,scanned by ,charles ,keller with ,omni,page ,professional ,,ocr software ,,tb is a triple bond4 4 is a dotted 7coordinated7 bond4 ,emphasis italics have a 99 mark4 footnotes moved to ,e,o,paragraphs but ,,not renumbered4 7,they are numbered a or b when two pages of notes are together47 ,comments and guessed at characters in braces need stripped_/fixed4 ,greek letters are encoded in gr brackets1 and the letters are based on ,adobe's ,symbol font4 ,,organic ,,syntheses ,,an ,,annual ,,publication ,,of ,,satisfactory ,,methods ,,for ,,the ,,preparation ,,of ,,organic ,,chemicals ,,editorial ,,board ,,james ,,bryant ,,conant1 ,editor-in-,chief ,,hans ,,thacher ,,clarke ,,roger ,,adams ,,oliver ,,kamm ,,contributors ,g4 ,h4 ,,coleman ,j1 ,c4 ,,hessler ,e4 ,p4 ,,kohler ,c4 ,s4 ,,marvel ,w4 ,a4 ,,noyes ,g4 ,r4 ,,robertson ,e4 ,b4 ,,vliet ,f4 ,c4 ,,whitmore ,,vol4 ,,ii4 ,caveat3 ,some numbers did not ,,ocr correctly and may not have been corrected during the proofing6 ,check the #aida print edition before trying these6 ,,introduction ,,to ,,the ,,series ,,the publication of this series of pamphlets has been undertaken to make available in a permanent form complete detailed directions for the preparation of various organic chemical reagents4 ,in announcing this purpose it may be well to mention at the outset some of the difficulties in the way of the research chemist1 which it is hoped this series will be able to overcome4 ,the cost of chemicals is prohibitive to the majority of chemists2 this was true before the war when ,kahlbaum's complete supply was available1 and to-day with our dependence on domestic stocks1 this cost has increased4 ,the delay in obtaining chemicals1 especially from abroad1 even if the expense need not be considered1 is an important factor4 ,these difficulties have therefore thrown the research chemist on his own resources4 ,the preparation of materials for research1 always time consuming and annoying1 is made increasingly so by the inexactness of the published information which so often omits essential details4 ,because of this1 much needless experimentation is necessary in order to obtain the results given in the published reports4 ,as the additional information thus acquired is seldom published1 duplication of such experiments occurs again and again1-- a waste of time and material4 ,it is hoped these difficulties may be remedied by the publication of this series of pamphlets4 ,in other words1 the authors hope to make this a clearing house for the exchange of information as to methods of preparation of some of the most needed organic chemical reagents4 ,on account of the impossibility of obtaining the less common organic chemicals in the ,united ,states during the past few years1 university laboratories have had no option but to prepare their own supplies4 ,at the ,university of ,illinois1 for instance1 a special study has been made of this field1 and methods for the production of various substances have been investigated4 ,as a result1 reliable methods and directions have been developed for producing the materials in one-half to five pound lots4 ,such work as ,illinois has done is now being given an even more extensive scope at the ,research ,laboratory of the ,eastman ,kodak ,company4 ,it is felt that the results from these various laboratories should be available to all chemists and it is hoped that they eventually will be completely incorporated in these pamphlets4 ,the organic chemicals herein discussed have been quite arbitrarily chosen1 being those which have been needed in various research laboratories in the last years and for which the directions happen now to be ready for publication4 ,the methods are in only a few cases new ones2 they are in general the most satisfactory to be found in the literature4 ,only such details have been added as will enable a man with a reasonable amount of experience in organic chemistry to duplicate the results without difficulty4 ,to be absolutely sure that each set of directions can be repeated1 every experiment has been carried out in at least two laboratories4 ,only after exact duplication of the results in both laboratories are the directions considered ready for publication4 ,the names of the chemists who have studied the various experiments are given so that further information concerning any obscure point can be obtained if any question arises in using these directions4 ,and finally1 in describing the experiments1 special attention has been given to the explanation of why it is necessary to follow the directions carefully1 and what will happen if these directions are not followed4 ,although the main object in this series is to give the most convenient laboratory methods for preparing various substances in one-half to five pound lots1 an attempt has also been made to have these processes as far as possible adaptable to large scale development4 ,for example1 extractions have been avoided wherever possible1 cheap solvents have been sub-stituted for expensive ones1 and mechanical agitation1 a procedure extremely important in the success of many commercial processes1 has usually been specified4 ,the apparatus used is always carefully described and wherever necessary an illustration is given4 ,accompanying each preparation there will be found a bibliography containing references to all the methods for the production of the substance described in the literature4 ,this is given in order to aid any future investigator who may wish to study or improve the methods of preparation4 ,it is not claimed that the methods are1 in every case1 completely perfect1 but only that the yields are very satisfactory and allow the production of the substances at a reasonable cost4 ,it is hoped therefore that the pamphlets will benefit not only the scientific research man of the university1 but also the technical chemist who desires to develop the preparation of one of these substances to a large scale process of manufacture4 ,the editors trust also that this work may be used to advantage as a preparation manual in intermediate or advanced courses in organic chemistry in university laboratories1 and that it will aid small colleges in the production of necessary reagents which they are often financially unable to purchase4 ,the pamphlets are to be edited by the following committee3 ,roger ,adams1 ,university of ,illinois1 ,urbana1 ,illinois2 ,j4 ,b4 ,conant1 ,harvard ,university1 ,cambridge1 ,massachusetts2 ,h4 ,t4 ,clarke1 ,eastman ,kodak ,company1 ,rochester1 ,new ,york2 ,oliver ,kamm1 ,parke1 ,davis ,company1 ,detroit1 ,michigan2 each to act for one year as editor-in-chief and the other three to assist him as associate editors4 ,a new number of the series will appear annually1 and every five years the data will be rearranged1 revised1 corrected1 and then published in book form4 ,the number of preparations to be completed yearly is not fixed4 ,there will be1 it is certain1 about twenty2 and it is hoped1 as the interest is stimulated in this work1 that this number may increase considerably4 ,the editors especially desire to solicit contributions from other chemists1 not only in this country but abroad4 ,whenever a compound is thoroughly and extensively studied in connection with some research1 it is hoped that complete directions for its preparation will be assembled and sent to the editor4 ,he will then have them checked and published in a subsequent number4 ,directions for the preparation of substances already on the market are needed to make this work complete and will be gladly accepted4 ,it will1 of course1 be recognized that an occasional mistake or omission will inevitably be found in such a pamphlet as this which contains so many references and formulae4 ,the committee on publication will therefore deem it a favor if they are notified when any such error is discovered4 ,it is hoped also that if any chemist knows a better method for the preparation of any of the compounds considered1 or if anyone discovers any improvements in the methods1 he will furnish the authors with such information4 ,any points which may arise in regard to the various preparations will be gladly discussed4 ,in conclusion1 the editors are ready to do all they can to make this4 work successful1 and welcome suggestions of any kind4 ,they feel that the success of the series will undoubtedly depend upon the cooperation of others1 and as its success promises to be important to research chemists1 the editors urge all interested to assist4 ,,the ,,editors ,,table ,,of ,,contents ,,page ,i4 ,,benzalacetophenone44444444444444444444 4444444#a ,,ii4 ,,benzyl ,,benzoate44444444444444444444444444444# e ,,iii4 ,,benzyl ,,cyanide44444444444444444444444444444#i ,,iv4 a1 g-,,dichloroacetone44444444444444#ac ,v4 p-,,dimethylaminobenzaldehyde44444444444 4444444#ag ,,vi4 ,,ethyl ,,oxalate4444444444444444444444444444444 #bc ,,vii4 ,,ethyl ,,phenylacetate444444444444444444444444# bg ,,viii4 ,,glycerol a1 g-,,dichlorohydrin4444#bi ,,ix4 ,,glycerol a-,,monochlororydrin444444444444#cc ,x4 ,,hydrazine ,,sulfate4444444444444444444444444444#cg ,,xi4 ,,mesitylene4444444444444444444444444444 444444#da ,,xii4 ,,methyl ,,red444444444444444444444444444444444#d g ,,xiii4 p-,,nitrobenzoic ,,acid44444444444444444444444#ec ,,xiv4 p-,,nitrobenzyl ,,cyai,,de4444444444444444444444#eg ,,xv4 p-,,nitrophenylacetic ,,acid44444444444444444444#ei ,,xvi4 ,,nitroso-b-,,naphthol444444444444444444 44#fa ,,xvii4 ,,phenylacetic ,,acid4444444444444444444444444#fc ,,xviii4 ,,phenylacetylene44444444444444444444444 444#fg ,,xix4 ,,phenylhydrazine44444444444444444444444 44444#ga ,,xx4 ,,phthalimide444444444444444444444444444 444444#ge ,,xxi4 ,,quinoline44444444444444444444444444444 44444#gi ,,xxii4 ,,quinone4444444444444444444444444444444 4444#he ,,xxiii4 ,,sodium p-,,toluenesulfinate4444444444444444#hi ,,xxiv4 #a1c1e-,,trintrobenzene44444444444444444 44444#ic ,,xxv4 #b1d1f-,,trintrobenzoic ,,acid444444444444444444#ie ,,index444444444444444444444444444444444 4444#ii ,,organic ,,syntheses ,i ,,benzalacetophenone ,c#f;,h#e;,,cho ,c#f;,h#e;,,coch#c 7,na,o,h7-- ,c#f;,h#e;,,ch,,chcoc#f;,h#e ,h#b,o ,prepared by ,e4 ,p4 ,,kohler and ,e4 ,m4 ,,chadwell4 ,checked by ,h4 ,t4 ,,clarke and ,r4 ,p4 ,,leavitt4 #a4 ,procedure ,a ,,solution of #bah g4 of sodium hydroxide in #aifj g4 of water and #ajjj g4 of #ie per cent alcohol are introduced into a #eejj-;cc4 bottle which is loosely covered with a perforated disk of cardboard1 supplied with an effective stirrer1 and supported in a larger vessel so as to permit cooling with cracked ice4 ,into the alkaline solution1 #ebj g4 of pure acetophenone is poured1 the bottle is rapidly surrounded with cracked ice1 and the stirrer started2 #dfj g4 of benzaldehyde 7,u4 ,s4 ,p47 are then added at once4 ,the temperature of the mixture should not be below #ae'j and it should not be allowed to rise above #cj'j during the reaction4 ,if it tends to do so1 the stirring is not sufficiently vigorous4 ,it is advantageous1 though not essential1 to inoculate the mixture with a little powdered benzalacetophenone after stirring for half an hour4 ,after two to three hours1 the mixture becomes so thick that the stirring is no longer effective4 ,the stirrer is then removed and the mixture left to itself in an ice-box for about ten hours4 ,the mixture now is a thick paste composed of small shot-like grains suspended in an almost colorless liquid4 ,it is cooled in a freezing mixture and then either centrifuged or filtered on a large ,buchner funnel1 washed with water until the washings are neutral to litmus1 and finally washed with #bjj cc4 of alcohol1 which has previously been cooled to #j'j4 ,after thorough drying in the air1 the crude product weighs about #hhj g4 7yield #ig per cent of the theoretical amount7 and melts at #ej-ed'j4 ,it is sufficiently pure for most purposes but tenaciously holds traces of water4 ,it is most readily purified by recrystallization from four to four and a half times its weight of #ie per cent alcohol4 ,eight hundred and eighty grams of crude product give #ggj g4 7#he per cent of the theoretical amount7 of light-yellow material 7m4 p4 #ee-eg'j7 and #dj-ej g4 that require recrystallization4 #b4 ,notes ,the acetophenone should be as pure as possible 7m4 p4 #bj'j74 ,commercial acetophenone contains variable quantities of impurities which reduce the yield4 ,by distilling commercial acetophenone with the help of a good still-head 7preferably under diminished pressure7 and using only the fraction which boils at #bja-bjb'j 7#gf-gg'j_/aj mm47 greater quantities of benzalacetophenone can be obtained than by using the entire sample4 ,commercial benzaldehyde can be used in place of the purer product1 but the amount used must be increased to make up for the impurities which are present4 ,if the temperature is too low1 or the stirring too slow1 the product separates as an oil1 which later solidifies in large lumps4 ,if the temperature is allowed to rise above #cj'j1 secondary reactions diminish both the yield and the purity of the product4 ,the most favorable temperature is #be'j4 ,in recrystallizing benzalacetophenone1 the alcohol should be saturated at #ej'j4 ,if the solution is saturated above this temperature1 the benzalacetophenone tends to separate as an oil4 ,the solution should be allowed to cool gradually1 and should finally be chilled in a freezing mixture4 #c4 ,other ,methods of ,preparation ,the methods for producing benzalacetophenone are3 the action of acids on a mixture of benzaldehyde and acetophenone or on a solution of these substances in glacial acetic acid2#a the condensation of benzaldehyde and acetophenone with a #cj per cent solution of sodium methylate at low temperatures2#b the action of sodium hydroxide on an alcoholic solution of benzaldehyde and acetophenone4#c ,the methods based on the use of acids as condensing agents were not considered1 because ,claisen1 who devised them1 abandoned them after he found that alkaline condensing agents gave better results4 ,the preliminary experiments showed that condensation with sodium methylate takes a long time and gives a product which it is difficult to handle in large quantities4 ,the method devised by ,kostanecki and ,rossbach#c has therefore been developed4 #a ,ber4 #ad1 #bdfc 7#ahha74 #b ,ber4 #bj1 #feg 7#ahhg74 #c ,ber4 #bi1 #adib 7#ahif74 ,,ii ,,benzyl ,,benzoate #b ,c#f;,h#e;,,cho ,c#f;,h#e;,,ch#b,o,na-- ,c#f;,h#e;,,co#b;,,ch#b;,c#f;,h#e ,c#f;,h#e;,,ch#b,o,na ,prepared by ,o4 ,,kamm and ,w4 ,f4 ,,kamm4 ,checked by ,,roger ,,adams and ,r4 ,l4 ,,jenkins4 #a4 ,procedure ,,three grams of metallic sodium are dissolved by warming for half an hour in #gj g4 of pure benzyl alcohol 7see notes71 and after the mixture has cooled to room temperature the solution is added gradually1 with thorough mixing1 to #ded g4 of c4 p4 benzaldehyde 7which must contain ,,less than #a per cent of benzoic acid74 ,the reaction mixture has a tendency to become warm1 but the temperature should be kept slightly below #ej-fj'j by cooling1 if necessary4 ,a pasty gelatinous mass results4 ,after about half an hour the temperature of the mixture no longer rises2 it is then warmed on the water bath for about one or two hours1 with occasional shaking4 ,the cooled reaction product is treated with #bjj cc4 of water1 the layer of oil separated1 washed once with a second portion of water1 and subjected to distillation in vacuo4 ,the first fraction of the distillate contains benzyl alcohol together with unchanged aldehyde1 as well as a small quantity of water4 ,the temperature then rises rapidly to the boiling-point of benzyl benzoate1 when the receivers are changed4 ,the product boils at #ahd-ahe'j_/ae mm41 and analysis by saponification shows it to consist of #ii per cent ester4 ,a yield of #daj-dbj g4 is obtained1 which corresponds to #ij-ic per cent of the theoretical amount4 ,this benzyl benzoate supercools readily1 but after solidifying melts within one degree of the highest recorded value 7#ai4d'j7 and therefore need not be refractionated1 unless material of exceptional grade is required4 #b4 ,notes ,in the presence of sodium benzylate two molecules of benzaldehyde react with the alcoholate to form an addition product4 ,when the reaction mixture is overheated an important side reaction may occur1 as follows3 _/ ,,och#b;,c#f;,h#e ,c#f;,h#e;,c -- ,,och#b;,c#f;,h#e -- ,c#f;,h#e;,,co#b,na ,c#f;,h#e;,,ch#b,,och#b;,c#f;,h#e ,o,na ,dibenzyl ether no doubt forms the chief impurity in benzyl benzoate4 ,since the boiling-point of the former lies near that of the ester1 it is not removed during the process of purification by distillation4 ,the causes of variations in yield by the use of the older methods can now be explained4 ,when benzaldehyde is added ,,to ,,the ,,alcoholate1 and especially when the latter is still warm1 local overheating results2 in fact1 the temperature may rise far above #ajj'j with the result that benzyl ether is formed4 ,simultaneously1 the sodium benzylate is converted into sodium benzoate1 which is of no value for inducing the desired reaction1 and consequently very little benzyl benzoate is obtained4 ,the same side reactions explain the failure of this experiment when the benzyl alcohol used in preparing the catalyst 7sodium benzylate7 is contaminated with benzaldehyde4 ,the benzyl alcohol used in this preparation must be free from impurities1 especially aldehyde4 ,one cc4 dissolved in #ej cc4 of water and treated with a freshly prepared clear solution of phenylhydrazine acetate should give no appreciable precipitate4 ,if it is not pure1 it must first be treated with alkali as described below4 ,the benzaldehyde should be titrated in order to determine its acidity4 ,if it is found to contain sufficient benzoic acid to react with a considerable proportion of the sodium alcoholate1 a poor yield of ester will be obtained4 ,less than #a per cent of benzoic acid will not interfere seriously with the yields obtained1 but the presence of larger quantities of acid will be found to be detrimental and must be removed by washing the benzaldehyde with a sodium carbonate solution and redistilling with the precautions necessary to prevent too free an access of air to the distillate4 ,the order of mixing the reagents and the temperature of the ingredients at the time of mixing are the most important factors in the experiment4 ,the temperature at which the reaction mixture is maintained after mixing1 provided that it is held below #ajj'j1 is less important from the standpoint of purity4 ,the reaction mixture is not treated with acetic acid1 as usually recommended1 for the reason that such a procedure yields a final product contaminated with benzoic acid1 unless an alkaline wash is applied subsequently4 ,the recovered benzyl alcohol can be used for the preparation of a second lot of benzyl benzoate only after it has been boiled with strong sodium hydroxide to remove all traces of benzaldehyde4 #c4 ,other ,methods of ,preparation ,benzyl benzoate has been identified in certain natural plant products4#a ,in the laboratory it has been prepared by the action of 7a7 benzoyl chloride upon benzyl alcohol1#b 7b7 benzyl chloride upon sodium benzoate1 and 7c7 alcoholates upon benzaldehyde4#c ,recently1 ,gomberg and ,buchler#d have shown that reaction 7b7 may be conducted even with aqueous solutions of sodium benzoate4 #a ,ann4 #aeb1 #aca 7#ahfi74 #b ,gmelin's ,handbuch der ,organ4 ,chem4 #c1 #dj4 #c ,ber4 #bj1 #fdi 7#ahhg74 ,cf4 also ,j4 ,chem4 ,soc4 #ge1 #aaee 7#ahii74 #d ,j4 ,am ,chem4 ,soc4 #db1 #bjei 7#aibj74 ,the ,claisen method 7c7 furnishes the most convenient and practical procedure for the preparation of this ester4 ,the materials are cheap1 the experimental procedure simple1 and the product obtained is free from objectionable traces of benzyl chloride4 ,unfortunately the method has been found to be extremely erratic in regard to yield 7#aj-ie per cent71 as well as in regard to purity of the product 7#hg-ig per cent ester74#a ,as a result of the present study1#b causes for variations are fully accounted for and the procedure has been converted into a satisfactory method of preparation4 #a ,c4 ,a4 #ad1 #cejj 7#aibj74 #b ,j4 ,am4 ,pharm4 ,assoc4 #aa1 #eii 7#aibb74 ,,iii ,,benzyl ,,cyanide ,c#f;,h#e;,,ch#b;,cl ,na,c,n-- ,c#f;,h#e;,,ch#b;,,cn ,na,cl ,prepared by ,,roger ,,adams and ,a4 ,f4 ,,thal ,checked by ,o4 ,,kamm and ,a4 ,o4 ,,matthews4 #a4 ,procedure ,,in a #e-l4 round-bottom flask1 fitted with a stopper holding a reflux condenser and separatory funnel1 are placed #ejj g4 of powdered sodium cyanide 7#if-ih per cent pure7 and #dej cc4 of water4 ,the mixture is warmed on a water bath in order to dissolve most of the sodium cyanide1 and then #a kg4 of benzyl chloride 7b4 p4 #agj-ahj'j7 mixed with #a kg4 of alcohol is run in through the separatory funnel in the course of one-half to three-quarters of an hour4 ,the mixture is then heated with a reflux condenser on the steam bath for four hours1 cooled and filtered with suction to remove most of the sodium chloride4 ,it is well to wash the filtered salt with a small portion of alcohol in order to remove any benzyl cyanide which may have been mechanically held4 ,the flask is now fitted with a condenser1 and as much alcohol as possible is distilled off on the steam bath4 ,the residual liquid is cooled1 filtered if necessary1 and the layer of benzyl cyanide separated4 ,this crude benzyl cyanide is now placed in a ,claisen distilling flask and distilled in vacuo1 the water and alcohol coming over first1 and finally the cyanide4 ,it is advantageous to use a fractionating column or1 better still1 a ,claisen flask with a modified side-arm#a 7,vol4 ,i1 p4 #dj1 ,fig4 #c7 which gives the same effect as a fractionating column4 ,the material is collected from #ace-adj'j_/ch mm4 7#aae-abj'j_/aj mm474 ,the yield is #gdj-hcj g4 7#hj-ij per cent of the theoretical amount74 #a ,j4 ,am4 ,chem4 ,soc4 #ci1 #bgah 7#aiag74 #b4 ,notes ,the quality of the benzyl chloride markedly affects the yield of pure benzyl cyanide4 ,if a poor technical grade is used1 the yields will not be more than #fj-ge per cent of the theoretical1 whereas consistent results of about #he per cent or more were always obtained when a product was used that boiled over #aj'j4 ,the technical benzyl chloride at hand yielded on distillation about #h per cent of high-boiling material2 a technical grade from another source was of unusual purity and boiled over a #b'j range for the most part4 ,it is advisable to distil off the last portion of alcohol and water in vacuo and also to distil the benzyl cyanide in vacuo1 since under ordinary pressures a white solid invariably separates during the distillation4 ,one method of purifying the benzyl cyanide is to steam distil it after the alcohol has been first distilled from the reaction mixture4 ,at ordinary pressures1 this steam distillation is very slow and1 with an ordinary condenser1 requires eighteen to twenty hours in order to remove all of the volatile product from a run of #ejj g4 of benzyl chloride4 ,the distillate separates into two layers2 the benzyl cyanide layer is removed and distilled4 ,the product obtained in this way is very pure and contains no tarry material1 and1 after the excess of benzyl chloride has been removed1 boils practically constant4 ,this steam distillation is hardly advisable in the laboratory4 ,the benzyl cyanide1 prepared according to the procedure as outlined1 is collected over a #e'j range4 ,it varies in appearance from a colorless to a straw-colored liquid and often develops appreciable color upon standing4 ,for a product of special purity1 it should be redistilled under diminished pressure and collected over a #a-b'j range4 ,for most purposes1 such as the preparation of phenylacetic acid or ester1 the fraction boiling #ace-adj'j_/ch mm4 is perfectly satisfactory4 #c4 ,other ,methods of ,preparation ,benzyl cyanide occurs naturally in certain oils4#a ,the only feasible method of preparing it that has been described in the literature is the one in which alcoholic potassium cyanide and benzyl chloride#b are employed4 ,the cheaper sodium cyanide is just as satisfactory as the potassium cyanide and therefore is the best material to use4 ,gomberg has recently prepared benzyl cyanide from benzyl chloride and an aqueous solution of sodium cyanide4#c #a ,ber4 #g1 #eai1 #abic 7#ahgd72 #cb1 #bccg 7#ahii7 #b ,ann4 #if1 #bdg 7#ahee72 ,ber4 #c1 #aih 7#ahgj72 #ad1 #afde 7#ahha72 #ai1 #aiej 7#ahhf74 #c ,j4 ,am4 ,chem4 ,soc4 #db1 #bjei 7#aibj74 ,,iv a1 g-,,dichloroacetone ,,ch#b;,cl,c,h,o,h,c,h#b;,cl ,o7,na#b;,cr#b,o#g ,h#b,,so#d7-- ,,ch#b;,cl,c,o,c,h#b;,cl ,h#b,o ,prepared by ,j4 ,b4 ,,conant and ,o4 ,r4 ,,quayle4 ,checked by ,a4 ,w4 ,,dox1 ,l4 ,,yoder1 and ,o4 ,,kamm4 #a4 ,procedure ,,in a #b-l4 flask are placed #cge g4 of commercial sodium dichromate1 #bbe cc4 of water1 and #cjj g4 of dichlorohydrin 7b4 p4 #fh-ge'j_/ad mm474 ,the flask is set in a water bath and equipped with a thermometer and mechanical stirrer4 ,the contents are vigorously stirred1 and #dej g4 of sulfuric acid1 diluted with #aae g4 of water1 are introduced during the course of seven to eight hours4 ,it is convenient to add the acid at ten-minute intervals4 ,the temperature is kept between #bj'j and #be'j during the entire reaction2 this is accomplished by adding a little ice to the water bath from time to time4 ,the stirring is continued for sixteen to seventeen hours after all the acid has been added2 as there is very little heat evolved during this part of the reaction1 the water bath may be allowed to come to room temperature4 ,sufficient water is now added to the mixture to dissolve the pasty chromium salts 7#cjj-hjj cc474 ,the mass of crystals is then rapidly filtered on a ,buchner funnel and sucked as dry as possible4 ,the crystals are then transferred to a small laboratory centrifuge and centrifuged for several minutes4 ,the crystals are washed in the centrifuge with about #ae-be cc4 of ice water1 then with #aj-ae cc4 of cold petroleum ether1 and finally centrifuged till as dry as possible4 ,the crude dichloroacetone is dried in a vacuum desiccator over sulfuric acid overnight ,it weighs about #bbj g4 ,the crude product is best purified by distillation from a #bej-;cc4 distilling flask fitted with an air condenser4 ,a very small fraction 7#aj-ae g47 of low-boiling material is obtained1 and the dichloroacetone 7#agj-age'j7 is then collected4 ,it solidifies in the receiver to a white crystalline mass which weighs #bjj-bbj g4 7#fe-gj per cent of the theoretical amount74 ,a few grams more may be obtained by chilling the low-boiling fraction and filtering off the water4 #b4 ,notes ,great caution should be exercised in working with dichloroacetone1 as it is extremely lachrymatory and blisters the skin4 ,in transferring the crystals from the reaction flask to the ,buchner funnel it is necessary to use a certain amount of water to dissolve the pasty chromium salts which are otherwise quite impossible to filter4 ,the amount necessary varies greatly in different runs1 according to the manner in which the chromium salts separate4 ,the amount of this water is kept low in order to dissolve as little of the product as possible4 ,nevertheless1 #aj-ae g4 of dichloroacetone are thus dissolved2 this material1 together with a little unchanged dichlorohydrin1 may be recovered by a long procedure involving extraction with ether and sodium bisulfite4 ,this is not profitable1 however4 ,it is not necessary to wash the crystals in the centrifuge until they are white4 ,a small amount of chromic salt will not interfere with the subsequent purification4 ,commercial sodium dichromate is hygroscopic and contains varying amounts of water4 ,the #cge g4 required in these directions are equivalent to #cai g4 of anhydrous material4 ,the total time required for the oxidation is twenty-four hours4 ,it is convenient to start the reaction in the morning4 ,in this way the last part of the reaction1 which requires no attention1 will be accomplished during the night4 ,the regulation of the temperature is necessary1 as the reaction proceeds very slowly below #bj'j2 on the other hand1 the dichloroacetone itself is oxidized at a somewhat higher temperature than #be'j4 #c4 ,other ,methods of ,preparation ,the preparation of dichloroacetone by the following methods is described in the literature3 the direct chlorination of acetone2#a the oxidation of dichlorohydrin2#b the action of silver chloride on diiodoacetone2#c the action of dichloropropene 7,,ch#b;,cl-,c,cl,,ch#b7 and hypochlorous acid2#d the action of hydrochloric acid on ethoxymonochloroacetoacetic ester2#e and the hydrolytic cleavage of dichloroacetoacetic ester4#f #a ,jahresb4 #ahei1 #cde2 #ahga1 #eca2 ,j4 prakt4 ,chem4 7#b7d1 #eb 7#ahga72 ,ber4 #g1 #dfg 7#ahgd72 #h1 #accj1 #adch 7#ahge72 #bf1 #eih 7#ahic72 #db1 #cbcc 7#aiji72 ,ann4 #bgi1 #cae 7#ahid7 #b ,ber4 #f1 #abaj 7#ahgc72 #ac1 #agjf 7#ahhj72 #db1 #cbcc 7#aiji72 ,ann4 #bjh1 #cee 7#ahha72 #bfi1 #df 7#ahib72 ,ann4 chim4 phys4 7#f7 #i1 #ade 7#ahhf72 ,bull4 soc4 chim4 7#b7 #cf1 #ai 7#ahha74 #c ,ann4 #aib1 #ic 7#ahgh74 #d ,compt4 rend4 #id1 #adbh 7#ahhb74 #e ,ann4 #bfi1 #ah 7#ahib74 #f ,ber4 #dc1 #cecc 7#aiaj74 ,v p-,,dimethylaminobenzaldehyde 7,,ch#c7b,,nc#f;,h#e ,,hno#b-- 7,,ch#c7b,,nc#f;,h#d,,no ,h#b,o 7,,ch#c7b,,nc#f;,h#d,,no #b;,,hcho #b;,c#f;,h#e,n7,,ch#c7b -- 7,,ch#c7b,,nc#f;,h#d,n ,,chc#f;,h#d,n7,,ch#c7b #b;,h#b7 7,,ch#c7b,,nc#f;,h#d;,,cho 7,,ch#c7b,,nc#f;,h#d,n ,,chc#f;,h#d,n7,,ch#c7b ,,hcho--7 ,,ch#c7b,,nc#f;,h#d,n ,,ch#b 7,,ch#c7b,,nc#f;,h#d;,,cho ,prepared by ,,roger ,,adams and ,g4 ,h4 ,,coleman4 ,checked by ,h4 ,t4 ,,clarke and ,w4 ,w4 ,,hartman4 #a4 ,procedure ,,in a #c-l4 round-bottom flask fitted with a mechanical stirrer #aej g4 of technical dimethylaniline are dissolved in #gej cc4 of diluted hydrochloric acid 7#a part concentrated acid to #a part water74 ,this solution is now cooled to #j'j and a solution 7previously cooled to #j'j7 of #ij g4 of technical sodium nitrite in #aej cc4 of water is added through a separatory funnel4 ,during the addition of the nitrite solution1 mechanical stirring should be employed and the flask cooled well with ice and salt4 ,the addition is made at such a rate 7thirty to forty minutes for the entire addition7 that the temperature does not rise above #e'j4 ,the precipitate of nitroso dimethylaniline hydrochloride is filtered off with suction1 then washed with about #cjj cc4 of diluted hydrochloric acid 7#a3a74 ,in a #b-l4 beaker1 #ahj g4 of technical dimethylaniline1 #abe cc4 of formaldehyde 7technical #dj per cent71 and #cjj cc4 of concentrated hydrochloric acid are mixed and heated for ten minutes on a steam bath4 ,the mixture is now placed in a hood and the nitroso dimethylaniline added all at once1 or as rapidly as possible4 ,the beaker is then covered with a watch glass4 ,a vigorous reaction soon occurs and is complete in about five minutes4 ,the resulting solution is transferred to a #e-l4 flask and diluted to #d l42 stirring is started1 and a #be per cent solution of sodium hydroxide is added until the red color disappears 7about #fej cc4 are required74 ,the yellow benzylidene compound separates1 is filtered with suction and washed with water4 ,the moist precipitate is transferred to a #d-l4 glass jar1 covered with #ajjj cc4 of #ej per cent acetic acid and #bej cc4 of formaldehyde1 and stirred until twenty minutes after the benzylidene compound has gone into solution4 ,while the mixture is being stirred vigorously to prevent lumping of the precipitate1 #djj cc4 of water and #bjj g4 of cracked ice are added during the course of five minutes4 ,the dimethylaminobenzaldehyde generally separates gradually in fifteen to twenty minutes1 but in some cases does not4 ,if the precipitate does not form1 the solution is placed in a refrigerator for a few hours or overnight4 ,the mixture is filtered with suction and washed at least ten times with #cjj cc4 of water4 ,the precipitate is sucked as dry as possible for fifteen to thirty minutes4 ,the slightly moist aldehyde is distilled under diminished pressure from an oil bath1 by means of a #a-l4 ,claisen flask4 ,a small amount of water comes over first1 then the thermometer rises rapidly to the boiling point of the aldehyde 7#ahj'j_/bb mm474 ,in changing receivers between the water fraction and the aldehyde1 care should be taken to keep the side-arm of the distilling flask warm2 otherwise1 on starting the distillation again1 the aldehyde will solidify in the side-arm and cause trouble4 ,it is advisable not to collect the very last portion of the distillate with the main portion1 as the former is frequently quite red4 ,this is best added to crude material from another run4 ,the main distillate is dissolved in #ajj cc4 of alcohol in a #b-l4 beaker1 then #ajjj cc4 of water are gradually added with vigorous mechanical stirring to prevent lumping4 ,the aldehyde separates1 and is filtered with suction4 ,the product1 when dry1 weighs #abe-acj g4 7#ef-ei per cent of the theoretical amount71 and melts at #gc'j4 ,the aldehyde prepared in this way is in the form of small granular crystals1 which vary in different runs from a flesh color to a lemon yellow4 ,for practically all purposes1 this slightly colored product is entirely satisfactory and is essentially pure1 as can be judged by the melting point4 ,for reagent purposes it is desirable to remove the color completely1 particularly since the product obtained as just described has a tendency to take on a reddish tinge on exposure to light4 ,further purification can be accomplished by dissolving the aldehyde 7it dissolves slowly7 in dilute hydrochloric acid 7#a part of concentrated acid1 sp4 gr4 #a4ai1 to #f parts of water71 #abe g4 of aldehyde requiring #gjj cc4 of the acid4 ,the solution is placed in a jar and diluted with half its volume of water1 and dilute sodium hydroxide solution 7#ae-bj per cent7 is added slowly with mechanical stirring4 ,at the beginning1 the aldehyde comes down slightly colored4 ,after about #aj to #cj g4 are precipitated1 however1 the product appears white2 this point can be readily seen4 ,the first precipitate is filtered off and added to the next run of crude material1 or fractionally precipitated again from hydrochloric acid4 ,the rest of the aldehyde is now precipitated by means of more sodium hydroxide solution1 and comes down almost white4 ,at the very end of the neutralization1 particularly if the original product was quite yellow1 the last #d to #e g4 of aldehyde should be precipitated separately1 as they are inclined to be slightly colored4 ,if too much alkali is added towards the end of the neutralization1 a brown color appears1 but the addition of a little hydrochloric acid will destroy this color4 ,the main portion of the precipitate is filtered and dried2 it weighs #ie-ajj g41 m4 p4 #gc'j4 ,the succeeding runs yield #aae-abh g4 of finished product1 on account of the extra crude material obtained from the distillation and reprecipitation of the previous run4 #b4 ,notes ,the aldehyde that is obtained without reprecipitation gradually takes on a pinkish tinge on exposure to light4 ,after the reprecipitation1 however1 this characteristic disappears4 ,thorough washing of the crude aldehyde is particularly desirable1 as it removes a reddish impurity which tends to distil over and color the product lemon yellow or sometimes even brownish yellow4 ,when such a brownish product is obtained1 it is quite necessary to make a second precipitation1 as well as to observe the directions mentioned in the purification of the crude aldehyde1 namely1 to precipitate the first few grams and the last few grams of the aldehyde separately4 ,the precaution of rejecting the first and last portions of the precipitate is unnecessary in the reprecipitation4 ,in the reprecipitation of a deeply colored product1 the portion of aldehyde at the end may be even purplish in color and particular care must be taken to keep this separate4 ,vigorous mechanical stirring must be employed during the precipitation of the crude aldehyde1 as otherwise large lumps are formed which make washing difficult4 ,a previous investigator has mentioned that the crude product must be dried before distilling4 ,this1 however1 is unnecessary4 ,if the aldehyde is dried before distilling1 it is possible to use a #ejj-;cc4 distilling flask instead of a #a-l one4 ,in purifying the aldehyde by dissolving in acid and reprecipitating1 it is essential not to use stronger acid than that specified 7#a3f71 as stronger acid causes a deepening of the color of the solution4 ,if the concentrated acid1 which is to be diluted and used in this procedure1 does not have a sp4 gr4 of #a4ai1 it will be necessary to add the equivalent amount of weaker acid in order to dissolve the p-dimethylaminobenzaldehyde4 ,in purifying the aldehyde1 sodium carbonate may be used in place of sodium hydroxide for precipitation1 but it causes much foaming4 ,when the apparatus for distilling1 etc41 is all set up1 a run such as described above requires about five to six hours for completion4 #c4 ,other ,methods of ,preparation p-,dimethylaminobenzaldehyde has been made by the condensation of chloral with dimethylaniline1 and subsequent hydrolysis2#a by the hydrolysis of tetramethyldiaminobenzhydrol with acetic acid2#b by the condensation of dimethylaniline1 formaldehyde and m-sulfo-p-tolyl hydroxylamine followed by hydrolysis2#c by the electrolytic reduction of a mixture of sodium nitrobenzene sulfonate1 dimethylaniline and formaldehyde1 and subsequent hydrolysis2#d by the reduction of a mixture of dimethylaniline1 formaldehyde and sodium nitrobenzene sulfonate with iron and hydrochloric acid1 followed by hydrolysis2#e by the condensation of alloxan with dimethylaniline followed by hydrolysis2#f by the condensation of dimethylaniline1 formaldehyde and sodium p-toluidine sulfonate in the presence of hydrochloric acid and potassium dichromate followed by hydrolysis4#g ,the most satisfactory method1 however1 is the condensation of dimethylaniline1 formaldehyde and nitroso dimethyaniline1 followed by hydrolysis1#h a method which was first described by ,e4 ,noelting and later perfected in detail by ,l4 ,baumann4 #a ,ber4 #ah1 #aeai 7#ahhe72 #ai1 #cff 7#ahhf72 ,d4 ,r4 ,p4 #fa1 #eea2 ,frdl4 #c1 #aji 7#ahib74 #b ,ber4 #bg1 #ccag 7#ahid74 #c ,d4 ,r4 ,p4 #ajc1egh2 ,frdl4 #e1 #aja 7#ahii74 #d ,d4 ,r4 ,p4 #aje1ajc2 ,frdl4 #e1 #ajg 7#ahii74 #e ,d4 ,r4 ,p4 #aje1aje2 ,frdl4 #e1 #aji 7#ahii74 #f ,d4 ,r4 ,p4 #ajh1jhf2 ,frdl4 #e1 #aag 7#ahii74 #g ,d4 ,r4 ,p4 #aah1efg2 ,frdl4 #f1 #acc 7#aija74 #h ,ber4 #cg1 #heh 7#aijd72 ,j4 ,biol4 ,chem4 #da1 #adf 7#aibj74 ,,vi ,,ethyl ,,oxalate 7,,co#b;,h7#b #b ,c#b;,h#e,,oh-- 7,,co#b;,c#b;,h#e7b #b;,h#b,o ,prepared by ,h4 ,t4 ,,clarke and ,,anne ,w4 ,,davis4 ,checked by ,,roger ,,adams and ,w4 ,b4 ,,burnett4 #a4 ,procedure ,,in a #e-l4 flask are placed #a kg4 of crystallized 7hydrated7 oxalic acid1 #a4ff kg4 of #ie per cent ethyl alcohol1 and #a4cc kg4 of carbon tetrachloride4 ,the flask is then fitted with a fractionating column1 ,i meter long1 to which is attached a condenser and an automatic separator so arranged that the lighter liquid flows off to a receiver 7,fig4 #a74 ,the heavier liquid flows through a tower of anhydrous potassium carbonate1 and then returns to the reaction flask4 ,the bottom of the tower is connected with a small separatory funnel through which any potassium carbonate solution1 which flows from the solid in the tower1 may be withdrawn from time to time4 ,the mixture in the flask is slowly distilled4 ,as soon as about #ejj cc4 of the lighter liquid has collected1 it is placed in a fractionating apparatus and distilled1 the material which boils up to #gi'j being collected separately4 ,this fraction1 which consists principally of alcohol1 with a little carbon tetrachloride and moisture1 is dried with potassium carbonate and returned to the reaction mixture4 ,the higher fractions are redistilled4 ,the above process is continued until the distillate no longer separates into two phases 7about twenty-seven hours74 ,the liquid in the flask is then distilled with the use of a column until the temperature of the vapor reaches #he'j2 the residue is then distilled under reduced pressure1 and the fraction which boils at #ajf-ajg_/be mm4 is collected4 ,the yield is #ibj-ifj g4 of a colorless liquid 7#hj-hd per cent of the theoretical amount74 #b4 ,notes ,water1 ethyl alcohol and carbon tetrachloride form a ternary mixture boiling at about #fa'j4 ,this vapor mixture1 on condensation1 separates into two phases2 the heavier liquid consists of carbon tetrachloride and alcohol with only small amounts of water2 the lighter liquid consists of approximately #fe per cent alcohol1 #be per cent water and #aj per cent carbon tetrachloride4 ,by taking advantage of this fact1 it is possible to conduct the esterification at a temperature so low that the ethyl hydrogen oxalate first formed does not decompose into ethyl formate and other products1 as is the case when the customary methods of esterification are employed4 ,the reaction may be carried out somewhat more expeditiously if the oxalic acid be dehydrated independently before it is mixed with the alcohol2 indeed1 it is also possible to remove the bulk of the water from the alcohol itself by a similar method1 before mixing it with the oxalic acid4 ,however1 since water is formed during the esterification1 little is gained by this procedure4 ,it is not absolutely necessary to remove the last traces of water from the alcohol-carbon tetrachloride layer by means of potassium carbonate before returning it to the reaction mixture2 this process is1 however1 so simple and requires so little attention that there is no doubt that it is of material aid in cutting down the time of operation4 ,the advantages of using crystallized oxalic acid and commercial #ie per cent alcohol1 instead of the anhydrous reagents1 are obvious4 ,when technical oxalic acid is used1 the yields are usually smaller by #e to #aj per cent4 ,the apparatus shown in ,fig4 #a may be somewhat more simply constructed by using rubber connections in several places1 thus eliminating a certain amount of glass blowing1 and making a more flexible piece of apparatus4 ,the side-arm of the separator may be made with two rubber connections1-- one above and one below the tube leading to the potassium carbonate tube4 ,the long return tube to the flask may be constructed with a rubber joint very near the carbonate tube and one near the flask4 #c4 ,other ,methods of ,preparation ,ethyl oxalate has been prepared in poor yields by the following methods3 by distilling a mixture of anhydrous oxalic acid and absolute alcohol2#a by heating a mixture of anhydrous oxalic acid and #ig per cent alcohol under a reflux condenser and fractionating the resulting mixture2#b by distilling a mixture of anhydrous oxalic acid and absolute alcohol1 the vapor of absolute alcohol being passed simultaneously into the mixture2#c by allowing a saturated solution of oxalic acid in alcohol to stand for a long time at #dj-ej'j4d ,a good yield has been obtained by ,anschutz#e by a method involving saturation of a mixture of crystallized oxalic acid and alcohol with hydrogen chloride1 removal of the alcohol and water by distillation under reduced pressure1 and repetition of the treatment with the alcohol and hydrogen chloride1 the process being carried out several times4 #a ,jahresb4 #ahfa1 #eih4 #b ,j prakt4 ,chem4 7#b71 #cd1 #ejj 7#ahhf74 #c ,monatsh4 #ag1 #fad 7#ahif74 #d ,ann4 #fe1 #cej 7#ahdh74 #e ,ber4 #af1 #bdad 7#ahhc71 ,,vii ,,ethyl ,,phenylacetate ,c#f;,h#e;,,ch#b;,,cn ,c#b;,h#e,,oh ,h#b,,so#d ,h#b,o-- ,c#f;,h#e;,,ch#b;,,co#b;,c#b;,h#e ,,nh#d;,,hso#d ,prepared by ,,roger ,,adams and ,a4 ,f4 ,,thal4 ,checked by ,,oliver ,,kamm4 #a4 ,procedure ,,in a #c-l4 round-bottom flask1 fitted with an efficient reflux condenser1 are mixed #gej g4 of #ie per cent alcohol1 #gej g4 of concentrated sulfuric acid and #dej g4 of benzyl cyanide4 ,the mixture1 which soon separates into two layers1 is heated to boiling over a low flame1 for six to seven hours1 cooled and poured into #b l4 of water1 and the upper layer is separated4 ,this is washed with a little #aj per cent sodium carbonate solution to remove small amounts of phenylacetic acid which may have been formed1 and then distilled in vacuo4 ,a small amount of water goes over first and then a pure product boiling #acb-ach'j_/cb mm4 7#abj-abe'j_/ag-ah mm474 ,the yield varies in general between #ebe and #eej g4 7#hc-hg per cent of the theoretical amount74 #b4 ,notes ,the benzyl cyanide can be most conveniently prepared according to the directions in preparation ,,iii 7p4 #i72 the product which boils over a #e'j range should be used4 ,in washing the layer of ethyl phenylacetate with sodium carbonate it is sometimes advisable to add a certain amount of sodium chloride so that the ester will separate more readily4 ,the product obtained is water-clear and practically colorless4 ,although the product is collected over a #e'j range1 most of the liquid is found to boil over a #a'j range1 if distilled slowly without superheating4 ,the boiling point of ethyl phenylacetate is near that of benzyl cyanide4 ,however1 a ,kjeldahl analysis of the product shows that only a trace of nitrogen compounds is present4 #c4 ,other ,methods of ,preparation ,ethyl phenylacetate may be prepared by the treatment of benzyl cyanide with alcohol and hydrochloric acid gas4#a ,it is much more convenient in the laboratory1 however1 to use sulfuric acid in place of hydrochloric acid2 in fact1 the yields obtained are better than those recorded in the literature4 ,this ester may also be made by the esterification of phenylacetic acid with hydrochloric acid and alcohol2#b or with alcohol and sulfuric acid2#c the following less important methods of preparation may be mentioned2 the action of benzyl magnesium chloride upon ethyl chlorocarbonate1#d and the action of copper on a mixture of bromobenzene and ethyl chloroacetate at #ahj'j4e #a ,ber4 #bj1 #eib 7#ahhg72 ,ann4 #bif1 #cfa 7#ahig7 #b ,ber4 #b1 #bjh 7#ahfi74 #c ,ann4 #bif1 #b1 footnote 7#ahig72 ,compt4 rend4 #aeb1 #ahee 7#aiaa74 #d ,ber4 #cf1 #cjhh 7#aijc74 #e ,ber4 #b1 #gch 7#ahfi74 ,,viii ,,glycerol a1 g-,,dichlorohydrin ,c#c;,h#e7,,oh7#c #b;,h,cl-- ,,ch#b;,cl,c,h,o,h,c,h#b;,cl #b;,h#b,o ,prepared by ,j4 ,b4 ,,conant and ,o4 ,r4 ,,quayle4 ,checked by ,o4 ,,kamm and ,a4 ,o4 ,,matthews4 #a4 ,procedure ,,one kilo of #ij per cent glycerol 7sp4 gr4 #a4bdc7 and #bj g4 of acetic acid are placed in a weighed #b-l4 flask which is immersed in an oil bath heated to #ajj-aaj'j4 ,the flask is fitted with a two-hole stopper1 which carries a long tube reaching to the bottom of the flask and a short exit tube4 ,the former is connected to a hydrogen chloride generator1 the latter to a catch-bottle and some system for absorbing any excess of hydrogen chloride4 ,a stream of dry hydrogen chloride is passed into the mixture4 ,the absorption of gas is very rapid at the start1 but gradually falls off towards the end of the reaction2 the stream of hydrogen chloride should be regulated accordingly4 ,the flask is removed from time to time and weighed2 when the absorption of gas practically ceases1 the increase in weight will be about #hge g4 7#be per cent more than the theoretical amount74 ,the product is now cooled1 placed in a #d-l4 beaker1 and treated with solid sodium carbonate until just alkaline to litmus4 ,water is added from time to time1 to facilitate the reaction with the sodium carbonate and to prevent the separation of salt2 about #ejj cc4 are required4 ,the mixture is transferred to a separatory funnel and the aqueous layer separated4 ,the crude dichlorohydrin1 which weighs #abej g41 is distilled in vacuo4 ,the first fraction boiling below #fh'j_/ad mm4 weighs #bbe g41 and consists of water and some dichlorohydrin2 the dichlorohydrin is collected between #fh-ge'j_/ad mm41 and weighs about #gge g4 ,the water is separated from the first fraction1 which is then redistilled and yields #ajj g4 of dichlorohydrin4 ,a still further amount of material 7#dj-de g47 may be obtained by extracting with benzene1 the aqueous layer obtained in the neutralization process4 ,this is1 however1 hardly profitable4 ,the neutralization and distillation will require about four hours4 ,the #hge g4 of dichlorohydrin thus obtained boils over a #g'j range2 this is #gj per cent of the theoretical amount4 ,redistillation yields #gjj-gbj g4 boiling #gj-gc'j_/ad mm4 7#eg per cent of the theoretical amount74 #b4 ,notes ,the most convenient hydrogen chloride generator is that described by ,sweeney4#a ,concentrated hydrochloric acid is introduced into concentrated sulfuric acid1 by means of a dropping funnel and a capillary tube leading to the bottom of the sulfuric acid container4 ,it is convenient to use a #c-l4 bottle for this container and a #a-l4 funnel to contain the hydrochloric acid4 ,the gas is dried by passing through a wash-bottle containing concentrated sulfuric acid4 ,an empty catch-flask should be connected between the generator and the absorption flask in case any glycerol tends to suck back at the start of the reaction4 ,about #f kg4 of concentrated hydrochloric acid and #aj kg4 of concentrated sulfuric acid are required in one run4 ,the generating flask will have to be recharged every six hours2 it should be half filled with sulfuric acid4 ,aside from this1 the apparatus needs no attention4 ,the oil bath can be conveniently heated on an electric hot plate4 ,the dichlorohydrin boiling over a #g'j range is sufficiently pure for most purposes4 ,it contains very little1 if any1 isomeric dichlorohydrin1 since on oxidation it gives dichloroacetone in good yields4 #c4 ,other ,methods of ,preparation ,the following methods of preparing dichlorohydrin are described in the literature3 the action of gaseous hydrogen chloride on glycerol2#a;b the action of gaseous hydrogen chloride on glycerol mixed with an equal volume of acetic acid2#b the action of hydrogen chloride gas on glycerol containing #a-b per cent of some organic acid1 as acetic1 as a catalyst2#c the action of aqueous solution of hydrochloric acid on glycerol containing acetic acid as a catalyst2#d the action of sulfur monochloride on glycerol4#e ,the previous work1 described in the literature1 indicated that the best yields were obtained by the treatment of glycerol containing #a-b per cent of acetic acid as a catalyst by gaseous hydrogen chloride4 ,therefore this method was employed4 #a;a ,j4 ,am4 ,chem4 ,soc4 #ci1 #bahg 7#aiag7 #a;b ,ann4 #hh1 #caa 7#ahec72 ,ann4 chim4 phys4 7#c7 #da1 #big 7#ahed72 7#f71 #bb1 #dcg 7#ahia72 ,bull4 soc4 chim4 7#b71 #dh1 #bcg 7#ahhg72 ,z4 physik4 ,chem4 #ib1 #gag 7#aiah72 #ic1 #ei 7#aiai72 #id1 #fia 7#aibj72 ,d4 ,r ,p4 #bfc1ajf2 #bgb1ccg2 ,frdl4 #aa1 #cc 7#aiab74 #b ,ann4 ,spl4 #a1 #b;,i#h 7#ahfa72 ,ann4 chim4 phys4 7#c7 #fj1 #ah 7#ahfj74 #c ,d4 ,r4 ,p4 #aig1cjh2 ,frdl4 #i1 #cc 7#aijh74 #d ,d4 ,r4 ,p4 #aig1cji2 ,frdl4 #i1 #cc 7#aijc74 #e ,ann4 #abb1 #gc 7#ahfb72 #afh1 #dc 7#ahgc72 ,ber4 #e1 #ced 7#ahgb72 ,ann4 chim4 phys4 7#f7 #bb1 #dcg 7#ahia74 ,,ix ,,glycerol a-,,monochlorohydrin ,c#c;,h#e7,,oh7#c ,h,cl-- ,,ch#b;,cl,c,h,o,h,c,h#b,,oh ,h#b,o ,prepared by ,j4 ,b4 ,,conant and ,o4 ,r4 ,,quayle4 ,checked by ,o4 ,,kamm and ,a4 ,o4 ,,matthews4 #a4 ,procedure ,,five ,,hundred grams of glycerol 7#ij per cent7 and #aj g4 of glacial acetic acid are mixed in a weighed #a-l4 flask1 which is placed in an oil bath heated to #aje-aaj'j4 ,a rapid stream of dry hydrogen chloride is introduced into the mixture4 ,the flask is removed from the bath from time to time and reweighed4 ,at the end of about four hours the flask will have gained #aij g4 in weight4 ,the reaction is then complete4 ,the product is distilled under diminished pressure4 ,below #aad'j_/ad mm41 #bbj-bej g4 distil2 this portion is mostly water4 ,the monochlorohydrin is collected between #aad-abj'j_/ad mm42 it weighs #cfj g41 which is #ff per cent of the theoretical amount4 ,about #bj g4 more may be obtained by neutralizing the first fraction and separating the aqueous layer4 #b4 ,notes ,the same apparatus is employed as in the preparation of dichlorohydrin 7preparation ,,viii1 p4 #bi74 ,the portion boiling #abj-acj'j_/ad mm4 only amounts to #ae-cj g41 showing that very little of the b-compound is formed4 ,this is further shown by the fact that the dichlorohydrin formed by continued action of hydrogen chloride under the same conditions contains very little1 if any1 a1 b dichloride4 ,two kilograms of concentrated sulfuric acid and #gej g4 of concentrated hydrochloric acid are sufficient to produce the necessary amount of hydrogen chloride4 ,a light straw-colored final product is obtained in some cases4 ,an alternative procedure which is slower and gives slightly lower yields1 but does not require a hydrogen chloride generator1 is as follows3 ,three hundred grams of glycerol1 #fjj cc4 of hydrochloric acid 7sp4 gr4 #a4ai7 and #ae g4 of glacial acetic acid are heated under a reflux condenser for ten hours1 in a #b-l4 flask4 ,the boiling should be very gentle in the early stage of the reaction1 as considerable hydrochloric acid vapor is evolved4 ,as the reaction progresses1 and the evolution of acid vapors diminishes1 the mixture is more strongly heated4 ,the reaction products are distilled under ordinary pressure until the temperature of the liquid has reached #adj'j 7thermometer bulb immersed in the liquid74 ,the residual products are distilled under diminished pressure1 and the following fractions obtained4 7#a7 ,up to #aae'j_/aa mm42 7#b7 #aae-aag'j_/ #aa mm42 7#c7 #aag-agj'j_/aa mm4 7#a7 is mostly aqueous hydrochloric acid2 7#b7 is the monochlorohydrin2 and 7#c7 is glycerol4 ,the second portion is redistilled and the portion boiling at #aae-aah'j_/aa mm4 or #acc-acf'j_/bj mm4 is collected4 ,the yield is #aij-bje g41 #ec-eg per cent of the theoretical amount4 #c4 ,other ,methods of ,preparation ,the following methods of preparing monochlorohydrin are described in the literature3 action on glycerol of gaseous hydrogen chloride2#a action of gaseous hydrogen chloride on glycerol mixed with an equal volume of acetic acid2#b action of aqueous hydrochloric acid on glycerol#c alone or with an organic acid 7#a-b per cent71 such as acetic1 as a catalyst2#d gaseous hydrogen chloride with an organic acid1 as acetic1 as a catalyst2#a;b gaseous hydrogen chloride with the ester of an organic or inorganic acid as a catalyst2#b;b the action of sulfur monochloride on glycerol4#c;b #a ,ann4 #hh1 #caa 7#ahec72 ,ann4 chim4 phys4 7#c7 #da1 #big 7#ahcd72 ,v4 ,r4 ,p4 #bed1gji2 #bfi1feg2 ,frdl4 #aa1 #ca 7#aiab74 #b ,ann4 chim4 phys4 7#c7 #fj1 #ah 7#ahfj74 #c ,d4 ,r4 ,p4 #ahj1ffh2 ,frdl4 #h1 #bg 7#aijg72 ,j4 ,am4 ,chem4 ,soc4 #db1 #bjif 7#aibj74 #d ,d4 ,r4 ,p4 #aig1cji2 ,frdl4 #i1 #cd 7#aijh74 #a;b ,d4 ,r4 ,p4 #aig1cjh2 ,frdl4 #i1 #cc 7#aijh74 #b;b ,d4 ,r4 ,p4 ,anm4 #bc1eaj2 #af1egi2 ,frdl4 #i1 #cf 7#aijh74 #c;b ,d4 ,r4 ,p4 #bja1bcj2 ,frdl4 #i1 #ce 7#aijh74 ,x ,,hydrazine ,,sulfate #b ,,nh#c ,na,o,cl-- ,,nh#b,,nh#b ,h#b,o ,na,cl ,prepared by ,,roger ,,adams and ,b4 ,k4 ,,brown4 ,checked by ,j4 ,b4 ,,conant and ,w4 ,l4 ,,hanaway4 #a4 ,procedure ,a ,,normal solution of sodium hypochlorite is prepared as follows3 in a #e-l4 round-bottom flask are placed #ahjj g4 of sodium hydroxide solution 7#cjj g4 of sodium hydroxide to #aejj g4 of water7 and #aejj g4 of ice4 ,chlorine gas is then passed into the solution until it has gained in weight approximately #bac g4 ,during this addition1 the solution must be kept thoroughly cooled with ice1 in order that chlorates will not be formed4 ,after all the chlorine has been passed in1 it is necessary to be certain that the mixture is slightly alkaline1 since any excess of free chlorine in the solution prevents the formation of hydrazine4 ,in a #ad-;inch evaporating dish are placed #aejj cc4 of c4 p4 ammonia water 7sp4 gr4 #j4ij71 #ijj cc4 of distilled water1 #cge cc4 of #aj per cent gelatine solution1 and #abjj cc4 of the normal sodium hypochlorite solution prepared as above4 ,this mixture is heated as rapidly as possible and boiled down until one-third of the original volume is left4 ,this solution is then cooled thoroughly with ice and filtered with suction1 first through two layers of toweling and then through one thickness of ordinary filter paper over cloth1 in order to remove finely divided solid impurities4 ,the solution is then placed in a precipitating jar1 and cooled down thoroughly 7#j'j7 with ice and salt2 #aj cc4 of concentrated sulfuric acid for each #ajj cc4 of solution are gradually added with constant stirring4 ,a precipitate of hydrazine sulfate 7,,nh#b,,nh#b4;,h#b,,so#d7 forms4 ,the mixture is allowed to stand in the cold for a few hours in order to complete the precipitation1 and is then filtered by suction in the usual way and washed with cold alcohol4 ,the yield varies from #ec g4 to #eh g4 per #aejj cc4 of ammonia water 7#cd-cg per cent of the theoretical amount74 ,the product is perfectly white and crystalline1 and satisfactory for almost any purpose4 ,if an absolutely pure product is desired1 it must be recrystallized from water4 ,for every #ba g4 of crude product1 #ajj g4 of boiling water are used4 ,if the crude hydrazine is brown1 it is advisable to use a little bone-black4 ,after the mixture has been filtered and cooled to #j'j1 #ai g4 of pure white crystals are obtained4 #b4 ,notes ,in the preparation of the sodium hypochlorite solution it is quite necessary that the mixture be kept cold and be alkaline to red litmus paper at the end of the reaction1 if good yields of hydrazine are to be obtained4 ,since iron is an anti-catalyzer1 it is necesssarysic to use distilled water throughout the process4 ,as a viscolizer1 a substance such as starch1 glycerol1 glue or gelatine may be used2 the last1 however1 gives by far the most satisfactory results4 ,in order to obtain a pure white hydrazine sulfate as the first precipitate1 it is necessary to cool the hydrazine solution thoroughly and filter it twice before the sulfuric acid is added4 ,moreover1 the sulfuric acid must be added slowly and with stirring4 ,if these conditions are not followed1 material containing brown particles results4 ,the mother liquor obtained from the crystallized hydrazine sulfate contains a small amount of hydrazine4 ,if #bjj g4 of copper sulfate are dissolved in water and added to #aj l4 of the filtrates from the above processes1 a light-blue crystalline precipitate of the double salt of copper sulfate and hydrazine sulfate will be formed after ten hours4 ,this salt1 when suspended in ten times its weight of distilled water and treated with hydrogen sulfide1 decomposes into copper sulfide and hydrazine sulfate4 ,after the copper salt has been filtered off1 the solution is concentrated until the hydrazine sulfate crystallizes4 ,the yield of product is small1 so that it is hardly advisable to undertake this recovery in the laboratory4 ,it is possible for one man1 simultaneously evaporating six dishes of the hydrazine mixture1 to turn out from #bj to #be runs in nine hours4 ,the time for the evaporation of a solution1 such as is mentioned in the experimental part1 with a four-flame ,bunsen burner1 is two to three hours2 if the evaporation is carried out more slowly than this1 the yield of product is distinctly diminished4 #c4 ,other ,methods of ,preparation ,hydrazine salts have been prepared by the action of hypochlorites on ammonia#a or urea2#b by the hydrolysis of salts of sulfohydrazimethylene disulfonic acid2#c by the hydrolysis of triazoacetic acid2#d by the reduction of diazoacetic ester2#e by the reduction of nitroguanidine followed by hydrolysis2#f by the reduction of the nitroso derivatives of hexamethylene tetramine2#g by the reduction of nitrates or nitrites with zinc in neutral solution2#h by the action of sodium bisulfite on hyponitrous acid followed by reduction2#a;b by the reduction of ,k#b,,so#c,n#b,o#b2b;b by the action of ammonia on dichlorourea2#c;b by the reduction of nitrosoparaldimin2#d;b by the action of copper sulfate on ammonia at high temperatures2#e;b by the reduction of methylene diisonitrosoamine2#f;b by the hydrolysis of the addition product of diazoacetic ester and fumaric or cinnamic esters4#g;b #a ,d4 ,r4 ,p4 #aib1ghc2 ,chem4 ,zentr4 #aijh 7,i71 #dbg2 ,chem4 ,ztg4 #ca1 #ibf 7#aijg72 ,d4 ,r4 ,p4 #aih1cjg2 ,chem4 ,zentr4 #aijh 7,i71 #aieg2 ,eng4 ,pat4 #bb1ieg2 ,c4 ,a4 #b1 #aiii 7#aijh72 ,u4 ,s4 ,pat4 #iaj1heh2 ,c4 ,a4 #c1 #ajfe 7#aiji72 ,french ,pat4 #chb1ceg2 ,c4 ,a4 #c1 #bceh 7#aiji72 ,ber4 #dj1 #dehh 7#aijg72 ,laboratory ,manual of ,inorganic ,preparations1 by ,a4 ,b4 ,lamb1 ,harvard ,university1 ,cambridge1 ,mass4 #b ,j4 ,russ4 ,phys4 ,chem4 ,soc4 #cg1 #a 7#aije72 ,chem4 ,zentr4 #aije 7,i7 #abbg2 ,d4 ,r4 ,p4 #afd1gee2 ,frdl4 #h1 #ec 7#aije72 ,french ,pat4 #cbi1dcj2 ,j4 ,soc4 ,chem4 ,ind4 #bb1 #ajfc 7#aijc72 ,chem4 ,zentr4 #aije 7,i7 #abbg4 #c ,d4 ,r4 ,p4 #gi1hhe2 ,frdl4 #d1 #bf 7#ahie72 ,ber4 #bh1 #bcha 7#ahie74 #d ,ber4 #bj1 #afcb 7#ahhg72 ,chem4 ,news #ee1 #bhh 7#ahhg72 ,d4 ,r4 ,p4 #dg1fjj2 ,frdl4 #b1 #eed 7#ahhi72 ,j4 prakt4 ,chem4 7#b7 #ci1 #bg 7#ahhi74 #e ,ber4 #bg1 #gge 7#ahid72 #bh1 #ahdh 7#ahie72 ,d4 ,r4 ,p4 #eh1gea2 ,frdl4 #c1 #af 7#ahia72 ,d4 ,r4 ,p4 #hg1aca2 ,frdl4 #d1 #bh 7#ahif74 #f ,ann4 #bgj1 #ca 7#ahib72 ,d4 ,r4 ,p4 #ei1bda2 ,frdl4 #c1 #af 7#ahia72 ,eng4 ,pat4 #f1ghf2 ,j4 ,soc4 ,chem4 ,ind4 #aa1 #cgj 7#ahib74 #g ,d4 ,r4 ,p4 #hj1dff2 ,frdl4 #d1 #bg 7#ahie72 ,ann4 #bhh1 #bcb 7#ahie74 #h ,eng4 ,pat4 #aa1 #baf2 ,j4 ,soc4 ,chem4 ,ind4 #ad1 #eie 7#ahie74 #a;b ,ber4 #cc1 #baae 7#aijj72 ,ann4 #bhh1 #cja 7#ahie74 #b;b ,ber4 #bg1 #cdih 7#ahid74 #c;b ,j4 ,chem4 ,soc4 #ie1 #bce 7#aiji72 ,chem4 ,news #ih1 #aff 7#aijh74 #d;b ,ber4 #bc1 #geb 7#ahij74 #e;b ,chem4 ,news #ff1 #bbc 7#ahib74 #f;b ,ber4 #bg1 #cbib 7#ahid72 #g;b ,ber4 #ba1 #bfcg 7#ahhh74 ,,xi ,,mesitylene #c ,,ch#c;,,coch#c 7,h#b,,so#d7-- ,c#f;,h#c7;,,ch#c7c #c;,h#b,o ,prepared by ,,roger ,,adams and ,r4 ,w4 ,,hufferd4 ,checked by ,h4 ,t4 ,,clarke and ,w4 ,w4 ,,hartman4 #a4 ,procedure ,,in a #ab-l4 round-bottom flask1 arranged so that the contents can be mechanically stirred1 are placed #dfjj g4 7#egej cc47 of technical acetone4 ,the flask is then well cooled with an ice-and-salt mixture1 until the temperature of the acetone is between #j'j and #e'j4 ,stirring is started1 and #dafj cc4 of commercial concentrated sulfuric acid is run in at such a rate that the temperature of the mixture never rises above about #aj'j4 ,this addition is accomplished in about five to ten hours4 ,the stirring is continued for three to four hours longer1 while the flask still remains immersed in the original freezing mixture to which no further amount of ice is added4 ,the mixture is then allowed to stand at room temperature for eighteen to twenty-four hours4 ,a #e-l4 round-bottom flask is fitted with a rubber stopper or a cork stopper coated with pitch1 carrying two glass tubes1 one of which 7for the entrance of steam7 reaches to the bottom of the flask1 while the other extends into the open end of a condenser set for downward distillation4 ,the stopper should be wired into the flask4 ,the glass delivery tube into the condenser should not be less than a #ab-mm4 bore1 and the condenser should consist of two #abj-;cm4 water-cooled condensers attached end to end4 ,to the end of the condensing system1 an adapter is attached1 the small end of which is at least #h mm4 in bore and is fitted tightly into a stopper in a #b-l4 suction flask4 ,to the side-arm of the suction flask is attached a tube leading to an exhaust fan1 in order to carry away the gases which are evolved during the subsequent distillation4 ,in the #e-l4 flask are placed about #b l4 of the sulfuric acid-acetone reaction mixture1 and the flask is then heated with a free flame and shaken occasionally4 ,a reaction starts at the end of about fifteen or twenty minutes1 as shown by the evolution of gas 7chiefly sulfur dioxide71 and is allowed to run for about three minutes4 ,at the end of this time1 a current of steam is passed in and continued for about three minutes4 ,during this period a large proportion of the mesitylene distils and should be kept separate from the subsequent distillate4 ,the steam distillation is continued at such a rate that about #hjj cc4 distils in twenty-five to thirty minutes and is collected as a second distillate4 ,at the end of this time1 the distillation is stopped1 the water poured off from the distilling flask and the tarry material emptied out while hot into waste jars4 ,the total amount of original reaction mixture requires five distillations similar to the one just described4 ,the first distillates from each of the five distillations are mixed1 and the layer of mesitylene is separated from the water4 ,this is shaken with sodium hydroxide solution until no more odor of sulfur dioxide is noticeable1 then washed twice with water and distilled4 ,the first portion of the distillate consists of a small amount of water and mesitylene and is added to the combined second distillates4 ,the fraction which distils up to #baj'j is saved4 ,the second distillates are combined1 washed in the same way as the first and then distilled2 the fraction which distils up to #baj'j is combined with the corresponding fraction from the first distillates4 ,these combined fractions 7which boil up to #baj'j7 and #ae g4 of sodium are placed in a #b-l4 distilling flask1 the side-arm of which is closed with a rubber tube and pinchcock and which is fitted with a reflux condenser4 ,the mixture is heated just below the boiling point for about three hours1 during which time the impurities are attacked by the molten sodium1 and a gelatinous1 reddish mass forms4 ,the reflux condenser is now removed and one set for downward distillation is attached to the side-arm4 ,the mixture is distilled and about two-thirds of the liquid removed in this way4 ,the residue is cooled1 the liquid poured off from solid material and distilled up to #baj'j4 ,the distillates from the sodium treatment are now fractionated with a good column 7at least #cj cm4 long71 and the portion which boils at #afc-afg'j is collected4 ,the yield of this fraction varies in different runs from #dcj to #dgj g4 7#ac-ae per cent of the theoretical amount71 but very often will be as high as #ejj g41 and has reached1 in certain experiments1 #fjj g4 ,an alternative method for the purification of the crude material has been employed by ,clarke and ,hartman1 and yields a slightly higher-grade product than the sodium method4 ,it is as follows3 ,the combined distillates are treated with an equal volume of concentrated sulfuric acid and the solution warmed on a water bath for an hour1 under a reflux condenser1 with occasional shaking or1 better1 with mechanical stirring4 ,upon cooling1 mesitylene sulfonic acid crystallizes and the unsulfonated material remains as an oil on the surface4 ,the mixture is filtered through flannel or a filtrose plate1 and the crystals are washed with #fj-gj per cent sulfuric acid4 ,the oily layer is again warmed with sulfuric acid1 as before4 ,the acid and oily filtrates from the two sulfuric acid treatments are steam distilled1 and the distillate combined with the next batch of material4 ,the crystals are mixed with #b l4 of #ae per cent hydrochloric acid and heated under a reflux condenser for two to three hours4 ,the reaction mixture is now steam distilled1 the mesitylene separated1 dried over calcium chloride and fractionated2 the portion which boils at #afc-afg'j is collected4 #b4 ,notes ,the cooling of the reaction flask must be very efficient1 a #aj-ae cm4 blanket of a thorough mixture of ice and salt being used4 ,if this precaution is not employed1 the time for the addition of the sulfuric acid is greatly increased1 provided the temperature of the reaction mixture is still kept within the limits mentioned4 ,if a cork is used for the steam distillation of the reaction mixture of acetone and sulfuric acid1 it should be coated well with pitch and wired into the flask4 ,this is necessary because the vapors of the reaction mixture attack an ordinary cork very badly1 and soften it so much that it is necessary to rewire it to prevent it from slipping out4 ,a rubber stopper is satisfactory and may be used in several runs4 ,the evolution of gas is so vigorous that it is not possible to distil more than #b l4 of the original reaction mixture at one time in the apparatus described4 ,the connections on the apparatus1 in which the mesitylene is obtained from the crude reaction mixture1 should be tight1 since the fumes evolved during the heating are very irritating4 ,the product which distils during the initial heating and the three minutes of steam distillation is mainly satisfactory material2 the rest of the steam distillation yields only a small amount of pure product4 ,the two portions of the distillate are1 therefore1 kept separate1 since the second distillate always contains a considerable amount of high-boiling product which tends to cause emulsification of the alkali in the purification4 ,no recovery of acetone is made4 ,the mechanism of the reaction is undoubtedly as follows3 when the sulfuric acid and acetone are in contact for long periods of time1 several molecules of the acetone condense to form aldol condensation products4 ,these do not break down into mesitylene until the temperature is raised in the second part of the experiment4 ,while the original reaction mixture is standing1 the temperature gradually rises to #dj'j or #ej'j in the course of six to ten hours1 and then gradually cools off again4 ,it is probable that at the end of this time 7when the flask has cooled again7 the reaction mixture could be distilled with nearly as good a yield as is obtained after standing eighteen to twenty-four hours4 ,the wide variation in yields which are mentioned in the experimental part is probably due to a slight change in the grade of the chemicals which are used in this preparation4 #c4 ,other ,methods of ,preparation ,the cheapest and most convenient method by which mesitylene may be prepared is by the action of a dehydrating agent upon acetone2 the agent most commonly used is sulfuric acid4#a ,it has been shown also that phosphoric acid will convert acetone to mesitylene4#b ,a number of other methods have also been used for the preparation of mesitylene3 the action of sulfuric acid on methyl acetylene2#c the action of sulfuric acid on mesityl oxide and phorone2#d the action of aluminiumsic7british7 chloride on methyl chloride and benzene2#e the action of mineral acids upon mesitoyl or benzoyl mesitylene2#f the action of phosphoric acid upon diaceto-mesitylene2#g the treatment of methylene-#c-;dimethyl-#a1 #e-;cyclo-hexene-#a with bromine and then with alcoholic potash4#h #a ,ann4 #ada1 #aca 7#ahfg72 #adg1 #dc 7#ahfh72 #bgh1 #baj 7#ahic72 ,bud4 soc4 chim4 7#b7 #dj1 #bfg 7#ahhc72 ,j4 prakt4 ,chem4 7#a7 #ae1 #abi 7#ahch72 ,am4 ,chem4 ,j4 #ae1 #bef 7#ahic72 #bj1 #hjg 7#ahih74 #b ,j ,chem4 ,soc4 #ii1 #abea 7#aiaa74 #c ,ber4 #h1 #ag 7#ahge74 #d ,ber4 #g1 #aafi 7#ahgd72 #aj1 #heh 7#ahgg74 #e ,ber4 #ab1 #cbi 7#ahgi72 ,ann4 chim4 phys4 7#f7 #a1 #dfa 7#ahhd74 #f ,ber4 #cb1 #aiaj 7#ahii74 #g ,ber4 #cb1 #aefc 7#ahii74 #h ,ber4 #dc1 #cjic 7#aiaj74 ,,xii ,,methyl ,,red 7o7,,ho#b;,,cc#f;,h#ds,,nh#b ,,hno#b ,h,cl--7 o7,,ho#b;,,cc#f;,h#d,n#b;,cl ,h#b,o 7o7 ,,ho#b;,,cc#f;,h#d,n#b;,cl ,c#f;,h#e,n7,,ch#c7b--7 o7,,ho#b;,,cc#f;,h#d,n ,,nc#f;,h#d,n7,,ch#c7b ,h,cl ,prepared by ,h4 ,t4 ,,clarke and ,w4 ,r4 ,,kirner4 ,checked by ,,roger ,,adams and ,j4 ,b4 ,,davis4 #a4 ,procedure ,,technical anthranilic acid 7generally about #ie per cent pure7 7#fhe g47 is dissolved in #a4e l4 of water and #ejj cc4 of concentrated hydrochloric acid 7sp4 gr4 #a4ag71 by heating4 ,the insoluble dark impurity present in small amounts is filtered off1 and the filtrate is transferred to a #aj-l4 crock and chilled with stirring4 ,it is then mixed with a mush of #b4e kg4 of ice and #gej cc4 of concentrated hydrochloric acid4 ,the crock is cooled externally with ice1 and the contents stirred continuously4 ,when the temperature reaches about #c'j1 a filtered solution of #cfj g4 of sodium nitrite in #gjj cc4 of water is dropped in slowly1 through a long capillary tube reaching below the surface of the liquid1 until a faint but permanent reaction to starch potassium iodide paper is obtained2 the temperature is kept between #c'j and #e'j4 ,this operation requires all but about #cj cc4 of the nitrite solution and occupies one and a half to two hours4 ,to the solution of the diazonium salt are now added #hdh g4 of dimethylaniline2 this may be done rapidly1 as the temperature does not rise appreciably4 ,stirring is continued for one hour1 the temperature being kept at #e'j ,five hundred cc4 of a filtered solution of #fhj g4 of crystallized sodium acetate diluted to #abjj cc4 are then added1 and the stirring continued for four hours4 ,if a foamy solid rises to the surface during this time and refuses to become incorporated by the stirrer1 a few drops of ethyl acetate may be added to reduce the foam4 ,the mixture is allowed to stand overnight in an ice bath which is well insulated by several thicknesses of burlap2 the temperature must be kept below #g'j to get a good yield of product4 ,the remainder of the sodium acetate solution is then added with stirring1 and after the mixture has been stirred for an additional period of one to three hours1 the temperature is allowed to rise slowly to #bj-be'j in the course of twenty-four hours4 ,just enough sodium hydroxide solution is then added1 with stirring1 to cause the mixture to have a distinct odor of dimethylaniline 7about #bdj cc4 of a #dj per cent solution are generally required71 and the mixture is allowed to stand for forty-eight hours or longer at room temperature 7#bj-be'j74 ,the solid is then filtered off1 washed first with water1 then with #djj cc4 of #aj per cent acetic acid 7to remove the dimethylaniline7 and finally with distilled water4 ,the last filtrate is generally pale pink4 ,the solid is sucked as dry as possible1 spread out on a tray in order to allow most of the water to evaporate 7fifteen to twenty hours7 and then suspended in #d l4 of methyl alcohol in a #ab-l4 flask4 ,this mixture is stirred on the steam bath under a reflux condenser for one to two hours1 allowed to cool slowly1 and then chilled in an ice bath and filtered4 ,the solid product is washed with a second #d l4 of cold methyl alcohol4 ,after being dried in air1 the product varies in weight from #hbj to #hgj g4 ,the product is extracted with boiling toluene in the following manner3 #aej g4 are placed in a fluted filter paper of #bi cm4 diameter in a #be-;cm4 glass funnel which passes through the cork of a #b-l4 flat-bottom conical flask containing #abej cc4 of toluene 7,fig4 #b74 ,the flask is heated on an electric stove1 and a #ab-l4 round-bottom flask is placed on the funnel to act as a condenser1 cold water being run through the flask4 ,the toluene is boiled until the condensed liquid runs through almost colorless 7this requires from four to ten hours74 ,the heating is then discontinued1 and1 as soon as the liquid ceases to boil1 the flask is removed to a bath containing water at #ij-ajj'j2 the level of the water should be slightly above the level of the liquid in the flask4 ,this arrangement permits the temperature to fall slowly so that large crystals are obtained4 ,in the meantime a second conical flask containing #abej cc4 of toluene is attached to the funnel1 and a new charge of #aej g4 of crude methyl red is placed in the paper4 ,when extraction is complete it is found that a certain amount of black amorphous insoluble matter remains on the filter2 this is discarded4 ,the crystals of methyl red are filtered off and washed with a little toluene4 ,the weight of pure material is #gee-hje g4 ,the mother liquors are concentrated to one-fourth of their volume1 and the crystals which separate on cooling are recrystallized from fresh toluene4 ,the recovered toluene can1 of course1 be employed again4 ,the total yield of pure methyl red is #gij--hdj g4 ,it melts at #aha-ahb'j4 ,the watery mother liquors from the crude methyl red are rendered alkaline with sodium hydroxide and distilled until no more dimethylaniline passes over4 ,in this way #bej to #djj g4 of moist dimethylaniline are recovered4 #b4 ,notes ,the amount of hydrochloric acid indicated must not be reduced2 otherwise1 diazoamino compounds are formed4 ,it is essential to keep the temperature low while unreacted diazobenzoic acid remains in solution1 in order to avoid decomposition4 ,if this precaution is not taken1 the yields are considerably diminished1 through the formation of tarry by-products4 ,the use of a capillary tube for the addition of sodium nitrite prevents loss of nitrous acid by local reaction at the surface of the acid solution4 ,the tube should not be tightly connected to the dropping funnel1 but should be so arranged that air is sucked through with every drop4 ,in this way1 the entrance of the acid liquor into the capillary is prevented4 ,the formation of the azo compound takes place slowly on the addition of the dimethylaniline1 but the speed of the reaction is greatly increased when the hydrogen ion concentration is lowered by the addition of the sodium acetate4 ,it is nevertheless necessary to allow the reaction mixture to stand a long time2 if the product be filtered off after only twenty-four hours1 a further quantity of dye will separate from the filtrate on standing4 ,the hydrochloride of methyl red is only sparingly soluble in cold water1 and is apt to separate in blue needles if the acidity is not sufficiently reduced4 ,the alcoholic filtrate1 obtained on digesting and washing the crude methyl red1 contains a more soluble red by-product which gives a brownish-yellow solution in alkali4 ,the methyl alcohol may be recovered with very little loss by distillation2 it is1 however1 impracticable to attempt to recover any methyl red from the residue1 owing to the tarry nature of the by-product4 ,the proportion of this by-product is greatly increased if the temperature of the mixture is allowed to rise too soon after the addition of the sodium acetate4 ,methyl red is described as crystallizing in needles from glacial acetic acid2 on recrystallization from toluene it separates in plates4 ,when the methyl red is crystallized from toluene1 it sometimes separates in the form of bright-red lumps1 probably on account of too rapid crystallization4 ,under these conditions it is advisable to crystallize again1 using a somewhat larger amount of toluene4 ,it is advisable to titrate the crude anthranilic acid with standard alkali and phenolphthalein before starting the experiment4 ,in checking these directions1 an #hj per cent anthranilic acid was used2 it gave a correspondingly lower yield of methyl red 7#fej-gjj g474 ,the yield of methyl red is about #fe to #gj per cent based on the dimethylaniline actually used up1 but only #eh-fc per cent based on the anthranilic acid actually present in the technical anthranilic acid employed4 #c4 ,other ,methods of ,preparation ,methyl red was first prepared#a by diazotization of anthranilic acid in alcoholic solution1 the product being allowed to react with dimethylaniline in the same solvent4 ,it has been stated#b that this process does not work satisfactorily and yields a different product1 of brownish-red color4 ,the preparation of methyl red in aqueous solution has been described by two workers1 one of whom#c gives but few details and claims a nearly quantitative yield2 the other#d gives fuller details and states the yield to be #dc4a per cent of the theory4 ,the recrystallization of methyl red from toluene is stated#e to yield a product melting at #ahc'j4 #a ,ber4 #da1 #cije 7#aijh74 #b ,chem4 ,zentr4 #aiaj1 7#a71 #ifj2 #aiaj1 7#aa71 #aefa4 #c ,j4 ,chem4 ,soc4 #ig1 #bdhe 7#aiaj74 #d ,c4 ,a4 #ad1 #cdjf 7#aibj7 #e ,j4 ,chem4 ,soc4 #ii1 #accd 7#aiaa74 ,,xiii p-,,nitrobenzoic ,,acid 7p7,,no#b;,c#f;,h#d;,,ch#cs #c,o7,na#b;,cr#b,o#g ,h#b,,so#d7-- 7p7,,no#b;,c#f;,h#d;,,co#b;,h #c;,h#b,o ,prepared by ,o4 ,,kamm and ,a4 ,o4 ,,matthews4 ,checked by ,h4 ,t4 ,,clarke and ,w4 ,w4 ,,hartman4 #a4 ,procedure ,,in a #e-l4 round-bottom flask1 fitted with a mechanical stirrer1 are placed #fhj g4 of sodium dichromate1 #aejj cc4 of water1 and #bcj g4 of p-nitrotoluene4 ,stirring is started1 and #agjj g4 of concentrated sulfuric acid are allowed to flow in during about thirty minutes4 ,the heat of dilution of the sulfuric acid will cause the nitrotoluene to melt1 and rapid oxidation will soon take place4 ,the last half of the sulfuric acid must be added gradually1 in order to prevent too violent a reaction4 ,since a small amount of nitrotoluene is volatilized1 it is advisable to carry on this work under a hood4 ,after the sulfuric acid has been added and the spontaneous heating of the reaction mixture has subsided1 the mixture is heated to gentle boiling for about half an hour4 ,after the reaction mixture has cooled1 #b l4 of water are added1 the cooled solution is filtered through a cloth filter1 and the product washed with about #a l4 of water4 ,in order to remove the chromium salts as completely as possible1 the crude nitrobenzoic acid is warmed on the water bath and agitated with #a l4 of dilute 7#e per cent7 sulfuric acid solution4 ,after cooling1 the product is again filtered4 ,it is then dissolved in #e per cent sodium hydroxide solution1 filtered from any chromium hydroxide remaining1 and also from unchanged nitrotoluene4 ,the filtrate1 which should be light yellow or greenish in color1 is acidified with dilute sulfuric acid1 with stirring4 ,it is usually preferable to run the alkaline solution into the dilute sulfuric acid1 rather than to use the reverse procedure1 for the precipitation of the nitro acid4 ,the precipitated product is filtered with suction1 washed thoroughly1 and dried4 ,the product should possess only a light-lemon color4 ,the yield should be #bcj-bdj g4 7#hj-he per cent of the theoretical amount74 ,for a product of special purity1 crystallization from benzene is advisable4 ,for most purposes1 however1 the nitrobenzoic acid may be used without crystallization1 since its melting point is found to be within #b'j of the correct value of #bch'j4 #b4 ,notes ,the above procedure differs from that recorded in the literature1 mainly in the use of a fairly large excess of sulfuric acid4 ,this shortens the reaction time from forty hours to about one hour1 which is especially convenient in the preparation of the acid on a laboratory scale4 ,because of the use of this large excess of sulfuric acid1 the reaction is apt to be rather violent if the directions given are not carefully followed4 ,the oxidation should be carried out under a hood4 ,small amounts of nitrotoluene are lost by volatilization1 but this loss is not serious1 as can be seen from the yield of product obtained4 ,ten or #bj g4 of unchanged nitrotoluene can be recovered from the reaction mixture by steam distillation1 but the value of the by-product would not pay for the time spent in recovery4 ,the washing of the crude reaction product with dilute sulfuric acid is advisable1 if good material is to be obtained4 ,if an efficient centrifuge is available for use at this stage of the operation1 this separate washing may prove to be less essential4 ,when a sparingly soluble organic acid is precipitated from fairly concentrated solution1 the precipitate is liable to carry down with it some of the salt of the organic acid4 ,addition of the salt solution to the mineral acid1 with stirring1 avoids this difficulty4 #c4 ,other ,methods of ,preparation ,the nitration of benzoic acid produces only very small yields of the p-nitro product4#a ,the only practical method for the preparation consists in the oxidation of p-nitrotoluene1 although for this purpose various oxidizing agents are used4 ,in addition to nitrotoluene1 p-nitrobenzyl alcohol1 p-nitrocinnamic acid and similar compounds may be oxidized1 but their cost is prohibitive in comparison with that of the cheaper nitro hydrocarbon4 p-,nitrotoluene may be oxidized by means of strong nitric acid1#b chromic acid mixture1#c or permanganates4#d ,electrolytic oxidation#e has also been proposed4 ,the procedure given above involves the use of chromic acid mixture1 but1 owing to a change in the concentration of sulfuric acid1 the time of reaction is greatly shortened and the preparation is thus considerably improved4 #a ,ber4 #h1 #ebh1 #ecf 7#ahge7 #b ,ann4 #abg1 #acg 7#ahfc72 #abh1 #beg 7#ahfc7 #c ,ann4 #aci1 #cce 7#ahff74 #d ,j4 ,am4 ,chem4 ,soc4 #da1 #aege 7#aiai74 #e ,r4 ,p4 #aag1 #abi2 ,frdl4 #f1 #aab4 ,,xiv p-,,nitrobenzyl ,,cyanide ,c#f;,h#e;,,ch#b;,,cn ,,hno#c-- 7p7,,no#b;,c#f;,h#d;,,ch#b;,,cn ,h#b,o ,prepared by ,g4 ,r4 ,,robertson4 ,checked by ,,roger ,,adams and ,h4 ,o4 ,,calvery4 #a4 ,procedure ,,in a #b-l4 round-bottom flask1 fitted with a stopper holding a dropping funnel and a mechanical stirrer1 is placed a mixture of #bge cc4 of concentrated nitric acid 7sp4 gr4 #a4db7 and #bge cc4 of concentrated sulfuric acid 7sp4 gr4 #a4hd74 ,this is cooled to #aj'j in a freezing mixture1 and #ajj g4 of benzyl cyanide 7free from alcohol and water7 are run in slowly1 at such a rate that the temperature remains at about #aj'j and does not exceed #bj'j4 ,after all the benzyl cyanide has been added 7about one hour71 the ice bath is removed1 the mixture is stirred for an hour and then poured on to #abjj g4 of crushed ice4 ,a pasty mass slowly separates2 more than half of this mass is p-nitrobenzyl cyanide1 the other constituents being o-nitrobenzyl cyanide1 and a variable amount of an oil which resists hydrolysis2 apparently no dinitro compounds are formed4 ,the mass is filtered on a porcelain funnel with suction1 pressed well to remove as much oil as possible1 and dissolved in #ejj cc4 of boiling alcohol 7#ie per cent74 ,on cooling1 p-nitrobenzyl cyanide crystallizes2 the mother liquor1 on distillation1 gives an impure alcohol which can be used for the next run4 ,recrystallization from #eej cc4 of #hj per cent alcohol 7sp4 gr4 #j4hf to #j4hg7 yields #gj to #ge g4 7#ej-ed per cent7 of a product which melts at #aae-aaf'j4 ,this product is satisfactory for most purposes1 and incidentally for the preparation of p-nitrophenylacetic acid4 ,occasionally it must be free even from traces of the ortho compound1 and in this case should be crystallized again from #hj per cent alcohol2 it then melts at #aaf-aag'j4 #b4 ,notes ,fuming nitric acid may be used in nitrating benzyl cyanide1 but the method here described is cheaper4 ,the yield of #gj g4 is obtained from benzyl cyanide1 which boils over a #e'j range prepared as described in preparation ,,iii 7p4 #i74 ,very pure benzyl cyanide will give a slightly higher yield1 while commercial grades may give only #ej g4 of p-nitrobenzyl cyanide and much oil4 ,the reaction has been also carried out with #ejj g4 of benzyl cyanide4 ,under these conditions a #e-l4 flask was used1 and it required two and a half hours to add the benzyl cyanide4 ,the yield of product was #cbe to #cgj g4 #c4 ,other ,methods of ,preparation ,nitrobenzyl cyanide has hitherto been prepared by the action of fuming nitric acid#a on benzyl cyanide4 #a ,ber4 #ag1 #eje 7#ahhd72 #cc1 #agj 7#aijj72 ,j4 ,biol4 ,chem4 #ci1 #ehe 7#aiai72 ,j4 ,am4 ,chem4 ,soc4 #dc1 #ahj 7#aiba74 ,,xv p-,,nitrophenylacetic ,,acid 7p7,,no#b;,c#f;,h#d;,,cn ,h#b,,so#d #b;,h#b,o-- 7p7,,no#b;,c#f;,h#d;,,ch#b;,,co#b;,h ,,nh#d;,,hso#d ,prepared by ,g4 ,r4 ,,robertson4 ,checked by ,,roger ,,adams and ,h4 ,o4 ,,calvery4 #a4 ,procedure ,,in a #a-l4 round-bottom flask are placed #ajj g4 of p-nitrobenzyl cyanide4 ,a solution of #cjj cc4 of concentrated sulfuric acid 7sp4 gr4 #a4hd7 in #bhj cc4 of water is prepared1 and two-thirds of this solution is poured on to the p-nitrobenzyl cyanide4 ,the mixture is shaken well1 until the solid is all moistened with the acid4 ,any solid material sticking to the walls of the vessel is now washed down into the liquid with the remainder of the acid1 the flask is attached to a reflux condenser1 then set1 without shaking1 over a #aj-;cm4 hole in a large sheet of asbestos board which rests on a tripod1 and heated until the mixture boils4 ,the boiling is continued for fifteen minutes4 ,the reaction mixture1 which becomes rather dark1 is diluted with an equal volume of cold water and cooled to #j'j or below4 ,the solution is filtered1 the precipitate is washed several times with ice water and then dissolved in #afjj cc4 of boiling water4 7,a few grams of animal charcoal are added in dissolving the precipitate1 if a technical p-nitrobenzyl cyanide has been used47 ,this solution is filtered as rapidly as possible through a large folded filter1 preferably with a steam funnel4 ,in spite of all precautions1 however1 some solid usually separates on the filter4 ,this must be redissolved in a minimum quantity of boiling water1 and this solution then filtered into the main solution4 ,the p-nitrophenylacetic acid separates in long1 pale-yellow needles1 which melt at #aea-aeb'j4 ,the yield is #ajc to #ajf g4 7#ib- #c per cent of the theoretical amount74 #b4 ,notes ,if the flask is not protected with an asbestos board or the equivalent1 decomposition occurs where the substance is super-heated on the side walls of the flask4 ,if crystals of the cyanide are allowed to remain on the upper walls of the flask1 they are not easily washed down and so are not hydrolyzed4 ,the solubility curve of p-nitrophenylacetic acid is very steep at temperatures near #ajj'j1 so that the filtering of the boiling solution should be rapid4 ,if a good grade of cyanide be used1 it is not necessary to add bone-black in order to obtain the acid in a pure state4 ,in making experiments with #ejj g4 of p-nitrobenzyl cyanide1 it was found that the time for hydrolysis was about the same as when smaller amounts were used4 #c4 ,other ,methods of ,preparation p-,nitrophenylacetic acid has been formed by the nitration of phenylacetic acid2#a by the hydrolysis of its ester#b or its amid1#c and by the hydrolysis of its nitrile with hydrochloric acid4#d #a ,ber4 #db1 #ceif 7#aiji74 #b ,ber4 #ab1 #agfe 7#ahgi74 #c ,ber4 #ad1 #bcdb 7#ahha74 #d ,ber4 #ae1 #hcd 7#ahhb74 ,,xvi ,,nitroso-b-,,naphthol ,c#aj;,h#g,,oh7b7 ,,hno#b-- ,c#aj;,h#f7,,oh7,,no7#a1b7 ,h#b,o ,prepared by ,c4 ,s4 ,,marvel and ,p4 ,k4 ,,porter4 ,checked by ,h4 ,t4 ,,clarke and ,w4 ,w4 ,,hartman4 #a4 ,procedure ,,in a #ab-l4 round-bottom flask fitted with a mechanical stirrer are placed #ejj g4 of technical b-naphthol dissolved in a warm solution of #adj g4 of sodium hydroxide in #f l4 of water4 ,the solution is cooled to #j'j in an ice-and-salt bath1 and #bej g4 of powdered technical sodium nitrite is added4 ,stirring is started and #aajj g4 of sulfuric acid 7sp4 gr4 #a4cb7 are added from a dropping funnel1 at such a rate that the whole is added in one to one and a half hours1 the temperature being kept at #j'j4 ,during the reaction crushed ice is added from time to time to maintain the temperature at #j'j2 about #a kg4 is usually used4 ,after all of the sulfuric acid has been added1 the solution should react acid to ,congo paper4 ,the mixture is stirred one hour longer at the low temperature and then the nitroso-b-naphthol1 which has gradually separated out during the reaction1 is filtered with suction and washed thoroughly with water4 ,the product is at first light yellow in color1 but after three to four days it gradually changes to a dark brown4 ,the moisture content seems to have some effect on the color4 ,after the product has been air-dried for about four days1 the yield is about #ffe g42 it melts at #ig'j4 ,a sample of this partially dried product1 on drying in vacuo over sulfuric acid for twenty hours1 loses about #aj per cent of its weight and the melting point is #ajf'j4 ,by longer drying under ordinary conditions1 the melting point of #ajf'j is reached4 ,the total yield of dry product is about #eie g4 7#ii per cent of the theoretical amount74 ,this product is satisfactory for all purposes4 ,it may be obtained in a crystalline condition1 however1 by recrystallizing from hot ligroin 7sp4 gr4 #j4ga-j4gb74 ,about #b g4 of nitroso-b-naphthol will dissolve in #ae cc4 of boiling ligroin4 ,the product is not very soluble in cold ligroin1 so that nearly all is recovered4 #b4 ,notes ,it is very necessary to keep the temperature near #j'j while adding the sulfuric acid1 or a tarry product will be obtained4 ,vigorous stirring and the addition of the sulfuric acid at the proper rate are essential for a good product4 ,a large vessel is needed for the reaction1 as the nitroso-b-naphthol separates in a finely divided condition and there is some tendency to foam4 ,the final air-dried product is pure except for its moisture content1 as is shown by the fact that on drying in vacuo it has a very good melting point4 ,a sample of ,kahlbaum's nitroso-b-naphthol melted at #aja--aje4 #c4 ,other ,methods of ,preparation ,nitroso-b-naphthol has been made by the action of hydroxylamine hydrochloride on b-naphtho-quinone-chlorimide2#a by the action of sulfuric acid upon a solution of potassium or sodium nitrite and the sodium salt of b-naphthol2#b by the action of sodium nitrite upon an alcoholic solution of zinc chloride and b-naphthol2#c by the action of sodium nitrite upon b-naphthol suspended in zinc sulfate solution2#d by the action of nitrous acid on b-dinaphthol methane2#e and by the action of nitrosyl sulfate upon the sodium salt of b-naphthol4#f #a ,ber4 #bg1 #bda 7#ahid74 #b ,ber4 #h1 #ajbf 7#ahge72 #bg1 #cjgf 7#ahid72 ,j4 ,chem4 ,soc4 #de1 #bie 7#ahhd74 #c ,ber4 #ah1 #gje 7#ahhe74 #d ,d4 ,r4 ,p4 #be1dfi2 ,frdl4 #a1 #cce 7#ahhc74 #e ,ber4 #cc1 #hjf 7#aijj74 #f ,j ,chem4 ,soc4 #cb1 #dg 7#ahgg72 ,ann4 #ahi1 #adf 7#ahgg74 ,,xvii ,,phenylacetic ,,acid ,c#f;,h#e;,,ch#b;,,cn #b;,h#b,o ,h#b,,so#d-- ,c#f;,h#e;,,ch#b;,,co#b;,h ,,nh#d;,,hso#d ,prepared by ,,roger ,,adams and ,a4 ,f4 ,,thal4 ,checked by ,o4 ,,kamm and ,a4 ,o4 ,,matthews4 #a4 ,procedure ,,in a #e-l4 round-bottom flask1 fitted with a mechanical stirrer and reflux condenser1 are mixed #aaej cc4 of water1 #hdj cc4 of commercial sulfuric acid and #gjj g4 of benzyl cyanide 7preparation ,,iii1 p4 #i74 ,the mixture is heated under a reflux condenser and stirred for three hours1 cooled slightly and then poured into #b l4 of cold water4 ,the mixture should be stirred so that a solid cake is not formed2 the phenylacetic acid is then filtered off4 ,this crude material should be melted under water and washed by decantation several times with hot water4 ,these washings1 on cooling1 deposit a small amount of phenylacetic acid which is filtered off and added to the main portion of material4 ,the last of the hot water is poured off from the material while it is still molten and it is then transferred to a #b-l4 ,claisen distilling flask and distilled in vacuo4 ,a small amount of water comes over first and is rejected2 about #bj cc41 containing an appreciable amount of benzyl cyanide1 then distils4 ,this fraction is used in the next run4 ,the distillate boiling #agf-ahi'j_/ej mm4 is collected separately and solidifies on standing4 ,it is practically pure phenylacetic acid1 m4 p4 #gf-gf4e'j2 it amounts to #fcj g4 7#gg4e per cent of the theoretical amount74 ,as the fraction which is returned to the second run of material contains a considerable portion of phenylacetic acid1 the yield actually amounts to at least #hj per cent4 ,for the preparation of small quantities of phenylacetic acid1 it is convenient to use the modified method given in the ,notes4 #b4 ,notes ,the standard directions for the preparation of phenylacetic acid specify that the benzyl cyanide is to be treated with dilute sulfuric acid prepared by adding three volumes of sulfuric acid to two volumes of water4 ,there action1 however1 goes so vigorously that it is always necessary to have a trap for collecting the benzyl cyanide which is blown out of the apparatus4 ,the use of the more dilute acid1 as described in the above directions1 is more satisfactory4 ,the phenylacetic acid may also be made by boiling under a reflux condenser for eight to fifteen hours1 without a stirrer1 but this method is not nearly so satisfactory as that described in the procedure4 ,when only small quantities of the acid are required1 the following modified procedure is of value4 ,one hundred grams of benzyl cyanide are added to a mixture containing #ajj cc4 of water1 #ajj cc4 of concentrated sulfuric acid1 and #ajj cc4 of glacial acetic acid4 ,after this has been heated for forty-five minutes under a reflux condenser1 the hydrolysis is practically complete4 ,the reaction mixture is then poured into water1 and the phenylacetic acid isolated in the usual manner4 ,the odor of phenylacetic acid is disagreeable and persistent4 #c4 ,other ,methods of ,preparation ,the standard method of preparation of phenylacetic acid is by the hydrolysis of benzyl cyanide with either alkali#a;a or acid4#b;a ,the acid hydrolysis runs by far the more smoothly and so was the only one studied4 ,there are numerous other ways in which phenylacetic acid has been formed1 but none of them is of practical importance for its preparation4 ,these methods include the following3 the action of water on phenyl ketene2#c;a the hydrolysis and subsequent oxidation of the product between benzaldehyde and hippuric acid2#a the reduction of mandelic acid2#b the reduction of benzoylformic acid with hydriodic acid and phosphorus2#c the hydrolysis of benzyl glyoxalidone2#d the fusion of atropic acid with potassium hydroxide2#e the action of alcoholic potash upon chlorophenylacetylene2#f the action of benzoyl peroxide upon phenylacetylene2#g the alkaline hydrolysis of triphenylphloroglucinol2#h the action of ammonium sulfide upon acetophenone2#i the heating of phenylmalonic acid2#aj the hydrolysis of phenylacetoacetic ester2#aa the action of hydriodic acid upon mandelonitrile4#ab #a;a ,ann4 #if1 #bdg 7#ahee72 ,ber4 #ad1 #afde 7#ahha72 ,compt4 rend4 #aea1 #bcf 7#aiaj74 #b;a ,ber4 #ai1 #aiej 7#ahhf74 #c;a ,ber4 #dd1 #ecg 7#aiaa74 #a ,ann4 #cgj1 #cga 7#aiji7;a #b ,chem4 7#b7 #a1 #ddc 7#ahfe72 ,ber4 #ad1 #bci 7#ahha74 #c ,ber4 #aj1 #hdg 7#ahgg7 #d ,j4 prakt4 ,chem4 7#b7 #hb1 #eb1 #eh 7#aiaj74 #e ,ann4 #adh1 #bdb 7#ahfh74 #f ,ann4 #cjh1 #cah 7#ahii74 #g ,j4 ,russ4 ,phys4 ,chem4 ,soc4 #db1 #achg 7#aiaj72 ,chem4 ,zentr4 #aiaa 7,i7 #abgi4 #h ,ann4 #cgh1 #bfc 7#aiaa74 #i ,ber4 #ba1 #ecd 7#ahhh72 ,j4 prakt4 ,chem4 7#b7 #ha1 #chd 7#aiaj74 #aj ,ber4 #bg1 7#ahid74 #aa ,ber4 #ca1 #cafc 7#ahih7 #ab ,inaugural ,dissertation of ,a4 ,kohler 7#aiji71 ,univ4 of ,bern4 ,,xviii ,,phenylacetylene ,c#f;,h#e;,,ch,c,h,br ,,koh-- ,c#f;,h#e;,,ctbch ,k,br ,h#b,o ,prepared by ,,john ,c4 ,,hessler4 ,checked by ,j4 ,b4 ,,conant and ,e4 ,r4 ,,barrett4 #a4 ,procedure ,,in a #ejj-;cc4 ,pyrex distilling flask are placed #aej g4 of potassium hydroxide4 ,the mouth of the flask is provided with a one-hole stopper holding a dropping funnel2 the side tube of the flask is connected with a condenser set for downward distillation4 ,the b-bromostyrene 7#ajj g47 is placed in the dropping funnel4 ,the distilling flask is gradually heated in an oil bath until the temperature of the bath is #bjj'j1 and the bromostyrene is then dropped in upon the molten potassium hydroxide1 at the rate of somewhat less than a drop a second4 ,since the boiling point of phenylacetylene is #adb-adc'j1 and that of bromostyrene is #bah-bbj'j1 the phenylacetylene distils away from the unchanged bromostyrene4 ,while the bromostyrene is being dropped in1 the temperature of the oil bath is raised very gradually to #bae-bbj'j1 and is kept at this temperature until all the bromostyrene has been added4 ,finally the temperature is raised to #bcj'j1 and is held there until no more distillate comes over4 ,the distillate is colorless2 it consists of two layers1 the lower one being water4 ,the upper layer is separated and dried with solid potassium hydroxide4 ,it is then distilled4 ,the yield of the distilled phenylacetylene1 boiling at #adb-add'j1 is #cg g4 7#fg per cent of the theoretical amount74 #b4 ,notes ,toward the end of the reaction1 a crust of potassium bromide may tend to cover the melted potassium hydroxide4 ,one can break the crust by shaking the distilling flask gently1 or by using a glass rod inserted through a second hole in the stopper holding the dropping funnel4 ,it is convenient to have such a rod or stirrer passing through a mercury seal in the stopper of the flask4 ,an occasional turn of this stirrer breaks the crust and facilitates the operation4 ,mechanical stirring should not be employed1 as it reduces the yield tremendously4 ,apparently this is because it facilitates the solution of bromostyrene in the tarry by-products and thus causes it to polymerize instead of reacting with the potassium hydroxide4 ,a single ,pyrex flask can be used for only three or four runs4 ,the flask should be emptied while still very hot4 ,the yield of material can be somewhat increased by working with small lots 7#be g4 of bromostyrene74 ,the use of steel or copper vessels in place of a glass flask seems to diminish the yield slightly4 #c4 ,other ,methods of ,preparation ,phenylacetylene has been prepared by the elimination of carbon dioxide from phenylpropiolic acid by means of phenol#a or aniline#b or by heating with barium hydroxide2#c from styrene dibromide1 by heating with potassium hydroxide in alcohol2#d by heating b-bromo or chloro styrene with sodium ethylate or potassium hydroxide in alcohol2#e by passing the vapors of a-dichloroethylbenzene over hot soda lime2#f by the action of alcoholic potassium hydroxide on dibenzal-acetone tetra-bromide2#a;b by the action of aqueous potassium hydroxide on phenyl propargylaldehyde2#b;b by the action of molten potassium hydroxide on b-bromo-styrene4#c;b #a ,ber4 #bj1 #cjha 7#ahhg74 #b ,rec4 trav4 chim4 #af1 #aeg 7#ahif74 #c ,arm4 #bba1 #gj 7#ahhc74 #d ,ann4 #aed1 #aee 7#ahgj72 #bce1 #ac 7#ahhf72 ,bull4 soc4 chim4 #ce1 #ee 7#ahha72 7#c7 #be1 #cji 7#aija74 #e ,ann4 #cjh1 #bfe 7#ahii72 #cdb1 #bbj 7#aije74 #f ,jahresb4 #ahgf1 #cjh2 ,gazz4 chim4 ital4 #bb 7#b71 #fg 7#ahib72 ,bull4 soc4 chim4 7#c7 #be1 #cji 7#aija74 #a;b ,ber4 #ci1 #dadf 7#aijj74 #b;b ,ber4 #ca1 #ajbc 7#ahih74 #c;b ,j4 ,am4 ,chem4 ,soc4 #dd1 #dbe 7#aibb74 ,,xix ,,phenylhydrazine ,c#f;,h#e,,nh#b4;,h,cl ,na,n,o#b ,h,cl-- ,c#f;,h#e,n#b;,cl ,na,cl #b;,h#b,o ,c#f;,h#e,n#b;,cl #d;,h7,na#b,,so#c7-- ,c#f;,h#e,,nhnh#b4;,h,cl ,prepared by ,g4 ,h4 ,,coleman4 ,checked by ,j4 ,b4 ,,conant and ,h4 ,r4 ,,thompson4 #a4 ,procedure ,,in a #ab-l4 round-bottom flask1 fitted with a mechanical stirrer1 are placed #ajde cc4 of concentrated commercial hydrochloric acid 7sp4 gr4 #a4ach74 ,the flask is surrounded with a freezing mixture of ice and salt1 and when the contents are at #j'j1 stirring is started and #ejj g4 of cracked ice are added2 then #cgb g4 of aniline1 also cooled to #j'j1 are run in during five minutes4 ,the mixture is treated with #ejj g4 more of cracked ice1 and a cold solution 7#j'j7 of #bij g4 of technical sodium nitrite dissolved in #fjj cc4 of water are allowed to run in slowly 7twenty to thirty minutes7 from a dropping funnel1 the end of which is drawn to a small tip1 and reaches nearly to the bottom of the flask4 ,during this addition1 the stirrer is operated rather vigorously1 and the temperature is kept as near #j'j as possible by the frequent addition of cracked ice 7about #a kg74 ,in the meantime1 a sodium sulfite solution is prepared by dissolving #hij g4 of sodium hydroxide1 of about #ij per cent purity1 in about #a l4 of water and then diluting to #f l4 ,a few drops of phenolphthalein solution are added and sulfur dioxide passed in1 first until an acid reaction is indicated and then for two or three minutes longer4 ,during the addition of the sulfur dioxide1 the solution is cooled with running water4 ,on account of the strong alkaline solution1 the original color produced by the phenolphthalein is very faint1 but this slowly increases until it becomes deep just before the acid point is reached4 ,it is best to remove a small sample of the liquid from time to time1 dilute with three or four volumes of water and add a drop more of phenolphthalein4 ,the sodium sulfite solution is placed in a #ab-l4 flask and cooled to about #e'j4 ,approximately #ejj g4 of cracked ice are added1 and then1 with mechanical stirring1 the diazonium salt solution is run in as rapidly as possible4 ,the mixture becomes a bright orange-red4 ,the flask is now warmed to about #bj'j on a steam bath1 until the solid sodium sulfite1 which has separated while cooling1 redissolves4 ,the total amount of liquid is now about #aj l4 ,one-half of this is poured into another #ab-l4 flask1 and both halves are warmed on the steam bath to #fj-gj'j1 until the color becomes quite dark 7thirty to sixty minutes74 ,sufficient hydrochloric acid 7#cjj-djj cc47 is now added to each flask to make the solutions acid to litmus4 ,the heating is continued and the color gradually becomes lighter until1 after four to six hours1 the solutions have become nearly colorless2 they may be heated overnight1 if desired4 ,to the hot solutions are now added about one-third of their volume of concentrated hydrochloric acid 7#b l4 to each portion7 and the mixtures cooled1 first in running water1 then in a freezing mixture1 to #j'j4 ,the phenylhydrazine hydrochloride precipitates in the form of slightly yellowish or pinkish crystals which may be filtered off and dried4 ,the free base is liberated by adding to the phenylhydrazine hydrochloride #a l4 of a #be per cent solution of sodium hydroxide4 ,the phenylhydrazine separates and is taken up with benzene 7two #cjj-;cc4 portions74 ,the combined extractions are well dried with #bjj g4 of solid sodium hydroxide1 poured off1 and distilled4 ,most of the benzene may be distilled under ordinary pressure1 and the remainder1 and any low-boiling impurities1 under diminished pressure4 ,the pure phenylhydrazine boils at #acg-ach'j_/ah mm41 and is obtained as a pale-yellow liquid4 ,it can be crystallized on cooling in an ice bath2 the crystals melt at #bcj4 ,the crude phenylhydrazine from two lots of aniline 7#gdd g47 is best distilled at one time and gives #fie-gbe g4 of pure product 7#hj-hd per cent of the theoretical amount74 #b4 ,notes ,if the sodium sulfite solution contains an excess of alkali1 a black tar tends to form when the solution is warmed1 and very little phenylhydrazine is obtained4 ,great care must be taken in determining the end point in the neutralization of the sodium hydroxide by the sulfur dioxide4 ,if the sodium sulfite-diazonium salt mixture is acidified before warming or before becoming dark1 the red color of the solution does not disappear on heating1 and the precipitated phenylhydrazine hydrochloride obtained is colored red4 ,the benzene solution of phenylhydrazine should be well dried before distilling1 since the presence of moisture causes an increased amount of foaming to take place just after the benzene has distilled off4 ,when the distillation is carried out carefully1 practically no phenylhydrazine distils with the benzene or other low-boiling impurities4 ,in order to obtain the maximum yield1 it is necessary to cool the hydrochloric acid solution of the phenylhydrazine hydrochloride from #bj'j to #j'j1 before filtration4 ,from #e to #aj per cent of product separates between these two temperatures4 ,when this is done1 no more phenylhydrazine hydrochloride is obtained by concentration of the mother liquor4 ,an increase in the amount of hydrochloric acid above #b l4 for the precipitation of the hydrochloride produces no increase in yield of product4 ,most published directions for the preparation of phenylhydrazine specify the use of zinc dust and acetic acid following the reduction with sodium sulfite4 ,no improvement in the quality or quantity of the product was obtained by using zinc and acetic acid4 ,it is best to use freshly prepared sodium sulfite for the reduction1 since the commercial quality is poor and gives a lower yield of phenylhydrazine4 ,a cylinder of liquid sulfur dioxide should1 of course1 be available4 ,the rapid addition of the diazonium salt solution to the sodium sulfite seems to be advantageous4 ,pure phenylhydrazine dissolves in dilute acetic acid to yield a perfectly clear solution4 ,the phenylhydrazine hydrochloride may be purified by crystallizing from water4 ,a #fjj-;cc4 portion of water is used for #ajj g4 of crude hydrochloride1 and the solution boiled a short time with a few grams of animal charcoal4 ,after filtering1 #bjj cc4 of concentrated hydrochloric acid are added1 and the mixture cooled to #j'j4 ,pure white crystals in a yield of #he-ij g4 are obtained4 ,rubber gloves should be worn when working with large quantities of phenylhydrazine1 since the product may cause serious injury to the skin4 ,the vapors of phenylhydrazine should not be inhaled4 #c4 ,other ,methods of ,preparation ,phenylhydrazine has been prepared by the reduction of benzene diazonium salts with sulfites2#a by the reduction of benzene diazonium chloride with stannous chloride2#b by the reduction of benzene diazonium hydrate with zinc or sulfur dioxide2#c by the reduction of sodium benzene diazotate with sodium stannite2#d by the reduction of diazoamino benzene2#e by the reduction of nitrosophenyl hydroxylamine or its methyl ether2#f and by the action of hydrazine hydrate on phenol4#g #a ,ann4 #aij1 #gi 7#chgh72 ,ber4 #bj1 #bdfc1 7#ahhg74 #b ,ber4 #af1 #bigf 7#ahhc72 #ag1 #egb1 footnote 7#ahhd74 #c ,ber4 #ca1 #cdf 7#ahih74 #d ,ber4 #cf1 #haf 7#aijc74 #e ,ber4 #ca1 #ehb 7#ahih74 #f ,ann4 #aij1 #gg 7#ahgh74 #g ,ber4 #ca1 #biaj 7#ahih74 ,the most feasible method consists in the reduction of diazonium salts with sodium sulfite4 ,although this method is given in several laboratory manuals1 the results were not found entirely satisfactory4 ,the present directions provide for a lengthy but essential heating of the diazonium-sulfite mixture1 omit the useless zinc dust reduction1 and supply exact details for preparation on a fairly large laboratory scale4 ,,xx ,,phthalimide ,,co ,,co ,c#f;,h#d ,o ,,nh#d,,oh-- ,c#f;,h#d ,,nh #b;,h#b,o ,,co ,,co ,,co ,,co #b;,c#fs,hs#d ,o 7,,nh#d7b;,,co#c-- #b;,c#f;,h#d ,,nh ,,co#b #c;,h#b,o ,,co ,,co ,prepared by ,w4 ,a4 ,,noyes and ,p4 ,k4 ,,porter4 ,checked by ,h4 ,t4 ,,clarke and ,j4 ,h4 ,,bishop4 #a4 ,procedure ,,in a #e-l4 round-bottom flask 7,pyrex7 is placed a mixture of #ejj g4 of phthalic anhydride and #djj g4 of #bh per cent ammonium hydroxide4 ,the flask is fitted with an air condenser not less than #aj mm4 in diameter and is then slowly heated with a free flame until the mixture is in a state of quiet fusion at a temperature of about #cjj'j4 ,it requires about one hour before all the water has gone and about one and a half to two hours before the temperature of the reaction mixture reaches #cjj'j and the mixture is a homogeneous melt4 ,it is advisable1 during the heating1 to shake the flask occasionally2 some material sublimes into the condenser and must be pushed down with a glass rod4 ,the hot reaction mixture is now poured out into a crock1 covered with a paper to prevent loss by sublimation1 and allowed to cool4 ,the product is practically pure without further treatment1 and melts at #bcb-bce'j4 ,the yield is #dgj-dhj g4 7#id-ie per cent of the theoretical amount74 ,phthalimide may also be made by using #ejj g4 of phthalic anhydride and #ejj g4 of ammonium carbonate which has been previously ground in a mortar4 ,the subsequent procedure is the same as when aqueous ammonia is used4 ,frequent shaking is necessary1 and the sublimed material must be occasionally pushed back into the reaction flask4 ,about two hours are required for completion4 #b4 ,notes ,several smaller runs of #be g4 of phthalic anhydride gave the same percentage yield4 ,phthalimide may be recrystallized from water1 but only about #d g4 of phthalimide will dissolve in a liter of boiling water4 ,it may also be crystallized from alcohol1 in which solvent it dissolves to the extent of five parts in a hundred at boiling temperature4 ,on a large scale1 it would be advisable to collect the small amount of ammonia given off during the reaction4 ,if desired1 the product obtained by pouring the reaction mass into the crock may be treated with hot water to soften the cake1 broken up with a glass rod1 transferred to a flask and boiled with water for a few minutes4 ,this treatment1 however1 is quite unnecessary2 for all practical purposes1 the crude cake1 as it is obtained1 may be ground up and used directly4 #c4 ,other ,methods of ,preparation ,phthalimide has been formed by heating ammonium phthalate2#a by heating acid ammonium phthalate2#b by passing dry ammonia over heated phthalic anhydride2#c by treating phthalyl chloride with dry ammonia2#d by heating phthalamide2#e by heating phthalic anhydride with ammonium thiocyanate2#f by heating phthalic anhydride with urea2#g by heating phthalic anhydride with ammonium carbonate2#a;b by heating phthalic acid with nitriles2#b;b by fusing o-cyanobenzoic acid2#c;b and by the action of potash on o-cyanobenzaldehyde4#d;b #a ,jahresb4 #ahfh1 #edi2 ,ann4 #ai1 #dg 7#ahcf72 #da1 #aaj 7#ahdb72 #db1 #bbj 7#ahdb72 #bje1 #cjj 7#ahhj72 #bae1 #aha 7#ahhb74 #b ,jahresb4 #ahdg-ahdh1 #eij4 #c ,am4 ,chem4 ,j4 #c1 #bi 7#ahha74 #d ,am4 ,chem4 ,j4 #c1 #bh 7#ahha74 #e ,ber4 #ci1 #bbgh 7#aijf74 #f ,ber4 #ai1 #acih 7#ahhf71 #g ,ber4 #aj1 #aaff 7#ahgg72 ,am4 ,chem4 ,j4 #ah1 #ccc 7#ahif72 ,j4 ,am4 ,chem4 ,soc4 #cb1 #aaf 7#aiaj72 ,z4 angew4 ,chem4 #cb1 ,i1 #cja 7#aiai74 #a;b ,j4 ,am4 ,chem4 ,soc4 #db1 #abhb 7#aibj74 #b;b ,j ,am4 ,chem4 ,soc4 #ah1 #fhj 7#ahif72 #bj1 #fed 7#ahih74 #c;b ,rec4 trav4 chim4 7,i7 #aa1 #ic 7#ahib74 #d;b ,ber4 #cj1 #afih 7#ahig74 ,of these1 the first three are the only ones which need be considered as methods for the preparation of phthalimide4 ,it was found that the third was by no means easy to bring about3 dry phthalic anhydride is apparently only superficially affected by the dry ammonia1 and it was difficult to introduce sufficient heat into the loose mass of crystals to cause the reaction to start4 ,,xxi ,,quinoline _/ _/ ,c#c;,h#e7,,oh7#c ,c#f;,h#e,,nh#b #d,o7,c#f;,h#e,,no#b7-- #d;,h#b,o _/ n_/ ,prepared by ,h4 ,t4 ,,clarke and ,,anne ,w4 ,,davis4 ,checked by ,,roger ,,adams and ,a4 ,w4 ,,sloan4 #a4 ,procedure ,,in a #e-l4 round-bottom flask1 fitted with an efficient reflux condenser of wide bore1 are placed1 in the following order1 #hj g4 of powdered crystalline ferrous sulfate1 #hfe g4 of glycerol 7c4 p471 #bah g4 of aniline1 #agj g4 of nitrobenzene1 and #djj cc4 of concentrated sulfuric acid 7sp4 gr4 #a4hd74 ,the contents of the flask are well mixed and the mixture heated gently over a free flame4 ,as soon as the liquid begins to boil1 the flame is removed1 since the heat evolved by the reaction is sufficient to keep the mixture boiling for one-half to one hour4 ,if the reaction proceeds too violently at the beginning1 the reflux condenser may be assisted by placing a wet towel over the upper part of the flask4 ,when the boiling has ceased the heat is again applied and the mixture boiled for five hours4 ,it is then allowed to cool to about #ajj'j and transferred to a #ab-l4 flask2 the #e-l4 flask is rinsed out with a small quantity-of water4 ,the #ab-l4 flask is then connected with the steam-distillation apparatus shown in ,fig4 #c1 a #ab-l4 flask being used as a receiver2 steam is passed in 7without external heat7 until #aejj cc4 have distilled 7ten to thirty minutes74 ,this removes all the unchanged nitrobenzene 7#aj-bj cc474 ,the current of steam is then interrupted1 the receiver is changed1 and #aejj g4 of #dj per cent sodium hydroxide solution are added cautiously through the steam inlet4 ,the heat of neutralization is sufficient to cause the liquids to boil and thus become thoroughly mixed4 ,steam is then passed in as rapidly as possible until all the quinoline has distilled4 ,in this process1 #f-h l4 of distillate are collected 7two and a half to three and a half hours are required1 unless a very efficient condensing apparatus is used1 under which conditions the distillation may be complete in one-half to one and a half hours74 ,the distillate is allowed to cool1 and the crude quinoline separated4 ,the aqueous layer of the distillate is again distilled with steam until all the quinoline has been volatilized and collected in about #c l4 of distillate4 ,these #c l4 of distillate are then mixed with the first yield of quinoline and #bhj g4 7#aej cc47 of concentrated sulfuric acid are added4 ,the solution is cooled to #j-e'j1 and a saturated solution of sodium nitrite added until a distinct excess of nitrous acid is present 7as shown either by starch-potassium iodide paper or by the odor74 ,this generally requires #ej to #gj g4 of sodium nitrite4 ,the mixture is then warmed on a steam bath for an hour1 or until active evolution of gas ceases1 and is then distilled with steam until all the volatile material has been expelled 7#da4 of distillate will result7 ,the receiver is then changed and the mixture in the distillation flask is neutralized1 as before1 with #gjj g4 of #dj per cent sodium hydroxide solution4 ,the quinoline is distilled exactly as described above1 the aqueous portions of the distillate being distilled with steam until all the quinoline has been isolated4 ,the crude product is then distilled under reduced pressure1 and the fraction which boils at #aaj-aad'j_/ad mm4 is collected4 ,the foreruns are separated from any water which may be present1 dried with a little solid alkali1 and redistilled4 ,the total yield is #bee-bge g4 7#hd-ia per cent of the theoretical amount based on the aniline taken74 #b4 ,notes ,although these directions have been used many times with results exactly as described1 in a few cases the yields have dropped to #fj-fe per cent without any apparent reason4 ,at present no explanation can be given for this4 ,in the ,skraup synthesis of quinoline the principal difficulty has always been the violence with which the reaction generally takes place2 it occasionally proceeds relatively smoothly1 but in the majority of cases gets beyond control1 with consequent loss of material through the condenser4 ,by the addition of ferrous sulfate1 which undoubtedly functions as an oxygen carrier1 the reaction is extended over a longer period of time4 ,it is thus possible to work with much larger quantities of material when ferrous sulfate is employed4 ,it is important that the materials should be added in the correct order2 should the sulfuric acid be added before the ferrous sulfate1 the reaction may start at once4 ,it is also important to mix the materials well before applying heat2 the aniline sulfate should have dissolved almost completely and the ferrous sulfate should be distributed throughout the solution4 ,to avoid danger of overheating1 it is well to apply the flame away from the center of the flask where any solids would be liable to congregate4 ,in the apparatus for steam distillation1 the greater portion of the condensation is effected by the stream of water passing over the receiver4 ,it is1 therefore1 necessary that the stream passing through the condenser should be sufficiently rapid to cause it to form a uniform film over the receiving flask4 ,a #ab-l4 flask is even more efficient as a condenser than the #e-l4 flask4 ,it is important that the tube through which the vapors leave the distillation flask should be neither too short nor1 especially1 too narrow4 ,where the external diameter of the steam inlet tube is #e-h mm41 the internal diameter of this steam head should be not less than #bh mm4 ,were it less1 the current of steam passing through it would be so rapid as to prevent small quantities of liquid from returning to the flask1 and these would be driven over into the receiver4 ,much time can be saved by the use of the steam distillation apparatus described1 especially when large quantities have to be handled4 ,the above directions avoid the use of extraction methods1 which not only consume more time but may lead to appreciable losses of material4 ,if the downward condenser is of iron1 the apparatus is even more efficient and the time for the steam distillation is halved4 ,the percentage yields have been based on the amount of aniline taken4 ,it would probably be more legitimate to base the calculation on the amounts of aniline taken and of nitrobenzene not recovered1 since undoubtedly the latter is reduced to aniline during the course of the reaction4 ,if this be done1 the yield is found to be only #ee to #fj per cent of the calculated amount4 ,in a number of experiments1 the glycerol used contained an appreciable amount of water4 ,under these conditions1 the yield of product is much lower4 ,dynamite glycerol containing less than half a per cent of water is best employed2 ,u4 ,s4 ,p4 glycerol contains #e per cent of water and usually gives lower yields4 #c4 ,other ,methods of ,preparation ,quinoline has been produced by passing the vapor of allylaniline over red-hot lead oxide2#a;a by heating acrylideneaniline1 or better1 a mixture of aniline1 glycerol and sulfuric acid2#b;a by heating aniline with glycerol and sulfuric acid1 using nitrobenzene as an oxidizing agent2#a by treating a mixture of glyoxal and o-toluidine with alkali2#b by treating a solution of o-aminobenzaldehyde with acetaldehyde and alkali2#c by heating methylacetanilide with zinc chloride2#d by heating aminoazobenzene with glycerol and sulfuric acid2#e by heating a mixture of aniline1 glycerol and sulfuric acid with arsenic acid4#f #a;a ,ber4 #ab1 #dec 7#ahgi74 #b;a ,ber4 #ac1 #iaa 7#ahhj72 ,monatsh4 #a1 #caf 7#ahhj74 #a ,monatsh4 #b1 #ada 7#ahha72 ,j4 prakt4 ,chem4 7#b7 #di1 #edi 7#ahid71 #b ,monatsh4 #ae1 #bgg 7#ahid74 #c ,ber4 #ae1 #begd 7#ahhb72 #af1 #ahcc 7#ahhc74 #d ,ber4 #bc1 #aijc 7#ahij74 #e ,ber4 #bd1 #bfbc 7#ahia7 #f ,ber4 #bi1 #gjd 7#ahif7 ,of the above methods1 the only ones which need be considered are those in which a mixture of aniline1 glycerol and sulfuric acid is heated with an oxidizing agent4 ,with the use of nitrobenzene1 the reaction1 according to the original method1 takes place with extreme violence4 ,the method above described is the most satisfactory for the preparation of quinoline itself1 but for the preparation of homologues of quinoline1 the use of arsenic acid is preferable1 since the yields are somewhat greater4 ,since the work was carried out1 a method has been published#g in which aniline1 glycerol and sulfuric acid are treated with ferric oxide4 ,by this method ,adams and ,parks were unable to obtain yields comparable with those resulting from the above directions4 #g ,chem4 ,news #aba1 #bje 7#aibj74 ,,xxii ,,quinone 7#a7;,,hoc#f;,h#d,,oh7#d7 ,o7,na#b;,cr#b,o#g ,h#b,,so#d7-- ,o,c#f;,h#d,o ,h#b,o ,prepared by ,e4 ,b4 ,,vliet4 ,checked by ,,roger ,,adams and ,e4 ,e4 ,,dreger4 #a4 ,procedure ,,in a #b4e-l4 beaker1 #ajj g4 of hydroquinone are dissolved in #bjjj cc4 of water heated to about #ej'j4 ,after the solid is completely dissolved1 the solution is cooled to #bj'j1 #ajj g4 of concentrated sulfuric acid are slowly poured in1 and the mixture is again cooled to #bj'j4 ,a concentrated solution of technical sodium dichromate is prepared by dissolving #adj g4 in #fe cc4 of water4 ,this solution is then added gradually to the hydroquinone solution1 with the use of a mechanical stirrer 7see notes71 the mixture being cooled so that the temperature never rises above #cj'j4 ,at first a greenish-black precipitate forms1 but upon further addition of the sodium dichromate solution1 the color changes to yellowish green4 ,as soon as this color remains permanent 7a slight excess of sodium dichromate does no harm7 the reaction is complete4 ,this requires about one-half to three-quarters of an hour2 #ij to #aaj cc4 of sodium dichromate solution is necessary4 ,the mixture is then cooled to about #aj'j and filtered with suction4 ,as much water as possible is pressed out of the crystals4 ,the filtrate is extracted twice1 #aej cc4 of benzene being used for each extraction4 ,the precipitate of quinone is transferred to a #a-l4 beaker1 and #ejj cc4 of benzene1 including the #cjj cc4 used to extract the filtrate1 are added1 ,the mixture is now heated with stirring on a steam-bath1 and as soon as most of the quinone has dissolved the benzene layer is decanted into another beaker4 ,it is dried while hot by stirring a short time with a little calcium chloride1 and then filtered through an ordinary funnel into a #a-l4 distilling flask before it cools4 ,there is a certain amount of quinone which does not go into the #ejj cc4 of benzene1 so that the residue is extracted a second time with about #ajj cc4 of benzene1 which is dried and filtered with the first extract4 ,during these extractions1 the benzene should not be at the boiling point1 as this will cause a considerable volatilization of the quinone4 ,the distilling flask is now attached to a condenser set for downward distillation1 and the benzene is distilled4 ,as soon as the quinone starts to separate1 the residue in the flask is transferred to a beaker and cooled in an ice bath4 ,the precipitate is filtered off with suction and the product spread out for a short time to dry4 ,the product is yellow in color and weighs #ge to #hj g4 7#gf-ha per cent of the theoretical amount74 ,material made in this way will hold its yellow color over long periods of time1 provided it is protected from light4 ,the benzene distillate is yellow and contains some quinone4 ,this1 as well as the benzene from the final filtration of the quinone crystals1 may be used in a subsequent run and thus raises the yield of the subsequent runs to about #he-ij g4 7#he-ij per cent of the theoretical amount74 #b4 ,notes ,as the mixture becomes thick during the oxidation1 it is very necessary to use a stirrer which will keep the whole mass agitated by reaching to the sides and bottom of the beaker4 ,if impure hydroquinone is used1 a black1 sticky precipitate will usually appear after the addition of the sulfuric acid to the hydroquinone solution4 ,this should be removed1 before the oxidation is started1 by filtration without suction through a fluted filter4 ,when technical sodium dichromate is used1 the solution should be filtered with suction1 before it is added to the hydroquinone1 in order to remove any insoluble impurities4 ,in the laboratory it is convenient to make several small runs of the size indicated1 as far as the oxidation is concerned2 but the benzene extractions can be combined4 ,it is also possible to obtain good yields of quinone in the following manner3 #aejj cc4 of water1 #dfe g4 of concentrated sulfuric acid and #cjj g4 of hydroquinone are mixed in a #c-l4 beaker4 ,the mixture is cooled to #j'j1 and #ccj g4 of sodium dichromate are added in powdered form1 the temperature being kept below #e'j at all times4 ,this procedure requires a longer time and much more care in the control of conditions than the method described above4 #c4 ,other ,methods of ,preparation ,quinone may be prepared by the oxidation of aniline with dichromate or manganese dioxide and sulfuric acid4#a ,this is a more feasible commercial method than the one given4 ,however1 the oxidation of hydroquinone is more rapid and convenient and1 hence is more desirable for use in the laboratory4 ,various materials have been oxidized by chemical means to give quinone3 they are quinic-acid1#b hydroquinone1#c benzidine1#d p-phenylenediamine1#e sulfanilic acid1#f p-phenolsulfonic acid1#g arbutin1#h aniline black1#i and the leaves of various plants4#aj ,quinone is also formed by several other methods3 by the fermentation of fresh grass2#aa by the action of iodine on the lead salt of hydroquinone2#a;b by the decomposition of the compound1 ,c#f;,h#d4b;,cr,o#b;,cl with water2#b;b by the action of sulfuric acid on phenol blue2#c;b by the electrochemical oxidation of aniline1#d;b hydroquinone#e;b or benzene2#f;b by the catalytic oxidation of benzene4#g;b #a ,jahresb4 #ahfc1 #dae2 ,ber4 #aj1 #aicd1 #bjje 7#ahgg72 #af1 #fhg 7#ahhc72 #ai1 #adfh 7#ahhf72 #bj1 #bbhc 7#ahhg72 #ca1 #aebd 7#ahih72 ,ann4 #bjj1 #bdj 7#ahhj72 #bae1 #abg 7#ahhb74 #b ,ann4 #bg1 #bfh 7#ahch74 #c ,ann4 #ea1 #aeb 7#ahdd7 j ,am4 ,chem4 ,j4 #ad1 #eee 7#ahib74 #d ,jahresb4 #ahfc1 #dae4 #e ,jahresb4 #ahfc1 #dbb4 #f ,ann4 #aei1 #g 7#ahga72 ,ber4 #h1 #gfj 7#ahge74 #g ,ber4 #h1 #gfj 7#ahge74 #h ,ann4 #ajg1 #bcc 7#aheh74 #i ,ber4 #aj1 #aicd 7#ahgg72 #cd1 #abhe 7#aija74 #aj ,ann4 #hi1 #bdg 7#ahed72 ,ber4 #cd1 #aafb 7#aija74 #aa ,ber4 #cj1 #ahgj 7#ahig74 #a;b ,ber4 #ca1 #adeh 7#ahih72 ,am4 ,chem4 ,j4 #bf1 #bj 7#aija74 #b;b ,ann4 chim4 phys4 7#e7 #bb1 #bgj 7#ahha74 #c;b ,ber4 #ah1 #biae 7#ahhe72 #ba1 #hhi 7#ahhh74 #d;b ,d4 ,r4 ,p4 #aji1jab2 ,frdl4 #e1 #ffd 7#aijj72 ,d4 ,r4 ,p4 #aag1abi2 ,frdl4 #f1 #aab 7#aija72 ,j4 ,soc4 ,dyers and ,colourists1 #cf1 #ach 7#aibj74 #e;b ,d4 ,r ,p4 #aag1abi2 ,frdl4 #f1 #aab 7#aija74 #f;b ,d4 ,r4 ,p4 #aag1bea2 ,frdl4 #f1 #aji 7#aija72 ,u4 ,s4 ,pat4 #a1cbb1ehj 7#aiai72 ,c4 ,a4 #ad1 #bhg 7#aibj72 ,rev4 produits chim4 #ba1 #bai 7#aiah72 #ba1 #bhh 7#aiah74 #g;b ,u4 ,s4 ,pat4 #a1cah1fca 7#aiai72 ,c4 ,a4 #ad1 #gj 7#aibj74 ,,xxiii ,,sodium p-,,toluenesulfinate #b;,,ch#c;,c#f;,h#d,,so#b;,cl #c,zn-- 7,,ch#c;,c#f;,h#d,,so#b7b,zn ,zn,cl#b 7,,ch#c;,c#f;,h#d,,so#b7b,zn ,na#b;,,co#c-- #b;,,ch#c;,c#f;,h#d,,so#b,na ,zn,c,o#c ,prepared by ,,frank ,c4 ,,whitmore and ,,francis ,h4 ,,hamilton ,checked by ,j4 ,b4 ,,conant and ,,paul ,,allen1 ,,jr4 #a4 ,procedure ,,five ,,hundred grams of technical p-toluenesulfonyl chloride are ground in a mortar to break up all lumps4 ,three liters of water are placed in a #ab-l4 crock provided with a large brass stirrer and a tube for passing steam directly into the liquid4 ,dry steam is passed into the water until the temperature reaches #gj'j4 ,the steam is then shut off and #djj g4 of zinc dust 7#ij to #ajj per cent pure7 is added4 ,the sulfonyl chloride is then added in small portions by means of a porcelain spoon4 ,the addition takes about ten minutes4 ,the temperature rises to about #hj'j4 ,stirring is continued for ten minutes after the last of the chloride has been added4 ,steam is then passed into the mixture until the temperature reaches #ij'j4 ,if it is heated any hotter1 bumping takes place4 ,the steam is shut off1 and #bej cc4 of #ab ,n4 sodium hydroxide solution is added4 ,finely powdered sodium carbonate is then added in #ej-;g4 portions until the mixture is strongly alkaline4 ,the mixture froths considerably1 but this causes no trouble unless too small a crock is used4 ,the stirrer is loosened and the crock is removed4 ,the mixture is filtered by suction in a large funnel4 ,the filtrate has a volume of about #d4e l4 ,the cake of unchanged zinc dust and zinc compounds is transferred to a #c-l4 battery jar and placed under the stirrer1 and the latter is clamped in place4 ,water 7#gej cc47 is added1 the stirrer is started1 and steam is passed in until the mixture starts to froth too violently4 ,the steam is then shut off1 but the stirring is continued for ten minutes4 ,the mixture is filtered and the filtrate is added to the main solution in a large evaporating dish4 ,the liquid is evaporated over a large burner to a volume of about #a l41 or until a considerable crust forms around the edges4 ,the mixture is then cooled4 ,large1 flat1 transparent crystals separate4 ,the thoroughly cooled mixture is filtered by suction1 and the crystals are air-dried until efflorescence just starts4 ,they are then bottled4 ,the product is ,,ch#c;,c#f;,h#d,,so#b,na4#b;,h#b,o4 ,yield #cfj g4 7#fd per cent of the theoretical amount74 ,careful acidification of the mother liquor with dilute hydrochloric acid yields #ae g4 of the free sulfinic acid4 #b4 ,notes ,the free sulfinic acid may be prepared by dissolving the sodium salt in cold water and carefully acidifying the solution with hydrochloric acid4 ,an excess of the latter must be avoided1 as it dissolves the acid to a certain extent4 ,the sulfinic acid is difficult to dry without partial conversion into the sulfonic acid4 #c4 ,other ,methods of ,preparation ,toluenesulfinic acid and its salts have been prepared by three general methods3 7#a7 ,the reduction of the sulfonyl chloride4 ,the reagents which have been used for this are sodium amalgam1#a zinc dust in alcohol or water1#b sodium sulfite1#c sodium sulfide1#d potassium hydrosulfide#e 7the thio acid being first formed7 and sodium arsenite4#f 7#b7 ,from toluene by the ,friedel and ,crafts reaction1 using either sulfur dioxide and hydrogen chloride#g or sulfuryl chloride4#h 7#c7 ,from p-toluidine by diazotization and subsequent treatment with sulfur dioxide and finely divided copper4#a;b ,the compound has also been obtained in certain reactions which1 however1 would not be suitable for preparative work2 thus it is formed by hydrolysis and reduction of certain thio derivatives#b;b prepared from the acid itself and also by the decomposition of ditolylsulfonmethylamine4#c;b #a ,ann4 #adb1 #ic 7#ahfg74 #b ,ber4 #i1 #aehf 7#ahgf74 #c ,ber4 #c1 #ife 7#ahgj74 #d ,d4 ,r4 ,p4 #bbd1jai2 ,chem4 ,zentr4 #aiaj1 7,,ii71 #eac4 #e ,ber4 #db1 #chba 7#aiji74 #f ,ber4 #da1 #ccea 7#aijh72 ,ber4 #db1 #dhj 7#aiji74 #g ,ber4 #da1 #ccah 7#aijh72 ,j4 ,chem4 ,soc4 #ic1 #ged 7#aijh74 #h ,rec4 trav4 chim4 7#b7 #cj1 #cha 7#aiaa74 #a;b ,ber4 #cb1 #aada 7#ahii72 ,j4 ,chem4 ,soc4 #ie1 #cdd 7#aiji74 #b;b ,ber4 #ae1 #acj 7#ahhb72 #bj1 #bjhh 7#ahhg72 #da1 #ccea 7#aijh74 #c;b ,j4 prakt4 ,chem4 7#b7 #fc1 #agj 7#aija74 ,,xxiv #a1c1e-,,trinitrobenzene ,c#f;,h#b7,,no#b7c;,,co#b;,h-- ,c#f;,h#c7,,no#b7c ,,co#b ,prepared by ,h4 ,t4 ,,clarke and ,w4 ,w4 ,,hartman4 ,checked by ,j4 ,b4 ,,conant and ,j4 ,j4 ,,toohy4 #a4 ,procedure ,,the crude trinitrobenzoic acid obtained by oxidation of #cfj g4 of trinitrotoluene 7prep4 ,,xxv1 p4 #ie7 is mixed with #b l4 of water at #ce'j in a #e-l4 flask provided with a stirrer4 ,fifteen per cent sodium hydroxide solution is added1 with continuous stirring1 until a ,,faint red color is just produced4 7,see ,notes47 ,the color is then immediately discharged by means of one or two drops of acetic acid1 and the liquid is filtered from unchanged trinibrotoluene4 ,the filtrate is transferred to a #e-l4 flask1 and #gj cc4 of glacial acetic acid are added4 ,the mixture is then gently heated1 with continuous stirring1 when trinitrobenzene separates in crystalline condition1 and floats on the surface of the liquid as a frothy layer4 ,after about one and a half hours the evolution of gas ceases2 at this point the crystals begin to stir into the solution4 ,the heating and stirring is continued for three-quarters of an hour1 when the mixture is allowed to cool1 and the crystals filtered off4 ,a sample of the filtrate should be tested for undecomposed trinitrobenzoic acid3 if a precipitate is produced by the addition of sulfuric acid the process must be continued4 ,after recrystallization from glacial acetic acid1 the product melts at #aba-abb'j4 ,the yield is #ade-aee g4 7#dc to #df per cent of the theoretical amount calculated from the trinitrotoluene74 #b4 ,notes ,during the solution of the trinitrobenzoic acid1 the temperature should not be below #ce'j1 owing to the slight solubility of trinitrobenzoic acid in cold water4 ,the heat of neutralization raises the temperature to #de-ee'j1 but the latter temperature should not be exceeded1 since any trinitrobenzene formed at this point would later be removed with the unreacted trinitrotoluene4 ,care must be taken that no more alkali is added than is just sufficient to produce the faint red color4 ,if an excess of alkali is added it produces a permanent color1 which is not removed by acid and colors the final product4 ,when once the evolution of carbon dioxide sets in1 the flame must be cut down so as to avoid the formation of a thick layer of froth which might foam over4 #c4 ,other ,methods of ,preparation #a1c1e-,trinitrobenzene can be prepared by heating m-dinitrobenzene with nitric acid and sulfuric acid to #abj'j2a by heating #b1d1f-trinitrotoluene with fuming nitric acid in a sealed tube at #ahj'j for three hours2#b by heating #b1d1f-trinitrobenzoic acid or its sodium salt with water1 alcohol1 dilute sodium carbonate or other suitable solvent4#c #a ,ber4 #i1 #djb 7#ahgf72 ,ann4 #bae1 #cdd 7#ahhb74 #b ,ber4 #af1 #aeif 7#ahhc74 #c ,d4 ,r4 ,p4 #gg1cec2 ,frdl4 #d1 #cd 7#ahid74 ,,xxv #b1 #d1 #f-,,trinitrobenzoic ,,acid ,c#f;,h#b7,,no#b7c;,,ch#c #c,o7,na#b;,cr#b,o#g ,h#b,,so#d7-- ,c#f;,h#b7,,no#b7c;,,co#b;,h ,h#b,o ,prepared by ,h4 ,t4 ,,clarke and ,w4 ,w4 ,,hartman4 ,checked by ,j4 ,b4 ,,conant and ,j4 ,j4 ,,toohy4 #a4 ,procedure ,to #cfjj g4 of concentrated sulfuric acid1 in a #e-l4 flask placed in an empty water bath1 are added #cfj g4 of technical trinitrotoluene1 while the mixture is stirred mechanically4 ,sodium dichromate 7,na#b;,cr#b,o#g #b;,h#b,o7 is now added in small quantities 7,,precaution3 see ,notes71 with constant stirring1 until the temperature of the mixture reaches #dj'j2 the empty water bath is now filled with cold water and the addition of sodium dichromate continued at such a rate that the temperature remains at #de-ee'j4 ,in all #edj g4 of sodium dichromate are added1 the addition taking one to two hours4 ,when all has been added1 the mixture1 which has now become very thick1 is stirred for two hours at #de-ee'j1 and poured into a crock containing #d kg4 of crushed ice4 ,the insoluble trinitrobenzoic acid is filtered off1 and carefully washed with cold water until free from chromium salts4 ,on drying it weighs #cbj-cdj g4 ,the product is now mixed with #b l4 of distilled water at #ce'j in a #e-l4 flask provided with a stirrer1 and #ae per cent sodium hydroxide solution is dropped in with continuous stirring until a ,,faint red color is just produced4 ,should this disappear1 it is restored by the addition of a few drops more4 ,when it has persisted for five minutes1 the color is discharged by the addition of a few drops of acetic acid1 and the insoluble unattacked trinitrotoluene filtered off and washed with a little water4 ,the trinitrobenzoic acid is precipitated from the filtrate by the addition of a slight excess of #ej per cent sulfuric acid4 ,the solution is chilled1 and the acid filtered and washed free from salts with ice water4 ,when dried in air it weighs #bcj-bhj g4 7#eg to #fi per cent of the theoretical amount74 #b4 ,notes ,the mother liquors and washings lose carbon dioxide on boiling1 and the insoluble trinitrobenzene separates see preparation ,,xxiv72 after filtering1 washing1 and drying1 it weighs #ae-bj g4 7#d to #f per cent of the theoretical amount74 ,it is essential that the stirring should be most efficient1 so that when the mixture becomes thick the dichromate will be evenly distributed throughout the liquid1 as rapidly as it is added4 ,if the stirring is not efficient1 local reactions of extreme violence 7in certain cases leading to conflagration7 will occur4 ,an iron stirrer may be employed in the oxidation reaction1 but not in the purification4 ,technical sodium dichromate generally contains a certain amount of chlorides1 and the chlorine liberated from these tends to cause a troublesome foam towards the end1 of the reaction4 ,only a very efficient stirrer1 which draws down the surface of the liquid1 is able to combat this difficulty4 ,the amount of solid sodium dichromate given is for the dry crystalline compound containing two molecules of water of crystallization4 ,great care should be taken in dissolving the crude acid in the alkali4 ,if an excess of alkali persists for any length of time1 a permanent color is produced which will discolor the final product4 ,the acid is fairly soluble in cold water and should be washed with care4 #c4 ,other ,methods of ,preparation #b1d1f-,trinitrobenzoic acid has been prepared by heating trinitrotoluene with fuming acid in a sealed tube to #ajj'j1 for two weeks1#a;a the oxidation being only partial4 ,it can also be prepared by heating trinitrotoluene under a reflux condenser1 with a mixture of #e parts of concentrated nitric acid and #aj parts of concentrated sulfuric acid2#a this method is1 however1 unsuitable in the laboratory owing to the difficulty of devising suitable apparatus4 ,another method is to dissolve trinitrotoluene in nitric acid and1 to this solution 7at #ie'j71 to add potassium chlorate at such a rate that the temperature does not fall2#b this method has been found to be difficult to control on a laboratory scale4 #a;a ,ber4 #c1 #bbc 7#ahgj7 #a ,d4 ,r4 ,p4 #gg1eei2 ,frdl4 #d1 #cd 7#ahid7 #b ,d4 ,r4 ,p4 #bbf1bbe2 ,frdl4 #aj1 #afg 7#aiaj74 ,the method described above is a modification of a patented process1#c in which trinitrotoluene suspended in sulfuric acid is treated with chromic anhydride4 #c ,d4 ,r4 ,p4 #abg1cbe2 ,frdl4 #f1 #adh 7#aija74 ,,index ,a ,acetic acid1 #ah1 #cc1 #fd ,acetone1 #da ,acetophenone1 #a ,ammonium carbonate1 #ge ,ammonium hydroxide1 #cg1 #ge ,aniline1 #ga1 #gi ,anthranilic acid1 #dg ,b ,benzalacetophenone1 #a ,benzaldehyde1 #a1 #e ,benzoic acid1 #e ,benzyl alcohol1 #e ,benzyl benzoate1 #f ,benzyl chloride #i ,benzyl cyanide1 #i-aa1 #bg1 #eg1 #fc ,bromostyrene1 #fg ,c ,carbon tetrachloride1 #bc ,chlorine1 #cg ,copper sulfate1 #ch ,d ,dibenzyl ether1 #f a1 g-,dichloroacetone1 #ac-ae ,dimethylaminobenzaldehyde1 #ag-ba ,dimethylaniline1 #ag1 #dg ,e ,ethyl alcohol1 #bc1 #bg ,ethyl oxalate1 #bc-bf ,ethyl phenylacetate1 #bg-bh ,f ,ferrous sulfate1 #gi ,formaldehyde1 #ag ,g ,gelatine solution1 #cg ,glycerol1 #bi1 #cc1 #gi ,glycerol a1 g-dichlorohydrin1 #bi-ca ,glycerol a-monochlorohydrin1 #cc-ce ,h ,hydrazine sulfate1 #cg #dj ,hydrochloric acid1 #ag1 #cj1 #cd1 #dg1 #ga ,hydroquinone1 #he ,m ,mesitylene1 #da-de ,methyl red1 #dg-fa ,n ,naphthol1 #fa ,nitric acid1 #eg ,nitrobenzene1 #gi p-,nitrobenzoic acid1 #fc-ff p-,nitrobenzyl cyanide1 #fg-eh1 #ei p-,nitrophenylacetic acid1 #fidj ,nitrosodimethylaniline hydrochloride1 #ag ,nitroso-1#c-naphthol1 #fa-fb ,nitrotoluene1 #ec ,o ,oxalic acid1 #bc ,p ,phenylacetic acid1 #aj1 #fc-fe ,phenylacetylene1 #fg-fi ,phenylhydrazine1 #ga-gd ,phthalic anhydride1 #ge ,phthalimide1 #ggh ,potassium hydroxide1 #fg ,q ,quinoline1 #gi #hc ,quinone1 #hf #hh ,s ,sodium acetate1 #dh ,sodium benzylate1 #f ,sodium cyanide1 #i ,sodium dichromate1 #ac1 #ec1 #he1 #ie ,sodium hydroxide1 #a1 #cg1 #fa1 #ic ,sodium hypochlorite1 #cg ,sodium1 metallic1 #e1 #db ,sodium nitrite1 #ag1 #dg1 #fa1 #ga1 #hj ,sodium sulfite1 #ga ,sodium p-toluene sulfinate1--#ia ,sulfur dioxide1 #ga ,sulfuric acid1 #ac1 #bg1 #cj4 #cd1 #cg1 #da1 #dc1 #ec1 #eg1 #ei1 #fc1 #gi1 #he1 #ie ,t ,toluene1 #dh ,toluenesulfonyl chloride1 #hi ,i1 #c1 s-,trinitrobenzene1 #ic-- #id1 #if #b1 #d1 #f-,trinitrobenzoic acid1 #ic1 #if #ig #b1 #d1 #f-,trinitrotoluene1 #ic1 #ie ,zinc dust1 #hi