,transcriber's ,notes3 ,typographical and punctuation errors have been silently corrected4 ,a ,further ,investigation of the ,symmetrical ,chloride of ,paranitroorthosulphobenzoic ,acid4 ,dissertation4 ,submitted to the ,board of ,university ,studies of the ,johns ,hopkins ,university for the ,degree of ,doctor of ,philosophy4 -- by -- ,william ,e4 ,henderson4 #ahig ,acknowledgment4 ,the author esteems it a privilege as well as a pleasure to give expression to his sincere sense of gratitude to ,prof4 ,remsen1under whose guidance this work was carried on not only for instruction received in the lecture room1 but for his frequent suggestion1 and his constant and friendly interest in the work as it progressed4 ,these have at all times been an encouragement and an incentive4 ,he wishes also to express his appreciation of the instruction and kindly guidance in the laboratory1 of ,drs4 ,morse and ,renouf1 as well as of ,dr4 ,ames of the ,physical ,laboratory4 ,contents4 ,i4 ,introduction4 ,page #a ,,ii4 ,preparation of the ,acid ,potassium ,salt of ,paranitroorthosulphobenzoic ,acid4 #f ,,iii4 ,preparation of the ,symmetrical ,chloride of ,paranitroorthosulphobenzoic ,acid4 #ab ,,iv4 ,properties of the ,symmetrical ,chloride of ,paranitroorthosulphobenzoic ,acid4 #ai ,v4 ,the ,action of ,benzene and ,aluminium ,chloride on the ,symmetrical ,chloride of ,paranitroorthosulphobenzoic ,acid4 #bb ,the ,barium ,salts of ,paranitroorthobenzoybbenzenesulphonic ,acid4 #bd ,,vi4 ,the ,action of ,alcohols on the ,symmetrical ,chloride of ,paranitroorthosulphobenzoic ,acid4 #cj #a4 ,methyl ,alcohol4 #ca #b4 ,ethyl ,alcohol4 #cb ,action of ,ethyl ,alcohol on the ,unsymmetrical ,chloride4 #cf ,,vii4 ,the ,action of ,phenols on the ,symmetrical ,chloride of ,paranitroorthosulphobenzoic ,acid4 #ch #a4 ,phenol4 #dj #b4 ,orthocresol4 #dh #c4 ,paracresol4 #ea #d4 ,hydroquinone4 #ec #e4 ,resorcin4 #ef #f4 ,pyrogallol4 #ei #g4 -naphthol4 #fa ,,viii4 ,the ,action of ,aniline on the ,symmetrical ,chloride of ,paranitroorthosulphobenzoic ,acid4 #fb ,,ix4 ,the ,action of ,phosphorus ,oxychloride on the ,fusible ,anilid of ,paranitroorthosulphobenzoic ,acid4 #ga ,x4 ,the ,action of ,reagents on the ,dianil of ,paranitroorthosulphobenzoic ,acid4 #gg #a4 ,of ,hydrochloric ,acid4 #gg #b4 ,of ,alcoholic ,potash4 #gh #c4 ,of ,glacial ,acetic ,acid4 #gi ,,xi4 ,conclusions4 #hb ,biographical4 #he ,i4 ,introduction4 ,the sulphobenzoic acids have been the subject of investigation in this laboratory for a number of years past4 ,among the many interesting facts that have been brought to light in the course of this study1 perhaps no others have been attended with more interest than the discovery of well characterized isomerism in the case of the chlorides of orthosulphobenzoic acid1 and its paranitro derivative2 together with the preparation of a series of isomeric derivatives of these substances4 ,the chlorides themselves have been isolated in the crystalline condition1 and have been found to differ markedly1 not only in chemical1 but in physical properties as well4 ,the first evidence that such isomerism existed1 was obtained by ,remsen and ,coates#a who1 in the course of an investigation of the action of aniline upon the chloride of orthosulphobenzoic acid1 obtained two isomeric anilids quite different in properties1 which they designated as fusible and infusible respectively4 ,the following year1 ,remsen and ,kohler#b obtained one of the chlorides in crystalline form1 together with an oil which they did not succeed in crystallizing4 ,this however was accomplished the succeeding year by ,remsen and ,saunders#c1 and a still more satisfactory result was obtained by ,remsen and ,mc,kee#d in #ahie4 ,the chloride melting at #gi was found to yield only the fusible anilid1 together with an anil1 while from the lower melting chloride1 in addition to these1 the infusible anilid was also formed4 #a ,am4 ,chem4 ,journ4 ,,xvii1 #caa4 #b ,ibid ,,xvii1 #bcj4 #c ,ibid ,,xvii1 #ced4 #d ,ibid ,,xviii1 #gid4 ,in #ahie1 ,gray#e isolated the two corresponding isomeric chlorides of paranitroorthosulphobenzoic acid1 the lower melting chloride being obtained in small quantity only4 ,the succeeding year ,hollis#f made a more careful study of this lower melting chloride1 and prepared it in considerable quantity4 ,from evidence drawn from the action of ammonia upon these chlorides1 taken in connection with a number of other facts1 the higher melting chloride is identified as the one possessing a symmetrical structure1 while the lower melting chloride possesses an unsymmetrical structure4 ,the first one1 when treated with ammonia is slowly transformed into the ammonium salt of paranitrobenzoic sulphinide3 #e ,inaug4 ,diss4 ,j4 ,h4 ,univ4 #ahie4 #f ,inaug4 ,diss4 ,j4 ,h4 ,univ4 #ahif4 ,,co _/ ,c,o,cl _/ ,n4,,nh _/ _/ _/ ,c,h----,,so,cl #d,,nh ,c,h----,,so #b,,nh,cl4 ,,no ,,no while the lower melting chloride is quickly transformed into the ammonium salt of paranitroorthocyanbenzenesulphonic acid3 ,c,cl _/ _/ ,o ,,cn _/ _/ _/ ,c,h----,,so #d,,nh ,c,h----,,so,,onh #b,,nh,cl4 ,,no ,,no ,gray's study of the symmetrical chloride was confined for the most part to the preparation of a series of salts of this latter acid1 and to an investigation of the action of aniline upon the chloride itself4 ,it was thought to be of interest to extend this study to a wider range of reactions1 as well as to improve1 if possible1 the method of preparing the chloride in pure condition4 ,at the suggestion of ,prof4 ,remsen this work was accordingly undertaken4 ,,ii4 ,preparation of ,material4 ,the method employed in the preparation of paranitroorthosulphobenzoic acid was essentially that described by ,hart1#g ,kastle1#h ,gray#i and ,hollis4#aj ,the details of it are repeated here for the purpose of calling attention to certain facts that came under the author's notice4 #g ,am4 ,chem4 ,journ4 ,i1 #cej4 #h ,ibid ,,xi1 #agg4 #i ,inaug4 ,diss4 ,j4 ,h4 ,univ4 #ahde4 #aj ,inaug4 ,diss4 ,j4 ,h4 ,univ4 #ahif4 #ajj grams of paranitrotoluene are added to #djj grams of fuming sulfuric acid1 and the mixture heated in a balloon flask at #ajj on a water bath4 ,the heating is continued until a few drops of the mixture1 added to cold water1 dissolves completely to a clear solution4 ,the time required for this operation varies much with the conditions4 ,continued stirring very considerably hastens the reaction1 as paranitrotoluene forms a layer on the acid1 which presents a small surface to its action4 ,with constant stirring the reaction is complete in a few hours1 whereas if no stirring is resorted to1 as much as several days may be required1 especially when large quantities are employed at one time4 ,when the reaction is complete1 the mixture is poured into a large volume of water1 and neutralized with calcium carbonate4 ,in the filtrate from calcium sulphate1 the calcium salt of paranitroorthotoluene sulphonic acid is found1 and this is converted into the potassium salt in the usual way4 ,the oxidation of the potassium salt is effected as follows4 #ej grams of the salt are dissolved in #b litres of water1 and to this is added a solution of #ae grams of potassium hydroxide4 ,the mixture is heated to #ajj on a water-bath1 and when this temperature is reached1 #aaj grams of potassium permanganate are added4 ,heating is continued until the solution is decolorized1 care being taken to prevent the evolution of free oxygen4 ,the oxides of manganese are then filtered off1 the filtrate neutralized with hydrochloric acid1 and evaporated to about one fifth of its original volume4 ,strong hydrochloric acid is them added in excess1 and on cooling the acid potassium salt of paranitroorthosulphobenzoic acid separates in very slender colorless needles completely filling the liquid4 ,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 together4 ,if the two substances lie together in solid form at the bottom of the flask1 a very slight elevation of temperature leads to the formation of an extremely troublesome red substance1 which is very difficult to remove4 ,it is almost impossible to remove it from the oxidation product by recrystallization1 since any considerable amount of it has a marked influence on the solubility of the salt1 rendering it much more soluble4 ,it persists throughout all subsequent transformations of paranitroorthosulphobenzoic acid1 and should therefore be carefully avoided4 ,otto ,fischer#aa has shown that in concentrated solution1 potassium hydroxide acts on nitro derivatives of toluene1 with the formation of various colored substances derived from stilbene4 ,in the case of paranitroorthotoluenesulphonic acid1 he describes the substance formed as possessing a cherry red color4 ,the reactions involved in its formation are3 ,,ch ,,hc ,,ch _/ _/ #b;,c,h----,,so,,ok ,c,h----,,so,,ok ,,ko4,o,s----,c,h #b;,h,o _/ ,,no _/ _/-- ,o -- _/ ,n ,n -- ,o --_/ ,by oxidation this passes to a nitro compound of the composition ,,hc ,,ch _/ ,c,h----,,so,,ok ,,koo,s----,c,h _/ ,,no ,o,n ,it was no doubt the formation of substances of this nature that occasioned the color observed in some of the oxidations4 #aa ,ber4 ,,xxvi-#bbca2 ,,xxviii-#bbha ,the only effective method of separating this colored substance was found to be to pass to the neutral salt of paranitroorthosulphobenzoic acid1 by making the solution slightly alkaline4 ,the salt of this colored substance is also formed and the two can be separated by a few recrystallizations in a fairly satisfactory manner4 ,the yield in both of the transformations involved in the preparation of paranitroorthosulphobenzoic acid does not fall far short of the theoretical4 ,,iii4 ,preparation of the ,symmetrical ,chloride of ,paranitroorthosulphobenzoic ,acid4 ,this chloride was first separated from its unsymmetrical isomer by ,gray#ab4 ,it was obtained by allowing a chloroform solution of the mixed chlorides to evaporate until the chloroform had almost entirely disappeared4 ,in the thick liquid so obtained1 crystals of the symmetrical chloride were formed4 ,it was also obtained by applying the method devised by ,bucher in connection with the corresponding chloride of orthosulphobenzoic acid--i4e4 by the action of dilute ammonia on the mixed chlorides4 ,gray also found that the best conditions for securing a relatively large proportion of the symmetrical chloride were1 the employment of as low a temperature as possible in the formation of the chlorides1 and of as small an excess of phosphorus pentachloride as would suffice for the reaction4 #ab ,inaug4 ,diss4 ,j4 ,h4 ,univ4 #ahie4 ,after many experiments1 under widely differing conditions1 the following method of procedure1 embodying the results of ,gray's work1 was adopted4 ,dehydrated acid potassium salt of paranitroorthosulphobenzoic acid1 and phosphorus pentachloride1 in the ratio of #dj3 #ee grams1 are brought together in a mortar and intimately mixed4 ,the mixture is put into an evaporating dish1 and placed on a sulphuric acid bath1 previously heated to #aej4 ,as soon as the action has been well started1 the dish is removed1 and the reaction allowed to proceed without further heating4 ,when it is complete1 and the contents of the dish has cooled down to the temperature of the room1 the oily product is poured slowly into a salts bottle containing ice water1 the bottle being frequently shaken during the process4 ,the shaking is continued with renewed portions of water1 as long as the wash water is cloudy4 ,the water is then poured off1 the brownish gummy chloride dissolved in chloroform1 and the solution placed in a good-sized separating funnel4 ,ice water is then added1 and the contents of the funnel treated with successive portions of ammonia 7desk ammonia diluted one half74 ,shaking is continued after each addition until the odor of ammonia has disappeared1 and ice is added from time to time as may be required4 ,when it is found that the odor of ammonia persists after several minutes' shaking1 the chloroform layer1 which is usually filled with a solid substance that has separated during the process1 is drawn off1 filtered1 and dried with calcium chloride4 ,by this process all of the unsymmetrical chloride is converted into the ammonium salt of paranitroorthocyanbenzenesulphonic acid1 according to the equation3 ,c,cl _/ _/ ,o ,,cn _/ _/ _/ ,c,h----,,so #d,,nh ,c,h----,,so,,nh #b,,nh,cl4 ,,no ,,no while the symmetrical chloride remains for the most part unchanged1 though some of it is converted into the ammonium salt of paranitrobenzoic sulphinide3 ,,co _/ ,c,o,cl _/ ,n4,,nh _/ _/ _/ ,c,h----,,so,cl #d,,nh ,c,h----,,so #b,,nh,cl4 ,,no ,,no ,it was found that working in this way the symmetrical chloride could be prepared in pure condition1 free from its isomer4 ,the chloroform completely evaporates in a short time leaving fine crystals of the symmetrical chloride4 ,in case the evaporation is slow and incomplete1 it may be concluded that not all of the unsymmetrical chloride has been removed4 ,the yield was uniformly about #dj per cent of the theoretical4 ,from the water used to wash the chlorides a considerable amount of the original salt can be recovered1 as the reaction under the conditions employed1 is never complete4 ,an examination was made of the substance mentioned as separating in the chloroform solution of the chlorides1 during the treatment with ammonia1 and it was found to possess the following properties4 ,it is insoluble in benzene1 chloroform1 acetone1 ether and ligroin2 soluble in glacial acetic acid1 from which it separates on cooling in colorless1 crystalline condition2 insoluble in the cold in water1 alcohol and ammonia1 but by boiling with these reagents1 or by long standing in the cold1 it is dissolved with decomposition4 ,it was dissolved in hot water and the solution1 which was acid in reaction1 was neutralized with potassium carbonate4 ,on adding an excess of hydrochloric acid to the solution1 and allowing it to cool1 characteristic crystals of acid potassium salt of paranitroorthosulphobenzoic acid separated4 ,these properties identify the substance as the anhydride of this acid4 ,the formation of the corresponding anhydride of orthosulphobenzoic acid by the action of phosphorus pentachloride upon its acid potassium salt was observed by ,sohon#ac1 who made use of the reaction to prepare this anhydride in quantity4 #ac ,inaug4 ,diss4 ,j4 ,h4 ,univ4 #ahif4 ,,iv4 ,properties of the ,symmetrical ,chloride of ,paranitroorthosulphobenzoic ,acid4 ,as first obtained1 the crystals of the symmetrical chloride resemble irregularly shaped pieces of amber1 both in color1 and in lustre4 ,on recrystallization from chloroform or ether1 they may be obtained perfectly colorless1 and are often of very simple crystallographic form4 ,the chloride crystallizes in the monoclinic system1 and possesses a very remarkable crystallizing power1 in which respect it differs noticeably form its isomer4 ,even in chloroform solution that is far from dry1 crystals appear with the greatest ease4 ,the habit of the crystals differs very much according to the conditions of crystallization4 ,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 complicated1 pinacoid and dome faces1 together with basal planes being prominent4 ,as a rule1 the crystals were not suitable for crystallographic work1 as the faces are usually uneven and the edges rounded4 ,by proper precautions however1 good ones were obtained1 and measurements of these will be found in this dissertation when it appears in print4 ,the size of some of the crystals obtained was unusual for substances of this class4 ,one crystal obtained with no special precautions1 save letting a solution of the chloride stand undisturbed for several days1 in a rather cool place measured #c #b4e #a4e cm41 and weighed #aa4b grams4 ,the crystals are quite compact1 their density being abut #a4he4 ,they melt at #ih 7uncorr47 ,the chloride is quite stable in crystalline condition4 ,even in moist air the crystals were unchanged1 and retained their lustre as long as they were in my possession4 ,an analysis for chlorine gave the following results4 4#bbjj gram gave 4#bbab gram ,ag,cl4 ,c,o,cl _/ ,cal4 for ,c,h----,,so,cl ,,no ,found4 ,cl #bd4id #bd4hc ,v4 ,the ,action of ,benzene and ,aluminium ,chloride on the ,symmetrical ,chloride of ,paranitroorthosulphobenzoic ,acid4 ,hollis#ad in his study of the action of these reagents upon the unsymmetrical chloride1 tested their action upon one portion of the symmetrical chloride1 and found the products to be identical in the two cases4 ,a few experiments were made in confirmation of these results1 and the same products1 in general1 were obtained4 ,it was observed however that the reactions differ in the relative ease with which they are brought about4 ,in the case of the symmetrical chloride1 the reaction is a much more vigorous one4 ,on adding aluminium chloride to a solution of the symmetrical chloride1 in benzene1 action begins at once the temperature of the hand1 and very little external heat1 and that only in the latter stages of the operation1 is needful for the completion of the reaction4 ,the application of much heat converts all of the product into thick tarry substances from which nothing satisfactory could be obtained4 #ad ,inaug4 ,diss4 ,j4 ,h4 ,univ4 #ahif4 ,when the reaction was complete1 the resulting product was isolated and purified in accordance with the directions given by ,hollis4 ,repeated trials showed that1 as in the case of the unsymmetrical chloride1 only one phenyl group could be introduced by this method4 ,the resulting compound1 paranitroorthobenzoylbenzenesulphon chloride1 was identical with that derived from the unsymmetrical chloride4 ,owing1 however1 to the fact that so much more decomposition occurs in the reaction with the symmetrical chloride1 in paranitroorthobenzoylbenzene sulphon chloride could not be obtained in perfectly pure condition4 ,in appearance it agreed closely with that described by ,hollis1 forming very characteristic greenish1 rhombic crystals4 ,these melted1 not very sharply1 at #agd instead of #agg as observed by ,hollis4 ,accordingly1 to establish the identity of the two compounds beyond any doubt1 the material on hand was converted into the barium salt of paranitroorthobenzoylbenzene sulphonic acid4 ,this was done by boiling the sulphon chloride with dilute hydrochloric acid until complete solution had been effected2 evaporating to dryness on a water-bath2 dissolving the residue in hot water1 and neutralizing with barium carbonate4 ,on filtering the hot solution from the excess of carbonate1 and allowing it to cool1 the barium salt separated4 ,the solution was somewhat colored by impurities1 and the long needles in which the salt crystallized were also somewhat colored4 ,they were analysed with the expectation that they would prove to be specimens of the salt described by ,hollis as having three1 or three and a half molecules of water of crystallization1 in as much as the conditions under which they were formed were favorable to the formation of salts with these ratios of water of crystallization4 ,hollis found that this salt could be obtained with at least four different ratios of water of crystallization viz4 three1 three and a half1 six and seven molecules respectively4 ,the analysis was as follows1 the amount of barium being calculated on the basis of the anhydrous salt4 #j4cjhg gram lost #j4jfd gram at #baj1 and gave #j4jgei gram ,ba,s,o4 ,cal4 for 7,c,h,o,,ns7,ba #aa;,h,o ,found4 ,h,o #bj4ij #bj4gc ,ba #ah4bi #ah4bc ,the mother-liquor1 in which the crystals remaining from analysis were redissolved1 was warmed1 but not boiled1 with boneblack1 to remove impurities4 ,when filtered1 the solution was perfectly colorless1 and on standing for some time1 well formed colorless1 rhombic crystals appeared4 ,on analysis they gave results as follows4 #j4bhjd gram lost #j4jdje gram at #baj1 and gave #j4jgei gram ,ba,s,o4 ,cal4 for 7,c,h,o,,ns7,ba #g;,h,o4 ,found4 ,h,o #ad4dj #ad4dd4 ,ba #ah4bi #ah4jc4 ,in making a further supply of the salt it was found that if the solution1 after filtering from the barium carbonate1 was diluted to such an extent that no crystals separated on cooling1 then on slow evaporation under a bell-jar the first crystals to appear were very long slender needles4 ,as evaporation proceeded1 these needles became much thicker assuming prismatic proportions1 and corresponded in appearance to the salt described by ,hollis as having six molecules of crystal water4 ,as growth proceeded1 the crystals became dark in color1 and the mother-liquor correspondingly clearer1 the crystals evidently absorbing the impurity in their growth4 ,when the solution had become quite colorless1 rhombic crystals of the salt containing seven molecules of water of crystallization appeared4 ,the larger prismatic crystals were carefully removed1 and redissolved in water in order to see if the same phenomena would repeat themselves4 ,this in fact was the case1 crystals of both types appearing in the same way as described4 ,without separating the crystals in this second experiment1 water was added1 and the crystals dissolved4 ,the solution was then warmed briskly with boneblack1 and filtered4 ,from the filtrate1 which was colorless1 nothing but rhombic crystals having seven molecules of water of crystallization could be obtained1 although a great many variations in the conditions were tried4 ,analysis of these last crystals was as follows3 #j4bdjj gram lost #j4jce gram at #baj1 and gave #j4jfcg gram ,ba,s,o4 ,cal4 for 7,c,h,o,,ns7,ba #g;,h,o4 ,found4 ,h,o #ad4dj #ad4eh ,ba #ah4bi #ah4bg ,hollis states that treatment with boneblack decomposes this salt1 and hence he did not purify it prior to crystallization4 ,from the experiments just described it seems probable that the impurities present affect the crystalline habit1 and the degree of hydration of this salt in a very striking manner4 ,by careful warming with boneblack no decomposition was observed1 and the crystals so obtained have constantly seven molecules of crystal water4 ,,vi4 ,the ,action of ,alcohols upon the ,symmetrical ,chloride of ,paranitroorthosulphobenzoic ,acid4 ,kastle#ae found that when the chlorides of paranitroorthosulphobenzoic acid 7which he supposed to be an individual7 were dissolved in alcohol1 and the solution boiled for some time1 the acid etherial salt of paranitroorthosulphobenzoic acid was the final product4 ,the reactions were shown to be3 ,c,o,cl ,,cooc,h _/ _/ ,i4 ,c,h----,,so,cl ,c,h,,oh ,c,h----,,so,cl ,h,cl4 ,,no ,,no ,,cooc,h ,,cooc,h _/ _/ ,,ii4 ,c,h----,,so,cl ,c,h,,oh ,c,h----,,so,,oc,h ,h,cl ,,no ,,no ,,cooc,h ,,cooc,h _/ _/ ,,iii4 ,c,h----,,so,,oc,h ,c,h,,oh ,c,h----,,so,,oh 7,c,h7,o ,,no ,,no #ae ,am4 ,ch4 ,journ4 ,,xi--#bha4 ,kastle1 it will be observed1 gave the symmetrical formula to this mixture of chlorides4 ,several acid etherial salts were made1 and a series of the neutral salts of various metals described by him4 ,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 chlorides4 #a4 ,action of ,methyl ,alcohol upon the ,symmetrical chloride4 ,a portion of the chloride was dissolved in methyl alcohol1 and the solution boiled until a drop added to cold water gave no precipitate1 of unchanged chloride4 ,the alcohol was then distilled off1 and the thick syrup remaining1 diluted with water4 ,this solution was neutralized with barium carbonate and filtered4 ,on cooling1 the barium salt crystallized in shining mica-like plates1 or in yellowish needles corresponding accurately with those described by ,kastle4 ,they gave the following analytical results4 #j4bffd gram lost #j4jbaa gram at #aej1 and gave #j4jhgj gram ,ba,s,o4 ,,cooch _/ ,cal4 for ,c,h----,,so,o ,ba #c;,h,o ,,no #b ,found ,h,o #g4gi #g4hh anhydrous salt ,ba #bj4he #bj4he #b4 ,in like manner the barium ethyl salt was made4 ,it also agreed perfectly with ,kastle's description1 crystallizing in fine1 colorless needles1 forming in tufts from a not too concentrated solution4 ,in case it is necessary to concentrate these solutions1 it is of advantage to add a small quantity of alcohol to the solution as this prevents any great amount of saponification1 which otherwise takes place to a noticeable extent4 ,analysis4 ,i4 #j4bhbd gram lost #j4jbgf gram at #ahj1 and gave #j4jhfj gram ,ba,s,o4 ,,ii4 #j4bfee gram lost #j4jbfb gram at #aij1 and gave #j4jhae gram ,ba,s,o4 ,,cooc,h _/ ,cal4 for ,c,h----,,so,o ,ba #d;,h,o4 ,,no #b ,found4 ,i ,,ii ,h,o #i4ea #i4gg #i4hf ,ba #bj4jj #ai4hd #bj4jb ,kastle also found that by dissolving the mixed chlorides in alcohol in the cold1 and allowing the solution to evaporate1 there separated after a time1 crystals of the chloride of the acid etherial salt of paranitroorthosulphobenzoic acid whose formation and composition are represented in equation ,i4 ,this same product was sought for when pure symmetrical chloride was employed1 but without success4 ,in every case1 crystals of unchanged chloride separated1 or else it was found that it had been completely converted into the acid etherial salt4 ,in another trial cold water was carefully added in small portions1 since ,kastle found that such treatment facilitated the separation of the substance2 the chloride alone appeared4 ,still other attempts were made to obtain the substance by adding a large amount of water to the solution of the chloride in alcohol1 after it had stood for some time4 ,in this way1 quite a precipitate was thrown down1 and this was filtered off and crystallized from ether4 ,it always proved to be the symmetrical chloride1 and none of the other substance was obtained4 ,karslake#af in working with the symmetrical chloride of orthosulphobenzoic acid1 was unable to isolate the analogous compound1 although from the mixed chlorides1 by the action of alcohols1 ,remsen and ,dohme#ag had obtained chloro-etherial salts4 #af ,inaug4 ,diss4 ,j4 ,h4 ,univ4 #ahie4 #ag ,am4 ,ch4 ,journ4 ,,xi1 #cda4 ,in as much as the pure symmetrical chloride is relatively stable in cold alcohol 7it can be crystallized from warm alcohol with very little loss71 it is possible that it is more stable than the chloro etherial salt1 and that in consequence the latter1 when formed1 yields more readily to the further action of alcohol than does the unacted on chloride4 ,hence when the action begins1 it at once proceeds to the limit4 ,the fact that the symmetrical chloride is rather sparingly soluble in cold alcohol1 making the use of concentrated solutions impossible1 may also be a factor in the case4 ,whatever may be the cause1 this substance could not be obtained under any conditions that were devised4 ,having in my possession a very small specimen of crystallized unsymmetrical chloride1 it was submitted to the action of ethyl alcohol1 under as nearly as possible the conditions employed by ,kastle4 ,crystals of a colorless substance were obtained1 which in every respect agreed with ,kastle's description of the chloride of the acid ethyl etherial salt of paranitroorthosulphobenzoic acid4 ,crystallized from ether they melted at #fh4 ,the conditions employed by ,kastle in preparing the chloride would undoubtedly lead to a relatively large proportion of unsymmetrical chloride1 and it is to this chloride that the formation of the chloro etherial salt is apparently due4 ,,vii4 ,the ,action of ,phenols upon the ,symmetrical ,chloride of ,paranitroorthosulphobenzoic ,acid4 ,remsen and ,saunders#ah in their investigation of the chlorides of orthosulphobenzoic acid1 studied the action of phenol upon these substances1 and from both the symmetrical chloride and the mixed chlorides1 they obtained a normal diphenyl ether together with a red substance which was not further studied4 ,it was formed in small quantity and was probably the corresponding sulphonphthalein4 ,later ,mc,kee#ai obtained these same substances from both the symmetrical and the unsymmetrical chlorides4 ,r4 ,meyer#bj obtained analogous substances by the action of various phenols upon phthalyl chloride4 ,it seemed probable1 therefore1 that the chlorides of paranitroorthosulphobenzoic acid would yield similar derivatives1 and a study was accordingly made of the reaction of the symmetrical chloride with a series of phenols4 ,the products in some instances were exceedingly difficult to deal with1 possessing properties that made it impossible to prepare them for analysis1 but even in such cases there could be little doubt as to the general nature of the reactions which had occurred4 #ah ,am4 ,chem4 ,journ4 ,,xvii1 #cdg4 #ai ,ibid4 ,,xviii1 #gih4 #bj ,ber4 ,,xxvi1 #bjd4 #a4 ,the ,action of ,phenol upon the ,symmetrical ,chloride of ,paranitroorthosulphobenzoic ,acid4 ,a portion of the symmetrical chloride was brought together with somewhat more than double the molecular amount of phenol4 ,the mixture was placed in a good-sized test-tube and the temperature gradually raised by means of a sulphuric acid bath4 ,as soon as the phenol melts1 some slight action occurs1 as is indicated by the fact that the mixture assumes a bright red color4 ,no appreciable amount of hydrochloric acid gas is evolved however1 until the liquid mixture has reached a temperature of about #aae4 ,at this point the gas is freely evolved1 and the action is complete at a temperature of #abe4 ,the temperature observations were made by means of a thermometer used as a stirring rod in the mixture4 ,during the heating1 the color of the liquid becomes a much more intense red1 growing darker in shade1 and the liquid itself becomes somewhat viscous but does not solidify while hot4 ,when cool1 the melt was repeatedly extracted with boiling water1 the aqueous solution being very deep purple in color4 ,the colored matter was removed very slowly in this manner1 and so the process was continued with dilute alkali4 ,a solid insoluble residue was thus obtained1 of a light-brownish color4 ,this was dissolved in alcohol1 boiled with boneblack and filtered4 ,on cooling1 needles of a straw yellow color were deposited from the alcoholic solution4 ,this proved to be the normal diphenyl etherial salt of paranitroorthosulphobenzoic acid1 the formation of this substance being expressed by the equation3 ,c,o,cl ,,cooc,h _/ _/ ,c,h----,,so,cl #b;,c,h,,oh ,c,h----,,so,,oc,h #b;,h,cl4 ,,no ,,no ,analysis of the substance gave the following results3 ,i4 #j4afbg gram gave #j4ccih gram ,,co and #j4jeaj gram ,h,o4 ,,ii4 #j4aiii gram gave #j4dahj gram ,,co and #j4jfjj gram ,h,o4 ,,iii4 #j4bfdi gram gave #j4aefa gram ,ba,s,o4 ,,cooc,h _/ ,cal4 for ,c,h----,,so,,oc,h ,,no ,found4 ,i ,,ii ,,iii ,c #eg4ad #ef4ig #eg4jc ---- ,h #c4bf #c4dg #c4cc ---- ,s #h4jb ---- ---- #h4ji ,this substance melts at #aai 7uncorr74 ,it possesses properties similar to those of the diphenyl etherial salt of orthosulphobenzoic acid described by ,saunders4 ,it is insoluble in water1 and is unaffected by hydrochloric acid or aqueous alkali4 ,on heating for a short time with alcoholic potash1 the needles were transformed into a voluminous precipitate4 ,this was filtered off1 dissolved in water1 and hydrochloric acid was added4 ,on cooling1 characteristic crystals of the acid potassium salt of paranitroorthosulphobenzoic separated4 ,analysis4 #j4acib gram lost #j4jji gram at #aej and gave #j4jche gram ,k,,so4 ,,cooh _/ ,cal4 for ,c,h----,,so,,ok ,h,o ,,no ,found4 ,h,o #e4ie ,h,o #f4ea ,k #ac4fe ,k #ac4ce ,no attempt was made to isolate the corresponding intermediate chlor-etherial salt of the composition ,,cooc,h _/ ,c,h----,,so,cl ,,no or its acid as was done by ,mc,kee#ba in his work on the analogous etherial salt of orthosulphobenzoic acid4 #ba ,am4 ,ch4 ,journ4 ,,xviii-#gii ,on evaporating the aqueous extract from the original melt almost to dryness on the water-bath1 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 alkalis1 or magenta1 if the solution was very dilute1 and orange-yellow in acids4 ,on acidifying the alkaline extract with hydrochloric acid1 this same substance was precipitated as a brownish flocculent precipitate4 ,it was1 however1 found to be impossible to obtain this substance in pure condition4 ,the amount formed in the reaction is small1 and its properties were such as to render work with it very difficult4 ,the method of precipitation is not satisfactory because1 owing to the fact that the substance is soluble in acid solutions to an unusual extent for substances of this class1 the solution had to be concentrated to such a degree as to render the precipitated substance very impure from acids and alkali salts4 ,these could not be removed by washing1 obviously1 without again dissolving the substance4 ,from its properties however1 and its color reactions1 there can be little doubt that the substance is a sulphonphthalen1 and that it is always formed in considerable quantities in the reaction of phenol upon the symmetrical chloride4 ,it was noticed that the aqueous extract of the mass left after fusion was almost always decidedly acid in reaction1 and it was thought that this might be due to the formation of an acid etherial salt1 whose formation would be expressed by the equations3 ,c,o,cl ,,cooc,h _/ _/ ,c,h----,,so,cl ,c,h,,oh ,c,h----,,so,cl ,h,cl4 ,,no ,,no ,,cooc,h ,,cooc,h _/ _/ ,c,h----,,so,cl ,h,o ,c,h----,,so,,oh ,h,cl4 ,,no ,,no ,accordingly1 the solution was saturated with barium carbonate1 the excess of carbonate removed by filtration1 the filtrate concentrated1 and allowed to cool4 ,crystals in the form of pearly scales separated1 which upon analysis proved to be the neutral barium salt of paranitroorthosulphobenzoic acid4 #j4bbia gram anhydrous salt gave #j4achf gram ,ba,s,o4 ,,coo _/ _/ ,ba _/ _/ ,cal4 for ,c,h----,,so,o ,,no ,found ,ba #ce4he #ce4eg ,this would seen to indicate that the reaction is an incomplete one even in the presence of excess of phenol4 ,no indications of the formation of an acid etherial salt was observed4 #b4 ,the ,action of ,orthocresol upon the ,symmetrical ,chloride of ,paranitroorthosulphobenzoic ,acid4 ,with orthocresol the reaction proceeds with more difficulty4 ,a higher temperature was required 7#ace-ade71 and quite an amount of tarry material was obtained from which very little could be extracted4 ,the product was warmed repeatedly with dilute alkali1 the solution so obtained neutralized with hydrochloric acid1 and distilled with steam for several hours to free it from cresol4 ,the resulting solution was then evaporated to small volume1 and acidified with hydrochloric acid4 ,a considerable precipitate was thrown down1 which was easily filtered off and dried4 ,in this condition it is a dark purple-red powder1 lumps of which possessed a yellowish-bronze metallic lustre4 ,in dilute alkaline solution it forms a deep-bluish purple solution1 while in acids it is crimson1 or light yellow if the solution is dilute4 ,it is a excellent indicator1 especially with ammonia4 ,in the insoluble tarry substance the etherial salt was sought for and obtained in small quantity only4 ,as this substance is soluble in alcohol1 and separates again on cooling in much the same condition1 the etherial salt could not be isolated be crystallization from this solvent4 ,by boiling the substance with benzene1 purifying the filtrate with boneblack1 and allowing the benzene to evaporate1 an almost colorless gummy substance was obtained1 which when dissolved in alcohol1 crystallizes in small colorless needles which melt at #hi-ij4 ,they were not obtained in quantity sufficient for analysis1 but there was little doubt that they were crystals of the diorthocresol etherial salt4 ,apparently much more decomposition occurred in this reaction than when paracresol was employed1 probably in consequence of the higher temperature required for the reaction4 #c4 ,the ,action of ,paracresol upon the ,symmetrical ,chloride of ,paranitroorthosulphobenzoic ,acid4 ,this reaction was conducted in the same manner as with phenol4 ,no hydrochloric acid was evolved until a temperature of about #aaj was reached1 although after melting1 the solution had steadily darkened to a deep reddish-brown color4 ,at #acj1 after heating for several hours1 hydrochloric acid ceased to be evolved4 ,the product was treated as in the last experiment4 ,the alkaline extract did not exhibit any marked color reactions1 such as were observed in most of these experiments1 being dull reddish-brown in both acid and alkaline solution4 ,the insoluble residue crystallized from alcohol in light brown transparent crystals1 which did not lose their color by repeated crystallization1 and boiling with boneblack1 and melted sharply at #aag4 ,from benzene they crystallized in colorless needles or flat1 narrow plates4 ,these become opaque on exposure to the air1 apparently through loss of benzene of crystallization4 ,analysis of the needles from alcohol gave the following results3 ,i4 #j4bcgb gram of substance gave #j4eacg gram ,,co and #j4jife gram ,h,o4 ,,ii4 #j4bbbc gram gave #j4abjc gram ,ba,s,o4 ,,cooc,h4,,ch _/ ,cal4 for ,c,h----,,so,,oc,h4,,ch ,,no ,found4 ,i ,,ii ,c #ei4jh #ei4jf ,h #c4ih #d4eb ,s #g4di #g4dc #d4 ,the ,action of ,hydroquinone upon the ,symmetrical ,chloride of ,paranitroorthosulphobenzoic ,acid4 ,action with hydroquinone occurs at #abj-ace1 the mixture at the same time becoming dark colored and viscous4 ,on cooling1 the product was powdered and treated with dilute alkali4 ,it readily dissolved1 without residue1 forming a dark red solution4 ,in concentrated solution the addition of acid produces a voluminous precipitate1 dark brown in color1 which when washed1 and dried in paper forms an almost black powder4 ,a dilute solution of this powder is dark red when alkaline1 orange-yellow when acid4 ,from the way in which this powder was obtained1 and owing to the fact that its solubility prevented repeated washing1 it was evident that it would not give close analytical results for a calculated formula4 ,it was thought1 however1 that analysis would give a general idea of the composition4 ,analysis of different specimens gave results for sulphur which averaged about #e4e4 ,the percentage required for the formula ,c,c,h7,,oh7 _/ _/ ,o _/ _/ ,c,h----,,so ,,no which represents the simplest sulphonfluorescen1 is #g4dc4 ,the compound could hardly have been so far from pure as to occasion such a discrepancy in results as this4 ,it would appear1 therefore1 that more than two molecules of hydroquinone enter into the reaction with one molecule of the chloride4 ,should four molecules be involved in the reaction1 leading to a compound of some such formula as ,c,c,h7,,oh7 _/ _/ ,o _/ _/ ,c,h----,,so,c,h7,,oh7 ,,no the theoretical percentage of sulphur would be #f4jj which corresponds much more closely with the results obtained4 ,this is in accord with the observations of a number of workers in this laboratory--,lyman1 ,gilpin1 ,linn and others--who have worked on various sulphonfluorescens1 and have found that in many cases four1 six and even eight phenol residues condense with one molecule of the anhydrous acid4 ,lyman#bb especially describes a tetra hydroquinone sulphonfluorescen derived from orthosulphoparatoluic acid4 ,no etherial salt was observed4 #bb ,am4 ,chem4 ,journ4 ,,xvi-#ebe #e4 ,the ,action of ,resorcin upon the ,symmetrical ,chloride of ,paranitroorthosulphobenzoic ,acid4 ,the reaction of resorcin with the chloride is a much cleaner one and proceeds more easily than in the case just described1 leading apparently to an individual compound which is well characterized4 ,during the reaction1 which is complete at #abe1 the mixture becomes almost perfectly solid1 and when cool1 it is quite brittle4 ,it was reduced to a reddish powder in a mortar and dissolved in sodium hydroxide1 there being no insoluble residue4 ,by the addition of hydrochloric acid1 the sulphonfluorescen was thrown down as a chocolate-brown precipitate1 which was filtered off1 washed to neutral reaction on a filter1 and dried on paper4 ,in this condition it is a light chocolate-brown powder4 ,in dilute alkaline solution it possesses a slight fluorescence being pink by transmitted and yellow be reflected light1 suggesting eosin in a general way4 ,it is interesting to note that the sulphonfluorescen of orthosulphobenzoic acid possesses a fluorescence that can hardly be distinguished from ordinary fluorescen 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 eosin4 ,in acid solution the color is reddish-orange4 ,analysis of the compound1 prepared as above described1 gave the following results4 ,i4 #j4agde gram gave #j4ccci gram of ,,co and #j4jei gram ,h,o4 ,,ii4 #j4adfg gram gave #j4bhbj gram ,,co and #j4jdcb gram ,h,o4 ,,iii4 #j4agcb gram gave #j4ccde gram ,,co and #j4jega gram ,h,o4 ,,iv4 #j4bjjj gram gave #j4aajd gram ,ba,s,o4 ,v4 #j4aeje gram gave #j4jhbj gram ,ba,s,o4 ,,oh _/ ,c,c,h _/ _/ ,o ,,oh #b _/ _/ ,cal4 for ,c,h----,,so ,,no ,found ,i ,,ii ,,iii ,,iv ,v ,c #eb4ff #eb4ah #eb4db #eb4fg ---- ---- ,h #c4df #c4gf #c4bg #c4ff ---- ---- ,s #g4ci ---- ---- ---- #g4eg #g4dh ,an effort to obtain the anhydride was unsuccessful4 ,some loss of weight was observed1 but the compound underwent decomposition before this loss amounted to much4 #f4 ,the ,action of ,pyrogallol upon the ,symmetrical ,chloride of ,paranitroorthosulphobenzoic ,acid4 ,the product of this action dissolves readily in dilute sodium hydroxide without residue1 producing a very deep purple-black color when concentrated1 passing to grayish-violet as the solution is diluted4 ,on adding hydrochloric acid1 precipitation occurs1 as in most of these reactions4 ,on attempting to filter off this precipitate1 it forms a sticky1 black mass on the filter with which little can be done4 ,it is best to evaporate to dryness before filtration and powder the residue4 ,this powder can then be washed fairly clean from alkali salts and acid4 ,nothing to suggest the formation of an etherial salt was observed4 ,analysis of this product for sulphur showed that in this gallen1 as in the case of the hydroquinone phthalen more than two pyrogallol residues had entered the acid residue4 ,the indications were that six had entered into one of the chloride4 ,this also agrees with the observation of ,lyman#bc1 who describes a hexapyrogallol gallen of orthosulphoparatoluic acid4 ,probably a mixture of varying composition was obtained1 and little importance was attached to the results save as they showed that no etherial salt is formed in the reaction4 #bc ,am4 ,ch4 ,journ4 ,,xvi-#ebg4 #g4 ,the ,action of -,naphthol upon the ,symmetrical ,chloride of ,paranitroorthosulphobenzoic ,acid4 ,it was hoped that here1 as in the case of the monohydroxy phenols an etherial salt would be obtained4 ,it was found1 however1 that very little action occurred1 save such as was indicated by the development of a bright carmine color in the melted mixture1 until a temperature of about #afj was reached4 ,at this point hydrochloric acid was evolved1 but the chloride itself undergoes decomposition4 ,nothing definite could be isolated among the reaction products1 save unchanged -,naphthol4 ,,viii4 ,the ,action of ,aniline upon the ,symmetrical ,chloride of ,paranitroorthosulphobenzoic ,acid4 ,as has been pointed out in the ,introduction1 it was in connection with the aniline derivatives of orthosulphobenzoic acid1 that the isomerism of the chlorides was first noticed1 two anilids being obtained4 ,accordingly1 when ,gray began his study of the chlorides of paranitroorthosulphobenzoic acid1 his first effort was to obtain evidence of the existence of two anilids4 ,these were not obtained1 however1 until after the chlorides themselves had been isolated1 as their properties made their isolation and preparation a matter of difficulty4 ,some points still remained in doubt after ,gray's study1 and a further investigation was thought to be desirable to clear these up4 ,some time was spent in an endeavor to obtain a method by which a good yield of fusible1 or symmetrical1 anilid could be obtained4 ,the yield in all cases tried1 is not a good one4 ,the presence of the nitro group appears to complicate the reaction1 leading to secondary reactions whose course could not be followed4 ,upon bringing aniline and the chloride together1 a very vivid red color was always observed1 and the same was true when it was necessary to employ alkali4 ,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 compounds4 ,jackson and ,ittner#bd have lately reviewed this subject4 ,if a solution of the symmetrical chloride in ether is slowly added to a similar solution of aniline1 no appreciable amount of heat is evolved4 ,if the resulting solution is allowed to stand at ordinary temperatures1 action proceeds very slowly1 aniline hydrochloride being precipitated as the reaction proceeds4 ,this can be filtered off from time to time and the rate of action so observed4 ,in such a way it was found that five grams of chloride required about fifty hours time to react completely with an excess of aniline4 ,similar results were obtained with chloroform as the solvent4 ,by boiling the solution for an hour or more the reaction is complete4 #bd ,am4 ,chem4 ,journ4 ,,xix-#aii ,the method employed was to bring the chloride and an excess of aniline--somewhat more than four molecules--together in chloroform solution4 ,the flask was then boiled for about an hour1 when the chloroform was distilled off4 ,during the boiling as well as the distillation more or less bumping occurs in consequence of the aniline hydrochloride which separates1 and constant shaking of the flask is sometimes necessary4 ,the residue which is in a thick1 gummy condition in consequence of the presence of an excess of aniline1 was digested with water acidulated with hydrochloric acid4 ,the excess of aniline is thus removed1 and the reaction product obtained as a reddish-brown solid substance4 ,this was treated with dilute sodium hydroxide1 all lumps being broken up with a stirring rod4 ,the undissolved substance is largely anil1 which was filtered off4 ,the anilid was then regained by acidifying the alkaline solution1 in which it was dissolved4 ,it separates immediately as a curdy colorless precipitate1 though it is frequently colored pink by impurity4 ,it was found that this color could be removed1 in case not much was present1 by redissolving the anilid in alkali1 and slowly pouring the solution into an excess of dilute acid4 ,in all cases a considerable amount of anil was obtained1 even when the substances were employed in the molecular ratios of #a3aj4 ,the reactions involved1 so far as the formation of anilid and anil are concerned are1 ,c,o,cl ,,co4,,nh4,c,h _/ _/ ,c,h----,,so,cl #d;,c,h,,nh ,c,h----,,so4,,nh4,c,h ,c,h,,nh,cl ,,no ,,no ,,co _/ ,c,o,cl _/ ,n4,c,h _/ _/ _/ ,c,h----,,so,cl #c;,c,h,,nh ,c,h----,,so #b;,c,h,,nh,cl ,,no ,,no ,on the whole the reaction seemed to be the most satisfactory in chloroform solution1 the main objection being1 that1 owing to the simultaneous presence of chloroform1 alkali1 an a trace of aniline1 phenyl isocyanide is always formed1 and renders the work more or less unpleasant4 ,a number of experiments were also made to see if the yield could be increased be employing a modification of the 8,schotten-,baumann ,reaction0#be for the formation of anilids4 ,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 carbonate4 ,the proportions of the substances were those demanded by the equation ,c,o,cl ,,co4,,nh4,c,h _/ _/ ,c,h----,,so,cl #b;,c,h,,nh #b,k,cl ,c,h----,,so,,nh4,c,h #b,k,cl #b,,khco ,,no ,,no ,very little anilid was1 however obtained1 but in its place a substance soluble in water1 of acid reaction capable of forming salts and yielding several well characterized derivatives4 ,i hope to investigate this reaction more fully at some future time4 #be ,ber4 ,,xvii-#bede2 ,,xxiii1 #cdcj4 99 99 99 99 99 ,the anilid is rather sparingly soluble in alcohol1 from which it is deposited on cooling in very small needles4 ,these melt1 as stated by ,gray1 at #bbb4 ,it is also soluble in chloroform and glacial acetic acid1 but does not form well defined crystals from any solvent4 ,it dissolves in dilute alkali from which solution acids precipitate it unchanged4 99 99 99 99 99 ,the anil is also soluble in alcohol1 glacial acetic acid etc4 ,it crystallizes in much better-formed crystals than does the anilid4 ,these melt at #ahh4 ,on boiling the anil with aniline for a time1 it is converted into the anilid ,,co _/ _/ ,n4,c,h ,,co4,,nh4,c,h _/ _/ _/ ,c,h----,,so ,c,h,,nh ,c,h----,,so,,nh4,c,h ,,no ,,no ,in none of these reactions was any infusible anilid observed4 ,,ix4 ,the ,action of ,phosphorus ,oxychloride upon the ,fusible ,anilid4 ,hunter#bf found that when either of the anilids of orthosulphobenzoic acid were treated with phosphorus oxychloride1 or similar dehydrating agents1 a molecule of water was abstracted with the formation of a new substance4 ,a careful study of the compound led to the belief that it was a dianil1 and that its formation and structure could be represented by the equation ,c,n4,c,h _/ ,,co4,,nh4,c,h _/ _/ _/ 4,n4,c,h ,c,h ,c,h _/ ,h,o4 _/ ,,so,,nh4,c,h ,,so ,a corresponding study of the fusible anilid of paranitroorthosulphobenzoic acid was undertaken4 ,the method employed in this study was as follows4 ,a tubulated retort of convenient size was fused onto the inner tube of a small condenser4 ,this was done to avoid connections1 which are nearly always attacked by the oxychloride4 ,another satisfactory plan is to have the neck of the retort of the same size as the inner tube of the condenser4 ,the ends are placed in contact1 and the tubes bound in position by wrapping with asbestos paper4 ,over the joint so made1 a tight rubber tube is drawn4 #bf ,am4 ,ch4 ,journ4 ,,xviii-#haj4 ,a convenient amount of phosphorus oxychloride 7#ej c4c47 was placed in the retort and the anilid 7#e gr47 added through the tubulus4 ,on boiling1 with the condenser inverted1 the anilid soon dissolved1 with evolution of hydrochloric acid gas1 and the solution became bright yellow in color1 sometimes inclining to orange4 ,the boiling was continued as long as hydrochloric acid was given off4 ,the oxychloride was then distilled off under diminished pressure1 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 operation4 ,the product remaining1 spattered over the walls of the retort1 was a greenish yellow solid4 ,water was then added1 and the whole allowed to stand for an hour or so to thoroughly dissolve the phosphoric acid formed in the reaction4 ,in case the anilid is not perfectly dry1 a much more energetic reaction occurs1 and on distilling off the oxychloride1 the product remains as a dark1 gummy mass4 ,this should be spread out on the sides of the retort while still liquid4 ,on cooling and adding water1 this gum gradually disappears1 and in its place is found the yellow solid product just described4 ,the gum appears to be a solution of this substance in phosphoric acid4 ,after the substance is filtered off and dried1 it can be crystallized from acetone1 benzene1 glacial acetic acid or alcohol4 ,from these solvents it crystallizes in small yellow needles resembling quinone in appearance4 ,the crystals obtained form acetone are rather larger than those from the other solvents1 and are more nearly orange in color1 apparently because of their greater compactness4 ,when glacial acetic acid is used1 care must be taken to avoid any unnecessary heating1 as continued heating produces a change that will presently be described4 ,the substance melts at #bjh4 ,analysis of the substance resulted as follows3 ,i4 #j4chbb gram gave #j4hccd gram ,,co and #j4abgb gram ,h,o4 ,,ii4 #j4bfde gram gave #j4ehab gram ,,co and #j4jiaj gram ,h,o4 ,,iii4 #j4bjbc gram gave #j4abhc gram ,ba,s,o4 ,,iv4 #j4bjfa gram gave #j4abhj gram ,ba,s,o4 ,v4 #j4ahec gram gave #af4gc ,c4,c4,n 7,standard74 ,c,n4,c,h _/ _/ 4,n4,c,h _/ _/ ,cal4 for ,c,h----,,so ,,no ,found4 ,i ,,ii ,,iii ,,iv ,v ,c #fj4aa #ei4dg #ei4ic ---- ---- ---- ,h #c4dd #c4fi #c4hb ---- ---- ---- ,s #h4de ---- ---- #h4gj #h4eb ---- ,n #aa4jh ---- ---- ---- ---- #aa4ce ,for analyses ,i amp2 ,,ii ,i am indebted to ,mr4 ,nakaseko1 who kindly made them for me4 ,x4 ,the ,action of ,reagents upon the ,dianil of ,paranitroorthosulphobenzoic ,acid4 #a4 ,the ,action of ,hydrochloric ,acid on the ,dianil ,when the dianil is boiled for some time with concentrated hydrochloric acid1 the yellow color of the substance disappears1 and the dianil is converted into a colorless substance without1 however1 passing into solution4 ,the substance so obtained was filtered off1 and crystallized from alcohol4 ,it crystallized in small colorless needles1 which melted at #ahc1 and possessed all the properties of the anil1 which1 in fact1 it proved to be4 ,the reaction was therefore ,c,n4,c,h ,,co _/ _/ _/ ,n4,c,h _/ ,n4,c,h _/ _/ _/ _/ ,c,h----,,so ,h,cl ,h,o ,c,h----,,so ,c,h,,nh,cl ,,no ,,no ,this reaction also explains the fact that some anil was always obtained in making the dianil from the anilid4 ,hydrochloric acid is formed in the reaction1 and in turn acts on the dianil in the sense of the equation just given4 #b4 ,the ,action of ,alcoholic ,potash on the ,dianil4 ,on boiling the dianil with alcoholic potash for a time1 the solution turned red1 and nothing but tarry products were obtained4 ,in this respect the dianil differs from the dianil of orthosulphobenzoic acid1 which under similar conditions1 is transformed into infusible anilid4 ,this observation is1 however1 in keeping with the fact that the nitro derivative1 is in general much less stable in the presence of alkali4 #c4 ,the ,action of ,glacial ,acetic ,acid on the ,dianil4 ,when the dianil is boiled with glacial acetic acid for some time1 the color of the solution changes to a much lighter shade of yellow1 or becomes colorless4 ,on evaporating the solution to small volume1 and allowing it to cool1 a colorless substance separates4 ,this is infusible anilid4 ,it could not be obtained in crystals from any solvent1 but always separated in flakes4 ,it does not melt or undergo change at #cdj4 ,like the fusible anilid it dissolves in dilute alkali1 but on acidifying the solution it does not immediately reappear4 ,after standing for some time1 however1 it gradually separates in perfectly pure form4 ,in this particular my observation differs from that of ,gray1#bg who states that this anilid is decomposed by solution in alkali4 #bg ,inaug4 ,diss4 ,j4 ,h4 ,unis4 #ahie4 ,a specimen that had been repeatedly precipitated gave the following results on analysis4 ,i4 #j4afjg gram gave #ac4hh ,c4,c4,n4 7standard74 ,,ii4 #j4baie gram gave #j4abhe gram ,ba,s,o4 ,,iii4 #j4aceg gram gave #j4jhjg gram ,ba,s,o4 ,c,,nh4,c,h _/ _/ ,o _/ _/ ,cal4 for ,c,h----,,so ,,no ,found4 ,i4 ,,ii4 ,,iii4 ,n #aj4eh #aj4he ---- ---- ,s #h4jf ---- #h4jj #h4af ,by this series of transformations it is possible to pass from one anilid to the other1 the steps being3 ,,co4,,nh4,c,h ,c,n4,c,h ,c,,nh4,c,h _/ _/ _/ _/ _/ ,n4,c,h _/ ,o _/ _/ _/ _/ _/ ,c,h----,,so,,nh4,c,h ,c,h----,,so ,c,h----,,so ,,no ,,no ,,no ,this is of special interest as affording a means of passing from a derivative of one of the chlorides1 to a substance derived from the other1 by steps that can be clearly followed4 ,conclusions4 ,in the course of this investigation several facts have been established4 #a4 ,by the methods described1 the symmetrical chloride of paranitroorthosulphobenzoic acid can be obtained in fine crystalline form1 perfectly free from its isomer1 with an average yield of forty percent4 #b4 ,by treatment of the chloride with benzene and aluminium chloride1 only one chlorine atom can be replaced by a phenyl group4 #c4 ,the barium salt of paranitroorthobenzoyl benzenesulphonic acid1 when perfectly pure1 crystallizes constantly with seven molecules of water of crystallization4 #d4 ,with alcohols1 the symmetrical chloride yields directly the acid etherial salt of paranitroorthosulphobenzoic acid1 no evidence having been obtained of an intermediate chloro-etherial salt4 ,the unsymmetrical chloride on the other hand yields the intermediate product4 #e4 ,with phenols1 two series of derivatives are obtained4 7#a7 ,with monohydroxy phenols1 both etherial salts and sulphonphthalens are formed1 the former predominating4 7#b7 ,with polyhydroxy phenols no etherial salts were obtained1 but compounds of the unsymmetrical type1 usually containing more than two phenol residues4 #f4 ,with aniline an anil and an anilid of symmetrical constitution are formed4 #g4 ,with phosphorus oxychloride1 the anilid1 by loss of water1 forms a dianil4 #h4 ,this dianil undergoes transformation with 7#a7 ,glacial acetic acid1 forming an anilid of unsymmetrical constitution4 7#b7 ,hydrochloric acid forming the anil4 7#c7 ,alcoholic potash1 with the formation of colored decomposition products4 ,biographical4 ,the author of the foregoing dissertation was born at ,wilkinsburg1 ,pa41 ,jan4 #bi41 #ahgj4 ,owing to prolonged sickness in childhood his education1 prior to entering college1 was much interrupted1 and was largely confined to instruction received at home4 ,in the fall of #ahhg he entered ,wooster ,university 7,ohio71 from which institution he received the degree of ,bachelor of ,arts in #ahia4 ,the two following years were spent as a teacher of ,sciences in the ,college of ,emporia 7,kansas74 ,in #ahic he entered the ,johns ,hopkins ,university where he has since been a student of chemistry1 with physics and mathematics as subordinate studies4 ,in #ahie he was appointed ,university ,scholar in ,chemistry4 ,during #ahie-f he served as lecture assistant to ,prof4 ,remsen and ,dr4 ,renouf in the undergraduate courses4 ,in the spring of #ahif he was appointed ,fellow for the present year4