Dipalladaphosphacyclobutanes and a process for preparing the sam

Details Dipalladaphosphacyclobutanes and a process for preparing the sam Dipalladaphosphacyclobutanes and a process for preparing the sam

1999-07-19

2000-07-04

Nazario-Gonzalez, Porfirio

Organic compounds -- part of the class 532-570 series

Organic compounds

Heavy metal containing

556 16, 556 22, 556 23, 556136, 502155, 502162, C07F 902, C07F 1500

Patent

active

060841141

DESCRIPTION:

BRIEF SUMMARY
The present invention relates to new palladaphosphacyclobutanes and a process for their preparation.
Palladaphosphacyclobutanes play an important role as catalysts for a number of processes. Examples of such processes are the synthesis of substituted styrenes, stilbenes and cinnamic acids from aryl halides.
The literature discloses the following compounds of this type: Di-.mu.-chloro-bis[2-[bis(1,1-dimethylethyl)phosphino]-2-methylpropyl-C,P] dipalladium(II); H. C. Clark et al., Inorg. Chim. Acta 31, (1978), L441-L442; H. C. Clark et al. J. Organomet. Chem. 166, (1979) C29-C32, H. C. Clark et al., Inorg. Chem. 18, (1979), 2803-2808 Di-.mu.-bromo-bis[2-[bis(1,1-dimethylethyl)phosphino]-2-methylpropyl-C,P]d ipalladium(II); H. C. Clark et al., J. Organomet. Chem. 166, (1979) C29-C32; H. C. Clark et al., Inorg. Chem. 18, (1979), 2803-2808 Di-.mu.-trifluoroacetato-bis[2-[bis(1,1-dimethylethyl)phosphino]-2-methylp ropyl-C,P]dipalladium(II); H. C. Clark et al., J. Organomet. Chem. 166, (1979) C29-C32; H. C. Clark et al., Inorg. Chem. 18, (1979), 2803-2808 Di-.mu.-chloro-bis[2-[(1,1-dimethylethyl)phenylphosphino]-2-methylpropyl-C ,P]dipalladium(II); H. Werner et al., J. Organomet. Chem. 204, (1980), 415-422 .mu.-Chloro-.mu.-methoxy-bis[2-[bis(1,1-dimethylethyl)phosphino]-2-methylp ropyl-C,P]dipalladium(II); A. B. Goel et al., Trans. Met.
Chem 5, (1980), 378-379
In J. Chem. Soc. (A) (1971), 2976-2980, Shaw describes the addition of tert-butylphosphines of the formula P(t-Bu).sub.n R.sub.3-n onto palladium(II) compounds to give the corresponding complexes of the formula Pd(P(t-Bu).sub.n R.sub.3-n).sub.2 X.sub.2 and Pd.sub.2 (P(t-Bu).sub.n R.sub.3-n).sub.2 X.sub.4. In the synthesis, the palladaphosphacyclobutanes of the present invention are not obtained.
In Inorg. Chim. Acta 31, (1978), L441-L442, Clark describes the reaction of PdCl.sub.2 (NCPh).sub.2 with two equivalents of P(t-Bu).sub.3 to give the corresponding palladaphosphacyclobutane in 70% yield. This process employs the toxicologically dubious solvent methylene chloride in which both the starting material and the product are soluble. To isolate this palladaphosphacyclobutane, the solvent is taken off, the product is extracted with benzene and subsequently precipitated by addition of hexane. Owing to the use of two equivalents of P(t-Bu).sub.3 per equivalent of palladium and the use of methylene chloride and benzene, the process is ecologically and economically disadvantageous.
In Inorg. Chim. Acta 31, (1978), L441 -L442, Clark describes the reaction of K.sub.2 PdCl.sub.4 with two equivalents of P(t-Bu).sub.3 to give the corresponding palladaphosphacyclobutane in 72% yield. In this process, dimethylformamide is used as solvent. To isolate this palladaphosphacyclobutane, the solvent is taken off and the product is precipitated by addition of ethanol. In Organometallics 1, (1982), 658-666, Clark describes an analogous process in which Na.sub.2 PdCl.sub.4 and three equivalents of P(t-Bu).sub.3 are used as starting materials and the corresponding palladaphosphacyclobutane is obtained in 75% yield. Owing to the use of two or three equivalents of P(t-Bu).sub.3 per equivalent of palladium, both processes are ecologically and economically disadvantageous.
In Inorg. Chem. 18, (1979), 2803-2808, Clark describes the reaction of PdCl.sub.2 (NCPh).sub.2 with one equivalent of P(t-Bu).sub.3 to give the corresponding palladaphosphacyclobutane without indicating the yield. This process employs the toxicologically dubious solvent methylene chloride in which both the starting material and the product are soluble. To isolate this palladaphosphacyclobutane, the solvent is taken off, the product is extracted with benzene and subsequently precipitated by addition of hexane. Owing to the use of methylene chloride and benzene, the process is ecologically and economically disadvantageous.
In J. Organomet. Chem. 204, (1980) 415-422, Werner describes the reaction of Pd(P(t-Bu).sub.3).sub.2 Cl.sub.2 and Pd(P(t-Bu).sub.2 Ph).sub.2 Cl.sub.2 with silver acetate to prepare the correspondin

REFERENCES:
patent: 5831107 (1998-11-01), Beller er al.
Werner et al., "Intramolecular Metalation of PBut2PH and PBut3 in Palladium Acetate Complexes", Journal of Organometallic Chemistry, vol. 204, 1981, pp. 415-422.
Goel et al., "Isolation and Characterization of an Unusual Mixed Methoxy- and Chloro-bridged Dinuclear Palladium Complex", Transition Met. Chem., vol. 5(6), 1980, pp. 378-379.
Clark et al., "Facile Intramolecular Metalation of Tri-tert-butylphosphine in Palladium(II) Hydride Complexes", Journal of Organometallic Chemistry, vol. 166(2), 1979, pp. 2803-2808.
Clark et al., "Solvent Effects on the Metalation of Tri-tert-butylphosphine, Preparation and Characterizatio of 'PtPBu2tC(CH3)2CH2C1!2 and 'pdPBu2tC(CH3)2CH2CL!2", Inorganica Chimica Acta, vol. 31(2), 1978, pp. L441-442.
Clark et al., "Facile Intramolecular Metalation of Tri-tert-butylphosphine in Palladaium(II) Hydride Complexes", Journal or Organometallic Chemistry, 1979, pp. C29-C32.

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