Ab Initio Molecular Orbital Study of Reactivity of Active Alkyl Groups. III. Nitrosation of Acyclic Carbonyl Compound with Methyl Nitrite via Na+ Chelated Transition State.
この論文をさがす
説明
The mechanism of the nitrosation of sodium enolate of acetone [CH3COCH2]-Na+ (1) with methyl nitrite CH3ONO (2) to give 1-hydroxy-imino-2-oxo-propane CH3COCH=NOH (3) was studied by the ab initio molecular orbital (MO) method. The complex [CH3COCH2NO(OCH3)]-Na+ (C-II) was first formed from the adduct (C-I) of 1 and 2 through the pericyclic transition state (TS1). Finally, Z-hydroxyimino compound (3Z) was obtained through demethoxylation of 2 moiety and abstraction of an active hydrogen atom in C-II with a base. In the final formation of 3Z, two leaving groups, the methoxy group and the active hydrogen atom in C-II, should be situated in positions with respect to each other which permit their elimination, i.e., they are antiperiplanar to one another. It has become apparent that 3Z tends to be formed predominantly when a countercation of a base coordinates to the oxygen atom of the enolate of acetone.
収録刊行物
-
- CHEMICAL & PHARMACEUTICAL BULLETIN
-
CHEMICAL & PHARMACEUTICAL BULLETIN 45 (9), 1387-1392, 1997
公益社団法人 日本薬学会
- Tweet
キーワード
詳細情報 詳細情報について
-
- CRID
- 1390282679136007680
-
- NII論文ID
- 130003947362
-
- COI
- 1:CAS:528:DyaK2sXmtl2qsLY%3D
-
- ISSN
- 13475223
- 00092363
- http://id.crossref.org/issn/00092363
-
- 本文言語コード
- en
-
- データソース種別
-
- JaLC
- Crossref
- CiNii Articles
-
- 抄録ライセンスフラグ
- 使用不可