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NMR Spectroscopic Studies on the 1:1 Interaction of Tris(hydroxymethyl)phosphine with Cinnamic Acids
Author(s) -
Moiseev Dmitry V.,
James Brian R.,
Gushchin Aleksey V.
Publication year - 2014
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201402889
Subject(s) - chemistry , phosphine , medicinal chemistry , hydroxymethyl , stereochemistry , nuclear magnetic resonance spectroscopy , methanol , stereospecificity , tris , cinnamic acid , acetone , organic chemistry , catalysis , biochemistry
A 1:1 reaction of (HOCH 2 ) 3 P with the cinnamic acids ArCH=CHCO 2 H (Ar = Ph, o ‐ and p ‐C 6 H 4 OH) in acetone at 60 °C affords a phosphobetaine of the type (HOCH 2 ) 3 P + CH(Ar)CH 2 CO 2 – in 70–80 % yields; the products were characterized by 31 P{ 1 H}‐, 1 H‐, and 13 C{ 1 H}‐NMR spectroscopy, and mass spectrometry. In methanol, the compounds decompose partially to a tertiary phosphine of the type (HOCH 2 ) 2 PCH(Ar)CH 2 CO 2 H; the degree of decomposition decreases in the order Ar = o ‐C 6 H 4 OH > p ‐C 6 H 4 OH > C 6 H 5 . The 1:1 reaction of (HOCH 2 ) 3 P with cinnamic acid in CD 3 OD generates (DOCH 2 ) 3 P + CH(Ph)CH(D)CO 2 – and (DOCH 2 ) 2 PCH(Ph)CH(D)CO 2 D, whereby addition of a deuteron to the α‐C atom is stereospecific and leads to ( R , S )‐ and ( S , R )‐stereoisomers.