A simple one-pot, multi-component synthesis of cyano-functionalized bis-beta-diketones

Aron Urbatsch, William James Gee, Glen Berenger Deacon, Stuart Robert Batten

Research output: Contribution to journalArticleResearchpeer-review

4 Citations (Scopus)

Abstract

Mild, multi-component Knoevenagel condensation/Michael addition reactions of dibenzoylmethane (Hdbm) and methylene-active cyano molecules with formalin in ethanol gave cyano methylene-bridged bis-diketones. The syntheses of 1,1,5,5-tetrabenzoyl-3,3-dicyanopentane (1) and 1,1,7,7-tetrabenzoyl-3,5-dicyano-3,5-dimethoxycarbonyl-heptane (4) are reported. Increasing the reaction time with the reagents for 1 led to the formation of the ester (2,2-dicyano-4-benzoylbutyl) benzoate (2). The isolation of 2,2-dicyano-4,4-dipivaloyl-1-butanol (3a), the tert-butyl analogue of a proposed intermediate in the formation of 2, provides evidence for a possible reaction pathway. Methylene-bis(dibenzoylmethane) (mdbm) was obtained in good yield from the reaction between Hdbm and formalin, by the addition of the base triethylamine. The X-ray crystal structures of 1–4 and mdbm were determined using synchrotron radiation.
Original languageEnglish
Pages (from-to)2661 - 2664
Number of pages4
JournalTetrahedron Letters
Volume54
Issue number21
DOIs
Publication statusPublished - 2013

Cite this

@article{987df383196c4535914866daf4839b69,
title = "A simple one-pot, multi-component synthesis of cyano-functionalized bis-beta-diketones",
abstract = "Mild, multi-component Knoevenagel condensation/Michael addition reactions of dibenzoylmethane (Hdbm) and methylene-active cyano molecules with formalin in ethanol gave cyano methylene-bridged bis-diketones. The syntheses of 1,1,5,5-tetrabenzoyl-3,3-dicyanopentane (1) and 1,1,7,7-tetrabenzoyl-3,5-dicyano-3,5-dimethoxycarbonyl-heptane (4) are reported. Increasing the reaction time with the reagents for 1 led to the formation of the ester (2,2-dicyano-4-benzoylbutyl) benzoate (2). The isolation of 2,2-dicyano-4,4-dipivaloyl-1-butanol (3a), the tert-butyl analogue of a proposed intermediate in the formation of 2, provides evidence for a possible reaction pathway. Methylene-bis(dibenzoylmethane) (mdbm) was obtained in good yield from the reaction between Hdbm and formalin, by the addition of the base triethylamine. The X-ray crystal structures of 1–4 and mdbm were determined using synchrotron radiation.",
author = "Aron Urbatsch and Gee, {William James} and Deacon, {Glen Berenger} and Batten, {Stuart Robert}",
year = "2013",
doi = "10.1016/j.tetlet.2013.03.044",
language = "English",
volume = "54",
pages = "2661 -- 2664",
journal = "Tetrahedron Letters",
issn = "0040-4039",
publisher = "Elsevier",
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A simple one-pot, multi-component synthesis of cyano-functionalized bis-beta-diketones. / Urbatsch, Aron; Gee, William James; Deacon, Glen Berenger; Batten, Stuart Robert.

In: Tetrahedron Letters, Vol. 54, No. 21, 2013, p. 2661 - 2664.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - A simple one-pot, multi-component synthesis of cyano-functionalized bis-beta-diketones

AU - Urbatsch, Aron

AU - Gee, William James

AU - Deacon, Glen Berenger

AU - Batten, Stuart Robert

PY - 2013

Y1 - 2013

N2 - Mild, multi-component Knoevenagel condensation/Michael addition reactions of dibenzoylmethane (Hdbm) and methylene-active cyano molecules with formalin in ethanol gave cyano methylene-bridged bis-diketones. The syntheses of 1,1,5,5-tetrabenzoyl-3,3-dicyanopentane (1) and 1,1,7,7-tetrabenzoyl-3,5-dicyano-3,5-dimethoxycarbonyl-heptane (4) are reported. Increasing the reaction time with the reagents for 1 led to the formation of the ester (2,2-dicyano-4-benzoylbutyl) benzoate (2). The isolation of 2,2-dicyano-4,4-dipivaloyl-1-butanol (3a), the tert-butyl analogue of a proposed intermediate in the formation of 2, provides evidence for a possible reaction pathway. Methylene-bis(dibenzoylmethane) (mdbm) was obtained in good yield from the reaction between Hdbm and formalin, by the addition of the base triethylamine. The X-ray crystal structures of 1–4 and mdbm were determined using synchrotron radiation.

AB - Mild, multi-component Knoevenagel condensation/Michael addition reactions of dibenzoylmethane (Hdbm) and methylene-active cyano molecules with formalin in ethanol gave cyano methylene-bridged bis-diketones. The syntheses of 1,1,5,5-tetrabenzoyl-3,3-dicyanopentane (1) and 1,1,7,7-tetrabenzoyl-3,5-dicyano-3,5-dimethoxycarbonyl-heptane (4) are reported. Increasing the reaction time with the reagents for 1 led to the formation of the ester (2,2-dicyano-4-benzoylbutyl) benzoate (2). The isolation of 2,2-dicyano-4,4-dipivaloyl-1-butanol (3a), the tert-butyl analogue of a proposed intermediate in the formation of 2, provides evidence for a possible reaction pathway. Methylene-bis(dibenzoylmethane) (mdbm) was obtained in good yield from the reaction between Hdbm and formalin, by the addition of the base triethylamine. The X-ray crystal structures of 1–4 and mdbm were determined using synchrotron radiation.

U2 - 10.1016/j.tetlet.2013.03.044

DO - 10.1016/j.tetlet.2013.03.044

M3 - Article

VL - 54

SP - 2661

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JO - Tetrahedron Letters

JF - Tetrahedron Letters

SN - 0040-4039

IS - 21

ER -