C-Nitroso compounds.  Part XXXVII.  The reactivity of α-chloronitroso compounds towards organoaluminum reagents.

J. Lub; M.L. Beekes; T.J. de Boer

doi:10.1002/recl.19861050103

C-Nitroso compounds. Part XXXVII. The reactivity of α-chloronitroso compounds towards organoaluminum reagents.

J. Lub, M.L. Beekes, T.J. de Boer

Research output: Contribution to journal › Article › Academic › peer-review

10 Citations (Scopus)

Abstract

With sterically unhindered and certain moderately hindered α-chloronitroso compds. R1R2C(NO)Cl [R1 = R2 = Et; R1 = Me, R2 = Me2CHCH2, CH2Ph; R1R2 = (CH2)5], Me3Al at low temp. gives the methylnitrones R1R2C:N+MeO-. Several intermediate complexes lose methane upon heating and rearrange to α-chloroimines. More sterically hindered α-chloronitroso compds. contg. quaternary C undergo C-C rupture when treated with Me3Al, thus forming hydroxaminic acid chlorides, e.g., CH2:CMe(CH2)3CMe2CCl:NOH, formally HCl adducts of nitrile oxides. In the latter case, subsequent reactions lead to overall ring enlargement, i.e., formation of the seven-membered cyclic oxime I. With Et3Al and triisobutylaluminium, α-chloronitroso compds. are mainly reduced to oximes and the isomeric amides. [on SciFinder(R)]

Original language	English
Pages (from-to)	22-27
Number of pages	6
Journal	Recueil des Travaux Chimiques des Pays-Bas
Volume	105
Issue number	1
DOIs	https://doi.org/10.1002/recl.19861050103
Publication status	Published - 1986
Externally published	Yes

Bibliographical note

M1 - Copyright (C) 2018 American Chemical Society (ACS). All Rights Reserved.

CAPLUS AN 1987:83940(Journal)

Keywords

chloro nitroso reaction organoaluminum
aluminum methyl reaction chloro nitroso

Access to Document

10.1002/recl.19861050103

Cite this

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title = "C-Nitroso compounds. Part XXXVII. The reactivity of α-chloronitroso compounds towards organoaluminum reagents.",

abstract = "With sterically unhindered and certain moderately hindered α-chloronitroso compds. R1R2C(NO)Cl [R1 = R2 = Et; R1 = Me, R2 = Me2CHCH2, CH2Ph; R1R2 = (CH2)5], Me3Al at low temp. gives the methylnitrones R1R2C:N+MeO-. Several intermediate complexes lose methane upon heating and rearrange to α-chloroimines. More sterically hindered α-chloronitroso compds. contg. quaternary C undergo C-C rupture when treated with Me3Al, thus forming hydroxaminic acid chlorides, e.g., CH2:CMe(CH2)3CMe2CCl:NOH, formally HCl adducts of nitrile oxides. In the latter case, subsequent reactions lead to overall ring enlargement, i.e., formation of the seven-membered cyclic oxime I. With Et3Al and triisobutylaluminium, α-chloronitroso compds. are mainly reduced to oximes and the isomeric amides. [on SciFinder(R)]",

keywords = "chloro nitroso reaction organoaluminum, aluminum methyl reaction chloro nitroso",

author = "J. Lub and M.L. Beekes and {de Boer}, T.J.",

year = "1986",

doi = "10.1002/recl.19861050103",

language = "English",

volume = "105",

pages = "22--27",

journal = "Recueil des Travaux Chimiques des Pays-Bas",

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TY - JOUR

T1 - C-Nitroso compounds. Part XXXVII. The reactivity of α-chloronitroso compounds towards organoaluminum reagents.

AU - Lub, J.

AU - Beekes, M.L.

AU - de Boer, T.J.

PY - 1986

Y1 - 1986

N2 - With sterically unhindered and certain moderately hindered α-chloronitroso compds. R1R2C(NO)Cl [R1 = R2 = Et; R1 = Me, R2 = Me2CHCH2, CH2Ph; R1R2 = (CH2)5], Me3Al at low temp. gives the methylnitrones R1R2C:N+MeO-. Several intermediate complexes lose methane upon heating and rearrange to α-chloroimines. More sterically hindered α-chloronitroso compds. contg. quaternary C undergo C-C rupture when treated with Me3Al, thus forming hydroxaminic acid chlorides, e.g., CH2:CMe(CH2)3CMe2CCl:NOH, formally HCl adducts of nitrile oxides. In the latter case, subsequent reactions lead to overall ring enlargement, i.e., formation of the seven-membered cyclic oxime I. With Et3Al and triisobutylaluminium, α-chloronitroso compds. are mainly reduced to oximes and the isomeric amides. [on SciFinder(R)]

AB - With sterically unhindered and certain moderately hindered α-chloronitroso compds. R1R2C(NO)Cl [R1 = R2 = Et; R1 = Me, R2 = Me2CHCH2, CH2Ph; R1R2 = (CH2)5], Me3Al at low temp. gives the methylnitrones R1R2C:N+MeO-. Several intermediate complexes lose methane upon heating and rearrange to α-chloroimines. More sterically hindered α-chloronitroso compds. contg. quaternary C undergo C-C rupture when treated with Me3Al, thus forming hydroxaminic acid chlorides, e.g., CH2:CMe(CH2)3CMe2CCl:NOH, formally HCl adducts of nitrile oxides. In the latter case, subsequent reactions lead to overall ring enlargement, i.e., formation of the seven-membered cyclic oxime I. With Et3Al and triisobutylaluminium, α-chloronitroso compds. are mainly reduced to oximes and the isomeric amides. [on SciFinder(R)]

KW - chloro nitroso reaction organoaluminum

KW - aluminum methyl reaction chloro nitroso

U2 - 10.1002/recl.19861050103

DO - 10.1002/recl.19861050103

M3 - Article

SN - 0165-0513

VL - 105

SP - 22

EP - 27

JO - Recueil des Travaux Chimiques des Pays-Bas

JF - Recueil des Travaux Chimiques des Pays-Bas

IS - 1