Solvent-free mechanochemical preparation of phosphonium...

Chemistry of hydrocarbon compounds – Unsaturated compound synthesis – By addition of entire unsaturated molecules – e.g.,...

Reexamination Certificate

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C568S008000, C568S009000, C560S055000, C585S600000

Reexamination Certificate

active

07105714

ABSTRACT:
The present invention provides a method of preparing a phosphonium salt of the formula [R1R2R3P—CR4R5R6]X, comprising ball-milling a phosphine of the formula R1R2R3P with a compound of the formula XCR4R5R6; a method of preparing a phosphorus ylide of the formula R1R2R3P═CR4R5, comprising ball-milling a phosphonium salt of the formula [R1R2R3P—HCR4R5]X in the presence of a base; and a method of preparing an olefin of the formula R4R5C═CR7H or R4R5C═CR7R8, comprising ball-milling a phosphorus ylide of the formula R1R2R3P═CR4R5with a compound of the formula R7C(O)H or R7C(O)R8. The inventive method produces phosphonium salts and phosphorus ylides by mechanical processing solid reagents under solvent-free conditions. The advantages of the present invention over conventional solution methods, include: (1) extremely high selectivity; (2) high yields; (3) low processing temperatures; (4) simple and scalable reactions using commercially available equipment; and (5) the complete elimination of solvents from the reaction.

REFERENCES:
patent: 2905717 (1959-09-01), Sarnecki et al.
patent: 3524886 (1970-08-01), Fried
patent: 3538013 (1970-11-01), Graff
patent: 4122123 (1978-10-01), Hestermann et al.
patent: 4182731 (1980-01-01), Schulz et al.
Balema et al.,J. Am. Chem. Soc., 124, 6244-6245 (May 10, 2002).
Bestman et al.,Chem. Abstracts, CA:96:85024 (Abstract ofSynthesis, 12, 998-999) (1981).

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