Synthesis of some new α,α-dioxoketene-N,S- and -N,N-acetals derived from secondary aliphatic amines

Wedad M. Al-Adiwish, Bohari Mohd. Yamin, Wan Yaacob Wan Ahmad

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

A total of 11 new α,α-dioxoketene- N,S -acetals (2a-2k) and two new α,α-dioxoketene- N,N -acetals (3j and 3k) have been synthesised by treating 3-[bis(methylthiol)methylene]pentane-2,4-dione (1) with increasing mole ratios of secondary aliphatic amines at room temperature, in either toluene or ethanol. Eight non-cyclic N -methylalkyl and N -ethylalkyl amines and the azacyclopentane of pyrrolidine yielded exclusively mono-substituted N,S -acetals (2a-2i), while the azacyclohexanes of piperidine and morpholine yielded the mono-substituted N,S -acetals 2j and 2k and the double-substituted N,N -acetals 3j and 3k. The conversion yields for the reactions in ethanol are considerably higher than those in toluene. Furthermore, the secondary aliphatic amines with an N -methylalkyl moiety, which have one primary α-carbon and less steric crowding around the nucleophilic nitrogen, appear to be more reactive towards 1 than those with the N -ethylalkyl group, which have two primary α-carbons; further, the latter amines are more reactive than the amines with secondary α-carbons.

Original languageEnglish
Pages (from-to)897-905
Number of pages9
JournalJournal of the Iranian Chemical Society
Volume10
Issue number5
DOIs
Publication statusPublished - Oct 2013

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Acetals
Amines
Carbon
Toluene
Ethanol
Nitrogen

Keywords

  • α,α-Dioxoketene- N,S - and α,α-dioxoketene- N,N -acetals
  • Mono- and double substitutions
  • Nucleophilic addition-elimination
  • Secondary aliphatic amines

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Synthesis of some new α,α-dioxoketene-N,S- and -N,N-acetals derived from secondary aliphatic amines. / Al-Adiwish, Wedad M.; Mohd. Yamin, Bohari; Wan Ahmad, Wan Yaacob.

In: Journal of the Iranian Chemical Society, Vol. 10, No. 5, 10.2013, p. 897-905.

Research output: Contribution to journalArticle

Al-Adiwish, Wedad M. ; Mohd. Yamin, Bohari ; Wan Ahmad, Wan Yaacob. / Synthesis of some new α,α-dioxoketene-N,S- and -N,N-acetals derived from secondary aliphatic amines. In: Journal of the Iranian Chemical Society. 2013 ; Vol. 10, No. 5. pp. 897-905.
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AB - A total of 11 new α,α-dioxoketene- N,S -acetals (2a-2k) and two new α,α-dioxoketene- N,N -acetals (3j and 3k) have been synthesised by treating 3-[bis(methylthiol)methylene]pentane-2,4-dione (1) with increasing mole ratios of secondary aliphatic amines at room temperature, in either toluene or ethanol. Eight non-cyclic N -methylalkyl and N -ethylalkyl amines and the azacyclopentane of pyrrolidine yielded exclusively mono-substituted N,S -acetals (2a-2i), while the azacyclohexanes of piperidine and morpholine yielded the mono-substituted N,S -acetals 2j and 2k and the double-substituted N,N -acetals 3j and 3k. The conversion yields for the reactions in ethanol are considerably higher than those in toluene. Furthermore, the secondary aliphatic amines with an N -methylalkyl moiety, which have one primary α-carbon and less steric crowding around the nucleophilic nitrogen, appear to be more reactive towards 1 than those with the N -ethylalkyl group, which have two primary α-carbons; further, the latter amines are more reactive than the amines with secondary α-carbons.

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