Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Patent
1988-02-29
1992-10-27
Elmore, Carolyn
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
564205, C07C23110
Patent
active
051591138
ABSTRACT:
A unique two-step process is disclosed for the surprisingly high rate of amidation of vinyl chloride (VCl) with carbon monoxide and certain amines catalyzed by an effective amount of monodentate tertiary phosphonium complexes of Pd(0). The rate is orders of magnitude faster than that of other monochloroalkenes. When compared with the three chloropropenes, the simplest alkyl-substituted derivatives of VCl, rates differ by a factor of about 40 to 70 with ammonia as the amine. The reaction product with VCl is mainly the Michael adduct of the amine with the acrylamide produced. However, the chloroprenes give the propenamides with retention of configuration in the case of cis- and trans-1-chloropropene, and no adduct formation. The formation of this adduct has an important influence on catalyst stability since it can compete with the addition of the tertiary-phosphonium ligand from the catalyst complex. The latter reaction produces small amounts of a phosphonium chloride, and the resulting loss of ligand causes palladium metal to separate, thereby deactivating the catalyst. This understanding enables one to choose the best ligand/amine combination to suppress this catalyst deactivation mechanism. Triphenylphosphine and dimethylamine is a particularly effective combination.
REFERENCES:
patent: 3988358 (1976-10-01), Heck
patent: 3991101 (1976-11-01), Knifton
patent: 4128554 (1978-12-01), Heck
Mori et al., J. Org. Chem., 1983, 48, 4058-67.
Breinet et al., J. Org. Chem:, 1983, 48 1166-71.
Fitton et al., J. Organometallic Chem., 28 (1971), 287-91.
Ishii et al., J. Organometallic Chem., 73 (1974), 411-18.
Koketsu et al., Chubu Kogyo Daigaka, Kiyo, A. 16A, 103-9 (1980).
Johnson, et al., J. Chem Soc., (1974), 34-40.
Tolman, Chemical Reviews, 1977, vol. 77, No. 3, 313-48.
Heck et al., Catalysis in Organic Synthesis, Patel, 1978, 7th Ed. 195-218.
"Chelate-Assisted, Pd-Catalyzed Efficient Carbonylation of Aryl Chlorides" by Y. Ben-David, M. Portnoy and D. Milstein, J. Am. Chem. Soc. 1989 111, p. 8742-8744.
"Oxidative Addition of Water to the Ru.sup.11 Catalyst K[Ru.sup.11 (Hedta)CO)]: Homogeneous Catalysis of the Water-Gas Shift Reaction under Ambient Conditions."
"Palladium-Catalyzed Amidation of Aryl, Heterocyclic, and Vinylic Halides", by A. Schoenberg and R. F. Heck J. Org. Chem. vol. 39, No. 23, 1974 pp. 3327-3331.
"Amidation of Chloroalkenes Catalyzed by Tertiary Phosphine Complexes of Palladium (0)" by Paul P. Nicholas, J. Org. Chem. vol. 52, No. 23, 1987 pp. 5266-5272.
Elmore Carolyn
Lobo Alfred D.
Shust Nestor W.
The B. F. Goodrich Company
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