick, gummy condition -in consequence of the presence of an excess of aniline, was digested -with water acidulated with hydrochloric acid. The excess of aniline is -<span class="pagenum" id="Page_66">[Pg 66]</span> -thus removed, and the reaction product obtained as a reddish-brown -solid substance. This was treated with dilute sodium hydroxide, all -lumps being broken up with a stirring rod. The undissolved substance -is largely anil, which was filtered off. The anilid was then regained -by acidifying the alkaline solution, in which it was dissolved. It -separates immediately as a curdy colorless precipitate, though it is -frequently colored pink by impurity. It was found that this color could -be removed, in case not much was present, by redissolving the anilid in -alkali, and slowly pouring the solution into an excess of dilute acid. -<span class="pagenum" id="Page_67">[Pg 67]</span></p> - -<p>In all cases a considerable amount of anil was obtained, even when the -substances were employed in the molecular ratios of 1:10. The reactions -involved, so far as the formation of anilid and anil are concerned are,</p> - -<p class="left120 space-below2 no-wrap"><b> -<span class="ws1">COCl</span><span class="ws10">CO.NH.C₆H₅</span><br /> -<span class="ws3-5">/</span><span class="ws12">/</span><br /> -<span class="ws2-5">C₆H₃—SO₂Cl + 4C₆H₅NH₂ = C₆H₃—SO₂.NH.C₆H₅ + C₆H₅NH₃Cl</span><br /> -<span class="ws4">\</span><span class="ws12">\</span><br /> -<span class="ws4">NO₂</span><span class="ws11">NO₂</span><br /> -</b></p> - -<p class="left120 space-below2 no-wrap"><b> -<span class="ws14-5">CO</span><br /> -<span class="ws17">/</span><span class="ws1-5">\</span><br /> -<span class="ws4">COCl</span><span class="ws10">/</span><span class="ws2-5">NH.C₆H₅</span><br /> -<span class="ws4">/</span><span class="ws12">/</span><span class="ws2-5">/</span><br /> -<span class="ws2-5">C₆H₃—SO₂Cl + 3C₆H₅NH₂ = C₆H₃—SO₂ + 2C₆H₅NH₃Cl</span><br /> -<span class="ws4">\</span><span class="ws12">\</span><br /> -<span class="ws4">NO₂</span><span class="ws11">NO₂</span><br /> -</b></p> - -<p>On the whole the reaction seemed to be the most satisfactory in -chloroform solution, the main objection being, that, owing to the -simultaneous presence of chloroform, alkali, an a trace of aniline, -phenyl isocyanide is always formed, and renders the work more or less -unpleasant.</p> - -<p><span class="pagenum" id="Page_68">[Pg 68]</span> -A number of experiments were also made to see if the yield could -be increased be employing a modification of the “Schotten-Baumann -Reaction”<a id="FNanchor_25" href="#Footnote_25" class="fnanchor">[25]</a> -for the formation of anilids. For this purpose an etherial -solution of the chloride was added to a like solution of aniline in -which was suspended finely powdered anhydrous potassium carbonate. The -proportions of the substances were those demanded by the equation</p> - -<p class="left120 space-below2 no-wrap"><b> -<span class="ws1-5">COCl</span><span class="ws13">CO.NH.C₆H₅</span><br /> -<span class="ws4">/</span><span class="ws15-5">/</span><br /> -<span class="ws2">C₆H₃—SO₂Cl + 2C₆H₅NH₂ + 2K₂Cl₃ = C₆H₃—SO₂NH.C₆H₅ + 2KCl + 2KHCO₃</span><br /> -<span class="ws4">\</span><span class="ws15-5">\</span><br /> -<span class="ws4">NO₂</span><span class="ws14">NO₂</span><br /> -</b></p> - -<p class="space-below2">Very little anilid was, however obtained, but -in its place a substance soluble in water, of acid reaction capable of -<span class="pagenum" id="Page_69">[Pg 69]</span> -forming salts and yielding several well characterized derivatives. -I hope to investigate this reaction more fully at some future time.</p> - -<hr class="tb" /> - -<p class="space-below2 space-above2">The anilid is rather sparingly -soluble in alcohol, from which it is deposited on cooling in very small -needles. These melt, as stated by Gray, at 222°. It is also soluble -in chloroform and glacial acetic acid, but does not form well defined -crystals from any solvent. It dissolves in dilute alkali from which -solution acids precipitate it unchanged.</p> - -<hr class="tb" /> - -<p class="space-above2">The anil is also soluble in alcohol, glacial -acetic acid etc. It crystallizes in much better-formed crystals than -does the anilid. These melt at 188°. -<span class="pagenum" id="Page_70">[Pg 70]</span></p> - -<p>On boiling the anil with aniline for a time, it is converted -into the anilid</p> - -<p class="left120 space-below2 no-wrap"><b> -<span class="ws1-5">CO</span><br /> -<span class="ws4">/</span><span class="ws2">\</span><br /> -<span class="ws3-5">/</span><span class="ws3">N.C₆H₅</span><span class="ws5-5">CO.NH.C₆H₅</span><br /> -<span class="ws3">/</span><span class="ws3">/</span><span class="ws8">/</span><br /> -<span class="ws2">C₆H₃—SO₂ + C₆H₅NH₂ = C₆H₃—SO₂NH.C₆H₅</span><br /> -<span class="ws3">\</span><span class="ws11-5">\</span><br /> -<span class="ws3">NO₂</span><span class="ws10">NO₂</span><br /> -</b></p> - -<p>In none of these reactions was any infusible anilid observed.</p> - -<hr class="chap x-ebookmaker-drop" /> -<p><span class="pagenum" id="Page_71">[Pg 71]</span></p> -<div class="chapter"> -<h2 class="nobreak">IX. The Action of Phosphorus Oxychloride<br /> upon the Fusible Anilid.</h2> -</div> - -<p>Hunter<a id="FNanchor_26" href="#Footnote_26" class="fnanchor">[26]</a> -found that when either of the anilids of orthosulphobenzoic -acid were treated with phosphorus oxychloride, or similar dehydrating -agents, a molecule of water was abstracted with the formation of a new -substance. A careful study of the compound led to the belief that it -was a dianil, and that its formation and structure could be represented -by the equation</p> - -<p class="left120 space-below2 no-wrap"><b> -<span class="ws13-5">C=N.C₆H₅</span><br /> -<span class="ws16">/</span><span class="ws1">\</span><br /> -<span class="ws4">CO.NH.C₆H₅</span><span class="ws6">/</span><span class="ws2">\</span><br /> -<span class="ws4">/</span><span class="ws11">/</span><span class="ws2-5">.N.C₆H₅</span><br /> -<span class="ws2">C₆H₄</span><span class="ws8">= C₆H₄</span><span class="ws2">/</span><span class="ws4">+ H₂O.</span><br /> -<span class="ws4">\</span><span class="ws11">\</span><span class="ws1-5">/</span><br /> -<span class="ws4">SO₂NH.C₆H₅</span><span class="ws6">SO₂</span><br /> -</b></p> - -<p>A corresponding study of the fusible anilid of -paranitroorthosulphobenzoic acid was undertaken. -<span class="pagenum" id="Page_72">[Pg 72]</span></p> - -<p>The method employed in this study was as follows. A tubulated retort -of convenient size was fused onto the inner tube of a small condenser. -This was done to avoid connections, which are nearly always attacked by -the oxychloride. Another satisfactory plan is to have the neck of the -retort of the same size as the inner tube of the condenser. The ends -are placed in contact, and the tubes bound in position by wrapping with -asbestos paper. Over the joint so made, a tight rubber tube is drawn.</p> - -<p>A convenient amount of phosphorus oxychloride (50 c.c.) was placed in -the retort and the anilid (5 gr.) added through the tubulus. On boiling, -<span class="pagenum" id="Page_73">[Pg 73]</span> -with the condenser inverted, the anilid soon dissolved, with evolution -of hydrochloric acid gas, and the solution became bright yellow in -color, sometimes inclining to orange. The boiling was continued as long -as hydrochloric acid was given off. The oxychloride was then distilled -off under diminished pressure, care being taken to shake the retort -constantly during the distillation as violent bumping is almost sure -to occur especially towards the end of the operation. The product -remaining, spattered over the walls of the retort, was a greenish -yellow solid.</p> - -<p>Water was then added, and the whole allowed to stand for an hour or so -<span class="pagenum" id="Page_74">[Pg 74]</span> -to thoroughly dissolve the phosphoric acid formed in the reaction.</p> - -<p>In case the anilid is not perfectly dry, a much more energetic reaction -occurs, and on distilling off the oxychloride, the product remains as a -dark, gummy mass. This should be spread out on the sides of the retort -while still liquid. On cooling and adding water, this gum gradually -disappears, and in its place is found the yellow solid product just -described. The gum appears to be a solution of this substance in -phosphoric acid.</p> - -<p>After the substance is filtered off and dried, it can be crystallized -from acetone, benzene, glacial acetic acid or alcohol. From these solvents -it crystallizes in small yellow needles resembling quinone in appearance. -<span class="pagenum" id="Page_75">[Pg 75]</span></p> - -<p>The crystals obtained form acetone are rather larger than those from -the other solvents, and are more nearly orange in color, apparently -because of their greater compactness. When glacial acetic acid is used, -care must be taken to avoid any unnecessary heating, as continued -heating produces a change that will presently be described. The -substance melts at 208°.</p> - -<p class="fontsize_120"><b>Analysis of the substance resulted as follows:</b></p> - -<table class="fontsize_120" border="0" cellspacing="0" summary=" " cellpadding="0" > - <tbody><tr> - <td class="tdl" colspan="6"> I. 0.3822 gram gave 0.8334 gram CO₂ and 0.1272 gram H₂O.</td> - </tr><tr> - <td class="tdc" colspan="6"> </td> - </tr><tr> - <td class="tdl" colspan="6"> II. 0.2645 gram gave 0.5812 gram CO₂ and 0.0910 gram H₂O.</td> - </tr><tr> - <td class="tdc" colspan="6"> </td> - </tr><tr> - <td class="tdl" colspan="6">III. 0.2023 gram gave 0.1283 gram BaSO₄.</td> - </tr><tr> - <td class="tdc" colspan="6"> </td> - </tr><tr> - <td class="tdl" colspan="6"> IV. 0.2061 gram gave 0.1280 gram BaSO₄.</td> - </tr><tr> - <td class="tdc" colspan="6"> </td> - </tr><tr> - <td class="tdl" colspan="6"> V. 0.1853 gram gave 16.73 C.C.N (Standard).</td> - </tr><tr> - <td class="tdc" colspan="6"><span class="pagenum" id="Page_76">[Pg 76]</span></td> - </tr><tr> - <td class="tdc"> </td> - <td class="tdl"><b><span class="ws6-5">C=N.C₆H₅</span><br /> - <span class="ws6">/</span><span class="ws1">\</span><br /> - <span class="ws5-5">/</span><span class="ws2">.N.C₆H₅</span><br /> - <span class="ws5">/</span><span class="ws2">/</span><br /> - Cal. for C₆H₃—SO₂<br /> - <span class="ws5">\</span><br /> - <span class="ws5-5">NO₂</span></b></td> - <td class="tdc_bott" colspan="4"><span class="fontsize_120"><b>Found.   </b></span></td> - </tr><tr> - <td class="tdr bb"> </td> - <td class="tdr bb"><b>I</b> </td> - <td class="tdr bb"><b>II</b> </td> - <td class="tdr bb"><b>III</b> </td> - <td class="tdr bb"><b>IV</b> </td> - <td class="tdr bb"><b>V</b> </td> - </tr><tr> - <td class="tdr">C = 60.11</td> - <td class="tdr br">59.47 </td> - <td class="tdr br">59.93 </td> - <td class="tdr br">—— </td> - <td class="tdr br">—— </td> - <td class="tdr">——</td> - </tr><tr> - <td class="tdr">H = 3.44</td> - <td class="tdr br">3.69 </td> - <td class="tdr br">3.82 </td> - <td class="tdr br">—— </td> - <td class="tdr br">—— </td> - <td class="tdr">——</td> - </tr><tr> - <td class="tdr">S = 8.45</td> - <td class="tdr br">—— </td> - <td class="tdr br">—— </td> - <td class="tdr br">8.70 </td> - <td class="tdr br">8.52 </td> - <td class="tdr">——</td> - </tr><tr> - <td class="tdr">N = 11.08</td> - <td class="tdr br">—— </td> - <td class="tdr br">—— </td> - <td class="tdr br">—— </td> - <td class="tdr br">—— </td> - <td class="tdr">11.35</td> - </tr><tr> - <td class="tdc bt" colspan="6"> </td> - </tr> - </tbody> -</table> - -<p>For analyses I & II I am indebted to Mr. Nakaseko, -who kindly made them for me.</p> - -<hr class="chap x-ebookmaker-drop" /> - -<div class="chapter"> -<p><span class="pagenum" id="Page_77">[Pg 77]</span></p> -<h2 class="nobreak">X. The Action of Reagents upon the Dianil<br /> - of Paranitroorthosulphobenzoic Acid.</h2> -</div> - -<p id="X_1"><span class="fontsize_120 space-above1"><b>1.</b></span> -The Action of Hydrochloric Acid on the Dianil</p> - -<p>When the dianil is boiled for some time with concentrated hydrochloric -acid, the yellow color of the substance disappears, and the dianil is -converted into a colorless substance without, however, passing into -solution. The substance so obtained was filtered off, and crystallized -from alcohol. It crystallized in small colorless needles, which melted -at 183°, and possessed all the properties of the anil, which, in fact, -it proved to be. The reaction was therefore</p> - -<p class="left120 space-below2 no-wrap"><b> -<span class="ws2-5">C=N.C₆H₅</span><span class="ws8">CO</span><br /> -<span class="ws5">/</span><span class="ws1">\</span><span class="ws11">/</span><span class="ws1">\</span><br /> -<span class="ws4-5">/</span><span class="ws2">N.C₆H₅</span><span class="ws7"> /</span><span class="ws2">N.C₆H₅</span><br /> -<span class="ws4">/</span><span class="ws2">/</span><span class="ws10">/</span><span class="ws2">/</span><br /> -<span class="ws2">C₆H₃—SO₂ + HCl + H₂O = C₆H₃—SO₂ + C₆H₅NH₃Cl</span><br /> -<span class="ws4">\</span><span class="ws12">\</span><br /> -<span class="ws4">NO₂</span><span class="ws11">NO₂</span><br /> -</b></p> - -<p><span class="pagenum" id="Page_78">[Pg 78]</span> -This reaction also explains the fact that some anil was always obtained -in making the dianil from the anilid. Hydrochloric acid is formed -in the reaction, and in turn acts on the dianil in the sense of the -equation just given.</p> - -<p id="X_2"><span class="fontsize_120 space-above1"><b>2.</b></span> -The Action of Alcoholic Potash on the Dianil.</p> - -<p>On boiling the dianil with alcoholic potash for a time, the solution -turned red, and nothing but tarry products were obtained. In this -respect the dianil differs from the dianil of orthosulphobenzoic acid, -which under similar conditions, is transformed into infusible anilid. -This observation is, however, in keeping with the fact that the nitro -<span class="pagenum" id="Page_79">[Pg 79]</span> -derivative, is in general much less stable in the presence of alkali.</p> - -<p id="X_3"><span class="fontsize_120 space-above1"><b>3.</b></span> -The Action of Glacial Acetic Acid on the Dianil.</p> - -<p>When the dianil is boiled with glacial acetic acid for some time, the -color of the solution changes to a much lighter shade of yellow, or -becomes colorless. On evaporating the solution to small volume, and -allowing it to cool, a colorless substance separates. This is infusible -anilid. It could not be obtained in crystals from any solvent, but -always separated in flakes. It does not melt or undergo change at 340°.</p> - -<p>Like the fusible anilid it dissolves in dilute alkali, but on -<span class="pagenum" id="Page_80">[Pg 80]</span> -acidifying the solution it does not immediately reappear. After -standing for some time, however, it gradually separates in perfectly -pure form. In this particular my observation differs from that of -Gray,<a id="FNanchor_27" href="#Footnote_27" class="fnanchor">[27]</a> -who states that this anilid is decomposed by solution in alkali.</p> - -<p class="fontsize_120"><b>A specimen that had been repeatedly -precipitated gave the following results on analysis.</b></p> - -<table class="fontsize_120" border="0" cellspacing="0" summary=" " cellpadding="0" > - <tbody><tr> - <td class="tdl" colspan="4"> I. 0.1607 gram gave 13.88 C.C.N. (standard).</td> - </tr><tr> - <td class="tdc" colspan="4"> </td> - </tr><tr> - <td class="tdl" colspan="4"> II. 0.2195 gram gave 0.1285 gram BaSO₄.</td> - </tr><tr> - <td class="tdc" colspan="4"> </td> - </tr><tr> - <td class="tdl" colspan="4">III. 0.1357 gram gave 0.0807 gram BaSO₄.</td> - </tr><tr> - <td class="tdc" colspan="4"> </td> - </tr><tr> - <td class="tdc"> </td> - <td class="tdl"><b><span class="ws6-5">C[NH.C₆H₅]<big>₂</big></span><br /> - <span class="ws6">/</span><span class="ws1">\</span><br /> - <span class="ws5-5">/</span><span class="ws1-5">O</span><br /> - <span class="ws5">/</span><span class="ws2">/</span><br /> - Cal. for C₆H₃—SO₂<br /> - <span class="ws5">\</span><br /> - <span class="ws5">NO₂</span></b></td> - <td class="tdc_bott" colspan="2"><b>Found.   </b></td> - </tr><tr> - <td class="tdr"> </td> - <td class="tdr"><b>I.</b> </td> - <td class="tdr"><b>II.</b> </td> - <td class="tdr"><b>III.</b> </td> - </tr><tr> - <td class="tdr">N = 10.58</td> - <td class="tdr">10.85</td> - <td class="tdr">——</td> - <td class="tdr">——</td> - </tr><tr> - <td class="tdr">S = 8.06</td> - <td class="tdr">——</td> - <td class="tdr">8.00</td> - <td class="tdr">8.16</td> - </tr> - </tbody> -</table> - -<p><span class="pagenum" id="Page_81">[Pg 81]</span> -By this series of transformations it is possible to pass from one -anilid to the other, the steps being:</p> - -<p class="left120 space-below1 no-wrap"><b> -<span class="ws2">CO.NH.C₆H₅</span><span class="ws5">C=N.C₆H₅</span><span class="ws3">C[NH.C₆H₅]₂</span><br /> -<span class="ws4-5">/</span><span class="ws10">/</span><span class="ws1">\</span><span class="ws6">/</span><span class="ws1">\</span><br /> -<span class="ws4">/</span><span class="ws10">/</span><span class="ws2">N.C₆H₅</span><span class="ws2"> /</span><span class="ws1-5">O</span><br /> -<span class="ws3-5">/</span><span class="ws10">/</span><span class="ws2">/</span><span class="ws5">/</span><span class="ws2">/</span><br /> -<span class="ws2">C₆H₃—SO₂NH.C₆H₅ ➡ C₆H₃—SO₂ ➡ C₆H₃—SO₂</span><br /> -<span class="ws3-5">\</span><span class="ws10">\</span><span class="ws7">\</span><br /> -<span class="ws3-5">NO₂</span><span class="ws8-5">NO₂</span><span class="ws5-5">NO₂</span><br /> -</b></p> - -<p>This is of special interest as affording a means of passing from a -derivative of one of the chlorides, to a substance derived from the -other, by steps that can be clearly followed.</p> - - -<hr class="chap x-ebookmaker-drop" /> -<p><span class="pagenum" id="Page_82">[Pg 82]</span></p> -<div class="chapter"> -<h2 class="nobreak">Conclusions.</h2> -</div> - -<p>In the course of this investigation several facts have been established.</p> - -<div class="blockquot"> -<p>1. By the methods described, the symmetrical chloride of -paranitroorthosulphobenzoic acid can be obtained in fine crystalline -form, perfectly free from its isomer, with an average yield of forty -percent.</p> - -<p>2. By treatment of the chloride with benzene and aluminium chloride, -only one chlorine atom can be replaced by a phenyl group.</p> - -<p>3. The barium salt of paranitroorthobenzoyl benzenesulphonic acid, when -perfectly pure, crystallizes constantly with seven molecules of water -of crystallization.</p> - -<p><span class="pagenum" id="Page_83">[Pg 83]</span></p> - -<p>4. With alcohols, the symmetrical chloride yields directly the acid -etherial salt of paranitroorthosulphobenzoic acid, no evidence -having been obtained of an intermediate chloro-etherial salt. The -unsymmetrical chloride on the other hand yields the intermediate -product.</p> - -<p>5. With phenols, two series of derivatives are obtained.</p> - -<div class="blockquot2"> -<p class="neg-indent">(1) With monohydroxy phenols, both etherial salts and -sulphonphthaleïns are formed, the former predominating.</p> - -<p class="neg-indent">(2) With polyhydroxy phenols no etherial salts were obtained, -but compounds of the unsymmetrical type, usually containing -more than two phenol residues.</p> -</div> - -<p>6. With aniline an anil and an anilid of symmetrical constitution are -formed.</p> - -<p>7. With phosphorus oxychloride, the anilid, by loss of water, forms a dianil. -<span class="pagenum" id="Page_84">[Pg 84]</span></p> - -<p>8. This dianil undergoes transformation with</p> - -<div class="blockquot2"> -<p class="neg-indent">(1) Glacial acetic acid, forming an anilid of unsymmetrical constitution.</p> - -<p class="neg-indent">(2) Hydrochloric acid forming the anil.</p> - -<p class="neg-indent">(3) Alcoholic potash, with the formation of colored decomposition products.</p> -</div></div> - -<hr class="chap x-ebookmaker-drop" /> -<p><span class="pagenum" id="Page_85">[Pg 85]</span></p> -<div class="chapter"> -<h2 class="nobreak" id="Biographical">Biographical.</h2> -</div> - -<p>The author of the foregoing dissertation was born at Wilkinsburg, Pa., -Jan. 29., 1870. Owing to prolonged sickness in childhood his education, -prior to entering college, was much interrupted, and was largely -confined to instruction received at home.</p> - -<p>In the fall of 1887 he entered Wooster University (Ohio), from which -institution he received the degree of Bachelor of Arts in 1891. The two -following years were spent as a teacher of Sciences in the College of -Emporia (Kansas). In 1893 he entered the Johns Hopkins University where -he has since been a student of chemistry, with physics and mathematics -as subordinate studies.</p> - -<p><span class="pagenum" id="Page_86">[Pg 86]</span> -In 1895 he was appointed University Scholar in Chemistry. During 1895-6 -he served as lecture assistant to Prof. Remsen and Dr. Renouf in the -undergraduate courses. In the spring of 1896 he was appointed Fellow -for the present year.</p> - -<hr class="chap x-ebookmaker-drop" /> - -<div class="footnotes"> -<p class="f150 u"><b>Footnotes:</b></p> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_1" href="#FNanchor_1" class="label">[1]</a> -Am. Chem. Journ. XVII, 311.</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_2" href="#FNanchor_2" class="label">[2]</a> -Ibid XVII, 230.</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_3" href="#FNanchor_3" class="label">[3]</a> -Ibid XVII, 354.</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_4" href="#FNanchor_4" class="label">[4]</a> -Ibid XVIII, 794.</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_5" href="#FNanchor_5" class="label">[5]</a> -Inaug. Diss. J. H. Univ. 1895.</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_6" href="#FNanchor_6" class="label">[6]</a> -Inaug. Diss. J. H. Univ. 1896.</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_7" href="#FNanchor_7" class="label">[7]</a> -Am. Chem. Journ. I, 350.</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_8" href="#FNanchor_8" class="label">[8]</a> -Ibid XI, 177.</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_9" href="#FNanchor_9" class="label">[9]</a> -Inaug. Diss. J. H. Univ. 1845.</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_10" href="#FNanchor_10" class="label">[10]</a> -Inaug. Diss. J. H. Univ. 1896.</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_11" href="#FNanchor_11" class="label">[11]</a> -Ber. XXVI-2231; XXVIII-2281</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_12" href="#FNanchor_12" class="label">[12]</a> -Inaug. Diss. J. H. Univ. 1895.</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_13" href="#FNanchor_13" class="label">[13]</a> -Inaug. Diss. J. H. Univ. 1896.</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_14" href="#FNanchor_14" class="label">[14]</a> -Inaug. Diss. J. H. Univ. 1896.</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_15" href="#FNanchor_15" class="label">[15]</a> -Am. Ch. Journ. XI—281.</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_16" href="#FNanchor_16" class="label">[16]</a> -Inaug. Diss. J. H. Univ. 1895.</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_17" href="#FNanchor_17" class="label">[17]</a> -Am. Ch. Journ. XI, 341.</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_18" href="#FNanchor_18" class="label">[18]</a> -Am. Chem. Journ. XVII, 347.</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_19" href="#FNanchor_19" class="label">[19]</a> -Ibid. XVIII, 798.</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_20" href="#FNanchor_20" class="label">[20]</a> -Ber. XXVI, 204.</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_21" href="#FNanchor_21" class="label">[21]</a> -Am. Ch. Journ. XVIII-799</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_22" href="#FNanchor_22" class="label">[22]</a> -Am. Chem. Journ. XVI-525</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_23" href="#FNanchor_23" class="label">[23]</a> -Am. Ch. Journ. XVI-527.</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_24" href="#FNanchor_24" class="label">[24]</a> -Am. Chem. Journ. XIX-199</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_25" href="#FNanchor_25" class="label">[25]</a> -Ber. XVII-2545; XXIII, 3430.</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_26" href="#FNanchor_26" class="label">[26]</a> -Am. Ch. Journ. XVIII-810.</p> -</div> - -<div class="footnote"><p class="no-indent"> -<a id="Footnote_27" href="#FNanchor_27" class="label">[27]</a> -Inaug. Diss. J. H. Unis. 1895.</p> -</div></div> - -<div class="transnote bbox space-above2"> -<p class="f120 space-above1">Transcriber’s Notes:</p> -<hr class="r5" /> -<p class="indent">The cover image was created by the transcriber, and is in the public domain.</p> -<p class="indent">Typographical and punctuation errors have been silently corrected.</p> -</div> -<div style='display:block; margin-top:4em'>*** END OF THE PROJECT GUTENBERG EBOOK A FURTHER INVESTIGATION OF THE SYMMETRICAL CHLORIDE OF PARANITROORTHOSULPHOBENZOIC ACID ***</div> -<div style='text-align:left'> - -<div style='display:block; margin:1em 0'> -Updated editions will replace the previous one—the old editions will -be renamed. -</div> - -<div style='display:block; margin:1em 0'> -Creating the works from print editions not protected by U.S. copyright -law means that no one owns a United States copyright in these works, -so the Foundation (and you!) can copy and distribute it in the United -States without permission and without paying copyright -royalties. 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