Synthesis and cyclization of N-methyl-O-cinnamonylhydroxylamine and its bearing on Baldwin's rules for ring closure

%trahedron LettersNO. 42, PP 3985 - 3986. @Pergsmon Press Ltd. 1978. PFintmiin Great Britain.

15 hrs reflux in o-dichlorobenzene

desired.

The hyk&loridesaltwasstableandgmecorrect

(50.3) analytkal Lesultsand the

mpoMl~m3ultjngfraotheneutralizatiaaofthissaltwithNaa!D3 spectraldatain mkhaml~4 had a (X3-N signalat g2.92 atpM3-9 @y&%m paper). Ihe Ui3-N signalof N-m~lhydmxy~at

~2.7OalsoappeamdinM.smixture

(authenticsanplecmfimm

value). Theai~signalsfranboth~and~~~~qui~~dependent, shifti.ng~lomrfieldsatlmerpH.

TheCE13Nsignalof~wasalsoquitepH&pendmt,but atp3I=8-9absorbedat c2.80. Ihe signalat 52.45 nqorted earlierby us y asduetm

N-mz~lllydIm%ylaluine,aswsllas~~l~te

@cD3),waspresent. Ihe CB3N signalat

3986

Aftwallofgvas cyclisationof~

consul&

the ratio of qzwas

4.4 (2 0.2) indicating that xllm direct

occurw.'Treatlrentofnethyl-- clnnama~witionetothreeeqliwG?ntsof

wnmUly~lamine9aveaily4_and5butIlo3. -zicmSzd

WlEllSlltkStartingeSterWElS

After 2 knlrs the qzratio th

ra&

was 1.89 (_I0.03).-&

was 1.31, and

trace of ieven by

'ITCcouldbefaundin~expwimants. EsutraGzationofthe

hydrrxfiLarideof~withtrie&ylamimsinether,

solvtm.kgaveanoilwhich

reuovalofsaltand

subsequentlysolidified. acnpleteremnral oftrie~laminewas

assuredbyrepeatedtrituraticnwithbenzeneandsolventrarpval.

Theresiduewasrefluxed

in brcmobenz;enefor 5 hours and the formation of i followed by the IR bar& of Qat1790-1780 -1 an. . knuval of part of the solvent follwed by n.m.r. clearly showd iwas -+sent by the U$N

signal at

~2.54([email protected]).

heatedat@lOO"wi~solvent, Bwitipetetkr.

4was

Likwisewhen~wasgeneratedand

fornmd,c&ainable

ThisZzas&stantial

in 45%yieldafter

5kurs,by

~0f~undernulchmilderccnditicms

thanthoseusedbyAnselme. ~~theenhanoedcyclizaticnof~~thetrydrazide~lyLieintherelati~y

Y.

enbanceanuc~~~oftheni~lonepairof~ovlerthelanepairinahydrazide

misis

suxprisingbeca&e~zineis

abetter

d~ucleophilethan~limdnetoward

pnitZDFt.lerrylaoetateX Brxever,thedelocaUzaticmoftbeamidelcmepairaffectsthe rnmilabilityofthe

amino-lonepairsinhydrazides.

excelkntnuclecphiles.

Ino&rast~hydrwm&acidsaI??

Inthepresentcxse~shonld~eahydnxamicacidinnuc~

philicity~~eStersdonotdelocatizethe~lonepairsaswellasirmidesdelocdlize uleni~lcnepaim3~. illthe

L) _

!nws ~formIisntxeinportantthanIIin~asexpressed

of 2of

PLNR-CK,

1735 cln-l, typical of esters.

Ph-cB=CIi-k-3

I

II

~ed9msntisamdetothedtwxsoftbepetrolemnIwearchFund, AmxicanUmmkalSocie~,forpartialmqportofthisresesr&.

administereabythe Wethankthethetraticm

of ~forparUalsuFportintheformofafacultymini-9rant. 1. a) J.E. Baldwin, J.C.S. Chen. cram., 734 (1976); b) J.E. Baldwin, JXutting, W.Dupont, L. 736 (1976). 2. J7PZZ.k 3. L.A. Caqdno, C.A. Gi and B.A. carpino, J. Amer. C&m. Sot., 81, 955 (1959); See W.J. Fenton, Cbsm.En9 g' 54 3 (1976) fbrcauticmaxrxrkqthi?&zep. R.&in,'T~karly and H.Kehl, Tetrakdxm letters, 3027 (1975). 4. K.R. ma, letters, 3607 (1976). 5. H. stanm and H. steudel, !ktrakdmn in "Tbe Cbeniistryof the Bydraw, Azo, and Azoxy Groups," S.Pati, ed., 6. P.J. w J.Wiley & Sons, Nsw York, 1975, p. 161. 7. W.P. Jewks and M.Gilu-ist, J. Auer. C&m. Sot., E, 2622 (1968). 8. J.D. Aubort and R.F. Hudscn, J.C.S. elan Ccem., -938 (1970). Kinetics, 5, 1 (1973). 9. N.J. Fina amd J.O. Edwards, Internat. J.&m 10. R.T. Cknley, "Iilfrzed spectroscapy,"Allyn ak Bacon, Inz, w, 2nd ed., 1972, p. 151. (Received in USB 10 August 1978; receivedin UK for publication 22 August 1978)