diff options
Diffstat (limited to 'old/67920-0.txt')
| -rw-r--r-- | old/67920-0.txt | 1893 |
1 files changed, 0 insertions, 1893 deletions
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. Project Gutenberg is a registered trademark, -and may not be used if you charge for an eBook, except by following -the terms of the trademark license, including paying royalties for use -of the Project Gutenberg trademark. If you do not charge anything for -copies of this eBook, complying with the trademark license is very -easy. You may use this eBook for nearly any purpose such as creation -of derivative works, reports, performances and research. Project -Gutenberg eBooks may be modified and printed and given away--you may -do practically ANYTHING in the United States with eBooks not protected -by U.S. copyright law. Redistribution is subject to the trademark -license, especially commercial redistribution. - -START: FULL LICENSE - -THE FULL PROJECT GUTENBERG LICENSE -PLEASE READ THIS BEFORE YOU DISTRIBUTE OR USE THIS WORK - -To protect the Project Gutenberg-tm mission of promoting the free -distribution of electronic works, by using or distributing this work -(or any other work associated in any way with the phrase "Project -Gutenberg"), you agree to comply with all the terms of the Full -Project Gutenberg-tm License available with this file or online at -www.gutenberg.org/license. - -Section 1. General Terms of Use and Redistributing Project -Gutenberg-tm electronic works - -1.A. By reading or using any part of this Project Gutenberg-tm -electronic work, you indicate that you have read, understand, agree to -and accept all the terms of this license and intellectual property -(trademark/copyright) agreement. If you do not agree to abide by all -the terms of this agreement, you must cease using and return or -destroy all copies of Project Gutenberg-tm electronic works in your -possession. If you paid a fee for obtaining a copy of or access to a -Project Gutenberg-tm electronic work and you do not agree to be bound -by the terms of this agreement, you may obtain a refund from the -person or entity to whom you paid the fee as set forth in paragraph -1.E.8. - -1.B. "Project Gutenberg" is a registered trademark. It may only be -used on or associated in any way with an electronic work by people who -agree to be bound by the terms of this agreement. There are a few -things that you can do with most Project Gutenberg-tm electronic works -even without complying with the full terms of this agreement. See -paragraph 1.C below. There are a lot of things you can do with Project -Gutenberg-tm electronic works if you follow the terms of this -agreement and help preserve free future access to Project Gutenberg-tm -electronic works. See paragraph 1.E below. - -1.C. The Project Gutenberg Literary Archive Foundation ("the -Foundation" or PGLAF), owns a compilation copyright in the collection -of Project Gutenberg-tm electronic works. Nearly all the individual -works in the collection are in the public domain in the United -States. If an individual work is unprotected by copyright law in the -United States and you are located in the United States, we do not -claim a right to prevent you from copying, distributing, performing, -displaying or creating derivative works based on the work as long as -all references to Project Gutenberg are removed. Of course, we hope -that you will support the Project Gutenberg-tm mission of promoting -free access to electronic works by freely sharing Project Gutenberg-tm -works in compliance with the terms of this agreement for keeping the -Project Gutenberg-tm name associated with the work. You can easily -comply with the terms of this agreement by keeping this work in the -same format with its attached full Project Gutenberg-tm License when -you share it without charge with others. - -1.D. The copyright laws of the place where you are located also govern -what you can do with this work. Copyright laws in most countries are -in a constant state of change. If you are outside the United States, -check the laws of your country in addition to the terms of this -agreement before downloading, copying, displaying, performing, -distributing or creating derivative works based on this work or any -other Project Gutenberg-tm work. The Foundation makes no -representations concerning the copyright status of any work in any -country other than the United States. - -1.E. Unless you have removed all references to Project Gutenberg: - -1.E.1. The following sentence, with active links to, or other -immediate access to, the full Project Gutenberg-tm License must appear -prominently whenever any copy of a Project Gutenberg-tm work (any work -on which the phrase "Project Gutenberg" appears, or with which the -phrase "Project Gutenberg" is associated) is accessed, displayed, -performed, viewed, copied or distributed: - - 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. - -1.E.2. If an individual Project Gutenberg-tm electronic work is -derived from texts not protected by U.S. copyright law (does not -contain a notice indicating that it is posted with permission of the -copyright holder), the work can be copied and distributed to anyone in -the United States without paying any fees or charges. If you are -redistributing or providing access to a work with the phrase "Project -Gutenberg" associated with or appearing on the work, you must comply -either with the requirements of paragraphs 1.E.1 through 1.E.7 or -obtain permission for the use of the work and the Project Gutenberg-tm -trademark as set forth in paragraphs 1.E.8 or 1.E.9. - -1.E.3. If an individual Project Gutenberg-tm electronic work is posted -with the permission of the copyright holder, your use and distribution -must comply with both paragraphs 1.E.1 through 1.E.7 and any -additional terms imposed by the copyright holder. Additional terms -will be linked to the Project Gutenberg-tm License for all works -posted with the permission of the copyright holder found at the -beginning of this work. - -1.E.4. Do not unlink or detach or remove the full Project Gutenberg-tm -License terms from this work, or any files containing a part of this -work or any other work associated with Project Gutenberg-tm. - -1.E.5. Do not copy, display, perform, distribute or redistribute this -electronic work, or any part of this electronic work, without -prominently displaying the sentence set forth in paragraph 1.E.1 with -active links or immediate access to the full terms of the Project -Gutenberg-tm License. - -1.E.6. You may convert to and distribute this work in any binary, -compressed, marked up, nonproprietary or proprietary form, including -any word processing or hypertext form. However, if you provide access -to or distribute copies of a Project Gutenberg-tm work in a format -other than "Plain Vanilla ASCII" or other format used in the official -version posted on the official Project Gutenberg-tm website -(www.gutenberg.org), you must, at no additional cost, fee or expense -to the user, provide a copy, a means of exporting a copy, or a means -of obtaining a copy upon request, of the work in its original "Plain -Vanilla ASCII" or other form. Any alternate format must include the -full Project Gutenberg-tm License as specified in paragraph 1.E.1. - -1.E.7. Do not charge a fee for access to, viewing, displaying, -performing, copying or distributing any Project Gutenberg-tm works -unless you comply with paragraph 1.E.8 or 1.E.9. - -1.E.8. You may charge a reasonable fee for copies of or providing -access to or distributing Project Gutenberg-tm electronic works -provided that: - -* You pay a royalty fee of 20% of the gross profits you derive from - the use of Project Gutenberg-tm works calculated using the method - you already use to calculate your applicable taxes. The fee is owed - to the owner of the Project Gutenberg-tm trademark, but he has - agreed to donate royalties under this paragraph to the Project - Gutenberg Literary Archive Foundation. Royalty payments must be paid - within 60 days following each date on which you prepare (or are - legally required to prepare) your periodic tax returns. Royalty - payments should be clearly marked as such and sent to the Project - Gutenberg Literary Archive Foundation at the address specified in - Section 4, "Information about donations to the Project Gutenberg - Literary Archive Foundation." - -* You provide a full refund of any money paid by a user who notifies - you in writing (or by e-mail) within 30 days of receipt that s/he - does not agree to the terms of the full Project Gutenberg-tm - License. You must require such a user to return or destroy all - copies of the works possessed in a physical medium and discontinue - all use of and all access to other copies of Project Gutenberg-tm - works. - -* You provide, in accordance with paragraph 1.F.3, a full refund of - any money paid for a work or a replacement copy, if a defect in the - electronic work is discovered and reported to you within 90 days of - receipt of the work. - -* You comply with all other terms of this agreement for free - distribution of Project Gutenberg-tm works. - -1.E.9. If you wish to charge a fee or distribute a Project -Gutenberg-tm electronic work or group of works on different terms than -are set forth in this agreement, you must obtain permission in writing -from the Project Gutenberg Literary Archive Foundation, the manager of -the Project Gutenberg-tm trademark. Contact the Foundation as set -forth in Section 3 below. - -1.F. - -1.F.1. Project Gutenberg volunteers and employees expend considerable -effort to identify, do copyright research on, transcribe and proofread -works not protected by U.S. copyright law in creating the Project -Gutenberg-tm collection. Despite these efforts, Project Gutenberg-tm -electronic works, and the medium on which they may be stored, may -contain "Defects," such as, but not limited to, incomplete, inaccurate -or corrupt data, transcription errors, a copyright or other -intellectual property infringement, a defective or damaged disk or -other medium, a computer virus, or computer codes that damage or -cannot be read by your equipment. - -1.F.2. LIMITED WARRANTY, DISCLAIMER OF DAMAGES - Except for the "Right -of Replacement or Refund" described in paragraph 1.F.3, the Project -Gutenberg Literary Archive Foundation, the owner of the Project -Gutenberg-tm trademark, and any other party distributing a Project -Gutenberg-tm electronic work under this agreement, disclaim all -liability to you for damages, costs and expenses, including legal -fees. YOU AGREE THAT YOU HAVE NO REMEDIES FOR NEGLIGENCE, STRICT -LIABILITY, BREACH OF WARRANTY OR BREACH OF CONTRACT EXCEPT THOSE -PROVIDED IN PARAGRAPH 1.F.3. YOU AGREE THAT THE FOUNDATION, THE -TRADEMARK OWNER, AND ANY DISTRIBUTOR UNDER THIS AGREEMENT WILL NOT BE -LIABLE TO YOU FOR ACTUAL, DIRECT, INDIRECT, CONSEQUENTIAL, PUNITIVE OR -INCIDENTAL DAMAGES EVEN IF YOU GIVE NOTICE OF THE POSSIBILITY OF SUCH -DAMAGE. - -1.F.3. LIMITED RIGHT OF REPLACEMENT OR REFUND - If you discover a -defect in this electronic work within 90 days of receiving it, you can -receive a refund of the money (if any) you paid for it by sending a -written explanation to the person you received the work from. If you -received the work on a physical medium, you must return the medium -with your written explanation. The person or entity that provided you -with the defective work may elect to provide a replacement copy in -lieu of a refund. If you received the work electronically, the person -or entity providing it to you may choose to give you a second -opportunity to receive the work electronically in lieu of a refund. If -the second copy is also defective, you may demand a refund in writing -without further opportunities to fix the problem. - -1.F.4. Except for the limited right of replacement or refund set forth -in paragraph 1.F.3, this work is provided to you 'AS-IS', WITH NO -OTHER WARRANTIES OF ANY KIND, EXPRESS OR IMPLIED, INCLUDING BUT NOT -LIMITED TO WARRANTIES OF MERCHANTABILITY OR FITNESS FOR ANY PURPOSE. - -1.F.5. Some states do not allow disclaimers of certain implied -warranties or the exclusion or limitation of certain types of -damages. If any disclaimer or limitation set forth in this agreement -violates the law of the state applicable to this agreement, the -agreement shall be interpreted to make the maximum disclaimer or -limitation permitted by the applicable state law. The invalidity or -unenforceability of any provision of this agreement shall not void the -remaining provisions. - -1.F.6. INDEMNITY - You agree to indemnify and hold the Foundation, the -trademark owner, any agent or employee of the Foundation, anyone -providing copies of Project Gutenberg-tm electronic works in -accordance with this agreement, and any volunteers associated with the -production, promotion and distribution of Project Gutenberg-tm -electronic works, harmless from all liability, costs and expenses, -including legal fees, that arise directly or indirectly from any of -the following which you do or cause to occur: (a) distribution of this -or any Project Gutenberg-tm work, (b) alteration, modification, or -additions or deletions to any Project Gutenberg-tm work, and (c) any -Defect you cause. - -Section 2. Information about the Mission of Project Gutenberg-tm - -Project Gutenberg-tm is synonymous with the free distribution of -electronic works in formats readable by the widest variety of -computers including obsolete, old, middle-aged and new computers. It -exists because of the efforts of hundreds of volunteers and donations -from people in all walks of life. - -Volunteers and financial support to provide volunteers with the -assistance they need are critical to reaching Project Gutenberg-tm's -goals and ensuring that the Project Gutenberg-tm collection will -remain freely available for generations to come. In 2001, the Project -Gutenberg Literary Archive Foundation was created to provide a secure -and permanent future for Project Gutenberg-tm and future -generations. To learn more about the Project Gutenberg Literary -Archive Foundation and how your efforts and donations can help, see -Sections 3 and 4 and the Foundation information page at -www.gutenberg.org - -Section 3. Information about the Project Gutenberg Literary -Archive Foundation - -The Project Gutenberg Literary Archive Foundation is a non-profit -501(c)(3) educational corporation organized under the laws of the -state of Mississippi and granted tax exempt status by the Internal -Revenue Service. The Foundation's EIN or federal tax identification -number is 64-6221541. Contributions to the Project Gutenberg Literary -Archive Foundation are tax deductible to the full extent permitted by -U.S. federal laws and your state's laws. - -The Foundation's business office is located at 809 North 1500 West, -Salt Lake City, UT 84116, (801) 596-1887. Email contact links and up -to date contact information can be found at the Foundation's website -and official page at www.gutenberg.org/contact - -Section 4. Information about Donations to the Project Gutenberg -Literary Archive Foundation - -Project Gutenberg-tm depends upon and cannot survive without -widespread public support and donations to carry out its mission of -increasing the number of public domain and licensed works that can be -freely distributed in machine-readable form accessible by the widest -array of equipment including outdated equipment. Many small donations -($1 to $5,000) are particularly important to maintaining tax exempt -status with the IRS. - -The Foundation is committed to complying with the laws regulating -charities and charitable donations in all 50 states of the United -States. Compliance requirements are not uniform and it takes a -considerable effort, much paperwork and many fees to meet and keep up -with these requirements. We do not solicit donations in locations -where we have not received written confirmation of compliance. To SEND -DONATIONS or determine the status of compliance for any particular -state visit www.gutenberg.org/donate - -While we cannot and do not solicit contributions from states where we -have not met the solicitation requirements, we know of no prohibition -against accepting unsolicited donations from donors in such states who -approach us with offers to donate. - -International donations are gratefully accepted, but we cannot make -any statements concerning tax treatment of donations received from -outside the United States. U.S. laws alone swamp our small staff. - -Please check the Project Gutenberg web pages for current donation -methods and addresses. Donations are accepted in a number of other -ways including checks, online payments and credit card donations. To -donate, please visit: www.gutenberg.org/donate - -Section 5. General Information About Project Gutenberg-tm electronic works - -Professor Michael S. Hart was the originator of the Project -Gutenberg-tm concept of a library of electronic works that could be -freely shared with anyone. For forty years, he produced and -distributed Project Gutenberg-tm eBooks with only a loose network of -volunteer support. - -Project Gutenberg-tm eBooks are often created from several printed -editions, all of which are confirmed as not protected by copyright in -the U.S. unless a copyright notice is included. Thus, we do not -necessarily keep eBooks in compliance with any particular paper -edition. - -Most people start at our website which has the main PG search -facility: www.gutenberg.org - -This website includes information about Project Gutenberg-tm, -including how to make donations to the Project Gutenberg Literary -Archive Foundation, how to help produce our new eBooks, and how to -subscribe to our email newsletter to hear about new eBooks. |