REACTION OF N-SUBSTITUTED 1,2,4-TRIAZOLINE-3,5-DIONES AND TRANS-CYCLOOCTENE - DIRECT OBSERVATION OF AN AZIRIDINIUM IMIDE

被引：33

作者：

POON, THW ^{[1
]}

PARK, SH ^{[1
]}

ELEMES, Y ^{[1
]}

FOOTE, CS ^{[1
]}

机构：

[1] UNIV CALIF LOS ANGELES,DEPT CHEM & BIOCHEM,LOS ANGELES,CA 90024

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1995年 / 117卷 / 42期

关键词：

D O I：

10.1021/ja00147a008

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

4-R-1,2,4-triazoline-3,5-diones (R = Me (MTAD), R = Ph (PTAD)) react stereospecifically with transcyclooctene (1) to give addition products 2, 3, and 4. The products of the reaction and those obtained from nucleophilic trapping of the intermediate with methanol and water suggest an aziridinium imide followed by an open cation that can lead to transannular ring closure and hydride shifts. At -83 degrees C a trans-aziridinium imide intermediate is formed nearly quantitatively and can be directly observed via NMR spectroscopy. An activation energy of 16.2 kcal/mol was measured for the decomposition of the aziridinium imide. A mechanism is proposed for the reaction.

引用

页码：10468 / 10473

页数：6

共 101 条

[81] STOCHASTIC SEARCHES FOR LACTONE AND CYCLOALKENE CONFORMERS [J].

SAUNDERS, M ;

JIMENEZVAZQUEZ, HA .

JOURNAL OF COMPUTATIONAL CHEMISTRY, 1993, 14 (03) :330-348

[82] EVALUATION OF STRAIN IN HYDROCARBONS - STRAIN IN ADAMANTANE AND ITS ORIGIN [J].

SCHLEYER, PV ;

WILLIAMS, JE ;

BLANCHARD, KR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1970, 92 (08) :2377-+

[83] PREFERENCE FOR SYN ENE ADDITIONS OF O-1(2) TO TRISUBSTITUTED, ACYCLIC OLEFINS [J].

SCHULTEELTE, KH ;

MULLER, BL ;

RAUTENSTRAUCH, V .

HELVETICA CHIMICA ACTA, 1978, 61 (08) :2777-2783

[84] MECHANISM OF TRIAZOLINEDIONE-OLEFIN REACTIONS - ENE AND CYCLOADDITION [J].

SEYMOUR, CA ;

GREENE, FD .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (20) :6384-6385

[85]

Sharp D.B., 1960, 138 NAT M AM CHEM SO 138 NAT M AM CHEM SO, p79P

[86]

Silverstein R, 1981, SPECTROMETRIC IDENTI, P442

[87] REACTIONS OF PHENYLTRIAZOLINEDIONE WITH ALKENES - STEREOCHEMISTRY OF METHANOL ADDUCTS TO AZIRIDINIUM IMIDE INTERMEDIATES [J].

SMONOU, I ;

KHAN, S ;

FOOTE, CS ;

ELEMES, Y ;

MAVRIDIS, IM ;

PANTIDOU, A ;

ORFANOPOULOS, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (27) :7081-7087

[88] INVESTIGATION OF THE MECHANISMS OF ENE REACTIONS OF CARBONYL ENOPHILES BY INTERMOLECULAR AND INTRAMOLECULAR HYDROGEN-DEUTERIUM ISOTOPE EFFECTS - PARTITIONING OF REACTION INTERMEDIATES [J].

SONG, ZG ;

BEAK, P .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (22) :8126-8134

[89] AN AZIRIDINIUM IMIDE INTERMEDIATE IN THE ENE REACTION OF TRANS-CYCLOHEPTENE AND N-METHYL-1,2,4-TRIAZOLINE-3,5-DIONE [J].

SQUILLACOTE, M ;

MOONEY, M ;

DEFELIPPIS, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (13) :5364-5365

[90] STEREOCHEMISTRY OF SINGLET OXYGEN ENE REACTION WITH OLEFINS [J].

STEPHENSON, LM ;

MCCLURE, DE ;

SYSAK, PK .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (23) :7888-7889

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