928265-49-0Relevant articles and documents
Versatile and efficient synthesis of a new class of aza-based phosphinic amide ligands via unusual P-C cleavage
Tsai, Shih-Chung,Fu, Yaw-Shien,Liao, Ju-Hsiou,Yu, Shuchun Joyce
, p. 3007 - 3017 (2007/10/03)
A new class of bidentate, aza-based phosphinic amide ligands of the type RN(H)P(=O)(2-py)2 (2-py=2-pyridyl) was synthesized within minutes via a one-pot process including Staudinger reaction of an organic azide (RN 3) with 2-pyridylphosphines, followed by partial, unprecedented hydrolysis under loss of one aromatic substituent. The structure of the unusual-hydrolysis product H2C=CH(CH2)9N(H)P(= O)(2-py)2 (5a) was characterized by IR, 1H- and 31P-NMR, as well as by X-ray crystal-structure analysis (Figure). The tetrahedral P-atom was found to be surrounded by a trigonal-pyramidal arrangement of the substituents. To gain insight into the formation of these novel phosphinic amides, a series of intermediate iminophosphoranes, H 2C=CH(CH2)9N=P(Ar)n(2-py) 3-n (n = 0-3), compounds 1a-1f, were synthesized, and their hydrolyses were studied. All tested compounds followed the classical hydrolysis route of P=N cleavage under acidic conditions. Sequential hydrolysis to 5a-5d only occurred under either basic conditions or in wet MeCN as solvent. Notably, H2C=CH(CH2)9N=P(C6H 5)(4-MeO-2-py)2 (1c) was hydrolyzed at a much slower rate compared to its analogue 1b lacking the MeO group. On the contrary, the halogenated compounds H2C=CH(CH2)9N=P(4-X- C6H4)3 (1f,g) (X = F, Cl) were hydrolyzed at a notably faster rate relative to the non-halogenated congener 1e (X = H).
Process for the carbonylation of acetylenic unsaturated compounds
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, (2008/06/13)
A method for the preparation of alpha,beta-olefinic unsaturated compounds by means of carbonylation of acetylenic unsaturated compounds with carbon monoxide in the presence of a hydroxy-containing compound in liquid phase, accomplished in the presence of a catalytic system that can be formed from: (a) a palladium compound, (b) a protonic acid, and (c) an organic phosphine according to the formula: STR1 wherein R1 represents a heterocyclic five- or six-atom ring, comprising, at least as hetero atom, nitrogen, which may be optionally substituted and/or may form part of a larger condensed ring structure that may be optionally substituted, and wherein R2 and R3 each have the aforesaid meaning of R1 or may represent an optionally substituted aryl group. The invention further comprises novel organic phosphines and compositions containing said phosphines as wel as the catalytic systems containing said phosphines.
