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

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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.

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Acknowledgments

The authors wish to thank the Ministry of Higher Education of Malaysia and Universiti Kebangsaan Malaysia for research grant UKM-GGPM-KPB-098-2010. In addition, the scholarship from the Libyan Government to Mrs. W.M.A. is greatly appreciated.

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Authors and Affiliations

  1. School of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600, Bangi, Selangor, Malaysia

    Wedad M. Al-Adiwish, B. M. Yamin & W. A. Yaacob

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  1. Wedad M. Al-Adiwish
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  2. B. M. Yamin
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  3. W. A. Yaacob
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Correspondence to Wedad M. Al-Adiwish.

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Al-Adiwish, W.M., Yamin, B.M. & Yaacob, W.A. Synthesis of some new α,α-dioxoketene-N,S- and -N,N-acetals derived from secondary aliphatic amines. J IRAN CHEM SOC 10, 897–905 (2013). https://doi.org/10.1007/s13738-013-0226-4

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