Reduction of 2-chloro-N-phenylpropanamide and 2-methyl-N-phenylaziridine with lithium aluminium hydride

Mie Højer Vilhelmsen; Lars Frøsig Østergaard; Mogens Brøndsted Nielsen; Steen Hammerum

Reduction of 2-chloro-N-phenylpropanamide and 2-methyl-N-phenylaziridine with lithium aluminium hydride

Mie Højer Vilhelmsen, Lars Frøsig Østergaard, Mogens Brøndsted Nielsen, Steen Hammerum

Department of Chemistry

7 Citations (Scopus)

Abstract

The reduction of 2-chloro-N-phenylpropanamide with LiAlH4 has been re-examined. In contrast to previous findings, we obtain in almost equal quantities two amines from this reaction, namely N-propylaniline and the rearranged product N-isopropylaniline. 2-Methyl-N-phenylaziridine is an intermediate in the reduction and can be isolated from reactions with less LiAlH4. Reduction of 2-methyl-N-phenylaziridine itself proceeds non-regioselectively to provide a mixture of propyl- and isopropylanilines. Formation of the amines by reduction of the aziridine is much slower than formation by reduction of the 2-chloropropanamide, which indicates that Lewis acid catalysis (by aluminium chlorohydrides) facilitates the reduction of the aziridine. In addition, Lewis acid catalysis increases the relative yield of the propylamine product. The reduction of 2-chloro-N-phenylpropanamide furnishes 2-phenylamino-1-propanol as a by-product, rather than the previously proposed 1-phenylamino-2-propanol.

Original language	English
Journal	Organic & Biomolecular Chemistry
Volume	6
Pages (from-to)	1773-1778
ISSN	1477-0520
Publication status	Published - 2008

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@article{429fa070182f11ddbee902004c4f4f50,

title = "Reduction of 2-chloro-N-phenylpropanamide and 2-methyl-N-phenylaziridine with lithium aluminium hydride",

abstract = "The reduction of 2-chloro-N-phenylpropanamide with LiAlH4 has been re-examined. In contrast to previous findings, we obtain in almost equal quantities two amines from this reaction, namely N-propylaniline and the rearranged product N-isopropylaniline. 2-Methyl-N-phenylaziridine is an intermediate in the reduction and can be isolated from reactions with less LiAlH4. Reduction of 2-methyl-N-phenylaziridine itself proceeds non-regioselectively to provide a mixture of propyl- and isopropylanilines. Formation of the amines by reduction of the aziridine is much slower than formation by reduction of the 2-chloropropanamide, which indicates that Lewis acid catalysis (by aluminium chlorohydrides) facilitates the reduction of the aziridine. In addition, Lewis acid catalysis increases the relative yield of the propylamine product. The reduction of 2-chloro-N-phenylpropanamide furnishes 2-phenylamino-1-propanol as a by-product, rather than the previously proposed 1-phenylamino-2-propanol.",

author = "Vilhelmsen, {Mie H{\o}jer} and {\O}stergaard, {Lars Fr{\o}sig} and Nielsen, {Mogens Br{\o}ndsted} and Steen Hammerum",

year = "2008",

language = "English",

volume = "6",

pages = "1773--1778",

journal = "Journal of the Chemical Society, Perkin Transactions 1",

issn = "1470-4358",

publisher = "Royal Society of Chemistry",

}

TY - JOUR

T1 - Reduction of 2-chloro-N-phenylpropanamide and 2-methyl-N-phenylaziridine with lithium aluminium hydride

AU - Vilhelmsen, Mie Højer

AU - Østergaard, Lars Frøsig

AU - Nielsen, Mogens Brøndsted

AU - Hammerum, Steen

PY - 2008

Y1 - 2008

N2 - The reduction of 2-chloro-N-phenylpropanamide with LiAlH4 has been re-examined. In contrast to previous findings, we obtain in almost equal quantities two amines from this reaction, namely N-propylaniline and the rearranged product N-isopropylaniline. 2-Methyl-N-phenylaziridine is an intermediate in the reduction and can be isolated from reactions with less LiAlH4. Reduction of 2-methyl-N-phenylaziridine itself proceeds non-regioselectively to provide a mixture of propyl- and isopropylanilines. Formation of the amines by reduction of the aziridine is much slower than formation by reduction of the 2-chloropropanamide, which indicates that Lewis acid catalysis (by aluminium chlorohydrides) facilitates the reduction of the aziridine. In addition, Lewis acid catalysis increases the relative yield of the propylamine product. The reduction of 2-chloro-N-phenylpropanamide furnishes 2-phenylamino-1-propanol as a by-product, rather than the previously proposed 1-phenylamino-2-propanol.

AB - The reduction of 2-chloro-N-phenylpropanamide with LiAlH4 has been re-examined. In contrast to previous findings, we obtain in almost equal quantities two amines from this reaction, namely N-propylaniline and the rearranged product N-isopropylaniline. 2-Methyl-N-phenylaziridine is an intermediate in the reduction and can be isolated from reactions with less LiAlH4. Reduction of 2-methyl-N-phenylaziridine itself proceeds non-regioselectively to provide a mixture of propyl- and isopropylanilines. Formation of the amines by reduction of the aziridine is much slower than formation by reduction of the 2-chloropropanamide, which indicates that Lewis acid catalysis (by aluminium chlorohydrides) facilitates the reduction of the aziridine. In addition, Lewis acid catalysis increases the relative yield of the propylamine product. The reduction of 2-chloro-N-phenylpropanamide furnishes 2-phenylamino-1-propanol as a by-product, rather than the previously proposed 1-phenylamino-2-propanol.

M3 - Journal article

SN - 1470-4358

VL - 6

SP - 1773

EP - 1778

JO - Journal of the Chemical Society, Perkin Transactions 1

JF - Journal of the Chemical Society, Perkin Transactions 1

ER -

Reduction of 2-chloro-N-phenylpropanamide and 2-methyl-N-phenylaziridine with lithium aluminium hydride

Abstract

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