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 ... o e pr c;,re ir t ex eri en • he n motmt • - 9

.J

2 b rams O!I TIOU HI 0

i r 2 ~10~

In ome of the exl)eriments conducted above , an orange- red color tion developed dur1ng the re;aotion period, instead of the yellow c-olor b longing to oxy compounds. Upon .ste m di ti~lat1.on, howev r, a yellow precipit te was formed. The orange color mey be explained in t JO vays: first; v1e might have the a. oxy derivative changed to the isomeric hydroxy-azo deriva 1ve, or

..... econd; we might haYe the azo derivati e formed directly in ·small amounts. The conditions not being ide 1 for this eaction to.go to completion, the a zo c mpound is oxidiz - d bac to the 0.zoxy, hich compound re have at th end o the exper it4.e nt. · In en endeavor to · explain this phenomenon the re -otion as c ,rrie d ont t dif erent terr,pe r ature and the resulting compounds studied nd compared with those at the original temperature. strbngly alkaline mixture was uae d . The temperatures used were: o0 c. , room temperature ( 30°0 •.) , 150° 0., and 250° 0 . The result r tabulated in t b3:-e IV. - ll-

BT f IV

6 grams of the ni tro compound; 60cc. xylene

t) grams of b nzyl alcohol;. 15 grams of U OH

xp. tempera.t re nitre compound grams re uction grams no . reduo ion co~' benzoic comp 1 d 1a cid

I oo •· m-nitro phenetole rio ree,c ion I 30~0. m-n ro phenetole 1. 6 . 0 2 . 3 .. III l o0 c • m-n-itro phenetole 3 . 3 77.10 4 .73 .. IV l50°c . p- nitro ani ole 3 .2 76.00 4.50

~v 250°0 . o-ni tro anisole carboni ed 5 . Z3 VI 2 o0 c. o-nitro a.nisole carboni ed 5 . 40 VII 250°c ~ m- 1itro aniso e 3 . 0 75.95 5 . 64

The .. :ci ous exper.imEnts a.t differ~nt

temper tu.res ve some interesting da • irst the re ction does not prooeed at low temperatures. t room temper ture a small' yield o:f the a:zoxy derivative as obtained. t 150° 0 . the yield, as increased. The· p-nitro nisole reduction product (I) proved o be identical to that one prepare·d at 100°0. (IV) . The melting point being 116- 117°0. The melting point of the m- nitro phenetol reduction product (;~III) was 86- 87°0. he c ornpound crystalliz d from ethyl alcohol in orange plate . The - 12-

m-a oxy phen tole crystallizes in yello ~ needles. The author as unable to comp re the melting point of m- azo

phenetole re corded in the liter t re v, i th that of th compound pre ared here . The melting points of azo

deri va-t i ve are usually higher than the corr spond:i.ng azoxy deriv tives, and re of a derker color usua.lly of' an orange or red color. On this somewhat circums an ial

evidence it .as thought thet the m- azo phenetole had been prepar d. t 250°0. the r duction product of o-ni~ro anisole was carboni e • s the re ao ion pr oce ded a.

, dirty-yell,o~ foll owe by an orange color dev loped. To a.rd the end of the heating per od he ho e mass turned bro n . Lack of time prohibited a repetition of the experi~n at a somewha lo~er temperature. But it is tnought that if carrie·d ou at a tell!)era.tur . about 50°0. lo er he o-nitro anisole oul result . !- nitro anisole

as re duce d to an orange, nee e shaped er yst 11 in solid melting _at 73-74.600. ~his compound compares .1ith

the azo anisole recorded in the literature .

~ e at i ve results \ere found in 11 tte mpts

to find any a.mine · present.

Benzad hyde as found to be present in all cases. - 13-

l . study has been ma.de of the ct ion of sodium benzylate on o-m-p nitre phenetol and o-m-p ni ro anisole .

2. Ben yl alcohol .r s lc:;;.rgely ·oxidized to benzoio cid. Tre.o s of benzaldehyde were also found. · 3 . Th temperature was found to have an ef=ect on the reduction of the nitro compounds. t 15000. the zo derivative v s formed with he zo:xy derivative being the product· formed t lower temper tures. 4 . trong alk line mixtures and hagh tempew ture s. iere found to have a diredt influence on the oxidation of th alcohol o the cid. Higher yie ds being pr educed in those c se • 6 . The isonitril tests for amines ~ere al\ ays negative . - I¥- LI 1. n n : • r t em. 36 , 93 (18 l) . • .eis ert:- Ber. 4 , 1364 (1909) .

: . eu : er b ~l (187)

inger and it ohke: Ber ia 55£ (1885) • 5. Lyons and mit : • m. Chem • oc . 48 3 65 (19 6). 6 . ter nd in • m. hem. oo 50 , 7 (1928)