SMALL CHARGED RINGS .11. SYNTHESIS AND REACTIONS OF 1,1,2,2-TETRASUBSTITUTED AZETIDINIUM SALTS

被引:26
作者
LEONARD, NJ
DURAND, DA
机构
[1] Department of Chemistry and Chemical Engineering, University of Illinois, Urbana
关键词
D O I
10.1021/jo01268a003
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
A convenient synthesis of 1,1,2,2-tetramethylazetidinium perchlorate (2) and 1-benzyl-1,2,2-trimethylazetidinium perchlorate (3) has been developed. The cyclization step in the sequence leading to these compounds involved treatment of γ-sec-aminoalkyl chlorides with silver perchlorate to afford the corresponding tertiary azetidine perchlorates in excellent yield. These were subsequently alkylated to give the quaternary azetidinium salts. 1,1-Dibenzyl-2,2-dimethylazetidinium perchlorate (4), as an intermediate, was found to undergo a facile eliminative ring opening in the presence of amines and could not be isolated. The structures of 2 and 3 have been verified by molecular weight determination and nmr spectroscopy. The tetramethyl salt 2 proved to be relatively unreactive, but the benzyltrimethyl salt 3 underwent solvolytic ring opening with alcohols to form N-(3-alkoxy-3-methylbutyl)-N-methylbenzylamine perchlorates. In the presence of sodium methoxide or upon heating in solution, both azetidinium salts exhibited a strong tendency to undergo eliminative ring opening to afford substituted 3-methyl-3-buten-1-ylamines. Azetidinium salt 3 combined with nitrones, specifically with substituted Δ1-pyrroline-1-oxides, to afford 1:1 adducts containing the 2-oxa-1-aza-6-azoniabicyclo[5.3.0]decane ring system. This reaction is representative of a new type of ring expansion, expressed as ④+ + 3 → ⑦+, in which a four-membered charged ring combines with a 1,3-dipolar moiety to form a seven-membered charged ring. The structures of the adducts were established by cleavage of the 6,7 bond with lithium aluminum hydride, followed by cleavage of the 1,2 bond with zinc and acetic acid, accompanied by spectroscopic and chemical identification of the ultimate degradation products. © 1968, American Chemical Society. All rights reserved.
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页码:1322 / &
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共 41 条
[1]   CONFORMATIONAL ANALYSIS .9. THE GEM-DIMETHYL EFFECT [J].
ALLINGER, NL ;
ZALKOW, V .
JOURNAL OF ORGANIC CHEMISTRY, 1960, 25 (05) :701-704
[2]  
BALLARD SA, 1950, HETEROCYCL COMPOUNDS, V1, P78
[3]   EXPERIMENTS TOWARDS THE SYNTHESIS OF CORRINS .2. THE PREPARATION AND REACTIONS OF DELTA-1-PYRROLINE 1-OXIDES [J].
BONNETT, R ;
BROWN, RFC ;
CLARK, VM ;
SUTHERLAND, IO ;
TODD, A .
JOURNAL OF THE CHEMICAL SOCIETY, 1959, (JUN) :2094-2102
[4]   ACID-CATALYZED REACTION OF DIAZOMETHANE WITH 6-MEMBERED AROMATIC NITROGEN HETEROCYCLIC COMPOUNDS [J].
DANIELS, R ;
KORMENDY, CG .
JOURNAL OF ORGANIC CHEMISTRY, 1962, 27 (05) :1860-&
[5]   RINGERWEITERUNGEN BEI REAKTIONEN VON 2-(N-METHYL-PYRROLIDINYL-)2))-1-CHLOR-ATHAN UND 2-)N-METHYL-PIPERIDYL-)2))-1-CHLOR-ATHAN MIT NUCLEOPHILEN REAGENZIEN [J].
EBNOTHER, A ;
JUCKER, E .
HELVETICA CHIMICA ACTA, 1964, 47 (03) :745-&
[6]   INVESTIGATION OF STRUCTURE OF 1,5-METHYLENE-QUINOLIZIDINIUM ION [J].
EDWARDS, OE ;
FODOR, G ;
MARION, L .
CANADIAN JOURNAL OF CHEMISTRY, 1966, 44 (01) :13-&
[7]  
ELDERFIELD RC, 1950, HETEROCYCLIC COMP ED, V1, P78
[8]  
ELIEL EL, 1965, CONFORMATIONAL ANAL, P191
[9]   PREPARATION OF ARYLDIAZOALKANES BY BAMFORD-STEVENS REACTION [J].
FARNUM, DG .
JOURNAL OF ORGANIC CHEMISTRY, 1963, 28 (03) :870-&