Photocyclization of N-chloroacetylbenzylamines to isoquinoline derivatives

Photocyclization of N-chloroacetylbenzylamines to isoquinoline derivatives

PergamonPress. Printed in Greet Britain. TetrahedronLettersBo. 13, pp 1181 - 1182, 1974. MasakiIkeda,Ken-ichiKirm,YohneiO~and~Y~~ F~ltyafPharmacEllt...

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PergamonPress. Printed in Greet Britain.

TetrahedronLettersBo. 13, pp 1181 - 1182, 1974.

MasakiIkeda,Ken-ichiKirm,YohneiO~and~Y~~ F~ltyafPharmacEllticdlSciences,HoWcaidoUniversity,Sapparo, Japan (Receivedin Japan 6 February1974; receivedin DK for publication19 Febroq

m

Pcmermz-Fritsch

mthcd

1974)

is useful fcr the pEpa_ratim of i'-and 5,i+UbstitUted iso-

~linesvlmicharedifficulttobesynthesizedbyotheri~linesyntheses.

Hcuever,

thereadicnusudlly~scnlyinastrargacid,wfiich~timesca~ssidereactians. VariausncxrelheterPcycleshavebeensynthesizedFbatocfranicallyfrcmN-cNaroacetylphene~lanines. * MKUKJ these @&mea&ims,

the most typical ax

is the fcmnatirnaf 1,2,4,5-

tetrahyd~x-3H-3-benzazepin-2-cmes and it is eqectedtcbeextended

farthesynthesiscfiscr

quinclinederivatives.

PihenN-chloroacetylbenzylanine.5

(I) inquecusethanoloraceknitrilewereirradiated,tk

correspcPrdi.ngN-acetylorN [email protected] fmmatim

cf cyclizaticmpralucts. Hmzver, @$&uxy

derivatives(II) gave easily 3-cxc-1,2,-

3,4-tet~zahydr0isquinolines (III) in fair yields. A 50% aquecus acetxnitrilesolutia~of II ka. 10 nM) was irradiatedwith a 100 Whigh P=s==mercury

lanpmdernitrqen

forl-3 hr. TetrahydmiscguinclinesIII, wimse sixuctures

~easilyconfjlmedbymassarad~spectra,~isolatsdbyrecrystallizati~~bychromatcgr~,ifnecessary.

Theresults are &mm

inTable.

& In

If d

aq.MeCN

=OH

Ia:

d=OMe,d=H

Ib:d,Fi+=OMe

F# =OH,H F? = H, Me ,C%Ar

IC : d.RkCHlO 1181

1182

No. 13

Table. PkkocycLizaticnof IIto III. III I1 I $

IIa

R2 R3

Ui H

IIb

Cf-IMH

IIC

MHMs

IId

H

cH Xi ?2=SH5

Yield (%I Rl

R2

IIIa

[email protected]

H

IIIa'

H

CXi

IIIb

cMea a4ea

[email protected]

55

236-238

7

227-228

45

191-l94

111~

M

H

74

228-230

IIIc'

H

CEi

13

218-220

IIId

p

H

69

200-201

IIId'

H

CH

16

170-171

IIe

OH CEi Ci2C6H5

IIIe

CH

OH

64

220-223

IIf

OH H

CH2&'b

IIIf

CH

H

49

174-175

ai H

U-I+ 2,c

IIg

IIh

OH M

cH2Ar2'C

IIIg

CIi

H

36

229-231

IIIg'

H

CR

7

169-171

IIIh

(3H

OH

59

260-263

a;treatedthexwcti~mixturewithdiazowthane. b; Arl = 4-1ns~yl.

anelectrm

c; Ar2 = 3,4,5-k-imet.

franthe siragletexcited state of ths armaticnucleus.

3

Th!zcleardifferencein

reactivityketmen I and IIcanbeinterpretedby~easeoftheeledfinejedionfmn~ls and/or the reactivityof thsresultantphenoxyrxlicals. Ekrthersyntheticapplicatialofthis react&m is in progress.

J.M.?&&itt,?+dvan.

Hetemcycl. =.,

15_#99 (1973); W. J. Gensler, =.

React.,&, 191

(1951). T.Iwahma,H.Nakai, s.,

0. Yawnitsu, D. S. Jones, I. L. Karle and B. Witkap, _-J. tir. CI-mn. 94, 5l.36(1972); T. Iwakma, K. Hirao and 0. Ymenitsu, ibid., in press, and refer-

encescitedtlrerein. S.Na~~to,O.Yanenit.~~,N.Kanmaru and K. Kimura, J. her. Chen. See., g, 4053 (1971); ---S. Namto and 0. Ycmmitsu, them. Pham. G. (To&o), 2l, 629 (1973); 0. Ymenitsu, H. -Nakai,Y.Chno,S.Namto,K.HemiandB.Witkop,Photodxm. Plmtobiol.I& 509 (1972):