Diethyl ethynylphosphonate: A versatile synthon for the preparation of 1-alkynyl- and 1,3-butadiyne-1,4-diylphosphonates

Article abstract of DOI:10.1080/10426500008043685

The cross-coupling reaction between diethyl ethynylphosphonate (1) and several aromatic iodides under the Sonogashira conditions (Cl₂Pd(PPh₃)₂ / Cul / Et₃N) gives only minute amounts of the expected 1-alkynylphosphonates. Yields of about 20% are achieved upon using Pd(OAc)₂ / 2 PPh₃ / Et₃N in place of the previous catalytic system. Side-reactions involving 1 and the amine are shown to be responsible for these low yields. Metalation of 1 with EtMgBr and t-BuLi has been carried out and the M-C≡C-P(O)(OEt)₂ (M = MgBr, Li) derivatives have been characterized via reaction with Me₃SiCl or Ph₃SiCl. The easy access to the organolithium compound has made possible the synthesis of the zinc analog (M = ZnCl) which reacts with aromatic iodides (C₆H₅I,p-MeOC₆H₄I,p-O ₂NC₆H₄I, 2-iodothiophene), in the presence of Pd(PPh₃)₄, to give diethyl 1-alkynylphosphonates in reasonable yields. Oxidative dimerization of 1 under the Hay conditions (CuCl / TMEDA.-acetone / air) gives the symmetrical diacetylenic diphosphonate (EtO)₂(O)P-C≡C-C≡C-P(O)(OEt)₂ in high yield.

Full text of DOI:10.1080/10426500008043685

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Phosphorus, Sulfur, and Silicon
and the Related Elements
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DIETHYL
ETHYNYLPHOSPHONATE: A
VERSATILE SYNTHON FOR THE
PREPARATION OF 1-ALKYNYL-
AND 1,3-BUTADIY NE-1,4-
DIYLPHOSPHONATES
Sylvain G. Dutremez a , Christian Guerin a , Bernard
J.L. Henner a & Veronique Tomberli a
a Laboratoire “Chimie Moléculaire et Organisation
du Solide”, UMR 5637 , Université Montpellier II ,
Case 007, Place E. Bataillon, 34095, Montpellier
Cedex 5, France
Published online: 04 Oct 2006.
To cite this article: Sylvain G. Dutremez , Christian Guerin , Bernard J.L. Henner &
Veronique Tomberli (2000) DIETHYL ETHYNYLPHOSPHONATE: A VERSATILE SYNTHON
FOR THE PREPARATION OF 1-ALKYNYL- AND 1,3-BUTADIY NE-1,4-DIYLPHOSPHONATES,
Phosphorus, Sulfur, and Silicon and the Related Elements, 160:1, 251-269, DOI:
10.1080/10426500008043685
To link to this article: http://dx.doi.org/10.1080/10426500008043685
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