A novel reaction of nitrosobenzene with benzylamine

Tetrahedron LettersN0.44,pp, 5109-5412, 1966. PergamonPressLtd. Printedin GreatBritain.

ANOVELRMCTIONOl?NITHOS-WITHICazuo

Guati*end

ElizabethK. Weie,burger

NaticmelCancerInetitute IiatiamlInstitutes of Health Bethesda,mlylnnd !a014 (Received

10 August 1966)

Nitroeobensewhae beenreportedto reactreedilyuithcaqpaurde cc&xi&g

8 sufficiently activatedmethylem (1) or methyl(2) group

and with arcmaticemlnee(3). PhcYtmlyEisof nitroEled chieflytoBz~nzampluB However,noref-escOloereiag

beenfaml.

Itiethepzpoee

cipeamnte whichhave a baudq

it6elfhM

several otherminorproaaets(4). it8 resatica with allphatic mlws

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As a first step, the abstraction of ahydrqen at.tolPfranthe methylenegraxpbythe negatively charged~nata~innltroaobenzene Is relatively easy due to the neighboring arcmaticm

participation.

AmPariaaadbenzaldehydeanformsdduringtbsattsch.ofthe~cond nltrosobenzene molecule. Reliefof strainIn the systemleads to amxybenzene. This is anew

reaction Wolvingthe fomatimand cleavagecf a

carbon-nitragen singlebodlbetweennltrosobenzene and benzylmine. UMsr the sems condltimm nitrosobenzene didnut reactappreciably witha primaryallphaticmine, such as n-propylamine. In atypical run nitrombenzene(lOOmM) inbensenewas

refluxed

gently for 12 hr.withbenzylsmine(50mM). Ths wuniagas

folmedwan

carriedwer inagentle streamafnltrogenandabsorbedinbydrochloric acid

to yield25 mbtof anmmium chlariae. Aportim afthe reacti~mFxturevaet~tsdwithe,lM~tro-

phenylhydrazinetoyleldbensaldehyde 2,~ltr@m3nylbydra2cae, correspondingtoj2mk4afbe.nzaldehydeweraU. manthe dnder

of the reactionmixture bensylsmine (8.14

was recweredbyextractionintodilutehydrocblorlc acid. ChreatwphY

of the residualbenzeneeolutionon aluminafollwedbyelutlantith ben~ne fkrnished28.3 ml4of azozybenzene.A smallsmwnt (1.5 8) of an unidentified oilymaterialwas also recovered. Whenchlaroformvasusedassalventinplsceclfbenzena,be~hyae (3%)r mmas chlcn.%de (@$),

(~3%)~azw+=--

(654),

L-~YW

Wd-

sgm-dibanzylurea (5) (1.54,m.p. 167%) and a bran oil

were isolatedas rescti~products,whilsbenzy~(~)wss

recwered.

Widentificaticnawere cmfirarsdbyeleuasntalanalyses, IRand W spectra,armixturemeltingpointswithauthenticccqounds.

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