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SYMMETRICAL DTISOPROPYL-HYDRAZINE 
 AND RELATED COMPOUNDS 
 
 BY 
 
 HARRY LOUIS LOCHTE 
 
 B. A., University of Texas, 1918 
 
 THESIS 
 
 SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS 
 FOR THE DEGREE OF DOCTOR OF PHILOSOPHY IN 
 CHEMISTRY IN THE GRADUATE SCHOOL OF 
 THE UNIVERSITY OF ILLINOIS, 1922 
 
 URBANA, ILLINOIS 
 
V 
 
 I 
 
 
 J 
 
 1 
 

 
 UNIVERSITY OF ILLINOIS 
 
 THE GRADUATE SCHOOL 
 
 May 23 192-Z - 
 
 I HEREBY RECOMMEND THAI' THE THESIS PREPARED UNDER MY 
 
 SUPERVI SION BY HAMY_ I^OU IS LOCHTE ■ 
 
 ENTITLED _S:UL£ET.RI CAL DI-IS OPHQPYL-IIYDPAaTRS AND RELATED 
 
 COi^OlT JDS 
 
 BE ACCEPTED AS FULFILLING THIS PART OF THE REQUIREMENTS FOR 
 
 THE DEGREE OF D octor of Philo sop)i;^ >- 
 
 
 
 In Charge of Thesis 
 
 ; ^ uCAAA^ 
 
 ^ Head of I^Iepartment 
 
 r 
 
 Recommendation concurred in* 
 
 
 
 
 
 pA ^ ^ ] i*‘ 4^ 
 
 Committee 
 
 on 
 
 Final Examination* 
 
 Required for doctor’s degree but not for master’s 
 

 
 
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 The writer wisxies to express his appreciation of the 
 inspiration and the helpiul suggestions of Professor W.A.l^ioyes 
 under whose direction tiiis investigation was carried out, 
 
 he also wishes to express iiis gratitude for the never- 
 failing help of Professor J.R, Bailey, of the University of Texas, 
 at whose suggestion Luis invest/igaoion was begun and under whose 
 direction tue first part of tiie work was carrieu out. 
 
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I IwiHUDUUTIUN 
 
 When reports on Lhe success of catalytic metnoas of re- 
 duction, using platinum or paliauium as catalysts and nyarogen gas 
 as reducing agent, showed more and more cases in wnich complexes 
 could be reuuced tiiat had not been reducible before, professor 
 Bailey, of txAe University of Texas, suggesieu tiie reduction of 
 
 cHj 
 
 dimethylketazine,-':^c.-'^-'^ - , oy uas me chod. Although all 
 
 old methoas haa iailea, catalytic reduction proved comparatively 
 easy. The problem was then transferred to the University of 
 Illinois where the work was continued under the direction of 
 Professor W.A.iMoyes. 
 
 The preparation and study of vai’ious derivatives of the 
 
 hydruzo compound (symmetrical diisopropylxxydrazine ) was next 
 
 undertaxen because neretofore alipnatic hyarazines nave been too 
 
 difficult to prepare to study tnem in detail. Tne mono-nitroso 
 
 uerivative of symmetrical diisopropyl-iiyurazine was prepared and 
 
 proved very interesting because, conorary to expectations, it 
 
 of 
 
 forms a sodium salt. The quesLion of the strucLure^ni troso-hydra- 
 
 A 
 
 zines ana tiieir metal salts is tnus raised again. 
 
 Both tiie azo and tiie hyurazone compound corresponding to 
 the symmetrical hydrazine were prepared as the first case of iso- 
 lation of both tautomers of purely alipiiatic compounds of this 
 type. 
 
 Primary isopropyl-hyarazine was prepared by reduction of 
 a mixture of equimolecular amounus of acetone, hydrazine-hyarate , 
 and hyurociiloric acid^ by the acid iiyurolysis of acetone- isopropyl- 
 
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 iiyd.razine7 and by tne acid nydrolysis of 2 , 2 * -azobispropane . 
 
 II THEOKETICAL 
 
 Since the discovery of nydrazine oy Gurtius,^ and tiie 
 
 2 
 
 development of a metxiod^by Kascnig , by means oi which hydrazine 
 and its salts may now readily be made at reasonable cost, the 
 interest in tne many types of nydrazines ana tneir derivatives 
 has grown constantly, 
 
 Emil I'ischer'^ made the first derivative of hydrazine when 
 
 he prepared and studied, in great detail, the poisonous base, 
 
 di 
 
 piienyl-hydrazine , made; by him througix the reduction of^azo- 
 
 A 
 
 benzene, Metiiods of preparing aromatic hyarazines are quite 
 numerous and these compounds have long been tnoroughiy stuaiea, 
 
 for tiie alipnatic hyarazines, nowever, few methoas of pre- 
 paration are known and almost without exception the yields obtained 
 by methods known before tne discovery of the method used in this 
 investigation, are poor, 
 
 I'or the preparation of the unsymme trical secondary hydra^-^ 
 
 4 
 
 zines Emil riscner worked out a method tnat gives fair yields. He 
 prepared the nitroso compounds of secondary amines and reduced 
 these with zinc dust and acetic acid. Another metnoa or preparing 
 unsymmetrioal hyarazines was developed oy tne same chemist and 
 may De expressed by the equatioii^, 
 
 KBr — ^ C .H^(h)iM-NH 9 ,HBr , Txiis method is usually 
 
 O -j 2 DO 
 
 used only to prepare mixed disubstituted hydrazines. 
 
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- 3 - 
 
 For tne preparation of simple primary ujurazines, Fiscner 
 
 also developed a metxioa. It may be iilus orated by; 
 
 Re auction &: 
 
 KWH 
 
 Ri\H 
 
 :u=o 
 
 ni\iO 
 
 Kivn 
 
 
 Alkali RiMHp + 
 K- w -w 0 Acid Kw Him H o 
 
 ^CrO 
 
 KRH RN NO RNnNHp 
 
 T b Alkali or^ --..-i ^ 
 
 HgN 
 
 IN Hr 
 
 NH. 
 
 ^2 acid — 'o 
 
 For symmetrical disubs LituLed hyarazines the use of alKyl 
 
 halides (usually the bromide) yields a mixture of symmetrical and 
 
 unsymmetrical hyarazines wnich may usually be separated with more 
 
 or less difficulty. A more serious difficulty exists through tne 
 
 fact oiiat it is almost impossible to prevent tiie formation of the 
 
 7 
 
 quarternary ammonium compounds, i'he safer and more economical 
 
 method of preparing these nyarazines oy alxylation protects tne 
 
 second H on each nitrogen atom uy acetylation or formylation. Then 
 
 the alkyl groups must go to uifferent nitrogens and thus produce tiie 
 
 symmetrical seconuary xiyurazines. This is the metnOd tuat was used 
 
 8 
 
 with some success oy Harries ana coworxers . Tney were aole to pre- 
 pare the symmetrical dimethyl ana dietnyl nydrazines by; 
 
 ChO-N-n-ChO » GhO-(R^iM-iM(R)-ChU > KNH“i\iHR 
 
 Vb 
 
 The yield was low tiiough and tney were aole to do little more 
 
 9 
 
 than isolate tne aoove compounus. Htolle also did much work on 
 this method of preparing aliphatic nyarazines and he and coworkers 
 were able to aajust conditions so as to obtain a certain, if 
 
 9 
 
 small, yield of symmetrical hyarazines. Buscn was aole to prepare 
 under these conuitions, small quantities of primary isobutyl- 
 hyarazine and smaller yielus of tne corresponaing symmetrical 
 and unsymmetrical seconuary compounus. 
 

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 Buscn and SLoile also used a uixferent metiiou for the 
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 may be expressed by; 
 
 I\iH2bK2 
 
 ,K^O 
 
 +• 
 
 
 OK 
 
 OK 
 
 .OK 
 
 i\iK2KHK •+ KHSO^'+ ^20 
 
 ana 
 
 kKK“'KH 2 bO^^,, — ^KKJM“1NHK-K KiibO^ 
 
 jiven uere tue yield is poor anu uncertain since sometimes 
 symmetrical and sometimes unsymmetrical hyurazines are formed as 
 
 the main yield. 
 
 Kischner developed a metnod that was originally used for 
 the preparation of primary hyurazines accoruing to the reactions; 
 
 RK ’ CH-NH2*b -br2 -h KuH ^ KR ' GH-KKBr-f. xv^r H2O 
 
 KK ‘ GH-Khxjr KhK-GHKR‘ > KR ' GH-im-iMrCRK ‘ 2H5r 
 
 Tii.e hyarazone tnus lormeu is buen uydroly zea , ii uiie primary 
 hyurazine is to be formed. Catalytic reuuction anouiu easily re- 
 duce the same rijurazone to one symmetrical seconuary iiyurazine. 
 
 finally, Gurtius anu. student s"^^ found tiiat hyurazine 
 hydraxe and aluenjaes or xe tones condense to lorm simple hydra- 
 zones; 
 
 KK ’ CrO -hK;j;U“hH2 .HoO — >KK’C-W“ wH 2 2 H2O. 
 
 Tnese Gompounus are very unstaule ana are eitner hyarolyzeu to 
 the original suustances or they react with anotxxer mol of 
 alaeiiyde or keLone to produce azines; 
 
 Rk’CZI\i-NH 2+ 0^5=CKR‘ — > KR'GsK-H=CRR' -v H2O 
 
 Althougn Gurtius auid others were aole oo reduce benzalazine and 
 some OLner aromatic azines, Lhey found txiai. tne aliphai-ic azines 
 are perfectly staole towards alKaline reducing agents v/nile no 
 
' 4 
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 are reaaily h^droi jzed by acias. 
 
 13 
 
 Gurtius as well as Vvonl and uesterlin made primary benzyl- 
 hydrazine by paroial reaucLion o! benzalazine and hyurolysis oi the 
 hyarazone lormed, 
 
 Dimetuyl-ketazine ,on reduction, yielas symmetrical diisopro- 
 pyl-hycirazine and tnis , in turn, yields azobispropane and other 
 inLeresting compounds. Always xiopaogLhat tne reduction could be 
 effected in som.e way, a number of chemists have recorded failures 
 in attempts to reauce this compound. Curtius^"^ trieu to reduce the 
 ketazine by alKaline reuucing agents, out found it peneculy stable 
 Lowarus L-iiese. ixiieie could noL reauce ii by an eiectrolyLic 
 method with which he had just reduced benzalazine to tiie corres- 
 
 1 K 
 
 ponaing hyurazo compound. He also aLtempiea to prepare the 
 symmetrical hydrazine ne iiad nopea to obtain by reduction of 
 aime thyl-ketazine through the elimination of 2 molecules of 
 carbon dioxide from hydrazo-isobuty ric-acid, . 
 
 ^ 'Go dH y G O dn 
 
 V/ieland reports tnat tne alipnatic alGazines are 'noL reducible. 
 
 18 
 
 kailhe was able to affect the reduction, but the product obtained 
 consisied of a mixiure of mono and di isopropyl-aonine instead of 
 the hydrazo compound he sougnt to obiain. 
 
 In the course of the present investigation many unsuccess- 
 ful attempts were made to reduce dime tnyl-ketazine by various 
 common reaucing agents, acid, neutral, and alkaline. Althougii a 
 few, such as sodium amalgam(4/j) , sodium in alconol, and aluminium 
 amalgam gave small amounts of reduction proaucts tixat were basic 
 
t 
 
- 6 - 
 
 none oi Liiem were idenLical wIlu uhe symmeLricai h^arazine uhau 
 
 was oeing prepared, in the meantime, the catalytic method 
 
 described hereailer. Otiier reducing agenos sucn as zinc in aciu 
 
 solution, potassium hydroxide and aluminium, iron witn hydrochloric 
 
 aciu or aceLic acid, and reauction oy stannous ciiioride; all failed 
 
 to give any nooiceaoie reauCLion oi the ketazine. 
 
 In tesLing for a possible basic product formed during one 
 
 of tue unsuccessful attempts descriueu above, white needles of 
 
 a dii'ferenL compound separax-ed out on aading benzoyl ciiioride in 
 
 Lxie hope 01 obtaining a benzoyl compound ox the reduction product. 
 
 Ine melting point, appearance, and analyses indicate that tiie 
 
 product formed is the benzoyl derivative of 5-methyl-5-dim.ethyl- 
 
 H -C C — GH^ 
 
 pyrazoline, " 
 
 lb 
 
 GH . 
 
 I'i 
 
 i'i— OQ— G ' il 
 
 Gurtius and cowSrxers, i^ranke, and j?rey and Hoiiman 
 
 found that ketazines, if they have a metnyl group next to tiie G=i\i 
 
 complex, readily rearrange, when under the influence of dilute 
 
 acids to form pyrazolines. Dimetnyl-ketazine , tiius treated, 
 
 rearranges to form o-metuyl-b-uimetnyl-pjrazoiirf©. Hven maleic 
 
 acid is aole to cause tuis rearrangement in tne case of tnis 
 
 19 
 
 ketazine, Gur tius anu Wirsing i ounu tuat tiie same pyrazoline 
 is also formed wnen mesityl oxide is treateu witn hyurazine.They 
 prepareu a benzoyl derivative of the compound tnus prepared. The 
 properties given by tnem agree witn those found in the present 
 investigation. The small acid concentration due to liydrolysis and 
 to formation of the derivative is then sufiicient to produce tiiis 
 rearrangement of dimetxiyl-xetazine , 
 

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 f t.) f , ii< ciV'ito A - > "f j ■ <'i:iva ivjrfiJj «t li) i u-f ^*/X 
 
 .i ~ rr-rr *cr ' .(05 **•) ^ •• - .-, va/- 3 - f ry r-^ *;i\Oi OJ 
 
 Uj .^ io * •• } i :'•*• r.- h/i-a o: *>[.-. cX »j2 
 
 t.ii' -(T >^2 '’rfJ ;irr. ^.• 7 . c i , t\i^ 
 
 . 3 ;-ii r A'j.‘ ,;.ff rJ.tr Jra.-Kcrf’ j i i'i ihoi/i n >fl-* x»«t: ) . i ubifi 
 
 ' . -*’r ■ . 6 «;r + ftp. J ; ‘^i v,'.'iw« *• oe ogj 
 
 J 't. ; 0 Mr.-' -1 "IX'^ “?cr .f lK*.t?^ **« '"niU > ci .-i.lJTr.qO 
 
 C'''.'i i Ir, 'i.*^ 4 ; c«^ *L,t- 'TiJ.'jT rrr u .co IIxtu f^T . rx 2 .i/?ni i 80 V J 
 
 ■ * ‘ •* ■ • * r -"i ■• t ^ ? r * T ♦ j > ... * i, > 
 
 i j 
 
 . - r »/ j j> 't(' xr.ci;? .tt/ i 
 
- 7 - 
 
 2(1 
 
 Zlehl attempted the cataijLio n^urogenation (SkiLa 
 methou) of a series of compounas of niLrogen. Among these were; 
 
 iminotriazomeLxiane — • and aiazoaminobenzene. He was 
 
 HH2 
 
 not able 10 reduce any of tiie wro or h=iM complexes shown. 
 
 In experiments with isocyanides ne was aule uo reduce the eom- 
 
 1 
 
 pounus to trie uorresponuing methji-amine aerivatives only in case 
 the isocyaniaes were so stable Liiat no formic acid was formed. In 
 the case of iminotriazomethane iie could observe no aosorbtion 
 of hydrogen, although he found that campnor oxime could readily 
 be reduced to bornyi- amine, 
 
 Quite recently, Staudinger, using a catalytic raetnod of re- 
 ducLion, reduced diazo compounds ana obtained hydrazones, but did 
 not reduce these lo Lhe nyurazine. In view of tne lact that, as 
 will ce Siiown later, saliiication 01 oixe base formed during the 
 reducLion is essential to success in cue reaucLion of most such 
 compounas, it is possiule cxiciL ne, too, could uave reauced the 
 G;N complex readily ii he nad run txxe last step of 'lxiIs reauccion 
 in an acid soluLion, 
 
 ine worx on Lnis problem snows tnat the re auction of di- 
 metnyl ketazine, and prouably oi otxxer azines, can be carried out 
 with very satisiactory yielus tnrough the use of catalytic 
 methods of reduction employing finely divided platinum or palladium 
 eitner as the platinum or palladium black, or in form 01 the pro- 
 tected coiloia of eiuxer metal, 
 
 GataiyLic reauction by cue use oi Lhese me cals ua.s been 
 xnown lor over ixaif a cencury, buL tne possiuilities of these 
 meLhoas were noc recognizea until afcer oixe year lyOO and inten- 
 
I ' 
 
 l! 
 
 1 
 
 il 
 
 t 
 
 - * t 
 
 ^ V J Si ^ Mi '**" ^ , X - * 
 
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 • tj $ i i.*»’U \* 
 
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 n- '•^»»4ii4 ; M m f, — • ,'*^’ w*^y* 
 
 W T tj'’" 
 
 ^ ,^-/|V4. 5*.« i > - t -Hf 
 
 * '. r .' \[, j V *. 'i •» St .* . - M «. 1 t <• _ ' M .« 
 
 T. 
 
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 . . .. , rr rx . n 
 
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 « 
 
 v't 
 
 4 . .>1 ...4... 
 
 ^ ...... 4, ; 
 
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 C>i3' .. hi 4 ;yn/i . .*vi .. 
 
 f 
 
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 fli xV.^ S4. .' 4 
 
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 t •’/.4 4 1; 
 
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 i - A J 4, _ . .VV 
 
 .if" •■-i , 
 
 L 
 
 V l 3 1 A V J r .t V A .. i j rt 
 
 - - 4 u: i»Mn }<.i*~.x - ' . . 
 
 
 
 L^w i|vl «# 
 
 J T -!W ‘ • 
 
 <-1- - *• - V . _ .-'.s. JK . .-. . .,J a;i 
 
 -.a-r -^-aa 
 
 .11 
 
- 8 - 
 
 sive investigation or txiese metnoas was not oegun until alter 1907, 
 
 oince tnen turee main metnoas nave oeen worKed out; (1) tne 
 
 22 
 
 Willstatter metnou, using platimim olack prepared according to the 
 
 metnou oi Loew^ bhe paal methoa ^*^employing colloiaai platinum or 
 
 palladium protected the soaium salt ol eitner protaluinic acid 
 
 or lysaibinic acid, availaule only for reduction in alkaline or 
 
 , . 25 
 
 neutral solutions j ( b) the 3kioa metnou uses gum arabic instead of 
 
 the sodium salt of <a.n acid as a protective colloid. In the case of 
 
 the 3kita metnOu tne protective colloid is effective in either 
 
 acid, neutral, or alKaline ciOliition . Ao ulie end ox the run the 
 
 colloiu is removed by precipitation with acetone and filtering, 
 
 Skita also originatea tne principle ox inoculation in catalytic 
 25a 
 
 reduction ; a small amount of piatinic or palladous chloride is 
 reduced separately, oy partial reduction in iiot aliialine solution 
 by means of a few cr;^stals of hydrazine njurocnioride in case oi 
 the platinum, and by passing nydrogen gas tiirough the hot palladous 
 chloride solution, in case of tne palladium, A few cubic centimeters 
 of this stock solution is then employed as a ’'seeding'* colloid 
 that aids in the reduction of tne main mass of platinum, which, in 
 turn, catalyzes the reduction of tne substance in question. 
 
 As it appearsG to be the most convenient and the most pro- 
 mising for tne reduction of tne azines, 3K.ita's method was selected 
 for worh at the University oi Te^as, It was successful from the 
 start althougix early runs on ketazine, water, ana colloidal plat- 
 inum protected oy a small amount oi gum arabic, required a large 
 amount of catalyst. Of xen as much as 100 c.c. of chloroplatinic 
 
41 V- 
 
 Oi;. 
 
 . J rC-Tv 
 
 
 (’••../ ;v 
 
 I I 
 
 '-.iU, it.) : •' 
 
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 \ 
 
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 'ir'^ 
 
 '-O. ( 
 
 
 
 
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 •jjrv 
 
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 f-tn. I'.'X 1 4 i> 
 
 ' V* " II mm ^ V- ^ 
 
 r*''< 
 
 VC^ 
 
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- y - 
 
 acia iiaa to oe emplo^ea in tne reduction of 100 c.c, of dimetnyl- 
 Ketazine. jiven witn tne large amount of catalyst the yiela was 
 only about eighty per cent and several days were required for 
 completion of tue reduction. In attempting to improve the yield or 
 at least curtail tne amount of platinum, it was found that neutral- 
 ization of the base formed as the reduction proceeds immensely 
 accelerates the reacLion and maKes it possible to complete the re- 
 uucLion in a single aay witii less than one lourch of the amount of 
 platinum lormerly used, liie ex^ra cnioroplaxinic acia used in the 
 initial experiments procaDly owed its main effect to tiie uydrochlor* 
 ic acid liberated on reduction oi the acid, ratner chan to the 
 
 additional amount of colloidal platinum tnis aaded to the re- 
 
 2 5e 
 
 auction mixture • oince txxen an article by oxita has appeared 
 in Wiiich he makes tne saijie ooservation on tne effect of hydrochlor- 
 ic acid in a similar case. Experience in Inis research indicates 
 ciiat salification is always advantageous when a case is formed 
 in catalytic reduction. 
 
 During the first few neutralizea runs txie necessary 
 nyarochloric acid was added at different times during tne run be- 
 cause it was I eared tnat hyarolysis of the ketazine by a >greater 
 concentration of acid woula diminish the yielas obtained. Later it 
 was iound that, in spite of tixe claims of Curtius and others that 
 ketazine is immeaiateiy nydroiyzed oy mineral acids ,tne 
 addition of tixe theoretical amount oi acia ac tne ueginning of the 
 run in no way diminishes tiie yielu of yu-yo/o of tixeoreticai (based 
 on the amount of xecazine usea) wnicn is obtainea wnen the 
 
- 10 - 
 
 neuLrallzation is aone in steps. 
 
 Since tiiis unexpected result seems to inaicate that dimethyl- 
 ketazine is not hy aroiyzea to an appreciable extent by the diluLe 
 mineral acid under the conuitions oi tiie experimen’^, it appeared 
 iikelj' that reduction ox a mixture of one mol of nydrazine nyarate, 
 one mol of nydrocnioric acid, and two mods of acetone woulu give 
 the same results while, at tne same time ooviating Lxxe isolation, 
 witn ratner unsatisfactory yields, of the xetazine. In tnree runs, 
 where ih each case, 25 g. of hydrazine hydrate in 250 c.c, of water 
 were employed, tne reduction required 5-4 iiours and the yields were 
 7s, 80, and 74 g. of tne nyurochloride oi symmetrical diisopropyl- 
 nydrazine, Altnough only once recrystallized and oiierefore not 
 pure, samples Oi txiis salt meiteu ac, 19 7-8'^, had a chlorine content 
 of 25.8 % (by titration witn silver nitrate uy MOhr’s method), and 
 5 iodine titrations gave an average purity of 95.5/0 (2 atoms o± 
 iodine to 1 mol of the ixydrazine) tuus indicating a yield that is 
 practically quantitative. 
 
 The hydrazo compound formed in tne reduction of dimethyl 
 ketazine is similar, in the main, to otner symmetrical hydrazines. 
 AS is often tne case with aliphatic nyurazines, it is difficult to 
 obtain the base completely anuj,urous. Like symmetrical dili€n 3 .*ji , and 
 
 in contrast to symmetrical dimethyl and diisobutyl hydrazines 
 
 27 , , . , ^ 
 
 wnich form uoch neutral anu c».cid salts , tne uase uerived xrom 
 dimethyl ketazine, in all reactions so far observed, is monobasic. 
 The behavior towards mild oxidizing agenus iso different from 
 tnat of the corresponding dimethyl ana uietnyl compounds. 
 

 
 i ' IP- ‘ I . J ; ' V . 'v *. t --. . ' 
 
 .1 
 
 "i 'iC-i- ^ j . ., 'J '. .: j Li-'.- ■..' .!?■ 
 
 *< 
 
 J /) ; (.W AC ■ >ij ) ( . ,i ' 
 
 y . 
 
 iV I '^nfl- *U’ibCl •>!. ' 
 
 / V 
 
 - i i 
 
11 
 
 iiie preparauion of Lhe usual simple SialLs and aerivaLives 
 
 of nyurazines ofiers no uiifiouiLies in tue case ol Lne symmelrical 
 hydrazine, except in the case of une oenzoyl derivative which does 
 not appear in satisfactory crystalline form uut as a smear which 
 could not ce made to crystallize. This cenavior of the benzoyl 
 aerivative is ratiier common, however, in Lne case of uydrazo 
 compounds. 
 
 most easily preparea derivatives of symmetrical diisopropyl-hyura- 
 
 zine, txie oxal .abe is orouulesome cecause, as in a number of ocher 
 
 29 
 
 oxal .ates of ayarazo compounus, it seems to form a mixture of salts. 
 In tne case of tne case unuer consiueration the aonormal results 
 ODtained on analyses seem to iiave ueen due to tae fact caat the 
 salt consisted ox a mixture, possiDlj ox tae simple ana tae douule 
 oxalJates. After 6-8 recrystallizations from alconol tae product 
 obtained has a melting point of 200° and analyses show tiiat tae 
 compound has the formula; ^ 
 
 Waen a mono-alxyl hyurazine is createu with nitrous acid, the 
 
 imide hydrogen atom is sucstituted as is seen from the fact that 
 these nitroso-hyurazines still condense with alueayaes. In the 
 presence oi c^myl nitrite and alkali cxie nitroso mono-alxyl ayara- 
 
 form an isoazo cate,K— NshOna, 
 
 xae raono-arjl-ayarazines here, as in most ocaer respeccs do 
 not uiffer greatly xrom cae alipnatic ones. In tae case of paenyl- 
 
 Altaouga it is one of cue most beauciful ana one of tiie 
 
 zines can ox ten be made to react again with nitrous acia 
 
 to 
 
I 
 
 f 
 
 I 
 
 I 
 
12 
 
 hydrazine and its suustilution produces and in tiie case or benz^l- 
 iijQrazine, sodium sal os are lormed from oxie nirroso compounds, 
 mis meral may tixen readily ue replacea vj alkyls v/nen alkyl naliue;; 
 are per.iiotea oo react witn tixe salts* Tne structure of onese 
 sodium salts has not jet ceen deiiniteiy established, probauly 
 two or more tautomeric forms exist in equilibrium, somewhat as in 
 the case of acetoacetic ester or in trie oximes. 
 
 In the case ni trosophenyl^hjdrazine a sodium salt is formed 
 wnen the base is allowea to react witxi sodium methylate in the ab- 
 sence of water, ihe sodium replaces an H from phenylhydrazine , but 
 tixe exact hyarogen atom involved xias not yet been uefinitely de- 
 termined, Tne salt could ue formed by any one of the x-ollowing 
 reacLions j 
 
 1) GfeKaH— NHgt- i<aUCH_3-> Cy-i^-W GK5OH 
 
 hO 
 
 2) Cmui'isNh -I- naUUH^ — ^ -J— CH 5 OH 1 
 
 imUH wQWa 
 
 5) CgH-NH-WrwUH+kaOGH3 — > C^H5-wh-i'j=N0Wa4bn30h 
 
 4) K — ri4kaOCH. — v G^fHr. Ciir^OH ' 
 
 IMOH ^ ^ iMQNa 
 
 The Lnira form is maue extremely unlikely because of the similarity 
 of ni trosophenyl-hyurazine to alkyl nitrosohydrazines, especially 
 nitrosobenzyl'-xjLjurazine , in wnicu tixe presence of an amino group 
 is established txxrough the condensation oi the ni troso-nydrazine 
 with aldehydesi?^ Moreover, careful oxidation of the nitroso com- 
 pound witn cupric sales leaas to a uyuroxylamine uerivacive. Tiiis 
 
 compound could naraly lorm unless tne siruciure were tnai given in 
 
 32 
 
 1) unaer tne condieions oi the experiment , Finally, the 
 reduction of the uenzoyl uerivative of niirosopnenyl-hydrazine 
 leads to,*^^ C. C». . 
 
 V. H H 
 

 
 i f . ■ ‘ 
 
 ‘ .Vlf , 
 
 a* f i |'.‘>|J|'' - 
 
 > . f ■■ . 
 
 o^' 
 
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 II 
 
 li 
 
 N>> 
 
 Vi 
 
 • ’ I 
 
 ' I ^ . •;'■! ( 
 
 ;< , r . 
 
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 > 
 
 ^ e-i.J nr /. I 
 
 --I 
 
 • . •■' . ,j 
 
 tr *> ’ 
 
 
 ur 
 
 r . . 
 
 - I 
 
 * ! 
 
 ' . ‘Tjlt’. -'»v. '■ '■• . j. • ^; ,'x^ 
 
 ji , ■ * t‘’-» ■ »• . "ill fv- **' 
 
 ;i 
 
 ji I;. . f #■' A J* 
 
 t 
 
 1,1, 
 
 ^ rj 
 
 I c oTfai if 
 T 
 
 Lr* 
 
lo 
 
 5 b 
 
 Fischer in nis original investigation oi nitroso-pnenj 1- 
 iij'urazine, consiuerea tnat it was a normal nitroso compouna oe- 
 cause;^l) reduction leads to aniline indicating that txie nitroso 
 group is not attacheu to tne benzene ring, ana (2) in amines nitroso 
 compounds are only formed with secondary amines, i.e* those with 
 an imide hydrogen atom. From tnis ne concludea that the secondari- 
 nitrogen of pnenjlhi'drazine is the one to which the nitroso group 
 is attached. Ke also pointed out tixat unsymmetrical secondary 
 hydrazines which iiave no imide hydrogen atom do not form nitroso 
 nyurazines, uut are promtly decomposed on treatment with nitrous 
 acid. In nis opinion txxe lormation of pxierijlazide on treatment 
 of nitroso-pxxenyinyurazine with dilute alnali snows that water 
 splits out between txie nitroso and txie amino group , again showing 
 that the nitroso group is attacixoa to tne seconuary nitrogen aoora, 
 
 Tixieie'^*)^^’ ^ in view oi new evidence, did not entirely ; 
 
 agree witn Fiscxier, He consiuerea that tnere naa to be some sort of 
 tautomerism to account lor some oi the facts oDserveu, If txie i 
 
 structure of ni troso-pxxenylhyurazine were accurately expresseu by 
 
 NK2 unuer all conuitions it would oe hara to avoid the as- 
 wU 
 
 sumption that the formation of a sodium salt is due to the activa- 
 tion of one of txxe two hydrogen atoms of txxe amino group — an as- 
 sumption that seems ixardly reasonaole, Furtxxermore ixxiele pointed 
 out tnat txxe quantitative elimination ox. i\i^O from txie phenylhyara- 
 zine derivative uj simple heating is uiflicult to understand on the 
 basis of the Fiscxxer formula alone* Moreover, ooth oenzaldehyde 
 
 and acetaldehyde uo not react normally with nitroso-pxxenylxxydrazinoj 
 
 G0H^-iN-W=CH-CgK5 34 3i' 
 
 but yield the tetrazine. 
 
 C6H5-iM-i\i-CH-CbH5 
 
 and 
 
 ' H *7 ^ 
 

 
 
 
 
 r 
 
 ■’ i, 
 
 »■ I 
 
 
 ' #kW A 
 
 
 
 r y 'll 
 
 :' -\ 
 
 -..iJ 1H 
 
 . ■* V, 
 
 \i; 
 
 
 
 
 !**»• lU 'I 
 
 -< 
 
 iv 
 
 I V C l (,■ ' < ~ •■ 
 
 *•• H"' V., V 
 
 'n^riWMUv •(»• 
 
 4 *^' , 
 
 '■ ' _. ,V'‘ L ' oq t . _ , 
 
 i cpr <5*vifti .[Tirt 
 
 
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 C l 'Jfr 
 
 A 
 
 ,•'4 
 
 .iS, ivr ; iVi. , c ■ 
 
 
 Cw cji. ,j^ ' r«* 
 
 c . 
 
 ^! 0 J| 
 
 
 .'I I 
 
 
 
 ) ^ 
 
 ■< « ( . X . M IJ £ 4 i .] jg^jt 
 
14 
 
 respectively. UurLius ±ound tnat ni troso-uenzylhyarazine wiiicn also 
 xorms a souium salt ana in OLner lespecLa is closely' related to 
 nitroso-piienjlnjarazine in properties xorms normal condensation pro- 
 
 r-» -T 
 
 ducts with the same alaenju.es. 
 
 56 
 
 Tiiiele found that the elimination of NgO is common to doth 
 
 the aromatic and the alipnatic primary n^urazines, while not a trace 
 
 of eliminated from the secondary nyurazines such as nitroso- 
 
 37 
 
 di-denzylnyarazine . Tniele and Sieglitz explain tne reaction of 
 denzoyl cnloriue on nitroso-phenylnydrazine by; 
 
 hO 
 
 ^ ^ JMO 0 ^ 
 
 bnuic ^ 
 
 bp gob 
 
 H1M02 
 
 All Of tnese facts coniirm liscner’s conclusion that the 
 
 nitroso group is attached lo the secondary nitrogen atom as one 
 
 form of tne nitroso compouna, but, to explain tne lormation of NgO 
 
 ana other reactions observed, it appears tnat we nave to agree 
 
 witn Tniele in nis assumpuion txiat anotner form oi the nitroso 
 
 ^ 56,57 . , 
 
 compound consisLS of a tnree membereu ring wnich exiscs as 
 an intermeuiate form in some of tne reactions encouniered . The 
 formation or aziaes ana the elimination or if 0 from nitroso 
 
 (a 
 
 hydrazines woula then ue explaineu by the following steps; 
 
 K-N — NHo^: — » R“W— -N-K < — ) K-NK-W-H ^ KNH 
 
 NO ^ n5h wo 2 2 
 
 hamberger suggested yet anotner lorm wnich may exist as 
 a tautomer of tne original f'ischer formula, JPecause iie found tnat 
 ni troso-pnenylnyurazine forms a copper salt wnicn on treatment 
 witn either acetic aciu or ammonia yielus a compounu of tne 
 formula; or G^n^-iii-hUn. Kizis , one oi rhiele's 
 
4 
 
15 
 
 stuaenLs^ poinLeu oul unaL Lue reaaj' trans formation oi' oC-nitroso- oc- 
 benzyl-^ -metnylhjurazine io <-nitroso- oC -methyl-j3-benzyili^ urazine 
 as well as the lormation of o(-nitroso- oC -methyl-J3 -Denzilidineiiydra- 
 
 zine by oxiciafion of o( -niLroso- o(^ - benzyl- -methylnyurazine 
 ai l orbs a sLrong proof of Lhe existence of one three tauoomers 
 mentioned, since Lne rearrangemen os aoove may tnen be readily 
 
 shown by one following reac Lions ana rearrangements; 
 
 G.H, -GHo-N — WfiCh^- 
 o 5 ^ X,-. o 
 
 i'lO 
 
 G^n -Gri^ -i'j iM-Gh-r 
 
 i'jQn 
 
 -X^CeH^-GKg-N^N -GK^ 
 N OH 
 
 G .H(--GKo-NrH — GK„ > C Hj- -GH. , -HH-N— CH 
 
 The sodium salts oi sucn compounds can Lixen ue expressed by 
 
 either of tixe following Lxxree foimuiae; 
 
 (1) (2) = (5) 
 
 HO Na hONa hOHa 
 
 It is very uixficult, if noL impossiule , lo uetermine at the present 
 time whicn oi tnese turee possible forms exist ana which is the 
 one tnat is found as one major produco at any Lime. Ghemical reac- 
 tions offer little iiope ior Lne soluLion oi tnis problem and 
 physical meLhoas nave so lar not seen developed far emoLigh LO 
 
 warrant tneir use in tne case of ni orogen compounds of onis type, 
 
 P 
 
 An interesting confirmaoion of the assumtlon that bhe oxime 
 form exists in Lne case of nitroso hydrazines is brougxxo oul 
 tnrougii the fact Lnat seconucxry niLroso nyurazines give an in- 
 tensive blue color witn ferric chloride in aqueous solution, a 
 green color in alooiiolic toOluoion, ana a red soiuoion in solution 
 
 of a non-dissociaLing solvent sucn as i^enzene, cnloroiorm, and 
 "'iV 
 
 ether, Alternaue uudiLion of wafer or aiconoi brings auOUL Lne 
 
r 
 
 t < 
 
 
 if 
 
 
 * ji 
 
 i \ 
 
 
16 
 
 corresponding oiiocnges or color. Tnis uenavior seems to indicate 
 racner aeiiniteiy uuat tne color is due to a strong ii^droxjl ion 
 formation in aqueous solution, a lower one in alcoholic solution, 
 ana tiie aDsence of Luis dissociation in such solvents as uenzene 
 ana ether. The same color changes are prouuced in ihe case of 
 the nitroso aerivative csl s^'mmetrical aiisoprop^'l-h^'drazine although 
 the color rapidly faaes cecause of the rapid reduction of the 
 ferric salts formed. Tnese color cuanges can nardlj oe understood 
 on tne assun^^tion that tne I’iscner iorrrn*ia is the only form in 
 wnich tiiese compouiius exiot. Aituough Lue proof is not y jt con- 
 clusive it appears very liii.eiy tuat tne salts of nitroso-hydra- 
 zines exist eitner as formula (2) or as (o) page 16, while the 
 ni troso-uyurazine as sucii may normally exist maixily in the form 
 assume a Cy liscner. 
 
 Nitrous acia reacts wl symmetrical disuhs ti tutea 
 
 iiyarazines in two aiiferent ways. In most cases the mono-nitroso 
 
 hy 
 
 compound is formed . In some cases, nowever, especially where 
 
 acia salts of the base are staule, the dinitroso compound is 
 
 iormed if an excess of nitrous acid is employea. ^he mono-nitroso 
 
 derivative may also be formed by tue alky la Lion of the correspond- 
 
 . , .69 
 
 mg primary nitroso nyurazme 
 
 The more interesting oi the two types of ni trsos<> compounds 
 of symmetrical nyurazines is the ui-nitroso derivative because it 
 decomposes readily to iorra an azo compound and 2 mods of nitric 
 oxide. Tuis reaction takes place even in tue cold in tne case of 
 tue dinitroso aerivative of uydrazome thane. 
 
17 
 
 In Liie oaae oj. s^mmeLrical u.iisopropj injurazine, ohe mono- 
 nitroso oompouau xias, t>o i'ar, ueen Lhe only nioroso (jompound iso- 
 laLed, Tne xact liiai inere is, in txie case oi the uerivative pre- 
 pared wiLh acet-ic aoiu and an excess oI sodium nitrite, always a 
 consiaeraoie amount oi evolution oi gas even alter tiie excess of 
 acid lias been neubralized may inulcate tnat there is always form- 
 ation of a small amount oi tue di-nitroso compound whicn would 
 prouauly be very unstaole and decompose before it could be isolated 
 Cooling slows dov.n tne gas evolution out uoes not stop it, and on 
 warming tue reaction continues at tue former rate for several 
 hours oeiore linall^ slowing uown ana stopping entirely. 
 
 The properties oi tue nitroso compound agree, in the main, 
 with tuose of ooaer nitroso compounds described in tue literature. 
 The intensely olue color with ferric cnloride, and the Lieberman 
 reaction are louiid uere, as in otuer nitroso compounds. Peculiarly 
 enougii, however, nitroso-Sj'mmetrical diisopropyl-iiydrazine yields 
 a sodium salt when treated with a concentrated solution of alcohol- 
 ic sodium hydroxide. It is impossible to say at this time v;nich 
 01 tiie structures advanced for such compounds (page 15) is the 
 most probable one for this sodium salt, but it seems reasonable to 
 hold tnat the oxime structures auvanced bp rhiele and hamuerger 
 arc more likelp to be tiie ones iound uere uuan tue xormula 
 assumea uy i-iscuer, 
 
 Keuucbion of one nitroso uerivative leads to ammonia and 
 
 symmetrical ui isopropyl-hydrazine instead of to tue amino cora- 
 CK. /Ch^ 
 
 pound, Gh-i,M“NK-b;H • 
 
 CHJ' hKg CH5 
 

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 Wiien tne ury lijarochioriae oi tne nj-arazo oomp^u is mixed 
 wiLu an excess of copper oxide, a peculiar sweeLisn odor is oDserved 
 in auouo 15 minutes. In the course oi an uour, ii tlie excess of 
 cooper oxide is not Loo great, some moisture may be observed on the 
 crystals, by nexu morning the mass is uistinctly moist while the 
 odor lias become much more nouiceaule. A! oer 5-4 days the mass is so 
 wet thau it may ue pourea irom txie flask in wnich the oxidation 
 tooK place. After anotxxer day or two tixe reaction mixLure in tiie 
 original flask is distilled in a water uath. If the xieat is applied 
 slowly the ruby red crystals oi an unstable copper sale wxxich is 
 
 firsi ouserved on the seconu or ixiiru uay of ixxe oxidation process, 
 are found to change suddenly from red to greenish wniie at 8B.5°. 
 
 At oxxe same time i.ue oxidation pfoauct distills over as a yellow 
 oil 01 a nauseatinglj sweet oaor, from y2-9B° tiie disbillate is 
 composeu largely of waier wxiich xorras a separate layer underneath 
 txxe oil layer* 
 
 The yellow liquia is reaaily uried over calcium chloride 
 
 and is pure afier one f ractiona bion. The analyses and tiie molecular 
 
 weigiit deuerminauions show that the compound has the empirical 
 
 iormula, G-H-. This lormula applies to 2 ,2 ’ -azobispropane and 
 
 b -L4: ^ 
 
 to the tauLomeric acecone isopropyl-hyurazone , The determination 
 
 of the structure of tixis compound constituted one of tiie most 
 
 diificult parts of this investigation. 
 
 Aromatic azo compounas have been known lor almost a 
 
 4u 
 
 century and have been txiorougniy stuuied, 
 
 hixed aromatic-aliphauic azo compounas are known and 
 are interesLing uecause txxey of uen cnange over very readily to the 
 
- ly - 
 
 45 
 
 tautomeric sLrucuure • 
 
 Kyurazines oi tne tjpe represented, by symmetrical di- 
 
 benzylnyurazine are usually oonsiaered as alipiiatio hyarazines 
 
 although their properties uiTfer considerably, in some cases, from 
 
 tne purely aliphaxic compounds represented by such compounds as 
 
 symmetrical ui-meUiyl-nydrazine and Lne hydrazo compound prepared 
 
 in txiis investigation, ihe uiiierence in properties is probaoly 
 
 due tO tne proximity oi the phenyl group. Symmetrical hyurazines 
 
 of ail types tenu to yield stable, slightly colored or colorless 
 , . 44 
 
 azo derivatives, 
 
 hone OI the azo compounds so far xnown are very closely 
 
 related to Lhe product to be expected on mild oxida.tion of the 
 
 hydrazo compound derived from uimetiiyl xetazine, Azo metnane is 
 
 is tne only homoiogue of 2,2 ’-azobispropane known so far, IL has a 
 
 very faint straw color in txie liquid state, but is colorless as 
 
 59 
 
 a gas (hence often erroneously called a colorless compound). As 
 is indicated by a boiling point of only 1,5°, its properties may 
 differ considerably from tiiose of tne higher homologues because 
 it is a well Known fact that the properties of the first members of 
 a homologous series are often markedly different from those of 
 member witii five or mors carbon atoms. 
 
 The light straw color tnat is observed in every specimen 
 prepared, tiie neutral reaction, tiie immiscibili ty witn water, 
 dilute alkali and diluLe acid, and tixe unexpected stability Lo- 
 wards nyurolyzing agents wnicn maxes it necessary to employ a 
 solution of 1 part of water to 1 part of concentrated hyarociiloric 
 acid if tixe hydrolysis is to oe completed within an hour of 
 

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20 
 
 boiling unuer reflux, all inuicaleci ouab lue oxidalion product, 
 is actually tne azo compounu. An examination ox tne t^-pe of 
 tauoomerism snowed tnat tne properties mencionea, although thej' 
 led to a strong presumption that Liie azo compound nad teen formed, 
 did not aosolutely excluv:ie tne possibility that the substance 
 niigiit be the hyurazone in spite or inaicauions to the contrary, 
 xhe i allowing uiscussion snows wnat basis there was for any un- 
 certainty in regard to the structure of tue oxidation product. 
 
 ae 
 
 Alipiiatic azo compounus tena to ^ompose in two different 
 ways. One is an actual aecomposi tion, the otner is a rearrangement. 
 (1) Azo compounds may rearrange from the azo to the hyarazone 
 structure; 
 
 -CHg-hsb-n »■ -Ch-h-hH-K 
 
 (2) Tiirougii elimination of one molecule of nitrogen gas, azo 
 compounas may uecompose to form hydrocarbons; 
 h-Nsh-R * K-K-/- ^2 
 
 Among cases so far observes tixe nydrazone seems almost always to 
 be trie more stable form, altiiouj^n , in the case of symmetrically 
 substituted hyarazines the azo is usually stable enough to be 
 isolated, while some, lixe azomethane are stable enough to with- 
 stand rather nigh temperatures without showing any sign ox re- 
 arrangement to tne lijurazone form. 
 
 43a 
 
 i’ischer was the lirst to observe a case of this kind of 
 isomerism wnen he notices tnat acetalcehyde-pnenylnydrazone is 
 formed readily wnen phenylazoe thane is treated witn acids or alkali. 
 In many C 0 .ses, isolated since, it nas not been possible to isolate 
 
It. 
 
 , 'I. 
 
 a ' sj - ' t' i. 
 
 * 1 ': 
 
 
 I » 
 
 
 ■■ c.V'j likit 
 
 * i»» 
 
 ^ : 'r; 6 xu , . .' : • 
 
 
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 I 
 
 » 
 
 fLi 
 
 r : .-r sjaefe 
 
 ■| 
 
 J 
 
 
21 
 
 the azo compouna txxau is supposed to De an intermeuiate in the 
 
 oxi nation of a symmetrical n^drazine to tne hyurazone Inat is 
 
 45 
 
 iinally isolaied. 
 
 In tne case of uiphenyl and tripiienyl metna^v? derivaiives 
 tne azo compound is also not stauie, Put in ouese cases cLe com- 
 position of the final products shows chat the second type of de- 
 composition of azo compounds has c-aken place, i.e. nitrogen gas 
 
 3S 
 
 and a iiydrocaroon are the products. 
 
 In Liie case oi Kiscnner's spuLhesis of nyurazones of tne 
 
 . . 44 
 
 type, R-hH-h-R , ine in uermeuiace azo compound is nou isolated • 
 
 Azo isobutyric acid and tue dinitrile irom which it is formed are 
 
 stable uecause tney cannot rearrange according to oixe first Lype 
 
 of rearrangement. Wiien, ni^ver, caruon dioxide is eliminated from 
 
 , . . . 4lc 
 
 tne compound it rearranges immeuiaoeiy to tne iiydrazone. 
 
 Wnether tne same rearrangement wouiu taxe place ii two, in^teau of 
 one mol or waroon dioxide , were eliminated could not oe snown by 
 Tiiiele.The compound obta.ined on oxidation of the hydrochloride 
 of 2,2 ' -hydrazobispropane, shows that the rearrangement would not 
 iiave taken place ii’ 'iniele hau been able to eliminate both mole- 
 cules of carbon dioxide at tiie same oime. 
 
 irom a consideration of the rearrangements just discussed, 
 it may readily oe seen 
 
 ^nat a compound wnicn, like the oxidation product under discussion, 
 may be refluxeu for ixOurs and may even be treated with sodium 
 alcoholate for severul uours at a time at 110° witnout any notice- 
 able cnange, mi^^iit well be mistaken for a uydrazone in spite of the 
 other properties mentioned. Since absorption bands could not be de- 
 
IT’ > 
 
22 
 
 tec ted in tne visiDle spectrum on examining the oxidation proauct 
 ior sucii bands, ana since Lne refractive constants for nii-rogen 
 
 in compounus nave not been aetermined for compounds of txiis typ® 
 wii-n sufficient accuracy to make them useful in proving cxie struc- 
 ture of a compouna fixe 2,2 ' -azobispropane , physical means did not 
 seem to offer any xxope of being aole to prove the structure at all 
 
 conclusively by their aid. 
 
 The only 'lvw f easily methods left now were; 
 
 (l}The preparation of a aerivacive of the oxiaation produce, and 
 (2) the preparation of tixe xx^arazone itseli by some otxxer metxxou, 
 Oi txxese, tixe xirse gave little xxope of success since if became 
 apparent, after a series of experimenes, that no derivaeives that 
 would be of value in proving its structure could oe obtained fron 
 tne oxidation product. Possibly' sucxx derivafives may some day oe 
 
 prepared by mecxious enat were not tried in 
 metnod xxelu out equally small nope at xirst 
 
 fxiis worn. Txxe 
 as 
 
 , in as mueix. 
 
 A 
 
 second 
 in spite 
 
 of numerous trials under varying condifions no xxydrazoixe could be 
 
 isoiafea alfxxougii the ouor of a new compound coulu be nofeu. in a 
 numuer of f rials. 
 
 ji ^ 
 
 heddelien’s metxxod of condensing aromatic amines with 
 aldehyues and ketones fo lorm aniles proved to be the only metxxod 
 that gave a good j'ield oi tiie h^'drazone. 
 
 Zinc cxxloride is very oi ten used as a dexiyurat ing agent 
 since it is one of txxe most hygroscopic of suustances. Moreover, 
 txxe vapor pressure of water over moist zinc cxxloride at 25*^is only 
 0.85 mm while at 50^it is still only 2.99 ram. Since txxe adsorbed 
 

 
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25— 
 
 waLer is noL given oif unoil one meioing point is reacheu at 2yu- 
 
 o , . ' . 
 
 297 , tuis salt , in manj' cases , oe used as a aehyarating 
 
 agent irom wnich one tiie dried substance may oe di skilled directly 
 Naourally, une tendency of zinc cnloride to form complex salts with 
 amines and many otner substances must ue taxen into account, 
 
 Keddelien made one peculiar ooservation that, in the pre- 
 paration of anileSjthe zinc cnloride does not act so much as a 
 aexiydrating agent as in me capacity of a catalyst; i.e.the salt 
 
 does not ’’bind” the water, out immeuiately li cerates it as steam 
 
 o 
 
 at the temperature of 170-180 employed oy this investigator in 
 his condensations. Tnus,in the preparation of benzophenone-anile, 
 he employed l/40 mol of zinc Cuioride to 1 mol of eacn of the 
 otner reagents, and ^et obtained a very satisfactory yield of the 
 anil . Tnere is nere tuen here some sort of catalytic action 
 similar to tnat of iodine when it is used as a condensing agent 
 in tne preparation of the same type of compounds. 
 
 makes 
 
 Anotner interesting observation tnat Heddelien^n tnis con- 
 
 nection, is tne fact tnat tne zinc Culoriue acts as a catalyst only 
 in cases in wnich the uases concerned form a definite compound 
 with the zinc salt. If sucn a salt is not proauced the zinc chlor- 
 ide acts simply as a denyarating agent; one moi oi uhe zinc salt 
 must be used to one mol of the uase and tne reaution must be run a 
 a nigner temperature than in tnose cases where the zinc salt acts 
 as a catalyst, 
 
 4? 
 
 The work of 2 oeppritz and Dimrotii ma^^ tnrow some light on 
 the mechanism of tnis type ox condensation reaction. They claim 
 
I 
 
 i 
 
 I 
 
 I 
 
 i; 
 
 I 
 
 ! 
 
 • »r* 
 
24 : 
 
 i/iiao anile (and presumaul^ also u^drazone) xormaLion takes 
 place in ovvo SLeps; 
 
 \ ^ 
 
 /C 3 O 4- Kj^N-K > C— K-k > ^C-K-k (k = aromatic.) 
 
 k H H n -f- 
 
 K^O 
 
 Tney isolated tne intermeoiate proauct. It is very easily decompose 
 ed uj heat eitner inco tue original subsLances or into tne de- 
 sired anile, xne lact tnat tne lirsL step coulu not be ouserved 
 in the preparation ox ace Lpne-isopropyl-hydrazone may mean that 
 in xnis case, Lnis suusLance is so unsLauie cnat it immediately 
 eliminaLes wacer and cixanges co tne hyarazone even at 40-60^ at 
 which this reaction is run with besc yields. 
 
 Contrary to the experience oi neudelien who naa to heat nis i 
 reaction mixtures to 170-180 uegrees, it is found tnat tne re- ' 
 action mixture of acetone, zinc cnloride,and primary isopropyl 
 iiyarazine heats up spontaneously and has to be coolea to xeep tne I 
 temperature irom rising auove 40-b0 degrees with too much loss of ' 
 acetone on boiling. Zinc chloride reauily forms a compound with 
 the primary hydrazine, but, as only a small amount of zinc salt is : 
 employed the amount of complex salt lorned uoes not greatly lower : 
 I'he yield of nyurazone obtained. The product is distilled directly ' 
 witnout attempting to filter tne zinc salts that are found in the ' 
 mixture. There is a slignt lowering of yield due to this dis- 1 
 
 tillation xrom tne salts, out this loss is not as great as that 
 uue to attempiing to filter off the gelatinous zinc salts tnat are ■ 
 iormed in txie reaction, me pro^auct Outaineu on distillation is 
 mixed with an equal voiume of ury etner and dried over anhyurous 
 
25 
 
 soaium sulphate for 5-4 uays. uistillation now gives a yiela, 
 sometimes as nign as of the calcuiaLea yield of the color- 
 
 less hydrazone boiling between 125-and 135°. On refrac oionation of 
 
 this part almj::.t ail of the producL comes over between 132 and 154°, 
 
 a 
 
 Thus prepared the hyarazone isy^colorless , basic, liquid witn sting- 
 ing menthol odor. It is extremely sensitive lo any nydrolysing 
 agent, even water reauily nydrolyzing it into its original 
 components. Ixiis explains vnhy it was so difficuiu Lo obtain tne 
 product in Lhe earlier experiments made in an attempt to produce 
 tnis hydrazone as a part of this investigation. All attempLs to 
 make the benzoyl, tiie phenylmustard oil, the cyanic acid, or the 
 hyarocyanic acia uerivauives of Lue h^arazones failed for the 
 same reason. Tne prouuct obtainea was always tiie derivative of 
 tne primary nyurazine — one oi tne ny aroly sis products. The hydra- 
 zone is the lirst one tiiat has been isolated among the purely 
 alipxiatic series of nitrogen compounus while the azo compound 
 is the second azo compound tnat nas ueen prepared in this series. 
 
 The azo and xiydrazone stand also as the first case in wnich both 
 txie azo and txie hydrazone corresponding to a single aliphatic 
 symmetrical ixydrazine nave been Isolated. 
 
 A comparison of txxe properties of txxe two tautomers leaves 
 no doubt as to the structure tnat must be assigned to each, For 
 convenience these properties are arranged in tabular form as 
 Table I on page 26., 
 
26 
 
 TABLii I • 
 
 Tabular Arrangement ox tne Most Important properLies or 
 
 2,2 ’ -Azouispropane and Acetoneisopropyl-Kydrazone , 
 
 Property — — 2,2 ‘ -Azobispropane — Acetone-Isopropyl-Aydrazone 
 
 Color — _ _ rainL Straw — — _ Colorless 
 
 boiling Pt, — — 68.5^ — _ _ _ 132-4° 
 
 Density t/4 — — - .7408 — — — _ ^ ,8223 
 
 Iwol.Wt _ _ _ _ 114 (110,119)- _ - 114 (106,108,104) 
 
 Mol, Volume _ _ _ 154 — _ _ _ _ 138.7 
 
 ^ (Abbe) _ _ _ lo3890 _ _ _ _ _ 1.4560 
 
 Carbon fa (63, lo Calc)_ 63.18,63.02, 63.02 — 62,69,63.00 
 Hyarogen/o( 12 ,28 “ )-12,03,12,0b,12,46 — 12.47,12,56 
 
 Hitrogen;>i( 24, 56 '• )- 24,67 — _ _ — 24.98, 24.34 
 
 Odor — _ _ _ 
 
 Synthesis 
 
 Nauseatingly Sweet _ 
 
 Oxidation of 
 GHv 
 
 CH3 
 
 Stinging, ken tiiol 
 
 CKv /GH'i- 
 
 CH3 ■ ''CH3 
 
 behavior towards j 
 
 Water _____ Insoluble _ _ _ _ Soluble. Hydrolysis 
 
 Dilute acids — — - — _ _ _ » 
 
 Dilute base — — “ — — — — Solution and slower 
 
 hyurol jsis 
 
 Gone. Alxali and Heau- Partial hearrange- — ho change to azo, any 
 
 ment Lo ii;iurazone conairions . 
 
 heauction _ - Sasily to Hyarazo basily to Hydrazo 
 
 Oxidation — _ - Staule oruinury , weak. — Decoraposi tion.ned color. 
 
I 
 
 c 
 
 I 
 
 
 I 
 
 c 
 
 - om 
 
 i 
 
 I 
 
 I 
 
 
 tl 
 
 ■I 
 
 - 1 
 
27 
 
 VVLen one azo oterivacive ox symmetrical aiisopropyl-uydra- 
 zine is uoilea un^er refiax witn b0;50 hydro'cnloric aciu and 
 wauer one supernatant oily layer of azo compound gets thinner 
 and tninner and aiLer about 30 minutes uisappears entirely. 
 After auout 30 rainuLes more the tixe condenser is arranged i'or 
 
 distillation and tne aceoone distillea oif . Tne rest of the 
 
 the 
 
 liquid is distilled off under^vacnum of a water pump until the 
 resiaue has uecome syrupy . If the syrup is now coolea in an ice 
 oatu the wnoie mass turns solid. The fine crystals are filoered off 
 rapidlji uy suction and the xiltrate concentrated some more ana i/ne 
 same procedure repeateu unoil only a few c.c, of filtrate remain, 
 Xhe last residue of one iiydrochloride of primary isopropy^l-ixydra- 
 zine may be removed irom inis filtrate now by adding a few drops 
 oi alcohol and several c.c, of etner, Unlixe the nyarochloride of 
 the symmetrical nydrazine ihe resiuue snoula noi ue evaporated to 
 dryness because the iiydrochloride apparently uegins lo decompose 
 lefore it crystallizes out of a syrupy solution like one one ob- 
 
 r . • . 
 
 tainea on concentration of ohe hydrolysis mixture. The hydrochlor- 
 ide is puriiied by rocrystallizaiion irom a very small amount of 
 alconol, or from a mixture ox a very small amount of alcohol to 
 whicn wnile not etner is auaed to tne first permanent cloudiness, 
 pie hyarochioriae prepareu tnru hyarolysis oi the azo compound by 
 2 onc. acid as described above is very hygroscopic , wnile the one 
 obtained by either of tne other metnods mentioned in the next 
 -wo paragrapiis is not hygroscopic or at most only slightly so. 
 
 ,30 bh salts yielu tiie same case on treatment with a concentrated 
 soluLion oi souium iiydroxide, probably tne iiygroscopic salt is 
 
2a 
 
 tiie acid salt since iz is prepareu in one presence of tne fairly 
 concentrated acid and since tne aciu salt is usually tne more 
 ii^'groscopic salt, decause oi tne aiii'icultj of wonting witn an 
 exLremely nygroscopic salt, no attempc was made to analyze tne 
 ii^'groscopic salt, uut the neutral salt was analyzed and proved 
 to de normal. 
 
 Primary iso^.ropyl-hydrazine is also obtained wnen the 
 hydrazone syntiiesized above is nydrolyzed by dilute acid or 
 even by water. The products formed here, as in the case above, 
 are acetone and tne primary nyurazine. Tne acetone was identified 
 in each case by means of the benzilidine derivative, by means of 
 tne iodoform test, ana finally uy the souium ni troprusside color 
 
 test. 
 
 and best 
 
 A txiir^t^rae txiod oi preparing tixe same primary hydrazine 
 
 consists in reducing an equi-moiecular mixture of 
 acetone, ny urocnioric acid, anu njurazine nyurate in exactly tiie 
 same manner tnat the symmetrical aisuusti tuted hydrazine is pre- 
 pared. The isolation of tne ny drocnloriae is accomplisneu in txc 
 same manner for any of the three metnods described. 
 
 n 
 
 The simple xiyurazone, was prepared by the 
 
 metiiod of (jur tius'^'^, but is too unstable to be used in obtaining 
 
 the physical constants of tnis class of nitrogen compounus. 
 
 tiie dibenzoyl and the phenyltniosemicarbazide derivatives 
 are readily prepared and were analyzed in connection witn the 
 positive identification of primary isopropyl-h^ urazine , 
 
 primary isopropylnyurazine may be liberated from tiie 
 
 
// ■ 
 
 ^ f 
 
 f 
 
 > 4 
 
 
 M 
 
 j G ■ ' i.\ . -vj ' 
 
 J' / . ' 
 
 
 
 i' 
 
 
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 t 
 
 ( , 
 
 I' 
 
 i'. 
 
 I 
 
 I'. ■ 
 
 /< 
 
 .4' ,/ 
 
 -i - 
 
 
 
 I 
 
 M 
 
 I 
 
 \ 
 
 '^1 » *■ — 
 
 dF ir ^ V 
 
lijurociiloride in tue usual manner oy vorj concenLraLeQ alKali 
 which causes it to rise to the surxace to lorm a supernatant 
 la^er ol jellovi/ oil, Tiiis la^er is then uriea lirst witxx i'useci. 
 potassium j.i^'Q.roxiu.e and Lnen wiori aluminium amalgam, Tne amal- 
 gam is slow in ios action, ouu the case is tiiorougiily dried by 
 it, Melanie sodium is found to be satisfactory and ver^' fast 
 in its acbion in drying tne symmeLrical hydrazine, but it seems 
 to decompose part of the primary liyarazine if an attempt is made 
 to use it here. In every case the base produced from the iiyaro- 
 chloriue constantly gives ofi' oin^ bubbles of gas even Wixen the 
 i'ij drazine hecs been tnorougiily dried and dist-illed in an atmos— 
 piiere of nitro^^en, kiscimer reports tne same beiiavior in the 
 case of neptyl ana ocLylhydrazines. No satisfactory analyses were 
 Obtained on tne xree base and a determination, of its pxiy’sical 
 constants is eviuently useless since refractive inaex determina- 
 tions show Lnat the compound gradually uecomposes. The boiling 
 point is between 104°anu lOG^for the fresnly uistillea base. The 
 primary hjdrazine was definitely iaentixied tlirough analyses of 
 the hydrochloride and oi the dioenzoyl and phenyltiiiosemicarbazidte 
 derivatives. 
 
 compounds uifiering in only small details, an attempt was made to 
 determine as many physicaj. constants as possible on all com- 
 pounds tuat are stable enough to permit a reasonauly accurate 
 
I 
 
 
 ■ >? 
 
 ^ , ... ■ ' ' i" ^ 
 
 i, >.iUjoJ , . . ' . 
 
 js I. X \,u'iJO, .1 
 
 ■ -I ’J 
 
 '• I 
 
 • ' ' ‘ I 
 
 • j 
 
 ' '•..M 4 - ,• ' ^ j’ 
 
 t 
 
 ) 
 
 j 
 
50 
 
 de lerminaiion oi sucn constanos. Tiie results of Lhese ueLermina- 
 Lions,as far as completed, are here offered as tne^ were obtained 
 witiiOuL any attempt at generalization. It is hoped, uowever, tnat, 
 wuen the corresponuing constants xor otiier series of such com- 
 pounus oecome availaole generalizations of value maj be arrived 
 at • 
 
P. 
 
 
 
 
 W' * 
 
 ■% 
 
 
 ” ' ' J 
 
 L;,-, 
 
 I ^ < r • _ ■''**; '■'i< •* j s‘ ■ i 
 
 
 I 
 
 V y T 'W « 5 
 
 . o|C»A -C - > -4» Jr-.»-, . U*. **l-( 
 
 . .. } 
 
 
 ■ . -V ' 7 ^ ,' ^ ' Mp 
 
 M-r-- -‘ t>*-:^Do4w 
 
 ''^i« ;Vtft wu.r.i/vf;,. ‘ ' h'i.“ •■'WjSIik:- j'jr 
 
 *’ . 7 ‘ • ’ ■■/' 
 
 
 
 ^ 1 ^ 
 
50 
 
 II iiiXPJihiMiii'j ixU-i 
 
 DlkiiTHxL ti-iilTAZINE.- Tiiis compouna V\^as prepared according to tiie 
 
 IBd 
 
 method oi Curtiub and Zinkeisen • _ue -ieid was not satisfactory 
 at any time. Vi/iiile the method, as given, gives a yield ox 60-70;;'o 
 ana a slignt moaix'icaLion ox the metnod^i.e. the use of a 
 excess Ox acetone, increases tue ^ielu to 70-75;3, uhis yield 
 can not De consiuered satisxactory in view of the nigh price of 
 hydrazine at L,nis time. Tne use of sodium hydroxide was abandoned 
 for a while and sodium carbonate suostituted for it buL the 
 yield remainea the same. 
 
 A rea oil was always obtained as a residue after Lhe 128- 
 135^ fraction nad ueen uistilled off. -ne residue, wnen hot, ig- 
 nites on contact witn air, showing InaL tiie substance is very 
 easily oxiutzea. Tne yield was coo small nowever to permit iso- 
 lation and iuentif ication of che oil. 
 
 ATTEkP^'8 TO iiEDUOS xHE KETAZINS. - Altnough not much hope of suc- 
 cess v/as entertained since a number ol chemists nau tried and 
 failed to reauce uimetnyl xetazine, anotner series of attempts 
 
 were made to reduce the xstazine with common reducing agents 
 
 through 
 
 alter tiie reauction products v;ere known^euuc Lion of the ket- 
 azine uy a metnou uescribed later. It was hopea txiat a knowledge 
 ox" tne compouna to ue expected would permit cne iuentix ication of 
 a small amount of riydrazo compouna tnat mhgnt nave escaped the 
 attention ox earlier investigators, oouium as amalgam^ and as metal 
 in alconol; alum-inium as amalgam^ and as xree metal in the pre- 
 sence of potassium hyuroxiue, gave traces of reduction compounds 
 
c* . 
 
 ri- 
 
 .M 
 
 tf 
 
 
 
 
 - ' r 
 
 r--iJ ■ .1 
 
 -ip. 
 
 be 
 
 ■•^-11 • .! 
 
 
 V'*' 
 
 %. 7-( 
 
 
 . SJ 
 
 / • 
 
 I 11^ 
 
 I'Ti .i ^• 
 
 iH- * '*•' 
 
 '. <*■ 
 
 
 , ?■ iO ii 
 
 itJ 
 
 
 sTitni* 
 
 -yr. *tiit(i^ L:.,\ 
 
 i 
 
 / 
 
 i .<-82i) Af. Lg 
 
 00-1 ^^■: 
 
 !tl. i:: : 
 
 
 
 oiij; y*'. 
 
 
 
 I Lane 
 
 -*i-‘ -u-Jtj 
 i ■■> '- i) - 'tU 
 
 tXy« 
 
 .. j T. 
 
 iVi 
 
-32- 
 
 Out tne h^urazo compound could not oe iuen tilled among them. 
 
 Zinc witn various acids, iron v^ith acido, ana stannous cnioride 
 
 laiiad to give anj reduction products ol the ketazine. 
 
 H 
 
 3-lViETHiL- 5-dDviiii'KYL PxKAZOLINii, K-cf Yhien a 
 
 II 
 
 lew drops ol uenzojl chloride l\i were added 
 
 i'j— H 
 
 to a lew c.c, ol tiie reuuction mixture ootaihea in one ol tiie 
 
 unsuccesslul attempts to reuuce dimeoxijl keuazine, a crystalline 
 
 compound melbing at 228-y*^ was oucained. iVielting point, appearance, 
 
 and analysis showed that the suostance is the oenzoyl uerivative 
 
 ol 3-metiiy 1-b-uimetnyl pyrazoline wxiicn was originally prepared 
 
 Idh 
 
 Oy (jurtius and Zinkeisen 
 Analysis: 
 
 CalculaLed, lor , N » 12,96^o 
 
 round; (humas) N = 12.92;6 
 
 Tne acid lormed during the reaction ana dy hydrolysis ol denzoyl 
 
 chloride is thus strong enough to elfect txie rearrangement 
 
 18d 18c 
 
 SLudied by Curcius, I’rey and Hoiiuian , and Iranxe , 
 
 AEjij'JriOw Ol riihxiiiixL niiTAZiuEo- Ss.ica's metiiOd ox reduction 
 
 by iiydrogen unuer one cataljtic inlluence oi colloidal platinum 
 
 protected ijy gum arable was ±inally useu with oomplece success 
 
 in tue reduction ol tue azine. 
 
 Tile apparacus used at lirst was modelled alcer the one 
 25a 
 
 descriseu by oxi oa , but was later modilied so as to be less 
 expensive and, especially, also less space consuming. The use ol 
 the troublesome pressure regulator oi Skita was also avoided. 
 
 Tne linal lorm ol the apparaous is sixo.n in ligure I. 
 
33 
 
 Figure I 
 
54 
 
 Trie open-cop mercurj manomeber iias a ientjCu oi 200 cm so 
 that a height consiaeraoly in excess of 180 cm of mercur^y or 
 over two atmospheres excess pressure may safely be employed in 
 bhe apparatus. The capacity of the tank, T, was so regulated by m 
 means of a small amount of distilled water tnat was placed in 
 the bottom to seal all stopcocxs and at the same time to pro -vide 
 for a flexiule capacity of the ^as hoiuer, Vuien tuo capacity is 
 about 20 liters the average running pressure of the apparstus 
 will ue suCii that the drop ox' 1 mm in pressure is equal to 10 c.c. 
 as an average. The exact values represented by a change of 
 pressure of 1 ram at any desired temperacure and any desired total 
 pressure (atmospheric plus extra) a^ e read uirectiy from a chart 
 made when the tank was calibraced with the wauer level fixed 
 permanently. In tuis way it is possible to use only tlie tiieoret- 
 ical amount of gas to complete tiie reduccion desired, tlius 
 avoiding incomplete reduction Liirougn stopping tne snaker too 
 early, or over-reouction tiirough adding more hydrogen than de- 
 sired. 
 
 The shaker is fastened to the wall by a strong hinge, by 
 tnis arrangement tiie shaker occupies little space when in use, 
 and practically no space when not in use as it may be folded 
 back against tne wall. The hinge and board are fastened to the 
 wall at an angle oi about 45 degrees as shovm in the figure. Tiiis 
 angle is found to proviue the most efficient stirring and shak- 
 ing when Lhe arm is swung cacx and forth by a common motor driven 
 snaker. The rocking arm oi tu.e shaker is xastened at tij.e pointy n. 
 

 
 -f 
 
 • — 1 * 
 
 •*11 
 
 X fa; 'iHi... 
 
 . t/i., k. . / 
 
 i '-TH/ .y 
 
 '*••*“ V 
 
 .* t/jJUj 0 
 
 V l(? ^• i 
 
 _ — •• 
 
 
 •>- 
 
 LUi tr 4 
 
 
 j: Tgs 
 
 \jr ts^i 
 
 i ( 
 
 ' i 
 
 
 
 ' ■< »% 
 
- o5 - 
 
 j.ne i'labk is lasoeneci in a rapid and verj satisfactory aianner 
 Dy means of two screen door springs tnaL are hooked into rings 
 behind tiie board© To prevent poisoning of catalyst due to con- 
 Lact of tiie liquid with Liie brass or copper tuoing, the coiled 
 Luce is cemenLed into a piece of glass Lubing wnich ohen passes 
 through tiie rubber stopper of tiie pressure flask© The rubber 
 SLopper is iield in place securely even unaer more than 2 atmos- 
 pheres of extra pressure, by means of the yoke damply© 
 
 PEOCkhUKE.- In maxing a reduction run for tiie first time tae 
 acetylene tank,!', is first evacuated, oiie open end of the copper 
 coil , v¥W ' , ueing closed bj lasuening into tae empoy pressure 
 ilask, Vhien txie pressure aas dropped as low as the wauer pump will 
 take it (20-30 mm|- the tiiree-way SLopcock ,5, is burned so as 
 to connect v/itii"G"' instead of with "v". "C” is connected to the 
 Hydrogen cylinuer by means of a snort length of ruboer pressure 
 tubing of not too great strength so that in case the pressure 
 is accidentally raised too high due to carelessness in ma.ni- 
 pulation of the valves or to stoppage of some passage, tiie 
 pressure will ce indicated by the bulging of tae tubing and the 
 eventual blowing out of the tubing, liien the tension of the 
 tubing, as ielt by tae aand, inaicates taac tiiere is a slight 
 pressure in tae system, biie gas is Lurned off again, the three 
 way stopcock turned back to ‘'V“,and tae evacuabion repeated. 
 
 Yaien again evacuated and refillea wita gas until a slight pressure 
 is inuicaLed by tae tuuing leaaing from tiie cylinuer to the 
 tank, the vaive 2 wnich iias been closer, up to now, is opened 
 ana the pressure in tae tanx permitLed to rise slowly to a total 
 
56 
 
 pressure oi‘ aoout 2500 mrn oi' raercur^’. Tixe valves 1 anu 4 and the 
 
 stopcock 5 are tiien cioseu and the xlask disconnected from the 
 
 tuDing and cnarged for tiie run. Tiie usual charge consists of 50 
 
 100 c.c. of 15^ hj'drochloric acid, 
 c.c, of ketazine, 100 c.c. of water, ^10 c.c. of a solution 
 
 oi platinic cliioride, and .5 g of gum arabic dissloved in hot . 
 water. To tnis mixture is then added the "seeding” colloid pre- 
 pareu eitner accoruing to tiie direcbions of oxiLa hj heating a 
 few cubic centimeters ox a palladous chloriue solution to boil- 
 ing and then, v/hile removed from tiie flame , allowing a slow 
 stream ox h^-drogen gas to pass througii the soluLion to reduce 
 the mexal to tue colloidal state, or oy parcially reducing 2--3 
 cc of chloroplatinic aciu hj making it alxaline, heating to 
 boiling, and adding a few crysdals ox n^drazine cnloriae or of 
 tne iiy urocnloride of symmetrical diisopropyl-h^drazine . As soon 
 as the mixture uuurns ulack it is rapidly poured into the 
 pressure flask where the alkali is neutralizeu by the acid present 
 The flasK is tiien connected to tne system again and evacuated 
 until tne acetone starts to boil. The air is tnen sufficiently 
 removeu to permit ti^e reduction to proceed. The gas is aamitted 
 to tne flash by opening valve 1 as soon as possible after the 
 valve 4 nas been closeu to cut off tixe vacuum. lx" the acetone 
 vapors are perrniLued to condense, in any amount, in the coiled 
 tube, the catalyst may oe poisoneu by txiis liquia wnen the gas 
 pushes it uach into Lne flask in course of the run. for this 
 reason tne gas suould ue Lurneu on us soon as possiole aiter the 
 evacuation is completed, if the desirea amount oi pressure is 
 now in the system tue snaner is soarteu ana Ghe total pressure, 
 
i; 
 
 !■ 
 
 (• 
 
 i' 
 
 
 tC t 
 
 X 
 
 ' - 
 
 - ^ - * ■ r -■ -' 
 
 .".. DfeA i - . .‘i.'j 
 
 ‘. -Sj 
 
 I *' 
 
 '.flu . h 
 
 
 « .. 11J I.^.UT 
 
 
 ;C rc« 
 
 f.: klOi 
 
 ' Vi i^un in 
 
 1 ' 
 
 * I .'uaCl^ ^.- j >r-^‘ 
 
 - lA.I'Oai :. 
 
 V) ; 
 
 \ 
 
 ■ ■•■ '. T.b%ii , i 
 
 , I 
 
 ■ 'a tij\.' 
 
 ■ ■ ^ 'I ua .•■ ‘ i 
 
 ’■ < ■ .'>a.t /ir n 
 
 l'.*'"-j . I' ' 
 
 ^ u. . . ., 
 
 - ( - 
 
 ' t ’ 4. .. I . . 
 
 I ■ ' . 
 
 • ’ . ‘ ‘ 
 
 i.u;-0«r • 
 
 . iT»J 
 
 
 ’' it^JL * ' . !' 
 
 I 
 
 -•. r -f i.Jpir ( 
 ^ I 
 
 >» 
 
 : sn’i 1 
 
 ! 
 
 r ^0 • 
 
 !=■ ev . 
 
 ' 
 
 / 
 
 L» .^> lOl'xa 
 
 • ■-• nt^c;j:iv (1 
 
 - ’1 
 
 
 
 -u if 
 
 \*r ' • n 
 
 
 ifcMfAKHW 
 
 *■ - --*• 4<.'c, 
 
 
 ,:siirlt4. 
 
- 67 - 
 
 ana temperamre read and recoraed, 
 
 i*'or a lew minuLes iirtie, ii anj , absorbLion is nouiceu. 
 ir tue acetone xias oeen properly purified aosorbtion v^ill start 
 in a few minutes and grov; steaaily more rapid for about an hour 
 when it reaches its maximum and gradually slows down only to 
 stop enitrely when the ketazine has been all reduced to the 
 symmetrical nydrazine. Tnis may take only 3-4 hours if no anti- 
 caralytic suostance is present, usually Lnere will be enougn of 
 sucn substances present as impuribies so maberially slow dOY/n Liie 
 run so thab 6-8 hours are required, unless bhe snaKer is stopped 
 alter the aosorobion slows down noticeably and more platinum 
 solution adueu, Tne rate of reduction aepends on tne amount of 
 catalyst present so that , presumably , the reduction could be 
 carriea out in muca.i less tuan 3 nOurs if we were willing to use 
 more platinum tuan necessary. Usually one additional addition 
 of 10 c.c. of cnloroplatinic acia suificeu to reduce a regular 
 charge in 3-4 xiours. In som.e sucn runs absorb Lion uook place at 
 tne rate of over 12000 c.c, an nour for over a hour at a time. 
 
 The solution in the flask warms up considerably when reduction 
 proceeds as rapidly as this. If it uoes not heat up to about 40 ^ 
 it is advisable to place a very small flame some 6 a' 8 incnes 
 below the flask to neat it to tne temperature of about 40^ 
 at wnicn aosorotion ../takes place at txie maximum rate. Should tixe 
 temperature in any run rise to the boiling point of acetone 
 the reduction wohld be materially sloweu down because of the 
 acetone vapor wnicn woulu not permit tne nydrogen to get in con- 
 tact witn txie liquid rapidly enougn to sustain the original rqte 
 
of reauction 
 
 li an atterapL is made to use 'cn.e acetone of commerce 
 disappointmenLs are almost sure to come. In airaosL all cases 
 in wnich t,ne acetone is lo ue used in caLalytic reduction pro- 
 cesses it nas to Pe purified to make it suitable for use. The im- 
 purity manifests itself curing a reduction run by preventing 
 absorption of hyurogen entirely, ii there is much catalyst poison 
 present, or, in case only a small amount of anticatalyst is 
 found, the aosorbtion may start but almost immediately reach a 
 maximum, far oelow tne maximum reached wuen pure acetone is em- 
 ployed, and tnen rapidly arop off until no gas is ausorbed. 
 
 . . ^ . 49 
 
 jO puriiy Uiie acetone one metuou of dhipley and Werner 
 
 was found satisfactory. If sodium iodide and acetone are refluxed 
 
 for an hour or more a very concentrated solution of sodium 
 
 iodide is oorained. un cooling the solution down to -10° or even 
 
 to -].5 ° . if convenient, tiie sodium iodide-acetone addition 
 
 compound precipitares out as large reddish needles, Tliese are 
 
 sucKed off rapidly on a large iiucuner funnel without filter 
 
 paper. The needles are so large that they do not pass through 
 
 tne funnel, me needles are then placed inro a distilling flask 
 
 and tne acetone is uis billed off. It practically ail comes over 
 
 between 5b. 5 and 56.6 at 750 mm and is apparently now entirely 
 
 free from anticatpLly tic acrion. The filtrate and tue residue of 
 
 sodium iodide from the distillation are mixed and ano 'v. . .r small 
 
 amount of aceu^n. aude^. Inis mixLure is refluxed as before and 
 
 a seconu quantity of pure acetone obtained irom it. If Lne acetone 
 
 as obtained fi’om stock is fairly pure, the puriiying process may 
 

 If' 
 
 •sicrs ■!- 
 
 ,1/ -r 
 
 -s, ’ 
 
 .:e9rt£l 
 
 f jb'/ rv<i^*>'' u „ 
 
 I A » *_ 
 
 C/fl 
 
 % 
 
 a fit . 
 
 ,fjn . CiO C ■' ■ p s. 
 
 '■** '. ■ \ 
 
 '• ©ij ^ ■> *1 . , . 
 
 I . - 1 J. <■•• _ I ' . 1. . . . 1 ' ,1 , t ■ ^, '- i *4, 
 
 ■' c I ■ ->^- - * • 
 
 ' ■" ' ’“* 
 
 I ' '*. • . '- .-. t A'-- • 
 
 t. I ■#<' I ■■ ■ >. . ■ .1- 
 
 li-‘. it}^\ .». 
 
 ' v'ftn .*»' 
 
 j i'. t 
 
 
 
 -’■t 
 
 ir 
 
 :nrpt;u' 
 
 :iOj;i 
 
 ac-, ;f-.. 
 
 ■ • 
 
 ua: w a i ^ 
 
 ‘) . 
 
 '! 
 
 ■f.J 
 
 a 
 
 t-t 
 
- 39 - 
 
 De repeateci. as mucii as 5-6 times before cleaning the iodide, 
 
 TO purify tne sodium ioaide so as to be able to use it 
 again for similar work or for other reac --ions the acetone is all 
 distillea off on a wai-er bath. The wee residue is then poured into 
 an enamelled pan W’here iL is lurLher dried by g^entie heat. V/ii^n 
 Lhoroughly ur^' txie neocb is gradually increased until all organic 
 mauter nas seen carsonized. Thus igniceu iL is ready for use in 
 acetone purii icaoion. For OLner chemical wor^v it must obviously 
 be puriiieu uy recr^ stallization before use, 
 
 1 A few early runs were run using the mixture of ketazine 
 
 water, and catalyst as descriued on page 37. The reduction was 
 lounu too slow iiowever and ane reuucLions as next modified gave 
 better yields in snorLer oime.It was observed that one addition 
 01 Ciiioroplatinic aciu always produced a rapid rise in absorbtion. 
 Tiie quesLion arose wnetner Luis rise could occur as suddenly as 
 it did if tne extra platinum audeu were the only factor trial in- 
 creased the rate of absorution of nydrogen. A small amount of 
 hy urociiloric acid was next lOunu to nave tne s:me effect, in case 
 no anticataiysL was present, as tne addition of cnloroplatinic 
 acid. By adding small portions at a Lime Lhe time of reduction 
 was soon cut down ta less tiian a uay. Tne neAb step v/as to add 
 tiie tneoreLical amounL of aciu, needed to salify all of tiie base 
 formed , aL one start. The first run failed oecause b^ie platinum 
 reiuseu to be reduced to the colloidal staLe unuer Lhese condiLions . 
 In subsequenL runs tne reduction was allowed to proceed for a xew 
 minutes anu Liie auiu tnen ull auueu. at one time. Tne yielu was 
 practically quanLiLative . 
 
- 40 - 
 
 Since Ine resuiLs snowed tnac Uie aadiLion or blie caicu- 
 latea amount of hyarocnloric acid in one 'lot . did not reduce 
 tiie yields and even shortened tue time requireu, tue question 
 or hyurolysis Oi tne ketazine was eliminated. The next step xor- 
 waru was txie used of oa mixture of acetone and hydrazine hydrate 
 instead of xetazine. This avoiued tue step that yielded txie 
 lowest yield -- tne preparation of dimetnyl keLazine. 2.2 mol 
 of acetone, 1 mol of hydrazine hydrate, and 1 mol of nydrochloric 
 with the original amounts of cnloroplatinic caid, gum arable and 
 ’’seeding” colloid now constitutes a regular run after dilution 
 wiLn 100 c#o. of uistilleu water. In tnree runs on wnicn u.ie 
 yieluS,Dy Lnis metnou,were ouLained, 25 g of nyarazine hydrate 
 tiie i'oilowing results wer^e outainea,- 
 
 I. 25 g n^drazine gave 78 g of hydrochloride in 4 nours, 
 
 II. 25 g iiydrazine gave BO g of hydrocxiloride in 5.5 ” 
 
 III. 25 g hydrazine gave 74 g of hydrochloride in 6 hours. 
 
 The salt was weighed after it nad been recrystallized once from 
 alcOiioi and uad uean x^ept on paper ovei- night. Its melting point 
 was 107-8 unsharp for eacn baten, a cnlorine ue terminations 
 
 oy Mohr’s meti.oa gave 23.8;^y Cl, anu titration witn n/ 10 iouine 
 gave an average purity of for the salt. These show tnat 
 
 the salt was practically pure anu tne yielu almost quantitative. 
 The more usual yields lay between 88 and 9i5yo xiowever because 
 the above runs were made on especially purified reagents. Evai 
 9 0;i is a nignly satisiactory yielu nowever wnen the isolation of 
 the Ketazine is avoiueu entirclj. 
 
' f . 
 
 V 
 
 i, — * 
 
 
 i\ 
 
 
 vi 
 
 (M y|’ 
 
 
 . - -■ d/. 
 
 i(i 
 
 ;T* 
 
 • '4 i 
 
 !' *’j 
 
 * »i 
 
 CjPAt.' '.■ ■ 
 
 / 
 
- - 
 
 Wnen poisoning of Lue catalj'Si- does occur, as shown oy 
 the phenomena descriuea previously, the poisoning , if it is 
 slight. , may oi ten te overcome by une use of an excess of catalyst. 
 If the poisoning oe severe Lhou^u it is eest to recover the 
 iiyarazine as urocnloriae and as much of tixe acetone as possible 
 and stare- out on a new run. The origin of the poison is often 
 very difficult to locate, in fact, in many cases subsequent runs 
 with the same reagents prove to be normal. In a number of cases 
 wnere txie catalyst lost ius acLiviuy more ana more, apparently 
 tiirough exiiaustion of its catalytic acti vi ty_^ wiiatever tnat may 
 be uue to, attempts were made to revive tne catalyst by shaking 
 it in contact witxi air for varying perious of time. Even on 
 sxiaxing for as long as two xiours no revival of activity could be 
 detected in any case. 
 
 IbOLATIOh OF IKB REDuCiIOK PROhoCrSo- Wnen the theoretical 
 amount of iiydrogen has ueen acsorued, the valve 1 is again closed 
 so as to save the gas in tfie tank for future runs and to avoid 
 the preliminary evacuation of tne tank. The flask is disconnected 
 from the system ana allowed to stand for a fev^ minutes. If the 
 colloid is still homogenous, and equal volume of acetone is added 
 to the mixture and tue contents ^ i the flask shaken violently for 
 a few minutes. The colloidal soiUbion will now usually be broken 
 up into large flakes which soon settle out, leaving the rest of 
 tiie mixture clear. In many cases tne colloia is found to nave 
 broken ao n wnile* the reaucoion was still going on. In such 
 cases, 01 course, no aadi .i nal acetone is adaed. In eit..er 
 case it is oest to let tne mixture stana overnight w.ien the clear 
 
n <- 
 
 t- 
 
 cL 
 
 t 
 
 i 
 
 •'.‘1 
 
 f 
 
 i: 
 
 i; 
 
 
 ■■ 
 
 
 i 
 
 > A' 
 
 
 
 ■y 
 
 : 0 .; 
 
 
 L'f ■ 
 
 t 
 
 
 i,' I 
 I 
 
 / 1 
 
 
 If? / 
 
 I' 
 
42 
 
 liquid, may Lhen be poured througii a large pleated filter in a 
 few minutes and the mass tnat nas settled out will urain within 
 an hour or less after it has been piaceu on tiie x'iltero If an 
 attempt is made to fiiber the mixture immeaiatel;, after tue 
 colloia lias been broken or ii suction is applied in an attempt 
 to save time it is very difficult to filter at all as tue black 
 mass oi flakes cannot be filtered unuer such conditions witn any 
 uegree of satisfaction. 
 
 To isolate tiie reduction proauct, tue solution is made 
 acid to Congo , unless already auiu.. In case acetone was used to 
 breau the colloidal state, the acetone is how recovered tiirougu 
 distillation. Tue remainder oi the solution is evaporated down 
 in vacuum on a steam ba-.h. As tue solution becomes more and more 
 concentrated fine long uairlike needles oi tue uyurochloride 
 begin to crystallize out on the walls of the flask. If some 
 lots of pure product are uesired, the residual solution is 
 now well cooled in an ice bath anu the mass oi' crystals tuat 
 separate out are filtered of oy suction. Tue filtrate is con- 
 centrated further in vacuum and anotner lot of pure crystals 
 obtained, finally tne iiltrate is evaoprated to dryness to get 
 the remainder of tue hydrochloride since it is very soluble in 
 water. If no special batches are uesired the evaporation is 
 carried to dryness in tne first place anu the time consumed in 
 cooling and filtering saveu. 
 
 hkbOVuRY Of Tiik Cal'ALMoT;- To recover tiie platinum the filter 
 and clacK mass of precipitate are permitteu to ury tuoroughly 
 before attempoing to work witn them. The ury filter is burned 
 
■ 1 " 
 
45 
 
 over a porcelain disii. To keep irom cracking tne uisn,ik is uest 
 
 LO nolci tne liiLer wiLu a pair oi glass roas until tne ashes crop 
 
 ox'r into tue clish. me asnes ana caroon in t^ie uish are tuen 
 
 careiully scrapeu into a crucicle ana ignited wiLh a clast lamp. 
 
 liie metal is nexL dissolved in aqua regia. Tixe first solution is 
 
 evaporated aown on a water uatii, water adaed, evaporateu to dry- 
 
 and 
 
 ness again, iiydrocnloric acia auaea,y<^evaporated again. This 
 alternate treatment witii water and witu K^drochloric aciu is re- 
 peated until tue platinum solution nas ceen evapprat ed, three ^ 
 
 times witu the acid. Water is again adaeu and the final evaporation 
 carried out in vacuum. The residue odtainea now is dissolved in 
 a few^ drops of water ana finally uilutea to tiie same color that 
 the original solution uad. It is now readj^ for use as a catalyst 
 in reduction runs. Tiic loss per recovery is small, Out when the 
 same platinum goes through dozens of runs the loss geos more , 
 
 and mors noticeaole. 
 
 SfMvikThICmj DIIdOPhOPYLwHfDhAZIh'E.- Tne hyurochloride obtained 
 on evaporation of tue reduction mixture is recrystallized a few ; 
 times from small quantities of alcoiiol or from acetone, before 
 liberating the base in case anciiyses are to be run on the sample 
 obtaineu. IT ohe uase is to oe useu for tne preparation of ae- 
 rivatives the puriiication is unnecessary, in either case the 
 base is liberated by means oi very concentralea sodium or 
 potassium uydroxide. It floats as a layer of yellow oil. x'his is 
 separatea from tiie water layer and the latter extracued twice 
 witii ether. The oil ana etiier extract are united and dried for 
 ■ 
 
44 
 
 at least 24 hours witn fuseu potassium u^aroxiue. Tiiis re- 
 moves most 01 the waver. Alter the alkali u.r^'in^ is complete, 
 
 Lhe mixture is pourea oil bue pooassium ujdroxiae and into 
 anotner tuoe.Tiie odor oh Lhe oxiuation produc L is easily noteu 
 along with tne ammoniacal ouor ox hue case. Tne iinal urying is 
 done by freshly preparea aluminium amalgam prepared irom clean 
 pieces of aluminium foil ana mercuric unloride. _ne amalgam is 
 allowe::. to react witn the base for a week or more, during this 
 time tiie jeilovj color and tne azo ouor uisappear as tne oxiaation 
 prouucts is reauced to the nydrazine again. This face makes 
 aluminium amalgam far superior to any of the oxide crying agents 
 sucii as barium oxiae and calcium oxide, ine same result - 
 drying and reduction - obtained ver^- much more rapidly by metal- 
 lic sodium but it is more uifficult to get rid of the slimy 
 sodium compounds tha u are formea during the crying and reduction. 
 At the ena of the drying period, tiie base is carefully poured off 
 the aluminium hydroxide and unciianged amalgam and distilled from 
 a small distilling ilask thru wnicn cry nitrogen gas nas been 
 passing for some time, to urive :.ut all oi the air, Tiie stream 
 of gas is kept going curing tne distillation. When the tempera- 
 ture reaches 124*^ tiie xirst reciever is removeu ax ter tne flame 
 nas seen removed to prevent loss curing the cuange ox re- 
 ceivers, nefore heating attain tne surf am of nitrogen is sent 
 througn tne nev; reciever for acout 10 minutes to remove all air. 
 On again heating- and distilling the remainder of tne base it is 
 found to practically all come over between 124 and 125° as a 
 mouile, colorless liquid of ammoniacal ouor. Titration by iodine 
 

- 45 - 
 
 or 'oj hj'uroCiiioric acid anows Lnac the case is not quite 
 
 pure ( 97 - 8/0 purity.). To obtain a ver- pure sample lor deoermin- 
 acion ol cue various pny sical consianos, une last trace of oxida- 
 tion product (azo compound) is removed uj using a small aosoro- 
 
 53 
 
 tion apparaLus ol tne tppe u.escriDeu by Noyes aiad 
 
 Alter the 124-5° Iraction nas been collected in tuis small reciev- 
 er under tne usual precautions, the dry nitrogen gas is allowed 
 to continue bubbling throw^ue absorber until tiie inu.ex ol reirac- 
 tion remains constant curing 15 minute intervals. There is some 
 loss ol symmetrical hyurazine along .vitn the azo compound tnat is 
 volatilizeu , hut the loss is far smaller and the purity greater 
 than by any otner metuoa tried. Analysds, by ra.piu iodine titra- 
 tions, showed that tue purity ol tiie base is ecout 99. 5;^, "'o 
 preserve the pure product, the absorber I 3 errptied, with the gas 
 still passing, into a small nitrogen iilleu bulb which is then 
 rapiuly seaieu by a blast lamp. Apparently the base thus collect- 
 ed may be kept indefinitely^ wnile in contact with air it is im- 
 mediately Qxiuizea partially, i^ven in viell stoppered tubes the 
 decomposition is consiuerable . 
 
 Q ana 
 
 The pure base boils at 124.5 at 751 mm pressure ^is a 
 colorless mobile liquid with an ammoniacal odor. It reduced 
 ammoniacal silver nitraie, aqueous silver nitrate, and lehling's 
 solution in the cold. 
 
 The inaex ol refraction (Abbe instrument.) is - 1.4125 
 
 D 
 
 The density , found- by picnometer, is D31/4 ....0,7712 
 
c - 
 
 
 
- 46 - 
 
 ketnods or Anaiybis.- The most oonvenienL metixoas of analysis of 
 
 bii6 iree nj-arazines , ana tne metnoas mosL commonly used in this 
 
 investigation, are volume uric metnoas. loaine tirations accord- 
 
 bO 
 
 ing to tiie meLhOv^ ox otolle are especially convenient and 
 accurate, the rea.Cbion. proceeas accoruing to; 
 
 C^hl 6 iM 2 ^2 — ^ 2 HI , xiie oxiaation product is 
 
 tne azo compound^ identified dj ouor, inuex of refracuion, and 
 soiling point, otolle assumed that tne use of nis meuiiod in tne 
 caae of primary njdrazines leaa to nj-drazo derivatives. In view 
 of the fact tnat in the present wort; the iiyu.razo compound is 
 titraLed with iodine under che conuitions emplo^ea uy Sbolle, it 
 is far more prodadle Lnat the reaction in tne case of primary 
 njurazines proceeds according to; 
 
 2RmI“Im2 + 2 Ig ^ n-K -v* 4 HI , which is uhe normal De- 
 
 havior oi' primary n^urazines towards mild oxidizing agents. 
 Another volumetric metnoa tnat ^ives good results, -results tiiat 
 may later be cnectea oy an iouine tiLrarion on the same sample, - 
 consists in tiuraoion oy H /lO nydrocnloric acid using methyl red 
 aS indicator. 
 
 To cnecic one results odtainea by titrations^ coraDustion 
 analyses were also resorced oo and proved to oe very troudle- 
 some au first, xne compound, as well as most of its derivatives, 
 is very easily partially Onidized, out some of one prouuccs 
 formea in tne parcial oxiaation seem to ue very staule. laej 
 pass over tne long la^er of copper oxide without cnange unless 
 Lne oxiue iias seen heatea to a pink color, Even thexi the de- 
 composibion must be very carex'ully regulaoea bO prevent pushing 
 
r 
 
 - 47 - 
 
 tiie ^ases over Ghe oxide aL too rapid a rate. In Liie Dumas 
 nitrogen ue terminations Liie results were always uign if the 
 decomposition proceedeu too fast xor even as little as a min- 
 uu-e 01 time. On tne otner hanu., caroon ana iijOrogen determinations 
 v;ere always low unuer tne same conuitions. After more tiian 
 twenty failures with the usual comdustion furnaces, an old fur- 
 nace was remodelled to fit the special conditions. The heavy 
 iron ^'OKes supporting ti^e uom.bustion tube were replaced by a 
 40 inch length oi angle iron. Tiie extra lengtii of bea permitted 
 the use of an extra burner outside of tne end supports, thus 
 making tne xurnace auout ^ incnes longer than it xi.ad been. The 
 tiles along botn sides of tne bed were so arranged tliat txie^ 
 are readily remov^able in case decomposition tnreatens to be- 
 come too fast. Six inch sections of asbestos board are used as 
 a roof I or the furnace. By removing the section above tlie 
 sample it may be rapidly cooled. To provide lor cases in 
 which the removal oi tiie tiles and roof sections uoes not bring 
 tne decomposition into immediate and accurate control, ice is 
 Kept available so tnat on an instants notice a small block of 
 ice may be rubbed along the lower side oi one ued. This radical 
 cooling was found necessary on m.any occasKions. The tendency 
 to very rapid decomposition is ver^ pronounced in nearly all 
 of the compounds studied. With tiie furnace as uescribed and 
 witn very slow and carexul uecomposi tion tne results are as 
 reliable and accurate as tiiose on more easily burned suuSuances. 
 Altnough tiie use oi oxygen during the decomposition in carbon 
 ana hydrogen determinations results in small explosions, one of 
 wnich vias severe enough to wreck the comoustion tube, air may be 
 
- 4:6 - 
 
 safely used to provide for a constant and even movemenL of ciie 
 gaseoufc) aecomposi Lion prouucus. 
 
 Anal y ses* OalculaLeci xor f Gjd<i»OBj Hjl3«80j I'jj24» 14^ 
 
 I'ound; G = 62. 3y; 62,17; H= 15.97,14.31; z 24 . 50 , 24 . 54^b 
 
 An afLempL v\/as made lo use Lue Kjeiiida.xil rnethou for the 
 nitrogen ueLerminations , out 'che usual metnou, of course, fails 
 enLireiy since tne nivrogen is all given off us free nirrogexi. 
 li an attempt is made lo reauce the compound to de analyzed bt 
 the hjenldahl metnod, the aisappoinLlng fact is revealed that the 
 substances do not seem to be reducible uy any ordinary means, 
 
 A large number oi attempus were maae to reduce the hydrazo 
 compound to one primary or possibly secondary amine, uut no 
 rnethou tried gave any sign of a reuuction to the amine. This great 
 stability Lowards reducing agents explains tne failure of the 
 hjehldaiil method for Lnese compounds, 
 
 A wet metnod for the determination oi the per cent of 
 nitrogen in Lnese compounds was worxed out in the course oi this 
 investigaoion . Except, for sligiiL mouii ications to fit 1l to 
 special conditions, the metnou and Lne apparatus useu is similar 
 LO a number of sucn meLiiOds developed in the past. A bulu of 
 about 2b c.c. capacity is blown at tne uottom of an ordinary 
 LesL oLiue , if no xlask ol sucii snape is available in stock. A 
 one hole rubber stopper fiLs into tne neck of the flask, A small 
 dropping funnel is sealed into an B mm piece of tubing in such a 
 W0.y that the tip'of the dropping funnel stem projects well down 
 into Lhe flasK wnen the b mm tuuing is passed just through a 
 iiOle in Lixe rubber stopper fiLLing into the neck of the de- 
 
49 
 
 composition flask. Above tixe ring seal a siiort sideoute is sealed 
 on the stem of tne dropping runnel. fhis siueneck is the opening 
 Lhrough wnich carbon dioxide ^as enters the apparatus to sweep 
 out tne air. between the ring seal and the rubber stopper, a 
 sideneck is sealeu. to the 8 mm tuoing. This opening server as 
 outleL for Lne decomposition prouucts and for tne carbon dioxido 
 useu in rinsing tne decomposiLion flask. 
 
 To determine tue per cent of Nitrogen contained in an un- 
 known substance, tne sample is weigned into the decomposition 
 flask and about 10 c.c. of waLer added to it. The stream of 
 carbon dioxide gas from a ..ipp generator is then started. After 
 about 10 m.inuues the bubbles of ^as will ce i ound to practically 
 uisappear wnen passed into an azoLometer wnich ib filled wiLh a 
 50/i solution of potassium nyuroxiae. The carbon dioxide is then 
 shut off and Lhe oxidizing mixture addeu thraugh the dropping 
 funnel. As oxidizing fluid a mixture of sulphuric acid and 
 
 potassium diciiromate is useu in mos'c cases. Just as effective 
 as this soluLion nov/ever is a mixLure of 40^b sulpnuric acid and 
 potassium permanganate . in eitner case Lhe mixture is added drop 
 by drop to prevent loo violenL decomposLion of Liie compound. 
 
 AfLer the mixture iias been added tne bulb of the dc;Comiposi tion 
 flask is carefully ueaLed to aoout 80^ unless this temperature 
 is reached spontaneously during tne oxidation, finally carbon 
 
 A 
 
 dioxide is ^sed Lhrough Lhe system again until the volume of 
 nitrogen in tne azoLometer no longer increases. Ail other sLeps 
 are similar lo tnose employed in Liie regular Dumas nitrogen 
 determination, -he metnod is noL applicaule lo substances that do 
 
' t '» u , 
 
 ■ r rt^‘- 
 
 
 • li 
 » ■ ■• 
 
 4 
 
 i .; . i 
 
 •■ ' i 
 
 
 f 
 
 
 r 
 
 
 
 
 I 
 
 1 - ' fi'l 
 
 r,l/ r . ' 
 
 I 
 
 re 
 
 
 
 4k 
 
 ^ a 
 
- 50 - 
 
 not give oTi the nitrogen reaaily. Heating to too nigh a temper- 
 ature causes nigii results since gases tnat are not aosorbea by 
 potassium Hj-aroxicie are liueraLed on boiling tne solution. 
 
 If tne substance is a liquid, it musL, oi course, be sealea in 
 a small bulb as in the jjumas luetnod. 
 
 In tne case oi the njurochloriue of s^-mmetrical diisopro- 
 pyl-h^drasine , fairly close results are obtaineu on using Mohr's 
 metnou in the iialogen determinations. The prim.arj isopropyl-hydra- 
 zine can not be used in tne presence of potassium chromate 
 since tne latter is immedia-tely reduced by tne base. 
 bSHIVAilVIIn Ur Sx%kiix*.lU/*L DI InOFROP >ffhwh'fDnAZIh2, - The neutral 
 hyurocnloride of tnis nyurazine is outaineu as outlinea in the 
 isolation oi tne reauction prouucts. -ne crude salt is recrystal- 
 lizeu 3-4 Limes from very small amounts of alconol to wnich etner 
 may be adueu to complete tne precipitation oi the salt, Otner 
 recry stall! zing agents tnat give good results are acetone ana 
 etnyl acetate. TTie salt is very soluule in water, and alcohol; 
 insoluble in ether and in petrolic ether; and slightly soluble 
 in all otner comm.on solvents. The ny urocnloride is non-hygroscop- 
 ic and has markea crystallizing properties, sometimes arranging 
 in long hairlike needles that twine along tiie sides of the 
 container for several Incnes. The substance melts at 198. 5°( corr . ) 
 Conductivity determinations revealeti tiie ract tnat, at nigh 
 dilutions, tne hydrociiloride is appreciably hyarolyzed. since the 
 nyarazine is only as strong a case as nyurazine itself, this be- 
 havior of tne nyurociiloriue is not unexpected. 
 
51 
 
 j^ji3.1 j'SOS# oS-IcllIs-X/Gcl iy*o5j 01^ ^ ^ 
 
 rOunu.- Gl,(Carius) 22,99; (iviOhr' s) 25. 77 ; 23. 75; 23. 78; 23. 69)i 
 N, (uumas) 18.21j'i ; (Vyet keLuoa) , 18.15;6 
 liie remaris.aule results ouoainea with kohr's metnou are interest- 
 ing, since three diiferent, indepenuently standardizeu silver 
 nitrate solutions were used ana yet the results are all unii'ormly 
 iiign in spite oi tne fact txial the samples analyzed were also 
 entirely different ones. 
 
 PKlil'J YLTiilOSEivilOxttliJiiZIljE Of 8YiViMhxri.lC^iL DIiSOPrtO?yL“hy^PatZIi\iS, - 
 ixiis derivative is preparea liy aading 1.25 mols of pxxenylmustard 
 oil to 1 mol of txxe free hjurazine. ro avoid overxieating , the 
 mixture is cooled until tixe reaction slo is doun. a good yield 
 
 of a yellowiSii crystalline precipitate is Obtained. ohS cTerlva- 
 uive putidied for analysis by recrystallization from absolute 
 
 alcohol or irom acetone, fxxe corrected melting point of tne 
 
 0 
 
 pure substance is 129.4 , It is insolucle in water, but fairly 
 soluule in txxe otxier common solvents. 
 
 Analyses.- dalculated for G. ,:-K N,,b, N rl6.747o; S = 12. 75;^, 
 
 found; 3, (Garius) 12.45; 12.45. N,( Dumas), 16.73;b 
 DEKZO^L DERIVATIVE.- A num.ber of attempts to prepare the benzoyl 
 derivative of tixe symmetrical xiyurazine failed because the pro- 
 duct was always a smear wnicn could not be obtained in a satis- 
 factory crystalline state. The 3cho Lten-nauman metnod and 
 variations, as well as the franzen metnod, using a benzene sol- 
 ution of tixe base instead Ox an alxaline solution is preparing 
 the derivative, were tried during txxis work. 
 oEIvIIGAR-'jAZI DS Of of ivilvin'i'-LiOAL DllnOf RO?lj_i-KlDi:.AZIx'iiE, - lixis 
 
f 
 
52 
 
 aerivat-ive is very reauily preparea, aiificult lo purify ior 
 analysis. 1 mol of bhe hydrociiloriae of tne base is dissolved 
 in a little v;ater to produce a saturated solution. lO Lliis mix- 
 ture is aadea a mol of potassium emanate. After a few minutes 
 tne mixture sudaenly v«arms up to about 40*^ and a half crystalline 
 half oily mass lises to the surface. On cooling the whole turns 
 crystalline. Kecrystallization, in turn, irom uot alconol, from 
 etner ana petrolic ether, irorn alcohol and peLrolic etner, and 
 from eLnyl acecate, finally prouuces a prouuct that melts at 
 100°!^ corr . } . lurther iieating to as iiigh as 225^ produces no 
 cnange in Lixe melted substance. 11 not purixlea by the number of 
 different cecrystallizations described above, the melting point 
 of the substance is unsharp usually beginning at 65^ and finally 
 melting at 85-90*^. 
 
 Analyses.- ualculated f.^r Nr 26.41/o 
 
 hound, N = 26.26;^ and 26,lb/o. 
 
 OXALiis-TE.- The oxallate is the most ueautiiul and tiie most easily 
 
 prepared salt of tne hydrazo compound, but, at the same time, the 
 
 most difficult to obtain in the pure stale, free base, liberated 
 
 as usual, is mixed with 10 volumes of dry ether and anhydrous 
 
 oxaliic acid acia auueu slowly until 1.2 mol of uhe acid has 
 
 been aduea to tv/o mols of tne base. The wnole mixture is a mass 
 
 of snow wnite crystals as tne precipitate lorms immediately and 
 
 is ratner voluminous, final puriiication is accomplished by 
 
 six or more recrystallizationx. from alcohol followed by drying 
 
 51 
 
 at 100° for 2 nours in a gtoren drying tuue evacuated by a good 
 water pump. The salt tnus puriiiea and dried melts at 200° and 
 appears to ue penectly pure, altnougn the cruue product is 
 

 .. M 4 
 
 0 ' " 
 4 
 
 I 
 
 u 
 
 I 
 
 )■ 
 
 ,1 
 
 » 
 
 t 
 
 i 
 
 II 
 
 I 
 
 I 
 
 
 I 
 
 A • ' t • 
 
 ( 
 
 'Jl 
 
 ,?) 'J : 
 
 ( 
 
 
 if 
 
 I 
 
 Q 
 
 t'' 
 
 
 I 
 
 
 I 
 
 ( 
 
- 53 - 
 
 composed or a mixLure o± suostances InaL nave ver^ nearly tlie 
 same properties. 
 
 Analysis.- calculated lor N r IV. 39^ 
 
 pound .- Wet method. Sulphuric acid- potassium dichromate 
 mixture, heateu to hoillng. N = 27.4;^ Alter 4 passages over 
 hot copper oxide the apparent per cent, of nitrogen decreased to 
 
 20;6. I 
 
 II Wet meLnod, same oxiuation method, Out no external heating. 
 N = 17.43> 
 
 III. Same metiiod. Same proceuure . 
 
 K = 17.51/0 
 
 Tne analyses snovi/ Lhat 
 
 tne 
 ¥ 
 
 salL has the 
 
 ® 6o 
 
 6o 
 
 .on.. 
 
 ^ o 
 
 dilr- 
 
 o 
 
 formula; 
 
 GH^ u GH5 
 
 GH-:: H GKi: 
 
 o o 
 
 AGTlOh Or ALKiL HALIDES.- Among derivatives that were m.ade only 
 as test tube trials is the metnyl iodide derivative. On heating 
 a mixture of meth^'l iodide, and the free dry base slightly the 
 tvi/o react, with consiuerable evolution of heat, to form a mass 
 of white cr jScals.The composition oi this derivatives nas not 
 been SLuuiea. I L is very soluble in water ana in alcohol. 
 
 Isopropyl iodide or bromide refuse lo reacL with the iree 
 base unuer ail conuiLions tried. Sven wnen a mixture of .i-propyl 
 alcohol, dry base, ana isopropyl bromide a^e heateu, in a closed 
 
 tube to 110^ for tnree nours no sign 01 a reaccion product 
 
 be de Lee fed. 
 
t 
 
 I 
 
 ' I' 
 
 
 w' 
 
 
 1 
 
 I 
 
 
 I 
 
 1 
 
 I 
 
 > 
 
 fj-j'-iw ,iOUC 
 
 I 
 
04 
 
 iviOiMU-i\i I TROSO Diijiil VAj- I VR Oi-' oi^IvUvifJTRloiAj j^ilSuPrvOPYi- xi^iJiLAZli'lR , - 
 
 Early in Liie wortc wilu Ine n^urazo compound Llie reaction 
 of nitrouB aciu on tue uo.se was shown to proauce a straw colored 
 light oil, tnat was oDtained in variable ^ield under tne con- 
 ditions then selected. The product uecomposed within a few hours 
 and the compound was left lor future stud^. 
 
 Wnen the stua^ of tue derivative was taken up systematically 
 two metnods of preparation were developeu. 
 i*lrst Metnod Twenty grams of th ; nyurocuioride of the 
 symmetrical ny urazine are uissolveu in the least amount of water 
 tnat -ill just dissolve the salt at room temperature. To this 
 solution, 15 c.c. of alcoriol are addeu and tne resulting mixture 
 cooleu by a freezing mixture and vigorously stirred by a motor 
 stirrer. When tiiorougniy cold a saturated aqueous solution of 
 25 g of soaium nitrite is aaaea, and tuen, arop by drop, 15 c.c. 
 oi glacial acetic acid. 
 
 ii thiCK la^er of oil separates out as 
 
 the reaction pro- 
 
 ceeds. When ail of tne acetic aciu has been added the super- 
 natant layer of yellow oil is separated from the lower layer. The 
 mixture of salts and water is tuen extracted repeatedly witii 
 ether and tne ether solution adaed to the separated oil. The 
 final volume of tne etner mixture should not exceed 100 c.c. 
 
 This solution contains , ac> tue most troublesome impurity a 
 considerable amount of ucetic acid. To remove the acid a few 
 cc Oj. wauer are addeu to tne euner excracc and che acid neutral- 
 ized by means of souium carbonate. After again separating the 
 nitroso compound from txie lower layer, tne lormer is now dried 
 for about 15 minutes witu lumps of fuseu calcium chloride. 
 

 
 1 
 
 
 •W 
 
 'V 
 
 \ 
 
 4 b ! V- 
 
 ♦:*.'» Oiu’ ., 
 
 I 
 
 «*}U : . U4J^ 
 
 ktf ■ 
 
 I >■ '<' %t , 
 
 ' ■ ' ./. ; 
 
 *• 
 
 ^ - i tr 
 
 VO 
 
 I 
 
aL biie ena Oj. I'linubes tue calcium cuioriae is replaced bj 
 i'resn lumps wnicn are allowed to stay in contact witn the ether 
 extract for 1-2 hours. The liquiu is then poured off and is 
 reauy for the final drying. 
 
 Second Method .- Txie second methou of preparing the nitroso de- 
 rivafive consists in thoroughly mixing molecular amounts Oi 
 ury souium nitrite and dry hydrochloride oi tue hydrazo compound, 
 To the well rnixeu po’-'aer, water is adaeu undil a thin paste is 
 formed, rhis paste is then warraea in a water batn to 70 degrees 
 ana kept at tnat teraperaLure for 1-1,5 iiours. Although tnere is 
 no noticeaule reaction oe tween the nltrice and the hydrociiloride 
 at room temperature, tue reaction proceeas smootly at 70'^. If 
 the temperature is raiseu to 80-00*^ the product is uiscoloreu 
 and the yielu materially decreased due to decomposition. In 
 tlie case oi tne product outaineu oy txie lirst method heating 
 to as much as 40^ during txie period wuen gas is li aerated in 
 tne solution txie whole lot oi the product suddenly decomposes ; 
 with evolution oi neat and white iumes. This behavior has not j 
 been oDserveu in case of the more stable product obtained by 
 tne second method. Tne layer of yellow oil is separated and 
 tne lower layer extracted with etuer as in case of the first 
 raetiiod. Tne etner solution is not drieu with calcium chloride 
 hovxever, but is cooleu in a Ireezing mixture to remove ..s much 
 of t.iS i. -lOiiano'Sd n^ULrociiioride as possible, :iiis is the main 
 impurity obtained by tne seconu metnod, and is reauily removed 
 on distillation. The yielu is not quite as good (60-65/0 instead 
 of 60-70/O in case of lirst metnod) as tnat obtained by tne 
 
 first metnod 
 
I 
 
 'j 
 
 
 [» i 
 
 . “ .A a. v'lr*; 
 
 ' ■ 'i 
 
 ■ 'A. s Jj6iJ'00)! •’ 
 
 T“ 
 
 . ^‘1 -'i',:' .,-. ij>z^ 
 
56 
 
 The treatment of Lae nitroso derivative obtained by the 
 Lwo methods is identical alter tne calcium chloride treatment 
 01 the product obtained by the first metnod and the removal 
 of the uncii‘'nged h^'urochloriae found in the product oi tiie 
 second metaoa. iaej^L/ier exLract is dried over night over an- 
 hyarous soaium sulphate and kept cool, in tiie meantime, in an 
 ice box. Tne decomposition oi Lae small amouno oi di-nitroso 
 compound LaaL seems to be formed by tne lirst metnod snould 
 be complete uy next morning. The ice cooling is then dis- 
 continued, cut tae extract leit in contact witn the sodium 
 sulphate ior 3-4 aays longer. ’Waen tae liquid is then carefully 
 pourea off the soaium sulpaate and distilled in vacuum the etner 
 is readily removed witnout exoernal ixeating, although time is 
 saveu by aeating tne solution to 25° by a water oath during 
 tiiis part of tne distillation. As soon as all of the etner is 
 removed, tne yellow residual oil is distilled under a higher 
 
 vacuum. At 6-8 mm the main protion oi the liquid distills over 
 
 On 
 
 between 64 and 66 . On reaistiallat ion about 9dfo of the oil 
 comes over between 65 and 66° at 7-8 mm pressure, 
 
 Txiis pure product has a ueep straw color, a peculiar 
 sweetish odor, anu is now stable at room temperature. Attempts 
 to distill tne oil at atmospheric pressure siiowed that this is 
 impr au ticaole since decomposition starts at aoout 150° and at 
 tne apparent boiling point of 16u-2° the nitroso uompound de- 
 composes ratner rapidly with evoluuion of wni ce fumes. The yield 
 of crude product could not well ue determined anu that oi tne 
 pure oil is variaole since tne losses during drying and 
 distillation are variable, on normal runs the jielu of pure 
 
II 
 
 ( 
 
 I 
 
 1 
 
 II 
 
 I 
 
 II 
 
 ‘i 
 
 I 
 
 f 
 
 
 • -‘in / . f-.o 
 
 ^ 1 '- f 
 
f 
 
 - b7 - 
 
 nitroso derivative ranged Irom 60 to an occasJiional 70^^ or 
 the calculated jlela. The product is iairly soluble in water, 
 slightly soluble in benzene and in petrolic ether, and readily 
 soluble in alcoiiol, ethyl acetate, and eLher. Tiie derivative 
 gives tue Lieosrman reaction, and shows otuer properties or . 
 nitroso compounds. Ii a arop of ferric chloride is added to an 
 aqueous solurion ol a lew drops ol tne derivative a blue-violet 
 color is proaucea, in case oi an alcoholic solution ferric chlor- 
 ide proQuces a green color, while a solution in chlorof orm( or 
 even tne diluce solution in oenzene ) shows a reu coioracion. 
 Analyses: dalculatea for , h = 2 b. 96 ;tJC= 49 . 65 j H=10. 
 
 found; C , 49.65, 49.39;oJ h, 10.43, 10.22)bJ N , 28.66, 28,20/o 
 
 = 1.4420 D 22/4 = .9440 
 
 oODIUm salt Of THE i\iITK0S0 HiDhAZIbE.- If the nitroso compound 
 made, preferably, by tiie seconu metnod is diluted with ether 
 and then treated wicn a sauurabed soiuLion of sodium hydroxide 
 in alcohol, the whole soluuion Lyrns to a mass of very fine 
 crystals aiter standing for a few nours. the same result is 
 outaineu wnen soaium metriyiaue or ethylate is used insteau of 
 tne saturateu alcoholic solution of rne hydroxide. The mass of 
 needles is lilterea oif oy suCLion, wasxieu with ether and dried 
 for 2-3 hours in a vacuum dessicator before tne analysis is 
 attempted. Since no solvent was i'ouiid from wnich tne salt could 
 ce recrystallized, tne analytical results are only approximate, 
 but suificienciy close to leave no douct as to the corapuund ob- 
 taineu. 
 
e 
 
 
 
 
 < 
 
 P6f!c 
 
 U'C - 
 
 I 
 
 i. 
 
 . :C‘. : ■. 
 
 ? 
 
 il/ 
 
 . M . ' 
 
 
 t 
 
 I 
 
 ■i 
 
 - 
 
 ;f; 
 
- 5b - 
 
 tlnalj'ses; baicuiatea lor Gj.K-|_^i\i;^Ul'}a, Na r 13. 77^^; N,= ki6.15/o 
 I'ounu.; Na = ; i4.54;^(? J N - 23.97;^o 
 
 Tiie sodium was u.eLermined aja tne suipiiaoe. 
 
 A peculiar reacLion Lnat was always observed wnen the 
 nitroso derivative was neateu in tiie presence oi alkali or when 
 iL stooQ in contact witxi Lne alnali lor longer periods or time, 
 is rue lormarion o± a small amount ol an isonicrile. An extort 
 was made ro isolate ruis prouuct^ uut uue ^iela is too small to 
 isolate or uerect the carbylarnine except by its odor. It would 
 thus ue impracticable ro prepare enougii of the nitroso compound 
 Lo be able to iuentiiy tue isonitrile obrained from it. 
 
 A number of attempts were made to reduce the nitroso 
 compound to oxie con ssponding amine, but, as is usually rhe 
 case wnen rnis type of nitroso compounu is reducea, the only re- 
 ducLion proaucts rnab could oe isolaceu were ammonia and the 
 ori^jinal hyurazo compound. Attempts to afiect tne reauction by 
 means of catalysis failed, apparently because tne plarinum 
 catalyst is immediately poisoned uy braces ox free nitrous acid 
 present, lu was uopea Ixxal reduction of txie souium salt by means 
 of Liie cataljbic mernou would ue a success, but only 4-5;^ of tiie 
 
 theoretical amount of n^urogen gas was auosrued. 
 
 CH^ ^dii^ 
 
 2 .2 ' -Azobispropane , uK-N::N-chi .- Twenty grams of dry hydro- 
 chloride of tne symmeLrical nyarazine are treated witn a 50)i 
 excess of ury po-wuered copper oxiue. The substances are then 
 thoroughly mixed by suaking tne ilask in which the reaction is 
 allowed to lake place. After about 15 minutes a peculiar sweet- 
 

 
 ' J. . < v 
 
 fe •• \ 
 
 o.".'.:f; 
 
 '■>1 
 
 !ie oi; 
 
 ■' -I 
 
- 59 - 
 
 isii odor becomes noticeable, aixer an iiour or two a crace of mois- 
 ture may be noLiced on some ox tne crystals, next morning the 
 WiiOle mass is aisLincoiy moist and Liie ouor of tne oxiaation pro- 
 auct is mucn more marxed. After 2-o nays tne mass is so wet tnat 
 it may be poured out ol tne reaction xiask as a tnick paste. Alter 
 several days more, one reaction may be consiaerea complete and 
 Lne xiask is connecLed to a condenser und heated gradually in a 
 water batn. li tne temperature is raiseu gradually, tne large 
 cubical ruu,/y red crystals of. an unstable copper salt, observed 
 on tne walls of one flask witiiih o6 hours ax oer the oxidation 
 mixture was made up, suddenly change from reu to greenish white 
 while, at the same time, at 88.5^, tne oxidation product begins to 
 distil over as ligbt, straw colored oil vjith a nausea oingl^ 
 sweet and very cxiaracteriztic odor — an odor tnat may be used as 
 a ver^' sensitive test for the hyurazo compound or its nydrochloridf . 
 Tiie fraction distilling over between 92 and 98° is composed 
 lar^^ely of water wnich forms a separate layer at tiie bottom of 
 tiie reciever, Tiie oil is readily separated irom the water layer, 
 the latter tnen extracted several times witn etiier,and the mixture 
 of etner extract and oily layer dried for 24 iiours over fresh 
 fused calcium cnloride.(Jn reuistillation tne product almost all 
 distills over beoween 88 and 89° as a mobile liquid witii a 
 faint straw color. The fact tnat the same intensity of color is 
 obtained with ever^' sample, snows tnat tne color is not uue to 
 some trace of impurity', tne corrected boiling point at 750 mm is 
 88.5° at which temperature over 90/o of the oil discills over. 
 
“ 60 
 
 Tne pure oxidation product is neutral lo litmus, is insoluble 
 in acius ana uases, and miscible wiLh all oi the common organic 
 solvents, ho derivabive could be outaineu witn aqueous hydro- 
 cyanic acid, wiun pouassium emanate, witn ororaine, and witn oLher 
 reagents that often aua on Lo uouble uonds, 
 
 Tlie product in a 10 dm tuoe showed no aosorution bands in 
 tiie visiole part of the spectrum wnen examined with a good spectro- 
 scoije. At Lhe extreme vioiet end of tne visible spectrum a slight 
 absorbtion seemed to occur, cut no attempt was made to determine 
 whether there is aosorbtion in the ultraviolet or not, since suit- 
 able apparatus was not available at the time. 
 
 The index of refraction for sodium light wnen an Abbe 
 
 25 
 
 ref ractom.eter was useu 'was ^ : 1.5690. On a number or otner 
 
 samples of the pure proauct this value was obtained so txiat it is 
 the most accurate value determ.ined on an^ of the compounds. 
 
 - .7408 as determined by means of a modij.ied Oprengel pic- 
 nometer. 
 
 -.lie yield of oxiuation prouuct from 20 g of tiie pure 
 hydrochloride is 21 cc of Liie moist and 19 cc of Lhe pure oil. 
 
 The calculatea yicla is 20 cc so tnat tiie yiela obtained is 
 practically quantitative. 
 
 Tne oxidation product is oest prepareu by tue me Luod de- 
 scribee, cut tnere are a numoer oi otner methods available for the 
 preparation. As inaicateu previcusly, ioaine titration goes 
 quantitatively to* tne azo compound. Oxidation by means or any 
 weak oxidizing agent prouuces ti^e azo compounu altxiough the 
 yield may oe poor. Even such powerxul oxidizing agents as 
 
■ . 
 
 
 ••«':»- *v. tm; 
 
 . % ,.• . .” 
 
 .•■■‘'•tj 
 
 * 
 
 V ' X. ■ 
 
 • ;'.'i 
 
 
 i'- 
 
 I I 
 
 ' f . ai liJ-.-L ^ 
 nH<~ 
 
 f 
 
 
 -t'v 
 
 
 — ^ , . ■’ 'M 
 • ■ ■ ' . tV'( 
 
 < ' • ■'.'A'' 
 
 
 
 
 
 It 
 
 »« » 
 
 ■ <' ’-'f a 
 
 . .. it 
 
 
 
 S, , 
 
 •I ' a 'V' .iX 
 
 I ■. •*- 
 
 i. 
 
 
 , .1 
 
 
 
 -I 
 
61 
 
 potassium per^manganate anu pouassium uiciiromaue prouuoe a small 
 amount oj. azo compound^ as suov/n oj one oaor • In case a small 
 amo- nt ox one oxioialion proauc o is needea on short notice it may 
 oe prepareu witn a :,iei^ of 60 Lo 70;t oy oxidizing the ease by 
 meoins oi^lKaline copper salt solution. Copper ace Late appears to 
 give one ueso resuio. xne ny urocnloride anu copper acetc^oe are 
 piacea in a aisoillin^ liask. A uilute solu..tion ox souium nydroxiae 
 is oi.en audeu and tne contents oi trie ilask neateu. on a steam bath. 
 Tne azo compound distills over as in case ol one copper oxiu.e- 
 oxdiation experiments and i is puriiieu as in 
 
 case 01 tiie regular metiiou. 
 
 Analyses; calculatea for C = 63.15p; ri 
 
 round ; G = 65.18/c;; 63.3S/o; 63.02p: H = 12.03 ; 
 
 H a 24 • 67^ _ 
 
 fv'iOlecular '?jeight uetermina oions; (j^reezing point 
 
 Galculaoed r 114 ; round 110 anu 119. 
 
 - 12.28^; K=24.56/o 
 12.45; 12.46;y 
 
 iov^eringjjyenzene ) 
 
 neuuction of tne Azo Derivative ; Two cubic centimeters of azo 
 compound reduced in a small reduction apparatus, absorbed the 
 calculatea amount of nyurogen in less txian an nour unuer tne in- 
 fluence of colloidal platinum us catalyso. iteuucoion with sodium 
 amalgam or witn sodium in alcoxiol yields tne same produco, one 
 symmetrical diisopropyl Ujuiazine. 
 
 H^.drolysis of Liie Azo oompounu .- me azo comp^una aoes not 
 change to any uppreciaole extent after rexluxing for an nour with 
 a 2% solution of nyurocliloric acid. Alter 4 hour of rexluxing with 
 a 4 ^ solution of the same acid no change could oe noted, al oer 
 4 iiours of refluxing w'itii a 10;b solution Ox the acid Lnere was 
 a considersujle aecrease in volume of the iioating la^er oi azo 
 

 
 
 -'^ ' 
 
 '■i'Ui 
 
 .U9 
 
 / 
 
 ^ ^ I 
 
 i : 
 
 '4 i 
 
 ^<j 
 
 ' < ' 
 
 1 
 
 I 
 
 i 
 
 I 
 
 < 
 
 L 
 
- 62 - 
 
 compound, Dut , nL tne same >rabe of n^urol^'sis aL least 3 nours 
 more would nave seen requirea to complete the hyarolysis. After 
 one hour of ireaLment witii a 20^3 solution of concentrated acid in 
 water, tne oily layer naa practically all oe usea up. The compound 
 is now nydrolyzed by refluxing with a mixcure of 1 part of concen- 
 traceu n^ arociiloric acid ana 1 pare oi wacer. V/iUi this concencrat 
 ea solution tne layer oi oil aisappeara wiLhin naif an nour of 
 reiluxing. An excra half nour is usually used to be sure that the 
 hydroi^'sis is complete, he mixture is then concentrated in 
 vacuum until- the resulting syrup becomes slightly colore a. The 
 hydrochloride of prima.r^- isopropyl hydrazine cr^-stallizes out as 
 small white needles on cooling the s^rup in a freezing mixture. 
 
 The salt is iiltered off rapidly and o^ie filtrate concentrateu 
 iurtner until again st'rup^ .The fhedzihgj. out and concentration 
 processes are '"e-oeateu. until Qni^ a verj small amount or resiuual 
 solution is left, rhe small amount of h^arociiloride left in this 
 is precipitated b^ means of a mixture of a few drops oi alcohol 
 and about 5 c.c. of ether. The h^ arochloriae maj' then be purifieu 
 ana analyzed or the ease ma^' be liceratea from the salt and 
 tue dibenzoj/1 derivative made in identiij'ing this n^-arol^sis pro- 
 duct . 
 
 To identify acetone - the otner iiyurolysis product- a second 
 lo-t of azo derivative is hydrolyzed bj a 10 % solution of 
 hydrochloric acid. This does not cause as much loss Ox acetone 
 as the more concentrated solution oi acid does. After the hydroly- 
 sis is complete, the acetone is simply distilled off and iaenti- 
 lieu by means of the uenziliuine compound, by tiie iodoform test. 
 
- 63 - 
 
 and. 'Dj tne souium ni Lroprussiae color lest. 
 
 Conversion Lo tlie Hydra zone IT the azo compound stands lor a week 
 or more over strong alkali or if it is heaueo. for a few hours au 
 180*^ with concentrated potassium njuroxide,in a closeu. Luije,Lhe 
 azo u6: ivative is partially converbed to one u”drazone as evidenceu 
 bj' tne nydrazone odor, the greaLly changeu index oi refraction, 
 and txie boiling point of lOO’ to 118 '’lor tiie resiuue left on dis- 
 tilling off tne unciiange^. azo compound. Since only a small amount 
 could be obtained in a run of this Kind tne n^'arazone could not 
 be analj'zeu because rhe purificacion of such a small amount of 
 prcducu is too uiificul'^. Tue iucc LuaL even sucn arastic treac- 
 ment as iieating bo 180° only parxiaily converbs tne azo to the 
 iijuiazone uerivuLive snows tnai tne azo derivative oi symmetrical 
 diisopropjl iij-urazine is an uncommonly stable compound. All at- 
 tempts to effect the reverse rearrangement - h^'drazone to azo- 
 f ailed. 
 
 P reparation of Di - isopropylj >’ in tetra substituted liyarazines =tnd 
 in a few symmetrical disubsti tubCn nyura tines oxidation or heat 
 tenu to uecompose tne azo compounds to produce nitrogen gas 
 along with the dialkyi compouuu produced tnrougix reuniting of 
 the two alkyl rests, in spite oi a large number of uifferent 
 experimiOxits carrieu out in an attempt to find a practical method 
 of uecomposing the azo compound obcaineu in tuis worn into nitro- 
 gen gas and di-isopropyl, none o± the metiiods trieu gave more 
 than traces df paraffins. . 
 
64 
 
 PKSPAKii'i'luw UF iviUWU ISO'^PrLUPYijhyjjKAZIi'^E. - Tile primary liyurazine 
 majf' be prepared oj laree dilierent metiiods. Two of tixese, the 
 hjdrolj'sis 01 tne azo aerivabive and oi Lne hj-drazone are similar 
 and nave ueen parbly uescribea. The ujdrol^sis ol tixe ixydrazone 
 id eifecteu by verj dilute acids, even water iiyurolyzes cnis 
 compound, so tae preparation of tiie primary' a^'urazine from Ixiis 
 compound is exorern ly simple. Vuietixer produced bj hyarol^sis of 
 tne hydrazone or of 2 , 2 ’ -azobispropane the ayarolysis mixture is 
 concentrated in vacuo as describeu before, tne iiydrocaloride is 
 isolateu,and purifiea uy recrystallization, and tlien dbcompQsed by 
 means of concentrated alkali. 
 
 The taird ana best melixod of preparing the primary hydrazine 
 consists in the catalytic reauction of a mixture of 1 mol of 
 pure acetone,! mol oi ayurazine iiyarate, and 1 mol of hydrochloric 
 acid in exactly tae same manner tnau tne reduction of ketazine 
 was efiectea. Tne procedure tarougiiout is the same except that 
 the aydrocnloride of primary isopropyl ayarazine decomposes too 
 easily to permit tae evaporation to uryness of tae reduction 
 mixture even in vacuo. Accordingly i^ne iiydrocaloride is isolated 
 by cooling the syrupy solution of Lhe hyarociiloride in a freez- 
 ing mixture to freeze out as m.ucii as possible oi the salt at a 
 time. The mass ox fine needle-like crystals is then filtered by 
 suction. The xiltrate is concentrated furtaer and the freezing 
 and iiltcring repeated until the amount of syrup leit aoes not 
 exceed b to 8 cc wnen the rest of the salt is • precipitated by 
 m^eans of a little alcoaol ana a large excess of ether, ny waat- 
 ever one of tne taree metaods mentioned, the salt may nave been 
 

 
 
 Ca-O. 
 
 n 
 
 
 1,. 
 
 
 I i 
 
 * 
 
 ■ ir* 
 
 V ^ 
 
 1«. 
 
 
 u i. 
 
 ) . 
 
 , t 
 
 ^ ® ; - '.yjO 
 
 f ‘<JW 
 
 
 
 ♦I . . f 
 
 ■ • . •• /Vi^ 
 
 '• ■'■' • 
 
 Tv " 
 
 •‘ '■ ■’■ 
 * -'iv -'jflJ. 'n, 
 
 , ' 
 
 ^ m w wf 
 
 - . Jf 
 
 c 
 
- bb - 
 
 ODLcdned, ine isolation ox' tne xij drocnioride is accomplisneu. in 
 
 exactly tue same manner, xne arocnioride ouLainea tnrougn 
 
 ujorol^sis of 2,2 ’ -azoDispropane by 50;b0 nydrocniorio acid is 
 
 verj hygroscopic, wnile chose obiaineu irom Lne hyarazone and 
 
 iiom the reduction of the acetone-liydrazinehyarate mixture are 
 
 onl^- verj sligntly hy groscopih . The h:,'groscopic salt was not 
 
 salt 
 
 analyzed, but since tne non-hygroscopic^^roves , chrougii analyses, 
 to oe the neutral salt, xuere is little doubt auout the identity 
 of the hygroscopic compound , especially since both hydrochlorides 
 yield the same base on treatment witn concentrateu alkali, so that 
 one must be cue acid and che otuer tue neutral salt unless tiiey , 
 be tne same compound. This is not che case , however , since re- 
 crystallization uoes nox ^ield a non-hygroscopic salt melting at 
 114.6®. 
 
 ISULnTION OP Phikhhx ISOPnOP'^Lh'^DRuZINE, • “ On treat- 
 
 ment of uhe liyarocnloride wicii solid sodium or potassium hydroxide 
 tiie mono isopropyl hydrazine is lioerabed as an oil tnat, in 
 appearance and odor, is very similur uo tne symmetrical hydrazine 
 describe^., previously. The base cannot , however, oe obtained in 
 a pure state by any metiiod or device tried so far. A constant of 
 tiny cubbies, usually starxing from some fine dust particle or 
 snarp point, is cnfn'm.Miith--- given off for an indefinite period of 
 time. The amount oi ^as given off is so small that a very large 
 amount of proauct or a very long perioa of time would be necessary 
 to collect enough tjSis to identity it. As the oxidation of primary 
 hydrazines results in tiie elimination of nitrogen, it is probable 
 tnau the ^as escaping is nitrogen gas. 
 
- 66 - 
 
 Tiie accurate determination oj. the uensit^ is made irnpossiole uy 
 
 the gas evolution, and inueed would ue of little value on a 
 
 compound tnaL is adaiittedly not pure. Tne index of reiraction 
 
 snows tnat tue nydrazine gradually decomposes. The purest fresn 
 
 base examined j^ave a boiling point oi 106-7 at 748 mm and had 
 
 2 
 
 a density of .814 at 25 degrees. ^ - 1.4280 
 
 The base is miscible with water, alcohol, acetone, and ethyl 
 
 acetate, but only slightly soluble in ether and peLrolic ether. 
 
 Primary isopropyl ny arazine is a verj strong reducing 
 agent, in tuis respect even excelling the symmetrical hydrazine. 
 In addition to reaucj.ng silver nitrate solutions and rehling’s 
 solution in tne cold, it also reduces potassium chromate as was 
 snown when an attempt vvas made to determine the chlorine of 
 the hydrochloride by mea.ns of kohr’s metuod. 
 
 Iodine Litracions and hjdrochloric aciu titra Lions may 
 be useu as in case of tne symmetrical hyarazine. 
 
 In 3.S much as Lne case is known to be impure, no attempt 
 -xds been made to analyze it. To prove its identity conclusively 
 the iiydrochloride , the plienyltuiosemicarbazide , and the di- 
 benzoyl derivatives were prepared and analyzed. 
 jJhRI VATIVEb OF PKIiViAHi ISOPROF Ynil^DKAZINE. - 
 
 The hydrochloride nas been partially described in con- 
 necLion with tne nydrolysis of the azo and xiyurazone derivatives 
 
 (page 64-65) The crystals isolated from the residue left on 
 concentration or the hydrolysis or the reduction mixture, are 
 dissolved in a very small amount of alcohol. After heating to 
 dissolve all of the crystals ether is adueu to the solution 
 

 I ' 
 
 
 f; 
 
 *1 
 
67 
 
 until Lhe liiot permanent cloudiness is oblaineu. On cooling unis 
 solution to -lO^or lower oy a good freezing mixture, the salt 
 crystallizes out. Tiie aiooliolic filtrate suouid never be dis- 
 caraea, however , since the hydroculoride is so extremely soluble 
 that, even at -10*^ much more stays in solution than is frozen out. 
 Two such treatments give a product that is sufficiently pure to 
 De analyzed. Ethyl acetate may be used as a recry stall! zing agent 
 but tue hyarociiloride is only very sligiitly soluble in etnyi 
 acetate and large amounts of the solvent must be useu to obtain 
 a xair sizeu crop of crystals on freezing the solution. 
 
 The pure nyarociiloride is non-liygroscopic( i , e , if we are 
 working with tiie neuLral salt) melts at 114.5° (corr,),and 
 is verj soluble in water and in alcohol, slightly soluble in 
 chloroform, benzene , ethylacetate , and acetone, and insoluule in 
 ether and petrolic etner. 
 
 Analyses; 
 
 Qalcuiated for C H^ 1 ^ 1 ,^ 11 ( 111 , 
 
 o XU ^ 
 
 h z 2 5 , 54 ;!b 
 
 found; N z 25.39;6 
 
 Pheny Ithio semi car bazide of primary I sop ro py 1 - Hydrazine . - 
 Wnen a mol of pnenylmustard oil is added to an etner solution of 
 1 mol of free primary isopropylnydrazine , fine long needles of the 
 mustard oil derivative precipitate out in a few minutes. These are 
 recrystallized from alcohol by adding water or ice to a hot 
 solution of the derivative in alconol, 'whien the first permanent 
 clouainess appears on adding water, tne solution is cooled well 
 w.ien tne derivative precipiuates out in good yield, fiie melting 
 point of tne pure uei ivative is ^.41 , 5°( Corr . ) . It is very soluble 
 in hot alcoxiol, in aceton.;, chloroform, and etxiylaacetate , and 
 insoluble in water > etner, ana petrolic ether. 
 
N r 20.09^^ 
 
 Analyses: Calculated 1‘or G Nr^S , 
 
 13 J-O o 
 
 Found. (Dumas) N z iy»B6 and 20.23/5. 
 
 Di-uenzoyl Derivative of Fnimar.y Isoprop.yl - H.ydrazin e . 
 
 CH3 
 
 ^CH-NK-F^ Two mols oi' benzoyl ciiloride 
 
 C1I3 ^“C,,n3 
 
 0 ^ are aaued to a concentrated sol- 
 
 ution of tue iiyarociiloride in waper. Sodium uarbonape, in excess 
 is aaue^ to this. After a lew minutes of lively stirring a react- 
 ion occurs with evolution of consideraole heat. A- first no pre- 
 cipitate or otiier- product can ue uetecced. Ax ter stirring and 
 ruDbing tne smear witn sodium carbonate a few minutes the deriv- 
 ative sudaenly crjStailizes out, Puriiication is accoraplisneu 
 witn alcouoi and vvater in exactly uhe same manner as in tne case 
 of the phenyl thiosernicarbazide aerivative. Tne pure product con- 
 sists of beautiiul white needles melting at 161 . o'^( corr . ) The 
 dioenzoj'i ueriva. uive insoluole in water, ether, and petrolic ether 
 Wiiile it is sofuufe in c^fcoiiOl, etiijl acetate, anu. cenzene. 
 Analyses: Calculated for C^3 H^qK 202> N r 9.93/5 
 Found: (Dumas) 9.85/5 and 10.09/a N • 
 
 Even When only one mol of oenzo^l chloride is added to 1 mol of 
 the base the same derivative is formxSd wnile tne remainder of tne 
 Case is not affected. 
 
 Other derivatives ; Test tube trials show tnat the oxallate, the 
 picrate, tiie seinicar uaziue , and the aromatic aldehyde derivatives 
 can readily oe prepared. To prepare tne aliphatic aldehyde and 
 ketone uerivatives, a condensing agent appears to be necessary. 
 
*«rj 
 
 j j 
 
 . iW. 
 
 
 
 1 
 
 f 
 
 I 
 
 y 
 
- 69 - 
 
 CH 
 
 A A fV 
 
 PKiiPAKiiriulT OP AGPiONE I^OPAOP VL-HYl)RAZONE, ^ GH-NH-N=C; 
 
 CHg 
 
 o 
 
 Although preliminary trials had shown that a small amount of 
 a new compound was ourained when the prim_ary ayarazine and 
 acetone were m.ixeu, the yield' was too small to permit tae isola- 
 tion and iaentii icarion of rhe new suustance. As it was very 
 urgently desired to make the condensation proauct of acetone 
 and rne primary ayarazine, to prove , ii possiule , rne strucLure 
 of tne oxiaaLion proauct obtainea from tne hydrocaloride of the 
 symmeorical hydrazine, a long series of experiments were carriea 
 out in an elforr to aeuermine wnetaer the condensation product 
 could ue produceu in good enouga yiela to permit, au least , its 
 isolation and identii ication. 
 
 The only metaoa taat aas seen triea taat gives good yields 
 is tae one aevelopea cy Aeddelien for tne preparation of aniles. 
 1.5 mols of acetone of acetone are added to a solution of 1 mol 
 of primary isopropyl hydrazine in 10 volumes of etaer that has 
 been carefully dried. No reaction can be noticed. A small piece 
 of anhydrous zinc chloride (less that ,5 g) is added to the 
 mixture. Immeaiately tiiere is a violent reaction with vigorous 
 heating and euulitian of acetone. To prevent too large a loss 
 of acetone oxie small flash is cooled unuer tne tap until the 
 reaction slows aoim, Tne mixture is again aeated almost to tae 
 uoiling point oi tne excess acetone and taen allowea to stand 
 for an hour or two. a.t tae end of tais time the reaction pro- 
 duct is distilled directly off tne liquid and clieesy zinc salts. 
 Tlie disLillate is taen dried over iresaly ariea anhydrous sodium 
 sulphate lor 3-4 days before iractionating tne mixture, up to 
 
70 
 
 65° UiG etner and excess acetone come over. At auout 65° the 
 tiiermometer suadenij rises until a temperature oi 132° ia 
 reached. The rest oi tne liquid distills over uetween 132 and 
 134 uegrees. The residue left aiter tuis, as 'well as tiie first 
 distillation is a deep red liquid containing zinc salts as some 
 of the residual substances, nhese substances were not examined 
 in detail. 
 
 The pure hjdrazone is a colorless, mobile liquid with a 
 stinging menthol odor that seems to be characteriztic of ketone 
 and aldenyde condensation proaucts v/itii primary isoprop^l-nydra- 
 zine, as it was also encountered in test tube experiments with 
 benzaldeiiyde and witii salicylaldehyde , 
 
 The density was found ; =,8225 
 
 22 
 
 The refractive inaex ; T\ - 1.4360 
 
 Analyses; Calcuiateu for G = 63.15; K = 12.28; N r 24.56^S 
 
 i<'ound; G z 62.69 and 63.00)^; H = 12 . 47 , 12,5570 ; h r 24.98,24.347b 
 IviOlecular weight ue termination , Lowering of freezing point of 
 benzene. found t 105,108, 104 . Theoretical ; 114. 
 
 The hy drazone is very easily hydrolyzed even by water. This 
 f8.ct explains why it nas been so aifficult to obtain alipiiatic 
 hyurazones in tue past. Tlie prouucts of iiydroiysis were identified 
 in the sam.e way tlxat tuose obtaineu from the azo compound were 
 iaentiiied. 
 
 Reduction to tne hyarazo compounu v^as readily effected 
 by means of colloidal platinum anu uydrogen as in tne case of tne 
 azo compound. .Jie product obtaineu was iuentixied by the melting 
 point of tne nydrocuioride and uj the odor oi tiie azo compound 
 
71 
 
 ODtaineu on Lreaoing Lne arociiioriue vjiun powderea copper oxide, 
 AbtempLs oo prepare one uenzoyl, tue puenjlmustara oil, and 
 tile semicar uazide aerivatives failed because , owing lo moisture 
 periiaps, Lne final proauct obfaineu was always the corresponding 
 derivative of the primary isopropyl hyarazine. It is possible 
 tnat some of . these may be obfained tarougir^the use oi’ some de- 
 hydrating agent, 
 
 VAiilOuo DEsEiraViIbAi IONS xb'Mb IviE'friObo; - 
 
 me inuex of refraction of tne uifferent compounds was 
 aeferminea by means of an Aube ref ractometer with daylight as 
 tne source of iigxiL, liie instrument waa frequenLiy ciiecked against 
 water. The remperarure was obtainea by means of a Kormal 
 tnermometer . 
 
 The specific gravity was determined, in each case ,by 
 means of a small moaiiieu Sprenkel type picnometer. because of 
 the small amounts of pure material preparea,in most cases, at one 
 uime, one capacity of the picnometer was made only 1,6219 cc at 
 4 degrees. The instrument was always filled to the mark on the 
 j-ine capillary side arm at the temperature at which ohe sample 
 and instrument nad been kept for some hours. This temperature 
 was Known anu was higher than that of the balance case. When 
 tne weigiiings were carried out the liquid drew av/ay Irom the 
 tip of the instrument thus preventing loss due to evaporation. 
 
 To determine tne strength of tiie symmetrical hydrazine, and 
 if possible, tnat o± tne primary nyurazine, conductivity 
 measurements were carried out. The temperature of tiie tnermo- 
 stat w^'S kept constant at 25 + .01*^, hie ceil nad platinized 
 
( , t 
 
 t • 
 
 
 1 . 
 
 '^v 
 
 
 
 
 *■' n>''5 
 
 c '^VWl ’jjbw. ii ’'1^^ 
 
 -ty i.0^., jrti'iw 
 
 • ' ' i'> t - 
 
 > i- 
 
72 
 
 electrodes faslenedjto a verLical uoudle v;ire inlet tube, 
 parallel to eacn otner and at a distance ol 2.5 mm. A stopcock 
 az zne bottom of tiie cell permitted the withdrawal of 5 cc of 
 so_^ tion alter eacii dilution wnile tiie added water was added 
 irora an accura.tely calibratod pipette. As the samples had to be 
 kept in an atmosphere of nitrogen, a strong capillary tube 
 reaciiing into the bottom of the cell served as an inlet for the 
 nitrogen wnich served as a stirring device as well as in the 
 capacity of an inert atmospnere. This proveu very satisiaciory 
 as trie buuDles SLirred me solution txioroughly witnout endanger- 
 ing the adjustment oi tne electroaes. 
 
 Tiie sourse of aluernaiing current was a special alterna- 
 tor furnishing 1000 cycles a second. Tne conductivity water 
 was preiDarea by means of the regular conauciivity water still. 
 
 AS tiie iiydrociilorivxe is appreciably hydrolyzed at nign 
 uilutions , x^reuig's metiiod of calculating the value of /\^was 
 employea, ho claim of great accuracy is maae for tne deterraina-1 j 
 lions in view of the fact that it is very diificult to prevent 
 tne base from oxiaizing to some extent and the assumption that 
 hydrolysis does not enter in in the conuuctivity determinations 
 on tne iiydrociiloride below 256 volumes is also hardly 
 justifiable. In view oi tne limitations places on tne conductivit 
 work by tne nature of the base, tne fact tnat the strength of the 
 symmetrical ease is very close to txxat of hydrazine, is all 
 that was hoped i or tne determinations. 
 
 The primary rij^drazine pioved to be extensively nydrol- 
 yzeu even at 16 volumes of water to 1 of oase. 
 
75 
 
 TAiiXjiii XX* 
 
 Conauctivity , at Variouy Concentrations, Of tne Hydrociiloriaes 
 
 
 Of 
 
 Some nitrogen 
 
 
 
 
 
 Voi'ojiies of 
 'jyater per Gram 
 oaXt • 
 
 6 
 
 of 
 
 lij'aroculoride of 
 
 2, 2 ‘ -Hydrazo- 
 
 propane NpK. (CK 5 )piMH 
 
 82.1 --- 
 
 o 
 
 GK^wHp 
 
 16 
 
 
 102.0 
 
 — 
 
 — 
 
 — 
 
 — 
 
 52 
 
 
 116.2 
 
 111.5 
 
 106.5 
 
 126.5 
 
 115.4 
 
 64 
 
 
 150.0 
 
 114.6 
 
 109.7 
 
 129.8 
 
 116.9 
 
 128 
 
 
 140.0 
 
 117.8 
 
 112.6 
 
 152.8 
 
 119.9 
 
 266 
 
 
 160.0 
 
 120.6 
 
 114.0 
 
 135.0 
 
 122.6 
 
 512 
 
 
 175.0 
 
 122.5 
 
 116.2 
 
 156.4 
 
 123.8 
 
 1024 
 
 
 182.0 
 
 125.0 
 
 117.5 
 
 157.9 
 
 125.1 
 
 jata, except for 2 ,2 ‘ -iiydrazopropane( 5^'mmetrical diisoprop^'l 
 
 52 
 
 iiyuraz3)n^, from oreaig#' 
 
 y 
 
1 • 
 
 1 
 
 / 
 
 I 
 
 r 
 
 t; 
 
 ./> . I 
 
 t*,' ' 
 
 i 
 
 C r 
 0 ^ ^ 
 
 
 if. 
 
 » •» 
 
 
 , V 
 
 V • 
 
74 
 
 T A3LIL III 
 
 |0O 
 
 Values of(Yir;^y7 ior a Kumber of Nitrogen Bases at 
 Various Goncentrations . 
 
 Base Volumes r 
 
 8 16 
 
 32 
 
 64 
 
 128 
 
 256 
 
 Average 
 
 Hydrazine • 
 
 00044,0005 . 
 
 00023 
 
 ,00021 
 
 .00020 
 
 .00021 
 
 .00027 
 
 3 ym. Di-iso 
 Propyl-hydrazine 
 
 .00023.00022 
 
 •00019 
 
 .00018 
 
 .00019 
 
 
 .00020 
 
 Aniline 
 
 ,15V ,165 
 
 .162 
 
 .159 
 
 « 156 
 
 .152 
 
 .158 
 
 I-Propyl-amine 
 
 .052 .054 
 
 .054 
 
 . 053 
 
 .052 
 
 .051 
 
 .053 
 
 Ammonia 
 
 .0023 .0023 
 
 .0025 
 
 .0023 
 
 .0023 
 
 .0024 
 
 .0023 
 
 kethyl- amine 
 
 .052 .052 
 
 .051 
 
 . 050 
 
 .049 
 
 .047 
 
 , 050 
 
 Dime 1-amine 
 
 .074 .074 
 
 .074 
 
 .074 
 
 . 0?'4 
 
 .074 
 
 .074 
 
 T rime thy 1-amine 
 
 .0069 .0073 
 
 . 0075 
 
 .0076 
 
 .0075 
 
 .0074 
 
 .0074 
 
 Bata, except for sjmmefricai biisoprop^ l-xiydrazine^ f rom Bredig^52 j 
 
Y5 
 
 IV SUMwArtY. 
 
 1) Tiie reuacLion or (limeLliji ketazine to symmetrical diiso- 
 propyl iiyurazine nas Deen accompli sixea oy means or catalytic 
 reduction using colloiaal platinum as a catalyse . 
 
 k) rue resulting hydrazine and its common derivatives have 
 been studied. 
 
 o) 2 , 2 ’ -Azobispropane lias been prepared by oxidaeion of the 
 hyurociiloride or tne symmetrical h^u.razine. The use or copper 
 oxiue as an oxidizing agent to prepare alipnatic azo compounds 
 constitutes a new metuou oT oxiaaeion ol sucn nierogen compounds. 
 
 4) Acetone-isopropyl hyurazone , a new zype o± alipiiaeic 
 compound xias ueen prepa.reu ana studied. The isolaeion or both 
 rne azo and the uydrazone derivaoives or tne symmetrical 
 hydrazine represents an acnievement tnar has not Heretofore 
 been accomplisned in the rield ox purely alipnaric hydrazines. 
 
 5) Tne mono-nitroso derivative of symmetrical diisopropyl- 
 hyurazine nab been prepared and stuv^ied. 
 
 6 ) The rirst sodium salt purely aliphacic nitroso - 
 
 hydrazine iias been prepared in the x orm of the sodium salt of 
 theimono-nitroso ^erivaoive of the Syrnwetrical hydrazi-ne. 
 
 7) The previously unknown primary isopropyl hydrazine has 
 boen prepared by the following metnods; 
 
 (a) hy reduction or a mixture of 1 mol of acetone and 
 1 mol of nydrazine nydrate to wxiicn 1 mol of hydrochloric acid 
 nad been auued. 
 
 (b} hy acid xxydrolysis ox acetone isopropyl hy drazone. 
 (c) hy auid xiyurolysis or 2,2 ' -azobispropane. 
 
76 
 
 TABLii I V 
 
 Relations Between tiie Dii'ierenL Proaucus ..-jtuuien in tBe 
 
 i X ;-.sent InvcstijaLion. 
 

 ■/'m^ ' 
 
 ,,y.i / 'i . > ^.t, . 4 
 
 - m 
 
 1 
 
 • it 
 
 •,. ^ ^;i^* ,u >r... ■ t %'^ ^4 t\fiui^:<§t. 
 
 Miim -. ■ .JH . . , ■' fr; ’■" 
 
 't«f. 
 
 
 
 vl‘ "iA 
 
 
 
 ''' ’i w'>' ’ f '* '* ** _ m '•» *< 
 
 iy'y 
 
 f 
 
 ■d: 
 
 ,v#'A 
 
 ■ r (■ 
 
 . tJ ' r/ 4M .Si ,'f. •_.. 
 
 A *f ' 
 
 M: ■''./ \h 
 
 
 
 y." -v- . , ■" - ''' '■♦^ . ’/i 
 
 !,'(l'! 
 
 fitf 
 
 
 I 
 
 
 
 v.,j <,<!'.^ ■'•■** ' ' ' ' -/^ 
 
 ' ('If 
 
 , r ,r^Vf-» " %■■ ■( f^' . ' ".Trf 
 
 : * * * '■*? - ;• ,S y 
 
 
 
 * f^' 
 
 
 fel 
 
 Iff-V 
 
 
 "nr 
 
 <¥f -T 
 
 
 
 
 ’X" 
 
 \ 
 
 
 Oi- **• . . ■ ^ _ I 
 
 vL?'il 
 
 
 f*»» 
 
 wfi:, 
 
 .= ■. ■, ■ ' 
 
 i^'- '-■ .If 
 
 ‘'■'® '"rf f t k.'*v’ 
 
 ' J' -4t 4J!.4i«. r.u- 
 
 
 ^ ' i‘X ■ ^ . i h At: ^ 
 
 ir, 
 
 *•' ' 
 
 (■’! •■^1 
 
 '-»: ..i£l 
 
 ' rlv'' 
 
 ,ff 1 ■ 'X 
 
 >lk^’ •*. 
 
 * ’ 
 
 1 1 '.' 
 
 tA / .'■■ / ' ■ 
 
 L 
 
 
 ■f^'fi ■ ',i^ , '’. -V. 
 
 ■ »W g » ^ " ~ * ' . ■ ---».• ,J"" ^ i4Juu;i ' Ujii/..Vg *^ -^-! a "- --: 
 
76 
 
 iJlBLIOuiiAPii i . 
 
 1. Curtius, J. prakt .(Jhem, , ( 2 ) ^,531 (1888) 
 
 2. Raschig, 3er.^, 4587 (1907) 
 
 3. i‘lscher, Ann« , 190 ,71 (1878) 
 
 4a. i'lscher, Ann., . 190 , 77 (1878) 
 
 4b, risciier, Ann., 199 , 308(1879) 
 
 4c. Riscner, Ber., 2i71(1880) 
 
 5a. Rischer, Ann. , 199 , 325 (1879) 
 
 5b. RisCiier, ibin. , 190 ,102 (la78) 
 
 6. RiscAer and jrillning, Ann. , 253 , 5 (1889) 
 
 7a. Rischer, Ann. , 199 , 330 (1879) 
 
 7b. i-i'i sober, 8er .,29,793 (1896) 
 
 7c. Harries and Haga, 8er.,_^, 58 (1898) 
 
 8. oLolle and j-jenratb, J.prakt .Gnem. , ( 2 ) 70,263( 1904) 
 
 9. Ruscn, DisserLaLion , Heiaeluerg, 1904, 
 
 10. Kisclnner, J. prakt .onem. , ( 2 ) ^,113 (1901) 
 
 lla, Curtius, J. prakt .Ciiem. , ( 2 ) ^,44 (1889) 
 
 llb. Gurbius and Pi lug, J , praKt .Gnern. , ( 2 ) (1891) 
 
 12a, Curtius, J. prakt. .Guem,(2) 62 , 83( 1900 ) 
 
 12b, Thiele, Ann. 376 , 261 (1910) 
 
 12c . Curtius ,?ropfe, and Haager , J. prakt .Gxiem. , (2)^, 164(1891) 
 13a, Curtius, J. prakL .Chem. ,( 2 ) 62 , 83( 1900) 
 
 13b.Vvohl and Oesterlin, cer ., 33, 2736 ( 19 00 ) 
 
 14, Curtius and Tnun, J.praKL.Ghem. , ( 2) 44,161(1891) 
 
 15, Thiele, Ann., £^,262 (1910) 
 
 16, Thiele and Iieusser , Ann. , 290 ,30(1896) 
 
 17, Wieland, "hie Hydrazine, Rerdinand Enke , Stuttgart , 1913.p 94 
 
=‘- " 
 
 ♦ 
 
 I 
 
 
 V 
 
 ■■ J 
 
 \ 
 
 . I 
 
 
- 77 - 
 
 18. Iviailiie, Compt.rena. , 170 ,1265 (1920) 
 
 iBa. Gurtius ana l'Oersterling,oer .27, 77Q( 1894) 
 
 18b. Gur Lius ana Zinkeisen, J.prakl .Giiem. , ( 2 ) 58, bl0( 1898) 
 18c .i-’ranke , konaLsh. ,£0, Bb5( 1699 ) 
 
 18d. krey ana Horfman, konatsh. , 22, 762(1901 ) 
 
 19. Guruius and Wirsing, J. prakt .Guem. ( 2 ) bO, 546( 1894) 
 
 20. Zieiil, Dissertation, Gdttingen, 1914. 
 
 21. otaudinger, Helv. Giiim. Acta, 4,212,217,239(1921) 
 
 22a. Kaufrman, Der.^, 123 (1918) 
 
 22b.Willstatter, 8er. ,^,767(1918) 
 
 22c.Rosenmund,Der. 680(1916) 
 
 22d. WillsLdater,and kayer, xier . ,41, 1475( 1908) 
 
 23a. Loew, per. ,2 5,2 89 ( 1890) 
 
 25b. Yv'illstdtter,ana KaLt, 3er . ,46,1471(1912 ) 
 
 24a. Paal ana ^pnberger, per. ,37,124(1904) 
 
 24b. Paal, Per .46 , 2221 ( 1912 ) 
 
 24c.porsche,x_.er . , 62, 2077( lyl9) 
 
 26a. Skita and keyer. Per . 3513, 5679 , 3689 ( 1912 ) 
 
 25b. Uaoe, per. ,46, 2166 1 , 1912 ) 
 
 25c. 3kita, per. , 42 , 1627( 1909 ) 
 
 25d, Skita, per. ,62,1620(1919) 
 
 27a. Harries, per. ,27,2279(1894) 
 
 27b. Harries and Klamt, per. 28, 504 ( 1895) 
 
 27c. knorr and £tthler,per . ,39,3259(1906) 
 
 2 7d. Thiele, Ber . 2577 ( 1909 ) 
 
 27e. Harries and Haga, 3er. 31 ,62(1898) 
 
 28a. Korte, DisserLarion , Heiaelberg, 1903. 
 

 
 
 
 / 
 
 L' u'h; 
 
 t 
 
 9 
 
I 
 
 - 78 - 
 
 28b, busch, ber. ,^,loy( 1905) 
 
 29a. Dr . J.K.Oailej,. Private Pcmrrur ication. 
 
 29b, harries ana iiaga, oer. , 51, 64( 1898) 
 
 29c, Harries, i^er .27_,22v6( 1894) 
 
 50a, liiiele, Her . , 41, 28Qb( 1908) 
 
 50b. Thiele, Her., 41, 2681 (1908) 
 
 50c. Stolle, Ber., ^,2811(1908) 
 
 51. Ourtius, per. , 55, 2562 ( 1900) 
 
 52 ,_;amberger and hausser, Ann. , 575 , 519 ( 1910) 
 
 55a. Voswinkel, Ber. , 55, 1945( 1910) 
 
 54,. pecuman, Ber. 26, 104 7(1 89 5) 
 
 55. Bamcerger, Ber. , 55, 758( 1902 ) 
 
 56. Thiele , Ann. , 576 , 245 (1910) 
 
 57. Kizis, Dissertation, Strassburg, (Date not given) 
 59. Wieland, loc.cit.page 44. 
 
 40. Baeyer, Ber . , 2 , 685( 1869 ) 
 
 41a. Gomberg, rUin. , 500 , 60 ( 1898) 
 
 41b. Sciimiltman, DissertaLion, Heidelberg, 1914) , 
 
 4lc. Thiele and Heusser, Ann., 290 , 261(1896) 
 
 42. kiitcherlich, Ann . 12 , 511 ( 1854 ) 
 
 45a. Fischer, Ber . , 29 , 795( 1896) 
 
 45b. Bamberger and Pemsel , .^er . , 56, 56( 1903) 
 
 43c.ElDers, Ann. , 227 , 554(lb85) 
 
 45d. ihiele, Ann. 576 ,267( 1910) 
 
 44fe. Thiele and Heusser , Ann. , 290 , 6( 1896) 
 
 44b.nantscn and Lilscndtz , Ber. , 45, 5016 ( 1912 ) 
 
- 7y - 
 
 46a. Eibers, Ann., 227, 564( IdbS ) 
 
 46b. iniele,iinn. ,676, 267( 1910) 
 
 45c. Kischner, J.prakt .Ohem. ,^, 424 (189 6) 
 45d. Kischner, J.prakt,Ohem. ,(2)64,125(1901) 
 46a. Headelien, 8er .42,4759( 1909 ) 
 
 46b. Reddelien, 6er. ,^,2479( 1910) 
 
 46c .Kedaelien, ibnn. ,588,170(1912) 
 
 46a. Lachowiez,iv.onaosh. ,^, 510( 1912 ) 
 
 46s. keadelien, oisseriation ,Leipzig( 1912 ) 
 
 47. DimroLh and Zoeppritz, ber. ,56,984(1902) 
 
 48. W-ieland, J^er . ,41, 5606( 1902 ) 
 
 49.3iiipley anaV/erner, J.pnem. Soc. , 105 , 1255( 1898) 
 
 50. 
 
 otolle. 
 
 J.prakL.ohem. , (2) 66,552(1902) 
 
 61. 
 
 Storch, 
 
 aentralbl. 1895, I ,915. 
 
 52. 
 
 ijredig. 
 
 J .prakt .Ohem. 15, 508( 1891) 
 
 55. 
 
 Noyes, 
 
 J.A.0.3. ,43,1779(1921) 
 
■si 
 
 
 y 
 
 
 
 
 
 ? * 
 
 A 
 
 
 t 
 
 / , 
 
 I 
 
 I 
 
BlOCri-l/uPi-iV 
 
 Tlie Witter was uorn in G-iilespie Gounty, Texas, on 
 OctoDer 18tn, 1892, He >^rauuateu rrom tue 3outiiwest Texas Normal 
 ocxiool in 1913, witn History as tlie major stua^. In 1918 iie re- 
 cieved a B.A. degree i'rom tne University of Texas v/Here He served 
 as student assistant in 1917-18, and as tutor in 1919-20. Previous 
 to and between nis years of study at the University of Texas, he 
 taught for four years in various public schools of Texas. 
 
 From April 1918 to September 1919, he served in the hospital 
 corps of the U.S.Navy, in clinical laboratory work. 
 
 he vifas a graduate assistant in (jnemistry during 1920-21 
 anu a Fellow during 1921-22 at tiie University of Illinois, 
 he is co-author of two articles, - 
 
 1) "The Conversion of kethyleneaminoacetonitrile to Iminiaceto- 
 nitrile" by J.R.nailey and li.L.Locnte, J.A.C.S. ^,2443 (1917) 
 
 2) "Symmetrical ui-Isopropyl-Hydrazine and Its derivatives." 
 
 A preliminary article by the writer witn J.rc. Bailey and W.A. Noyes. 
 J.A.C.S. 43,2597 (1921) 
 

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