ACID-CATALYZED ISOMERIZATION OF 1-ACYL- AND 1-THIOACYLAZIRIDINES .I. MECHANISM OF NUCLEOPHILIC SUBSTITUTION

被引：38

作者：

NISHIGUCHI, T

TOCHIO, H

NABEYA, A

IWAKURA, Y

机构：

[1] Department of Synthetic Chemistry, Faculty of Engineering, University of Tokyo, Tokyo

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1969年 / 91卷 / 21期

关键词：

D O I：

10.1021/ja01049a023

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

cis-1-(N-Phenylcarbamyl)- (1a) and cis-1-(N-phenylthiocarbamy1)-2,3-dimethylaziridine (lb) were isomerized to oxazoline and thiazoline derivatives with acids in several solvents, and the mechanism of the ring opening of the aziridine rings was investigated stereochemically. The isomerization of Ia with boron trifluoride etherate proceeded with complete retention of configuration in all the solvents tried. This retention of configuration was explained by front-side attack of the carbonyl oxygen on the ring carbon (SNi mechanism). With protonic acids, ring opening of Ia proceeded by an Sn2 mechanism. In the isomerization of lb, ring opening occurred by an Sn1 or an Sn2 mechanism, depending upon acid and solvent used. © 1969, American Chemical Society. All rights reserved.

引用

页码：5835 / +

页数：1

共 42 条

[11] STEREOISOMERIC 2,3-BUTANEDIAMINES, 3-AMINO-2-BUTANOLS AND 2,3-DIMETHYLETHYLENEIMINES - STEREOCHEMISTRY OF THE OPENING AND CLOSING OF THE IMINE RING
DICKEY, FH
FICKETT, W
LUCAS, HJ
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1952, 74 (04) : 944 - 951
[12] ELIEL EL, 1956, STERIC EFFECTS ORGAN, P79
[13] ELIEL EL, 1956, STERIC EFFECTS ORGAN, P83
[14] ELIEL EL, 1956, STERIC EFFECTS ORGAN, P479
[15] CHEMISTRY OF ETHYLENIMINE .4. PYROLYSIS OF 1-ACYL DERIVATIVES OF 2,2-DIMETHYLETHYLENIMINE
FANTA, PE
DEUTSCH, AS
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1958, 23 (01) : 72 - 74
[16] AZIRIDINES .14. 3-OXA-6-AZABICYCLO[3.1.0]HEXANE
FANTA, PE
WALSH, EN
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1966, 31 (01) : 59 - &
[17] Gabriel S., 1895, BER, V28, P2829
[18] GOULD ES, 1959, MECHANISM STRUCTURE, P640
[19] Heine H. W., 1962, ANGEW CHEM INT EDIT, V1, P528
[20] UMLAGERUNGEN VON AZIRIDIN-DERIVATEN
HEINE, HW
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1962, 74 (20) : 772 - &

← 1 2 3 4 5 →