Affiliations: Department of Chemistry and Chemical Biology,
University of New Mexico, Albuquerque, NM, USA
Note: [] orresponding author: Robert T. Paine, Department of Chemistry
and Chemical Biology, University of New Mexico, Albuquerque, NM 87131, USA.
E-mail: rtpaine@vnm.edu
Abstract: The 2,5-bis(phosphinoylmethyl)-thiophenes
[(Oct)(EtO)P(O)CH_{2}]_{2}C_{4}H_{2}S
and
[(Ph)(EtO)P(O)CH_{2}]_{2}C_{4}H_{2}S
are obtained from the appropriate phosphites, RP(OEt)_{2}
(R=Oct, Ph) and
(BrCH_{2})_{2}C_{4}H_{2}S
by using Arbusov reaction conditions. The analog
[(Oct)_{2}P(O)CH_{2}]_{2}C_{4}H_{2}S
is more conveniently obtained via the reaction of the phosphono-Grignard
reagent (Oct)_{2}P(O)MgBr and
(BrCH_{2})_{2}C_{4}H_{2}S.
An improved alternate Arbusov synthesis of the known
[Ph_{2}P(O)CH_{2}]_{2}C_{4}H_{2}S
is described along with its conversion to
[Ph_{2}P(S)CH_{2}]_{2}C_{4}H_{2}S
via Lawesson chemistry. The new compounds are characterized by MS, IR and NMR
methods, and the molecular structures of
[Ph_{2}P(O)CH_{2}]_{2}C_{4}H_{2}S
and
[Ph_{2}P(S)CH_{2}]_{2}C_{4}H_{2}S
have been confirmed by single crystal X-ray diffraction methods.
