Class Book _______ Accession 1-f c6-- 111 Vol. ______ MORRISON . LIBRARY OF THE Municipal University of Wichita WICHITA. KANSAS THE IVERSI~Y ·o v !CHIT. NIT O COMPOUH ]).) 0 ID! ING AGENTw . SUBMITTED TO THE G.1. IDATE FACULTY IN C DI CY FOR THE ·n~G. OF TERO TS ) ) :l)-, .l)) )) ) ! ~ ):> ) ) ) .) ) .). J ) ,, ) ) ..) )) )) .) } ::> ) ) ) ) J ) J ) J ) .) ) .) ) .) ) . ) , ) ) ) ) ..) ) ) ) ) } ) J).) ' .J ) "):) ) ) .) .) ) ::> .) J ) ) ' J .) J ) ) s JUN t J.~32 Acknov~e gment is made to Professor ·orth A. Fletcher for his direction and assistance in the con uctance of this study. (ii) (ii) T BLE ·0] 1 COMTiilllT :e G.J.:J CKU ONLE DGlJCNT • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • . ii LIT OFT BLE • • • • • • • • • • • • • • • • • • • • • • • • , • • • , , • • • i V LI T OF FIGUl ~ ••••••••••••••••••••••• ' •••••••••• V IN Tl ODUCTI ON ••••••••••••••••••• , •••••••••••••••• l ~ pv. 11JI:E:t.i T L •· • • • • • • • • • • , • , •· • , , • • , • • • • • • • • • • • • • • • t ]? T B DFEECT OF TE1ft.PER TUHE •••• • • • • • • • • • • • .Id • C ffi.,' • y •••• •••••••••••• ............ •' • • • • • •••••• 13 LI 11: J:RE: CI TE'D. • • • • ••• , • • • • • • • • • • • • • • • , • • • • • •• 14 (iii) LI T O · BLE Table page I• • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • .-:. • • • • • • 5 I I •• .. ................ ··~. ·~ ·· .....•..•........••.• 7 III. • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 8 rv~.. J ••••••••••••••••••••••••••••••• .•••••••••••• 11 • I " ... ( ;Vj_) LIT 0 i gur page • J"i a am of pp ar t • • • • • • ~ •.• • • • • • • • • • • • • • • • • 5 2. raph ho ~ing relat i on hip of l ili n ty t o peroent el ds •••••••••• • ••••• • ••••••••••• 10 'I ( :'.. ) NIT O COMP0UND"'t 0 IDIZING GENT NTRODUCTION It hes been de~initely proven that in an alkaline rnediumJ n1tro compounds are reduced to the corres­ ponding amines, p ssing through the following 1ntermediate stages: azoxy, azo, and hy~ zo riv ti ea. rl'he products formed nd the mounts o:f e oh have been found to depend . upon the lK 11nity temper .t re of ·the r ot1on, and tne strength of th reducing g nt. In .gener l 1 the re uc ng me~i mused a been an alooholate. In 1$481n1troben ene s re uoe in lcoholio pot esiun1 hyd.roxi e producing a oxybenzene. In 2 190<.I ... eissert obt 1ned. the correspondin zoxy deri e.tivea when nitr.obenzen o-nitroso toluene d p-nitroao toluene were reduced in alcoholic sodium hydroxide. Ohloro-n1tro­ benzene h s been'. reduced to the p-chloro- a. oxybenzene by means of so ium methox1dv.3 :M-dinitroben ene h s een reduoe to the m-nitro- zoxy enzene by means ot sodium methoxide.4 Lyons and mith5 report th t n1tro benz.ene reduced by means of benzyl alcohol' in alkaline solution will yield azobenzene. uter and Da.ins6 r port that benz l 1ooholatea reduce nitre ompoun a to the corresponding azoxy derivatives. In this inveatig tion as udy de of the reduction produo s of the isomers of nitro-phenetol d nitro- aniso1e. study of the effect of lkalin1ty and - l - -~ temperature on yields and reduction products was made. In every case sodium benzylate was used as the reducing agent. The majority of the experiments reported in the lit­ erature seemed to indicate that the azoxy derivatives would be the principle product of reduction of the nitro compound, and the products of oxidation of the alcohol, benzoic ~cid, with benzaldehyde as the intermediate product. The follow­ ing equations were used as a basis for calculations. 4 H3C-O-C 6H4~No 2 f 3 C6H5-CH20H: 2 H3C-o-C 6H4- N2o-C 6H4-0-CH t 3 C6H5-000H f 3 H20• 4 C8H5-o-C6H4- No2f3·C6H5-CH20H: 2 H5C2- o-C 6H4- N2o-c6H4-oc2H t 3 C5H5-COOH ! 3 .H20. The amount of alcohol used was in excess of that re­ quired to reduce the nitro compound to the azoxy .stage and was siffioient for the reduction to proceed to the azo. • I D R· F9L.R'SI< 8- STIRRINf. ROD c- 5£Plllt/lTORY FUIINCL D·CONOENSER ,1&'URC I - 3- In general the procedure was s follows: the desired amount of alcohol and sodium hydroxide w s placed in 500 oc. round bottom, three n~cke~ flask. whlch w s · e uiped with e. mechanical stirrer, . sep ratory funnel and. reflux condenser( fig-.l). The lkali and alcohol w re ref ux d until the alcohol had been changed into the aloo~ hol te. The nitro oonl!)ound• which was diesoLved 1n xylene, w a . dded dropw1se to the cooled ·alooho1ate mixture and • I . allo d to · react t various temperature_s for a period of five hours. The mixture . 1 s then steam distilled to remove J . the x~lene and any other re dily vo atil~ substances, such as an excess o~ a1oohol, traces of benzaldehyde, amino deriv tives· a.na unchanged nitro compounds. The contents of the distilling flask ere a1lowed t cool to room-temper ture and then filtered. The residu v-1 s dried and eigh d. The 1.1eight ·:as t ken as the yield. of the reduced nitro compound. The reduction com­ pounds ere reorystallize·d from 95% ethyl . alcohol. nd their melting poiI).ts determined. The filtrate was aoid1f1ed with hydroohlorio -ol.d, therby precipitating ·the . benzo1o acid. This w s 1 ltered, dried and eighed. The vo1ume of the :filtr te 'I s noted in each case and the amonnt of the dissolved benzoic ao1d calculated. This amount s then s.dd~d to the ight of the ir dried product end the total .,- ta.ken as the yield of benzoio _o1d . The distiil te v a tested for ben ldehyde. 8 It s lso tested for the possible presence of an mine . b The ylene Layer of the dist1llate contained the various volatiie substance that distilled over. The xylene layer s s par ted and the xylene distilled off, thus leaving principally unchange nitro compound and excess benzy1 loohol . These were aooord1ngly noted and their presence recod ed. ' In the first experiments the alcoholate and the nitro com.pound were allowed to react at room temp- .5"' erature for three hours t the conolue1on of this initlal re ction period t~e co~tenta of the flask were eated to 100-°o. for an dd1 tional t Jo hours. The data obtained :from these experiments, the amounts of re gents used nd the yi~lda obtained arectabulated. 1n table I , aF1 oo . o:f concentrate sulpb.ur1c -acid .. we. p!aced in a test tube d to 1t w s dded one drop of phenol. Upon the ddition of a solution containing ban - aldehyde a pinJ.l coloration deveolped. The 1son1trile re ot1on was employed. ..f) _ BLE I ----70 5 grams ·of th nitre compound; 5000.xyiene; tem-oer ture: 3 hours t room tem-oer ture and hours· t 100°c. J;lxp • Mitro compound Grams Gr ms Grams 'A"'oxy Ben~oio no. of 0 oxy Co~'d., aold .alcohol N OH Comp ' d zo gr ms I p-nitro phen tol.e* lO 8 6.3 5506 4. 0 II m-nitro phenetole 5 5 3 .1 7.6 l 6 5 6 • 5 ?6._ 8 III o-n ro phenet6le I • 1 • 1 -nitro 0 e 10 8 ..... 9 68.8 3 . 30 m-· itro a.nlso.Le 0 8 v•~'A 4 'l .() .95 * I 0-nitro i~ole 10 8 5.'.I 53 8 4.50 * 13 ams of the~e compounds ~ere ed. The re d~oti on compounds prepared above were yelbltl . all of a Je:t1. color. From this it was thought that they might be azoxy compounds. They were subjected to a (;, 1!) further reduction by ~eans of hydrochlorio acid and iron filings. In all cases a red coloration, charaoteristio of azo compounds ~eveloped, indicating that the above prepared derivatives were azoxy phen~toles and a~oxy anisoles. The melting points were determin~d and compared with those recorded. in the .literature for azoxy anisoles and azoxy phenetoles. Th~se are tabulated in table II. - 7- T BLE I I ,11ELTING OINT OF 20""-Y NI OLES ID A O Y l?HEI TOLE Compoun.d xperimeiltal Iiterature p- azoxy anisole 116. 500 . 11a 0 c. ll6°c. m- azoxy anisole 51-5200. 51°0. o~azoxy anisole 85- 86. 200 . * p~azoxy phenetole l3boc. ·13400. m- azoxy phenetole 46- 47°0. * o- azoxy phenetole· 100- 00 . 0°0. 10 cc. no melting points of these c_ompounds were found. · study as then ma e of the effect of de­ ore asing the a1kalini.ty of the solution. The procedure was the same as before with the exception that only t vo grams of sodium hydroxide were use • The experiment·was r pe~ted usin an increased ) f<) alk~linity. 15 grams of sodium hydroxide w re used. The results obta1r1ed from thes experirrents ia t bul ted in table III. - 8 - III 5 gr ms of n1 tro comp und; 50cc . xylene; temper .ture 3 ho rs t room emperat re and hou.r et oo 0 c. p . }. i ro compo nd Gr ms Gram Gr ms 0 y Gr ms no . loohol NaOH a X % ben oio comp ' 0 "I o- nitro aniso e. 5 2 1 . 8 4 .7 1 . 7 p-nit 0 phene ole 5 2 0 43. 7 1 . 3 o- nitro i ole b 15 4 . 0· ~ • 3 . 94 o-ni ro phen tole b 16 A. 5 ~Hj • 3 . '/4 • ~ 1 note from tn OV t b th n e ly ine r .. -lcr yield zo y oom·9 0 l an benzoic Cid are pro ce • il in trono-1 l li X. r the yiel s ,.~e incr . e re color of he er s 1· prod ce n ry ·n degr e ox al inity 1 he same n me in :po corr pon to ..