,transcriber's ,note3 ,every effort has been made to replicate this text as faithfully as possible4 ,some changes have been made4 ,they are listed at the end of the text4 ,synthesis of #b-methyl-#d-selenoquinazolone1 #b-phenylbenzoselenazole1 and ,its ,derivatives4 ,,dissertation ,,submitted ,,in ,,partial ,,fulfillment ,,of ,,the ,,requirements ,,for ,,the ,,degree ,,of ,,doctor ,,of ,,philosophy ,,in ,,the ,,faculty ,,of ,,pure ,,science ,,of ,,columbia ,,university ,,by ,y-,,gwan ,,chen1 ,m4 ,a4 ,,new ,,york ,,city #aibb ,,acknowledgment ,,and ,,dedication ,the following research was undertaken at the suggestion of ,professor ,marston ,taylor ,bogert to whose interest and advice this work owes whatever merit it may possess4 ,y4 ,g4 ,,chen4 ,,contents ,acknowledgment and ,dedication #b ,abstract of the ,dissertation #d ,purpose of the ,research #e ,introduction #g ,pharmacological ,review #h ,tinctorial ,review #ad ,experimental3 #af #b-methyl-#d-selenoquinazolone ,four ,methods of ,preparation ,analysis of ,selenium ,organic ,compounds #b-phenylbenzoselenazole ,mononitro ,derivative ,monoamino ,derivative ,monoacetyl ,derivative ,monobenzylidene ,derivative ,an ,azo ,dye ,dinitro ,derivative ,diamino ,derivative ,diacetyl and ,dibenzylidene ,derivatives ,dyeing with ,azo ,dyes ,bibliography #be ,vita #bh ,,abstract ,,of ,,the ,,dissertation #a4 ,what was attempted8 ,attempt was made to study organic selenium compounds of the heterocyclic series in reference to those properties leading to tinctorial and pharmaceutical possibilities4 #b4 ,what were the methods of attack8 7a7 ,organic selenium compounds were reviewed and their properties examined critically with those of allied compounds4 7b7 ,some new heterocyclic compounds of selenium were studied and their characteristic properties more closely examined along the desired line4 #c4 ,in how far were the attempts successful8 ,the literature was reviewed and classified with reference to the properties under consideration1 and new selenium organic compounds were prepared and studied which it is hoped may throw some additional light upon the problem4 #d4 ,what contribution actually new to the science of chemistry has been made8 7a7 ,compounds newly made have been shown to exhibit a distinct tinctorial value in comparison with their analogues4 7b7 ,they have been shown to be chemically easier to handle than the corresponding sulphur compounds4 7c7 ,selenium1 in the nucleus of cyclic compounds1 has been shown to be instrumental for a positive coloration at least equal to the --,,nh-- or --,s-- groupings4 ,the selenocarbonyl1 3,c3,se1 has been shown to be a more powerful chromophore than thiocarbonyl1 3,c3,s1 or carbonyl itself1 3,c3,o4 7d7 ,two series of azo dyes of selenium have been prepared and have been shown to possess a marked tinctorial value4 7e7 ,the following new compounds have been prepared3 #b-methyl-#d-selenoquinazolone #b-phenylbenzoselenazole,a #f-nitro-#b-phenylbenzoselenazole #f-;amino-#b-phenylbenzoselenazole #f-;acetylamino-#b-phenylbenzoselenazole #f-;benzylideneamino-#b-phenylbenzoselen azole 7,b-naphthyl7-#f-;azo-7#b-phenylbenzosel enazole7 ,dinitro-#b-phenylbenzoselenazole ,diamino-#b-phenylbenzoselenazole ,diacetyldiamino-#b-phenylbenzoselenazol e ,dibenzylidenediamino-#b-phenylbenzosele nazole ,,purpose ,,of ,,the ,,research ,since ,berzelius published the first resume of the chemistry of selenium1 in #ahah7a71 many articles have appeared in this field4 ,several reviews7#b7 of its compounds1 including references1 have been published1 besides the resumes in the chemical dictionaries4 ,these reviews are confined mainly to the inorganic side4 ,no attempt has ever been made to compile a bibliography of selenium organic compounds4 ,from time to time1 articles have appeared1 but the field is still a promising one1 with many alluring possibilities4 ,in the perusal of the organic records of the metal1 distributed over the span of a century1 there are indications of the value of selenium compounds for pharmaceutical and tinctorial uses4 ,an effort has been made to collect these scattered data for critical examination with other analogues and sulphur compounds in particular1 and to prepare and study some new organic compounds containing selenium1 for the purpose of gaining additional light upon the chemistry of such substances1 and in the hope of discovering some which may be of practical service in medicine or elsewhere4 ,synthesis of #b-methyl-#d-selenoquinalozone1 #b-phenylbenzoselenazole and ,its ,derivatives ,,introduction ,the general conception of selenium is that it is a comparatively rare element4 ,few realize that it has been known for over a century and that over twenty selenium minerals1 containing from one to sixty-six per cent4 of the metal1 are considered by the mining corporations as important4 ,beside being a by-product of sulphuric acid manufacture1 it is separated also in the electrolytic refining of copper4 ,the demand for the metal is so small that there are half a dozen concerns in the ,united ,states either willing to supply gratis any reasonable quantity for research work1 or to sell it at cost4 ,in a special report of the ,national ,research ,council on selenium7#c71 it is estimated that there could be produced annually1 without making any material additions to the present plants1 not less than #cjj1jjj pounds4 ,in fact selenium has1 in recent years1 gradually been brought more and more to the attention of the general public through its application to military uses and other purposes4 ,in the glass industry1 for example1 it was used as decolorizer during the ,war period4 ,it has been found that it imparts a violet red tint to the pyrex tubing after the latter has been used for a few combustions4 ,the coloration is especially noticeable when a broken piece is examined4 ,this may find an important place in the ceramic industry4 ,in turning off the gas light of the city at day break1 in controlling the draft of the factory chimneys1 and in regulating the rapidity of the manufacture of sulphuric acid1 the selenium cell is an important labor saving factor4 ,in a similar way it is used in automatically lighting and extinguishing light buoys4 ,it also finds application in photometry1 wireless telephony1 military telegraphy1 and army signaling as well as for the transmission of signatures1 handwritings1 finger prints1 and images in general7#c77d74 ,the question of the vulcanization of rubber also should be considered4 ,some experiments have been published claiming the similarity of the action of selenium and sulphur on rubber7#d77e74 ,the cost need not be prohibitive1 since the supply could be easily increased and the price reduced provided there were a demand4 ,in the personal experience of the writer1 when working with the hydrogen selenide gas1 the rubber connections of the apparatus soon turned red1 and after a few hours were so clear a red that visitors to the laboratory imagined that the writer was using the ordinary red rubber connections4 ,the rubber thus changed seems to be softer and more elastic than the original2 this observation will be followed up4 ,in this country the ,national ,research ,council has created a special committee of seven to investigate the various possible uses of selenium and tellurium4 ,,pharmacological ,,review ,duhamel and ,rebiere7#f77g7 showed that an injection of a trace of red colloidal selenium into rabbits increased urea excretion regularly4 ,in other cases satisfactory results were claimed and the liver showed some lesions4 ,the histological modifications produced by injections into rabbits are most apparent in the liver and kidneys4 ,in the distribution of colloidal preparations in the animal body by injection1 ,duhamel and ,juillard7#h7 found that the liver contained the greatest amount4 ,six years later the former7#i7 used a similar preparation introduced into the animal intravenously1 and selenium was again found in the liver1 although in smaller quantity4 ,sulphur compounds have similar physiological action4 ,it is known that triphenylstibine sulphide1 or sulphoform1 7,c,h7,sb,s1 has a curative effect in skin diseases1 as it liberates 8nascent0 sulphur on the skin4 ,it is equally natural to expect some organic selenium compound which liberates finely divided selenium to exert a remedial influence on animal bodies4 ,the selenoquinazolone prepared in the course of this research and described more fully in another section of the paper1 has this prospect4 ,the quinazolone has the following structure3 ,n _/ _/ ,c-,,ch ,,nh _/ _/ ,c ,se ,experiments were carried on at ,l',institut ,pasteur in ,paris under the supervision of ,m4 ,borel for the treatment of cancer in mice4 ,no human subjects were experimented upon1 although results were claimed by using selenides and their oxidized salts4 ,selenium dyes were found to be medicinals1 although no relation has yet been established between constitution of these organic dyes and their therapeutic value4 ,wassermann7#aj7 made several eosin preparations1 by coupling the sodium derivative with potassium selenocyanide4 ,the red dyestuff thus prepared is stated to be easily soluble in water4 ,wassermann1 ,keysser and ,wassermann7#aa7 made experiments with it1 chemotherapeutically1 on animal tumors4 ,when the solution was injected into mice tumors the latter turned red1 accompanied by the softening of the tumor after the third injection and complete resorption after ten injections1 unless the dose used was too great for the animal4 ,in that case death often occurred4 ,good results were also reported1 in connection with this experiment1 on four different strains of mouse carcinoma and one strain of mouse sarcoma4 ,in the latter case1 relief was found sooner but the former disappeared more slowly4 ,another preparation was made later7#ab7 and introduced into mice intravenously and again found to have good results4 ,the following is the structure of #b-selenocyanideanthraquinone-- ,o ,c ,se,c,n _/ _/ _/ _/ _/ _/ _/ ,c ,o which has also been reported to have medicinal uses7#ac74 ,p4 ,ehrlich and ,hugo ,bauer7#ad7 synthesized from p4p-diamino-diphenyl- methane the red dye #c1f-;diaminoselenopyronine4 ,,ch _/ _/ _/ ,h,n ,,nh _/ _/_/ _/ ,se ,the dye has been used upon mice and caused pronounced edema4 ,the toxicity of both the selenopyronine and the corresponding sulphur compound was compared under similar conditions in the same experiment1 and it was found that the selenium dye was toxic in #a_/cjjj gram1 but the sulphur dye was toxic in #a_/bejj gram per twenty gram weight of the animal4 ,this physiological activity was noted years ago with the inorganic compounds of selenium and ,berzelius7#ae7 described the poisonous effect of hydrogen selenide quite impressively2 8,in order to get acquainted with the smell of this gas ,i allowed a bubble not larger than a pea to pass into my nostril2 in consequence of its smell ,i so completely lost my sense of smell for several hours that ,i could not distinguish the odor of strong ammonia even when held under my nose4 ,my sense of smell returned after five or six hours1 but severe irritation of the mucous membrane set in and persisted for a fortnight40 ,the writer has been working on the gas for some time and was also quite seriously affected once1 the injury persisting for many days4 ,that it is more poisonous than the hydrogen sulphide is well known4 ,bruere7#af7 showed that when hydrogen sulphide was passed into blood solution sulphemoglobin was produced in considerable quantity1 due to the chemical action of sulphur and hematin4 ,he stated further that sulphemoglobin may be found in animal blood when a large amount of the gas has been inhaled4 ,he made selenhemoglobin in the same manner4 ,sixteen years later1 ,clarke and ,hurtley also proved that selenhemoglobin may be made by passing hydrogen selenide into blood7#ag74 ,these experiments may be interpreted to mean that the oxy-hemoglobin is transformed into an organic complex of sulphur or selenium1 and that the transference may be more rapid and powerful in the case of hydrogen selenide4 ,biological investigations have sufficiently proved that dyestuffs of the phenazine1 oxazine1 thiazine1 acridine series show an injurious effect on protozoa1 especially those dyes containing substituted amino groupings and of a simple structure7#ah74 ,in the case of the thiazine dyes of the methylene blue class1 the physiological importance has well recognized in their use as feeble antiseptics and analgesics4 ,ehrlich and ,guttmann7#ai7 initiated the use of methylene blue as an antiperiodic and its use in that line has been continued4 ,in the field of the selenazine dyes1 pharmacologists have not yet paid much attention to them1 on account of the newness of the discovery1 but ,p4 ,karrer claims that they are indisputably 8vital dyestuffs07#bj74 ,the prospect of synthesizing selenazine dyes and their use as drugs seems to be bright1 judging from the fact that they are easily prepared and capable of many combinations1 especially of the ease with which they form organic complexes with arsenic compounds4 ,,no ,,nh ,,no ,,nh ,,no 7,i7 _/ _/ _/ _/ _/ _/ _/ _/ ,,nh ,cl ,se,h ,,nc ,,no ,se,h ,,no ,,no _/ _/ _/ _/ _/ _/ _/ _/ ,o,n ,se ,formula 7,i7 is known1 as #a1 #c-;dinitrobenzoselenazine7#ba71 which was obtained by the action of picryl chloride on the zinc salt of o-aminoselenophenol2 the product 7picrylaminoselenophenol7 being then treated with alkali and thus converted to the dye1 which upon experimentation showed marked effects upon protozoa and bacteria4 ,n _/ _/ _/ ,n ,,nh _/ _/_/ _/ 7,,ii7 _/ _/ _/ _/ ,se _/ _/ _/ ,cl _/ ,se ,,ho,as ,,nh _/ _/ ,,ho,as ,formula 7,,ii71 known as #c-7p-phenylarsonic7-aminoselenazine1 is red in dilute alkali and green in mineral acid1 and is a typical dye in a series from the coupling of selenodiphenylamine with arsenic compounds4 ,all possess similar toxicity as the thiazine dyes7#bj74 ,other selenazines are listed in the bibliography7#bb74 ,no less than half dozen thioureas are commonly used as drugs4 ,thiourea itself paralyzes the nerve centers1 and is employed commercially for photograph fixing and for removing stains from negatives2 thiuret1 ,c,h,n,s1 serves as a substitute for iodoform2 thiosinamine-ethyliodide1 or tiodine1 ,,ih,c,h,,ncsnhc,h1 is used for relief of lesions of the central nervous system2 allylthiourea or thiosinamine1 7,,nh7,,sc4,,nhch,,ch3,,ch1 for aiding the absorption of connective tissues1 for treatment of burns1 keloids1 urethral diseases1 sclerotic conditions of the ear7#bc74 ,selenocarbamide and a number of its derivatives have been prepared and studied4 ,one class of seleno ureas has been patented as pharmaceutical products by ,chem4 ,fabrik von ,heyden7#bd71 and are prepared by the action of hydrogen selenide on alkylcyanamides1 ,,rnh4,,chn ,h,se ,,rnh4,c,se4,,nh ,they possess pronounced therapeutic value and1 serve as intermediate products in the production of more stable alkyl halide additive compounds4 ,other carbamides ranging from seleno urea itself7#be71 7,,iii7 and a cyclic urea7#bf7 7,,iv7 are described in the literature3 ,,nh ,,ch-,se _/ ,se3,c 7,,iii7 ,c3,,nh 7,,iv7 _/ ,,nh ,,ch-,,nh ,the latter1 known as ethylene-selenourea1 may be classified also in the azole group as #b-;iminotetrahydroselenazole 7,v74 ,h,c----,,nh 7,v7 ,h,c ,c3,,nh _/ ,se ,the literature for the other normal carbamides is listed in the bibliography7#bg74 ,selenoantipyrines1 selenosaccharine1 selenoindigoes have also been prepared4 ,thiophene and its derivatives are of considerable therapeutic interest4 ,thiophene itself is found to be useful in lessening the elimination of sulphuric acid in urine1 and is employed in the dermatological practice4 ,sodium thiophene sulphonate1 thiophenetetra-bromide1 thiophene diiodide1 are all medicinals7#bc74 ,a number of selenophenes are recorded in the literature4 ,their relation to the selenazoles may be easily seen from the following formulas3 ,,ch--,,ch ,,ch--,n ,,ch ,,ch ,,ch ,,ch _/ _/ ,se ,se ,selenophene ,selenazole ,dimethyl selenophene was prepared from acetonyl acetone and phosphorous pentaselenide1 ,,ch ,,ch _/ _/ ,,hc,c ,,hc,c ,,oh ,p,se ,se ,,oh _/ _/ ,,hc,c ,,hc,c ,,ch ,,ch ,the compound thus obtained is stated to have the same odor as thiophene1 but no mention is made in regard to its uses7#bh74 ,selenophene was prepared from sodium succinate and phosphorous triselenide1 or by conducting ethylselenide through hot tubes7#bi74 ,some selenazoles find application also in medicine4 ,at present only the isoazoles are known to have physiological uses4 ,one of them was prepared from anthraquinone selenocyanide1 by the action of ammonia under pressure7#cj74 ,,nh,h ,n-,se ,o ,c ,se,c,n ,c _/ _/ _/ _/ _/ _/ ,,hcn ,h,o _/ _/ _/ _/ _/ _/ ,c ,c ,o ,o ,another type of azoles1 benzoselendiazole 7piaselenol7 and five of its derivatives1 have been also described as medicinals7#ca74 ,the diazole itself has the following structure1 ,n ,n _/_/ _/ _/_/ _/ ,se or ,se _/ _/ _/ _/ ,n ,n ,diazoles of the following structure are also known1 but no data were found1 regarding their physiological action7#cb73 ,n-,n ,n-,n _/ _/_/ ,,ch,c ,,cch ,c,h,c ,,cc,h _/ _/ ,se ,se ,dimethyl-seleno-diazole ,diphenyl-seleno-diazole ,sulphides and disulphides have curative power4 ,dimethylsulphide is used for internal treatment1 di-o-aminophenyldisulphide is used for intramuscular injections4 ,diallyl sulphide is also a medicament4 ,methyl selenide has some effect on the internal parts of the body7#cc74 ,hanzlik and ,tarr7#cd7 at the ,american ,university ,experimental ,station1 showed that a number of selenium compounds act as skin irritants3 e4g41 dichlorodiethyl selenide1 dichlorovinyl selenide1 trichlorodiethyl selenide and selenium mustard oil4 ,the first mentioned proved as potent as the sulphide1 but the others fell somewhat below in their effects4 ,diantipyryl selenide is another therapeutical agent7#ce74 ,the diselenides occupy an important place of their own4 ,the selenophenols do not remain unchanged in the air1 but are always oxidized to the diselenides1 which can be again reduced to the selenophenols4 ,so far only the diselenides of anthraquinone and their phenols are recognized remedies7#cf74 ,,tinctorial ,,review ,many of the seleno organic compounds are colored1 while the corresponding sulphur derivatives are colorless4 ,,hc-,,ch ,,hc-,,ch ,,hc ,,ch ,,hc ,,ch _/ _/ ,o ,s ,furane1 colorless ,thiophene1 colorless liquid liquid ,,hc--,,ch ,,hc--,,ch ,,hc ,,ch ,,hc ,,ch _/ _/ ,,nh ,se ,pyrrol1 colorless liq4 ,selenophene1 yellow liq4 but turns brownish in air after repeated extraction,b ,this brings selenophene more akin to pyrrole than thiophene1 but the group -,,nh- in the molecule of pyrrole is an auxochrome4 ,the selenium atom in a cyclic compound also acts like an auxochrome4 ,selenoantipyrine7#cg71 ,c,h ,n _/ ,,ch,n ,c,se ,,ch,c,,ch forms pure yellow crystals from alcohol1 while the corresponding compounds of oxygen and sulphur are colorless4 ,similarly1 the #b-methyl-#d-selenoquinazolone is deep brown in color1 while the thio compound1 prepared by ,bogert and ,hand7#ch7 is light brown or yellow and the corresponding oxygen compound is colorless or nearly so4 ,diethyl selenide 7,c,h7,se1 is a yellowish heavy oil of unpleasant odor4 ,it combines readily with chlorine to form a chloride 7,c,h7,se,cl1 and the latter is oxidized by nitric acid to form an oxide 7,c,h7,se,o17#ci74 ,diethyl sulphide is a colorless syrupy liquid1 as well as diethyl amine and diethyl ether4 ,the gradation of color is quite pronounced in the case of selenonaphthene quinone7#dj74 ,,co ,,co ,,co ,,co _/ _/ _/ _/ _/ _/ _/ _/ ,,co ,,co ,,co ,,co _/ _/ _/ _/ _/ _/ _/ _/ ,o ,s ,,nh ,se ,it would be most natural to conclude that the chromophore 3,,cs is more powerful than 3,,co1 and that 3,c,se is most powerful of all1 as shown in our study of quinazoline compounds4 ,it would equally follow that 3,s is a more powerful color-forming radical in a cyclic compound than that of 3,o2 and 3,,nh than that of 3,s2 and 3,se again most powerful of the whole series4 ,lesser and ,weiss7#da7 in their research on selenoindigo stated that the selenium dyestuff1 on account of its greater molecular weight than sulphur1 shows a deeper blue4 ,this hypothesis meets a difficulty in the case of coumorandione1 thionaphthenequinone and isatin series1 where the -,,nh- radical has an atomic weight of #ae1 and -,s- #cb1 and showed the reversed order of color4 ,this seems to be the case in the selenophene series also4 ,therefore this theory is not without exceptions4 ,the diselenides present a very interesting study also4 ,methyl disulphide is colorless1 but methyldiselenide7#db7 is a reddish yellow liquid4 ,methyl disulphide only becomes yellow when it is treated with chlorine1 and in such cases 7,,ch7,s,cl is formed7#dc71 in yellow rhombic crystals4 ,ethyldisulphide is colorless3 ethyl- disulphidedichloride is a faint yellow oil7#dd74 ,but the corresponding ethyldiselenide is a red liquid7#de74 ,phenyl disulphide is colorless1 and phenyldisulphide dibromide is of mother-of-pearl appearance1 and practically colorless7#df71 while phenyl diselenide forms pure yellow needles7#dg71 and phenyldiselenide dibromide orange red ones4 ,while phenyldisulphide is colorless1 when an auxochrome group is added1 such as ,,nh1 the compound is colored4 ,this is the case with o-diaminodiphenyldisulphide7#dh7 which is yellow both in solution and in crystalline form4 ,in other words1 an auxochrome in addition to the chromophore group transforms a colorless chromogen into a colored one4 ,therefore groups like -,s4,s- and -,se4,se- are chromophores in the same sense as -,n3,n-4 ,this is in agreement with the chromophore ideas of ,hugo ,kaufmann4 ,the -,se4,se- is a more powerful chromophore than -,s4,s-4 ,this brings one directly to the inquiry as to why #b-phenylbenzo- selenazole1 which contains a 3,se radical1 should be colorless2 and that even #f-nitro-#b-phenylselenazole1 with the addition of a chromophore ,,no1 should be only faintly colored4 ,the benzothiazoles1 their isomers and derivatives are mostly colorless1 and similar causes are probably responsible in the case of the phenylbenzoselenazole1 for its lack of color4 ,but when this selenazole is combined with another chromophore1 for example an azomethine grouping1 the result is a more positively colored compound 7in this case benzalaminoselenazole71 the crystals being yellow4 ,the corresponding thiazole derivative is light colored4 ,the tinctorial value of the selenium derivative is further evidenced by the ease with which it forms azo dyes and the deep colors of the latter4 ,this was observed when #f-;amino-#b-phenylbenzoselenazole was diazotized and coupled with ,b-naphthol1 salicylic acid1 etc4 ,the corresponding aminothiazole has been considered difficult to diazotize1 on account of its insolubility in hydrochloric acid1 cold or hot1 but the aminoselenazole dissolves readily and completely1 the coupling is almost instantaneous1 and the dyes obtained are mostly red and of metallic lustre4 ,in view of the stability of benzoselenazoles toward hot concentrated acids 7with the exception of nitric1 when nitration ensues7 and alkalis1 these dyes may prove of some commercial interest4 ,the azole dyes of the benzoselenazole have been exposed to light for weeks1 and also exposed to acids and alkalis1 and have been found to be quite fast4 ,,experimental ,preparation of #b-methyl-#d-selenoquinazolone ,busch prepared quinazolines by the action of o-amino or o-nitro benzylamine with phosgene1 and thioquinazolines with carbon disulphide7#ea73 ,,ch,,nh ,,ch-,,nh _/ _/ ,c,h ,c,o,cl ,c,h #b;,h,cl ,,nh ,,nh--,,co ,,ch,,nhc,h ,,ch-,,nc,h _/ _/ ,c,h ,,cs ,c,h ,h,s ,,nh ,,nh--,,cs ,accordingly the same reaction was tried with o-nitrobenzylamine1 prepared by the method of ,lellmann and ,stickel7#ej71 using carbon diselenide7#ea74 ,the reaction seemed to work1 but the mixture formed was difficult to extract and it appeared that other reactions took place at the same time1 due to the impurity of the carbon diselenide1 as the latter has never been prepared in the pure state4 ,another method1 which is equally attractive because of its simplicity1 is that of ,gabriel and ,stelzner7#eb71 ,,cho ,,ch,n _/ ,,nh _/ ,h,o ,c,h ,c,h ,h,n-,,co ,,nh ,,nh ,,nh-,,co ,in accordance with the above reaction o-aminobenzaldehyde should work with equal ease with selenocarbamide1 but the initial materials were not available4 ,the reaction which was used successfully was that of ,bogert1 ,breneman and ,hand7#ec71 ,,nh ,,nhcor ,n,,cr _/ _/ _/ ,c,h 7,,rco7,o ,c,h ,c,h ,,csnh ,,cs-,,nh ,,cs-,,nh or ,h,s ,h,s ,n,,cr _/ ,c,h ,,nh ,,nhcor ,c,n _/ _/ ,c,h 7,,rco7,o ,c,h ,,sh ,,cn ,,cn ,the hydrogen selenide used in the reaction was prepared from ,fe,se by the action of hydrochloric acid1 or by heating paraffin and selenium1 in the proportion of four to one respectively1 at #cce to #cej;,c7#ed74 ,the selenoquinazoline was prepared from anthranilic nitrile by the following methods--the anthranilic nitrile being prepared from o-nitraniline7#eg71 7a7 #bj grams of acetyl-anthranilic nitrile was dissolved in absolute alcohol1 and dry hydrogen selenide and dry ammonia passed into the solution for three hours4 ,the quinazoline crystallized out gradually on cooling was filtered out and recrystallized from dilute alcohol4 ,the yield was about ten per cent4 7b7 #aj grams of acetyl-anthranilic nitrile was heated in a sealed tube at #aaj with alcohol saturated at zero degrees with dry hydrogen selenide and dry ammonia4 ,after five hours1 the tube was taken out and the quinazoline crystallized out on cooling4 ,yield was about sixteen per cent4 ,as hydrogen selenide was somewhat unstable and did not dissolve freely in alcohol1 freshly prepared sodium selenide was used in the following method and was found to be more satisfactory4 ,it was prepared from sodium hydroxide in absolute alcohol by passing dry hydrogen selenide into the solution for about three hours4 ,in the beginning and end of the reaction1 nitrogen was used to exclude the oxygen of the air4 ,the selenide was collected and dried in an atmosphere of nitrogen1 and then in a vacuum1 in presence of phosphorus pentoxide4 ,when thus prepared1 sodium selenide was colorless1 but on exposure to air it turns reddish and finally dark colored4 ,the ,c4 ,p4 selenide on the market was black and was found to be entirely useless4 7c7 #bj grams of anthranilic nitrile and fifty grams of sodium selenide were mixed and heated in a distilling flask in an atmosphere of nitrogen1 and forty grams of acetic anhydride dropped into the flask very slowly4 ,the temperature was kept at #aae for half an hour and then raised to distill off the acetic acid formed in the reaction1 as the condensation hardly went to completion in the presence of any trace of acetic acid4 ,the whole process took an hour and a half4 ,the flask was removed from the oil bath and1 after cooling1 dilute alkali was run in1 in successive portions1 to dissolve out the quinazoline4 ,into the clear alkaline extracts carbon dioxide was bubbled for an hour1 and common salt then added4 ,the precipitate was recrystallized several times from twenty-five per cent4 alcohol4 ,the yield was from twenty to twenty-five per cent4 7d7 #aj grams of anthranilic nitrile1 twenty grams of acetic anhydride1 and twenty-five grams of sodium selenide were mixed in a sealed tube and heated together for three hours and a half at #aaj-aae4 ,the condensation product was crystalline when the tube was cooled to room temperature4 ,the contents of the tube were extracted with dilute alkali as before1 filtered1 precipitated by carbon dioxide1 and recrystallized from dilute alcohol4 ,the yield was not over twenty per cent4 7e7 ,an attempt was made to make o-aminobenzoselenamide1 and from the latter1 by treatment with acetic anhydride1 to form the quinazoline1 but the yield of the amide was too small to carry the reaction further4 ,the substance prepared by the above methods crystallizes from dilute alcohol in needles or prisms of dark brown color4 ,it melts at #bac4e 7corr474 ,it dissolves readily in hot alcohol but on concentration sometimes forms a sticky mass with a peculiar but not unpleasant odor4 ,it dissolves readily in alkalis and is slightly soluble in hot benzene and chloroform1 but insoluble in hot water4 ,crystals purified from 7a7 were analyzed and gave the following results3 ,calculated for ,found ,c,h,n,se ,i ,,ii ,carbon #dh4ch #dh4de #dh4fb ,hydrogen #c4fa #c4hb #c4eb ,nitrogen #ab4ee #ab4ea #ab4ff ,selenium #ce4df #ce4fj #ce4db ,the crystals on standing in the presence of air and light decomposed with separation of finely divided selenium and methyl quinazolone4 ,analysis of ,selenium ,organic ,compounds ,in the quantitative determination of selenium in quinazoline the method adapted by ,becker and ,meyer was found to be quite satisfactory7#ef74 ,other methods are listed in the bibliography7#eg74 ,in the ultimate analysis of carbon and hydrogen1 the ordinary absolute method was followed with the use of copper oxide1 lead chromate1 and lead peroxide in the tube4 ,in the determination of nitrogen the ordinary absolute method was also followed excepting that a considerable quantity of specially prepared lead chromate powder was mixed with the sample in a number six porcelain boat4 ,this was found to be desirable when the dinitroselenazole was burned4 ,selenium dioxide1 which is a solid1 seems to be formed in the tube and carried away by the current of carbon dioxide with some difficulty4 ,in such a case the analysis usually took four hours after the combustion had actually started4 ,in the carbon and hydrogen determination selenium dioxide was easily absorbed in the presence of oxygen gas4 ,preparation of #b-,phenylbenzoselenazole ,the first method employed was a modification of the method described by ,fromm and ,martin7#eh74 ,method 7b7 is an adaptation of the method for preparing benzothiazoles4 7a7 ,twenty grams of benzanilide was mixed in a pyrex flask with #afj grams of selenium dust and the flask placed in a nitrate bath under an air condenser4 ,after heating for an hour at #bbj;,c41 the temperature was raised to #bej;,c41 and kept at #bej-bhj;,c4 for sixteen hours4 ,the dark mass was extracted with hot concentrated ,h,cl1 the acid extracts filtered through glass wool using a hot water funnel4 ,the combined extracts were poured into a large volume of water when the selenazole precipitated out immediately2 it was recrystallized from alcohol4 ,in some cases it was necessary to dissolve in hot ,h,cl again and to recrystallize4 ,the yield was twelve per cent4 ,the above method has the disadvantage that water is formed in the reaction and this in turn reacts upon benzanilid at the higher temperature necessary 7as selenium only melts at #bag;,c471 decomposing the benzanilid into aniline and benzoic acid4 ,,nhcoc,h ,n _/ _/ ,c,h ,se ,c,h ,c-,c,h ,h,o _/ ,h ,se ,,nhcoc,h ,,nh _/ _/ ,c,h ,,hoh ,c,h ,,hooc-,c,h ,h ,h ,furthermore benzanilid boils at #afj;,c4 and at such high temperatures as #bej;,c4 and over some of it is apt to be driven off4 7b7 #ajf grams of benzaldehyde were heated with #ic grams of redistilled aniline at #abj;,c41 for two hours or until the solution was clear4 ,the clear benzalaniline was then poured into #afj grams of selenium dust in a pyrex flask on a sand bath1 the flask being connected with an air condenser as before4 ,in order to distribute the flame to better advantage over the bath1 an air space was made between the ,meker burner and the bath by introducing a wire gauze4 ,hydrogen selenide was evolved freely4 ,complete reaction took three days4 ,the extraction and recrystallization were the same as in the former case4 ,the yield was sixty per cent4 ,the selenazole crystallizes in colorless long needles1 melting at #aag4e;,c4 7corr47 ,fromm and ,martin7#eh7 gave the melting point as #aag;,c4 ,it is insoluble in water1 and in the following solvents it is lightly soluble in the cold1 more easily hot3 ether1 methyl alcohol1 acetone1 acetic acid1 acetic anhydride1 chloroform1 and nitrobenzene4 ,it is difficultly soluble in ethyl alcohol1 ethyl acetate1 and carbon tetrachloride1 in the cold1 but easily soluble hot4 ,mononitro ,derivative ,the mononitro derivative of the selenazole1 #f-nitro-#b-phenylbenzo- selenazole1 was prepared by nitration with nitric acid at a low temperature3 ,twenty-five grams of the selenazole were dissolved in #aej grams of concentrated sulphuric acid1 keeping the temperature below the room temperature until complete solution took place4 ,it was then cooled on a freezing mixture and a mixture of sulphuric and nitric acids 7previously prepared and cooled by mixing #i4e grams of nitric and fifteen grams of sulphuric acids7 slowly dropped into it in the course of half an hour1 using mechanical stirring for four hours4 ,the solution was then poured into two liters of water 7ice water71 filtered1 dried1 and recrystallized from acetic acid1 and alcohol with the help of animal charcoal4 ,the yield was #ie per cent4 ,this nitro compound crystallizes in flattened needles of a light yellow color4 ,it melts at #bjb4d;,c4 7corr474 ,it is very insoluble in water2 but soluble in hot acetic acid1 acetic anhydride1 nitrobenzene1 nitrotoluene1 toluene1 benzene1 alcohol1 and difficultly soluble when cold4 ,the crystals were analyzed and gave the following results1 ,calculated for ,found ,c,h,n,o,se ,i ,,ii ,nitrogen #i4bd #i4cf #i4dh ,monoamino ,derivative ,the conversion of mononitro compound to #f-;amino-#b-phenylbenzoselenazole was accomplished by the action of tin and hydrochloric acid as follows3 #cj4c grams of nitro compound were mixed with #db grams of twenty mesh tin in a liter flask1 immersing the latter in cold water4 #age cc4 of conc4 ,h,cl were slowly added to the flask4 ,in some cases it was necessary to apply initial heating but when once the reaction started it took place rapidly4 ,after the effervescence had abated1 the flask was heated over a free flame1 under a return condenser1 for two hours4 ,the solution usually turned to a pasty mass1 due to the formation of a tin double salt4 ,the mixture was dissolved in a large volume of water and heated on a water-bath1 the precipitate filtered out1 washed1 and preserved4 ,the clear filtrate was treated with concentrated alkali1 in excess1 the separated amine collected1 washed with water1 dried and recrystallized from alcohol1 using bone-black4 ,the precipitate set aside was treated with strong alkali1 the insoluble residue washed1 recrystallized1 and added to the main product4 ,the yield was #ge per cent4 ,this amine crystallizes from alcohol in fine yellowish needles1 melting at #bja4b-bjb4c;,c 7corr474 ,it is insoluble in water and ether1 difficultly soluble in the hot2 and fairly soluble in aniline4 ,a pure sample was analyzed and gave the following results3 ,calculated for ,found ,c,h,n,se ,i ,,ii ,nitrogen #aj4be #aj4cd #aj4db ,carbon #eg4ah #eg4ag #eg4jj ,hydrogen #c4fi #c4gi #c4he ,decomposition of ,monoamino ,derivative ,five grams of the monoamino compound were mixed with powdered ,,koh1 heated together until the mixture just melted1 and maintained in that state for a few minutes4 ,when the latter had cooled down to room temperature1 cold water was poured over the mixture4 ,the filtered solution was acidified until no further precipitate was formed4 ,the precipitate was collected and recrystallized from water1 m4p4 #aba;,c4 ,one gram of this solid was placed in a test tube1 provided with a cork and a delivery tube1 and heated with soda lime2 a liquid with the smell of benzene was collected in another test tube cooled with water4 ,when this liquid was treated with a few drops of nitric acid mixture the smell of nitrobenzene was given off4 ,a gram of the crystals was heated with concentrated sulphuric acid and alcohol when the odor of ethyl benzoate was noted4 ,monacetyl ,derivative ,five grams of the monoamino selenazole were heated on a water-bath with #aj cc4 of acetic anhydride until the solution was clear1 which took about two hours4 #ajj cc4 of water were poured into the mixture1 which was then neutralized with dilute ammonium hydroxide4 ,the precipitate was filtered1 decolorized by animal charcoal1 and recrystallized from dilute alcohol4 ,the acetyl compound1 #f-;acetamino-#b-phenylbenzoselenazole1 forms colorless crystals1 melting at #ahh4a-4g;,c4 7corr474 ,it is insoluble in ether1 benzene1 carbon disulphide2 slightly soluble in toluene2 soluble in alcohol1 ethyl acetate1 amyl acetate1 acetone1 and acetic acid4 ,a pure sample was analyzed and gave the following result1 ,calculated for ,c,h,n,se,o ,found ,nitrogen #h4hh #h4ib #h4fh ,monobenzylidene ,derivative ,five grams of the monoamino compound were dissolved in #bjj cc4 absolute alcohol with the addition of #c cc4 of benzaldehyde and the clear solution was boiled on a water-bath1 with a return condenser1 for two hours4 ,after the solution was boneblacked1 the yellow precipitate was recrystallized from carbon disulphide4 ,the yield was #ij per cent4 ,it crystallizes in yellow plates1 melting at #aef4g-aeg4f;,c41 soluble in benzene1 ether1 ethyl alcohol1 carbontetrachloride1 acetone1 but difficultly soluble in ligroin4 ,an analysis of the crystals showed the following result1 ,calculated for ,c,h,n,se ,found ,nitrogen #g4ge #g4ib #g4fh ,an ,azo ,dye ,five and four tenth grams of the monoamino compound were dissolved in hot conc4 ,h,cl1 cooled in ice1 and diazotized with sodium nitrite solution1 until starch iodide paper showed excess nitrous acid4 ,the diazotization was performed in ice1 with mechanical stirring1 and required about an hour4 ,the diazo solution was poured into a solution of #c grams ,b-naphthol in #h grams of ,na,o,h and #fj cc4 of water1 while gradually stirring4 ,a very deep red solution formed4 ,this was acidified with excess ,h,cl1 salted out by ,na,cl1 and crystallized from aniline-alcohol mixture4 ,in the pure state1 it is a deep red powder1 with a metallic lustre when rubbed1 melting at #bhd4b;,c4 ,an analysis showed the following result1 ,calculated for ,c,h,n,o,se ,found ,nitrogen #i4ha #i4ge ,dinitro ,derivative ,the nitration for the production of dinitro derivative was at first carried out under the same conditions as in the preparation of mononitro compound and after the latter was formed more nitric acid mixture was added with the addition of heat3 conc4 sulphuric acid1 keeping it below room temperature4 ,it was then cooled in a freezing mixture and half the volume of a nitric acid mixture 7prepared and cooled by mixing #ai grams of nitric and #cj grams of sulphuric acids7 was introduced very slowly to the selenazole solution through a dropping funnel1 maintaining at this temperature for two hours 7using mechanical stirring74 ,the remaining half of the nitric acid mixture was then slowly introduced and the flask was heated on a water-bath for two hours4 ,the solution was poured into two liters of water1 the precipitate filtered off1 dried and recrystallized several times from acetic acid4 ,the yield was #hj per cent4 ,this dinitro compound crystallizes in fine yellow needles1 m4 p41 #bdf4h;,c4 7corr471 very insoluble in water1 but soluble in hot acetic acid1 acetic anhydride1 nitrobenzene1 nitrotoluene1 ethyl alcohol1 and difficultly soluble cold4 ,it was analyzed and the following results were found1 ,calculated for ,found ,c,h,n,o,se ,i ,,ii ,nitrogen #ab4jg #ab4cj #ab4ab ,diamino ,derivative ,the conversion of the dinitro to diamino derivative was accomplished in the same manner as the reduction of the mononitro derivative excepting that twice as much tin and ,h,cl were used4 ,this diamino compound crystallizes in yellowish glistening needles from alcohol and pyridine2 m4 p41 #bfi-bgj4e;,c42 was analyzed and gave the following results1 ,calculated for ,found ,c,h,n,se ,i ,,ii ,nitrogen #ad4f #ad4d #ad4g ,diacetyl and ,dibenzylidene ,derivatives ,the diacetyl and dibenzylidene compounds were also prepared from these diamino derivatives4 ,the former crystallizes in cubes from dilute alcohol2 m4 p41 #cjg;,c 7,corr47 and the latter in beautiful yellow plates from carbon disulphide1 m4 p41 #aie-aif;,c4 7,corr474 ,an analysis of these two compounds showed the following results1 ,calc4 for ,calc4 for ,found ,c,h,n,o,se ,c,h,n,se ,i ,,ii ,nitrogen #i4je #aa4ba #i4ba #aa4dc ,dyeing with ,azo ,dyes ,both the monoamino and the diamino derivatives form intensely colored dyes when diazotized and coupled with phenols and aromatic amines4 ,the dyes formed are fast to light4 ,in the following table silk is given to represent the fabrics used4 ,wool and cotton were dyed similar shades1 though with slight variation4 ,each silk sample was dyed in acid or alkaline baths as indicated and each bath contained #j4ja gram in twenty cc4 solution3 ,diazo4 ,on ,diazo4 ,on ,coupler monoamine silk diamine silk ,phenol deep red v4 light 7alk7 yellow 7alk7 yellow deep red ,dimethylaniline orange light orange-red yellow 7acid7 yellow 7acid7 ,p-nitraniline light brownish grayish brown 7acid7 brown 7acid7 ,p-toluidine light brownish brownish brown 7acid7 7acid7 ,pyrogallic dark grayish dark grayish acid brown brown 7acid7 7alk7 ,salicylic reddish light red brown acid 7alk7 brown 7alk7 ,b-naphthol deep red pink deep red red 7alk7 7alk7 ,sulphanilic light brownish brown brown acid brown 7alk7 7alk7 ,a-naphthylamine light brownish yellow yellow brown 7acid7 7acid7 ,resorcinol purple red dark deep red 7alk7 purple 7alk7 ,,bibliography #a4 ,berzelius1 ,annales de ,physique et ,chimie 7#b7 #i1 #bci1 #cef 7#ahah74 #b4 ,gmelin-,kraut1 8,handbuch der ,anorg4 ,chemie0 ,i 7#a7 #gje-hjd2 ,roscoe and ,schorlemmer1 8,treatise on ,chemistry0 ,i1 #dfg-hb 7#aibj72 ,browning1 8,introduction to the ,rarer ,elements10 #add-eb 7#aiag74 #c4 ,victor ,lenher1 ,j4 ,ind4 ,eng4 ,chem41 #ab1 #eig 7#aibj74 #d4 ,le ,seleneum et ses applications actuelles1 ,chimie et ,industrie 7#aiai7 #bde4 #e4 ,c4 ,r4 ,boggs1 ,u4 ,s4 ,a41 #a1bdi1bgb2 ,j4 ,ind4 ,eng4 ,chem4 #aj1 #aag-h 7#aiah74 #f4 ,duhamel ,robiere1 ,compt4 rend4 soc4 biol4 #gb1 #fgj 7#aiac72 ,am4 ,chem4 ,abs4 #g1 #bfbd 7#aiac74 #g4 ,b4 ,g4 ,duhamel1 ,compt4 rend4 soc4 biol41 #gb1 #hfe 7#aiac72 ,am4 ,chem4 ,abs4 #g1 #biga 7#aiac74 #h4 ,duhamel ,juillard1 ,compt4 rend4 soc4 biol41 #gb1 #gad 7#aiac72 ,am4 ,chem4 ,abs41 #g1 #bfbd 7#aiac74 #i4 ,b4 ,g4 ,duhamel1 ,compt4 rend4 soc4 biol41 #hb1 #gbd-f 7#aiai72 ,am4 ,chem4 ,abs4 #ad1 #bchc 7#aibj74 #aj4 ,wassermann1 ,d4 ,r4 ,p41 #bfa1eef2 #bhf1iej2 #bhg1jbj4 #aa4 ,a4 v4 ,wassermann1 ,keyser1 ,m4 ,wassermann1 ,duet4 ,med4 ,woch41 #cg1 #bchi 7#aiaa72 ,am4 ,chem4 ,abs41 #f1 #fej 7#aiab74 #ab4 ,a4 v4 ,wassermann ,hansmann1 ,berl4 klin4 ,woch41 #di1 #d1 7#aiaa72 ,am4 ,chem4 ,abs41 #f1 #hij 7#aiab74 #ac4 ,anthraquinone dyes1 ,d4 ,r4 ,p41 #bef1ffg4 #ad4 ,p4 ,ehrlich ,h4 ,bauer1 ,ber41 #dh1 #ejb 7#aiae74 #ae4 ,berzelius1 ,lehrbuch 7#e ,aufl47 #b1 #bac2 ,roscoe and ,schorlemmer1 8,treatise on ,chemistry10 ,i1 #dgc 7#aibj74 #af4 ,bruere1 ,j4 ,anat4 ,physiol41 ,oct41 7#ahia74 #ag4 ,t4 ,w4 ,clarke ,w4 ,h4 ,hurtley1 ,j4 ,physiol41 #cf1 #fb 7#aijg74 #ah4 ,hugo ,bauer1 ,ber41 #dg1 #ahgc 7#aiad74 #ai4 ,ehrlich ,guttmann1 ,berl4 klin4 ,woch4 7#ahia7 #bh2 ,u4 ,s4 ,disp41 #bjth ,edition4 #bj4 ,p4 ,karrer1 #di1 #eig 7#aiaf72 ,ber41 #ea1 #aij 7#aiah74 #ba4 ,hugo ,bauer1 ,ber41 #dg1 #ahgc 7#aiad72 ,d4 ,r4 ,p41 #bfa1ifi2 ,friedl41 #aa1 #aabd 7#aiac74 #bb4 ,selenazines1 ,d4 ,r4 ,p41 #bhj1gac2 #bfa1gic4 #bc4 ,u4 ,s4 ,disp41 #bjth ,edition4 #bd4 ,d4 ,r4 ,p41 #cje1bfb2 #cje1bfc2 ,am4 ,chem4 ,abs41 #ac1cbe 7#aiah74 #be4 ,bull4 soc4 chim41 #da1 #eii2 ,compt4 rend41 #ii1 #aaed-g 7#ahhe72 ,brit4 ,chem4 ,abs41 #ej1 #cgf 7#ahhe72 ,a4 ,ch41 7#f7 #i1 #bid1 #cjc1 #cbc4 #bf4 ,w4 ,baringer1 ,ber41 #bc1 #ajjc 7#ahhi74 #bg4 ,p4 ,spica1 ,gazz4 chim4 ital41 #g1 #ij-i 7#ahgg72 ,brit4 ,chem4 ,abs41 7#ahgg7 ,,ii1 #ahi2 ,compt4 rend41 #ii1 #aaed 7#ahhd72 #ajj1 #abif 7#ahhe72 ,frerichs1 ,arch4 ,pharm41 #bda1 #ahj1 #aif2 ,beil41 7#aiba7 ,,iii1 #bie1 #bfa4 #bh4 ,c4 ,paal1 ,ber41 #ah1 #bbee 7#ahhe72 ,gazz4 chim4 ital41 7,i4 ,zoppellari7 #bd1 ,,ii1 #cii1 7#ahid74 #bi4 ,ida ,foa1 ,gazz4 ,chim4 ital41 #ci1 ,,ii1 #ebg1 7#aiji72 ,c-,b41 7#aiaj7 ,i1 #hcg4 #cj4 ,d4 ,r4 ,p41 #bfd1aci4 #ca4 ,o4 ,hinsberg1 ,ber41 #bb1 #hfb1 #bhie 7#ahhi72 ,d4 ,r4 ,p41 #bfa1dab4 #cb4 ,j4 prakt4 ,chem41 7#aijd7 ,,ii1 #fi1 #eji4 #cc4 ,e4 ,abderhalden1 ,hand4 ,biol4 ,chem41 ,,iii1 #b1 #ied4 #cd4 ,hanzlik ,tarr1 ,am4 ,univ4 ,ezpt4 ,sta41 ,j4 ,pharmacol1 #ad1 #bba-h 7#aiai74 #ce4 ,hochst1 ,d4 ,r4 ,p41 #bii1eaj4 #cf4 ,d4 ,r4 ,p41 #bfd1idj2 #bfd1ifa4 #cg4 ,a4 ,michaelis ,m4 ,stein1 ,ann41 #cbj1 #cb 7#aijb74 #ch4 ,bogert ,hand1 ,j4 ,am4 ,chem4 ,soc41 #be1 #cgg 7#aijb74 #ci4 ,b4 ,bathke1 ,ann41 #aeb1 #baj 7#ahfi72 ,ann41 #ahe1 #cca2 ,richter1 ,organische ,chemie1 ,i1 #aff4 #dj4 ,lesser ,schoeller1 ,ber41 #dg1 #bbic 7#aiad74 #da4 ,lesser ,weiss1 ,ber41 #de1 #ahce 7#aiab72 #df1 #bfec1 7#aiac74 #db4 ,wohler ,dean1 ,ann41 #ig1 #e 7#ahef72 ,b4 ,rathke1 ,ann41 #aeb1 #baa 7#ahfi74 #dc4 ,cahours1 ,ann41 #fa1 #ib1 7#ahdg72 #ib1 #cef4 #dd4 ,h4 ,klinger1 ,ber41 #cb1 #baie1 7#ahii72 ,ann41 #aai1 #ia2 #aba1 #ajh4 #de4 ,c4 ,a4 ,joy1 ,ann41 #hf1 #ce1 7#ahec72 ,b4 ,rathke1 ,ann41 #aeb1 #bab1 #bai 7#ahfi74 #df4 ,wheeler1 ,z4 ,chem41 7#ahfg7 #dcf4 #dg4 ,krafft ,lyons1 ,ber41 #bg1 #agfb 7#ahid72 ,a4 ,ch41 7#f71 #bj1 #bbh4 #dh4 ,k4 ,a4 ,hoffmann1 ,ber41 #bg1 #bhji 7#ahid74 #di4 ,m4 ,busch1 ,ber41 #be1 #bhec1 7#ahib74 #ej4 ,lellmann ,stickel1 ,ber41 #ai1 #afje 7#ahhf74 #ea4 ,b4 ,rathke1 ,ann41 #aeb1 #bja 7#ahfi74 #eb4 ,gabriel ,stelzner1 ,ber41 #bi1 #acac 7#ahif74 #ec4 ,bogert1 ,breneman1 ,hand1 ,j4 ,am4 ,chem4 ,soc41 #be1 #cgc 7#aijc74 #ed4 ,am4 ,chem4 ,abs41 #c1 #hgj 7#aijc72 ,bull4 ,belg4 ,soc4 ,chem41 #bc1 #i-aa4 #ee4 ,bogert ,hand1 ,j4 ,am4 ,chem4 ,soc41 #bd1 #ajce1 7#aijb74 #ef4 ,becker ,meyer1 ,ber4 #cg1 #beea 7#aiad74 #eg4 ,h4 ,bauer1 ,ber4 #dh1 #ejg 7#aiae72 ,lyons ,shinn1 ,j4 ,am4 ,chem4 ,soc4 #aijb3 #ajib2 ,fritz von ,konek ,o4 ,schleifer1 ,ber4 #ea1 #hej 7#aiah72 ,a4 ,michaelis1 ,ber4 #cj1 #bhbg 7#ahig72 ,ber4 #dh1 #hgc 7#aiae72 ,h4 ,frerichs1 ,arch4 ,pharm4 #aijb3 #bdj1 #fef4 #eh4 ,fromm ,martin1 ,ann41 #dja1 #agh 7#aiac74 ,,vita ,y-,gwan ,chen was born in ,nanking1 ,china1 ,march #h1 #ahic4 ,after graduation from college in #aiae1 he further studied ,chinese classics1 #aiae-af4 ,he entered ,case ,school of ,applied ,science1 ,cleveland1 ,ohio1 as a special student in the ,department of ,chemistry1 #aiaf-ag4 ,he registered at ,columbia ,university to pursue graduate work in chemistry under the ,faculty of ,pure ,science2 and was awarded the degree of ,master of ,arts in #aiah4 ,from ,september #aiai to ,june #aibb1 he has been pursuing research in organic chemistry in the research laboratories of ,havemeyer ,hall1 ,columbia ,university4 ,,footnotes3 ,a ,not a new compound but prepared by a different method4 ,b ,note--dimethyl selenophene1 however1 is colorless4 ,transcriber's notes3 ,the diagram of #c-7p-phenylarsonic7-aminoselenazine1 labelled 7,,ii71 has been adjusted to make its structure clearer4 ,the l in #b;,h,cl in the first equation under ,preparation of #b-methyl-#d-selenoquinazolone was missing in the original4 ,the following is a list of changes made to the original4 ,the first line is the original line1 the second the corrected one4 selnoquinazolone prepared in the course of this research selenoquinazolone prepared in the course of this research on four different strains of mouse carcenoma and one strain on four different strains of mouse carcinoma and one strain in consequence of its smell ,i so completely loss my sense of smell in consequence of its smell ,i so completely lost my sense of smell of the phenazine1 oxasine1 thiazine1 acridine series show of the phenazine1 oxazine1 thiazine1 acridine series show and ,se again most powerful of the whole series4 and 3,se again most powerful of the whole series4 simplicity1 is that of ,babriel and ,stelzner7#eb71 simplicity1 is that of ,gabriel and ,stelzner7#eb71 on cooling was filtered out and recrystalized from dilute alcohol4 on cooling was filtered out and recrystallized from dilute alcohol4 ,it was prepared from ,sodium hydroxide in absolute alcohol ,it was prepared from sodium hydroxide in absolute alcohol a sealed tube at #aaj with alcohol saturated at zero degree with a sealed tube at #aaj with alcohol saturated at zero degrees with took an hour and half4 ,the flask was removed from the oil took an hour and a half4 ,the flask was removed from the oil ,the precipitrate was recrystallized several times ,the precipitate was recrystallized several times 7e7 ,an attempt was made to make o-aminobenzselenamide1 7e7 ,an attempt was made to make o-aminobenzoselenamide1 ,it dissolves readily in alkalies and is slightly soluble ,it dissolves readily in alkalis and is slightly soluble ,this was found to be desirable when the dinitroselezazole was burned4 ,this was found to be desirable when the dinitroselenazole was burned4 into a large volume of water when the selenozole precipitated out into a large volume of water when the selenazole precipitated out it was necessary to dissolve in hot ,h,cl again and to recrystalize4 it was necessary to dissolve in hot ,h,cl again and to recrystallize4 7b7 #ajf grams of benaldehyde were heated with #ic grams of 7b7 #ajf grams of benzaldehyde were heated with #ic grams of ,it is difficulty soluble in ethyl alcohol1 ethyl acetate1 and ,it is difficultly soluble in ethyl alcohol1 ethyl acetate1 and toluene1 benzene1 alcohol1 and difficulty soluble when cold4 toluene1 benzene1 alcohol1 and difficultly soluble when cold4 from alcohol in fine yellowish needles1 melting at #bja4bbjb4c;,c from alcohol in fine yellowish needles1 melting at #bja4b-bjb4c;,c carbontetrachloride1 acetone1 but difficulty soluble in ligroin4 carbontetrachloride1 acetone1 but difficultly soluble in ligroin4 #ai grams of nitric and #cj grams of sulphuric acids was introduced #ai grams of nitric and #cj grams of sulphuric acids7 was introduced in the same manner as the reduction of mononitro derivative in the same manner as the reduction of the mononitro derivative ,this diamino compound crystalizes in yellowish glistening needles ,this diamino compound crystallizes in yellowish glistening needles compounds were also prepared from this diamino derivatives4 compounds were also prepared from these diamino derivatives4 ,the former crystalizes in cubes from dilute alcohol2 ,the former crystallizes in cubes from dilute alcohol2