Solvent-free mechanochemical preparation of phosphonium salts, phosphorus ylides, and olefins
Abstract
The present invention provides a method of preparing a phosphonium salt of the formula [R.sup.1 R.sup.2 R.sup.3 P--CR.sup.4 R.sup.5 R.sup.6 ]X, comprising ball-milling a phosphine of the formula R.sup.1 R.sup.2 R.sup.3 P with a compound of the formula XCR.sup.4 R.sup.5 R.sup.6 ; a method of preparing a phosphorus ylide of the formula R.sup.1 R.sup.2 R.sup.3 P.dbd.CR.sup.4 R.sup.5, comprising ball-milling a phosphonium salt of the formula [R.sup.1 R.sup.2 R.sup.3 P--HCR.sup.4 R.sup.5 ]X in the presence of a base; and a method of preparing an olefin of the formula R.sup.4 R.sup.5 C.dbd.CR.sup.7 H or R.sup.4 R.sup.5 C.dbd.CR.sup.7 R.sup.8, comprising ball-milling a phosphorus ylide of the formula R.sup.1 R.sup.2 R.sup.3 P.dbd.CR.sup.4 R.sup.5 with a compound of the formula R.sup.7 C(O)H or R.sup.7 C(O)R.sup.8. 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.
- Inventors:
- Issue Date:
- Research Org.:
- Iowa State Univ., Ames, IA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1174833
- Patent Number(s):
- 6730812
- Application Number:
- 10/358,552
- Assignee:
- Iowa State University Research Foundation, Inc. (Ames, IA)
- Patent Classifications (CPCs):
-
C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07C - ACYCLIC OR CARBOCYCLIC COMPOUNDS
C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07F - ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- DOE Contract Number:
- W-7405-ENG-82
- Resource Type:
- Patent
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Pecharsky, Vitalij K., Balema, Viktor P., Wiench, Jerzy W., and Pruski, Marek. Solvent-free mechanochemical preparation of phosphonium salts, phosphorus ylides, and olefins. United States: N. p., 2004.
Web.
Pecharsky, Vitalij K., Balema, Viktor P., Wiench, Jerzy W., & Pruski, Marek. Solvent-free mechanochemical preparation of phosphonium salts, phosphorus ylides, and olefins. United States.
Pecharsky, Vitalij K., Balema, Viktor P., Wiench, Jerzy W., and Pruski, Marek. Tue .
"Solvent-free mechanochemical preparation of phosphonium salts, phosphorus ylides, and olefins". United States. https://www.osti.gov/servlets/purl/1174833.
@article{osti_1174833,
title = {Solvent-free mechanochemical preparation of phosphonium salts, phosphorus ylides, and olefins},
author = {Pecharsky, Vitalij K. and Balema, Viktor P. and Wiench, Jerzy W. and Pruski, Marek},
abstractNote = {The present invention provides a method of preparing a phosphonium salt of the formula [R.sup.1 R.sup.2 R.sup.3 P--CR.sup.4 R.sup.5 R.sup.6 ]X, comprising ball-milling a phosphine of the formula R.sup.1 R.sup.2 R.sup.3 P with a compound of the formula XCR.sup.4 R.sup.5 R.sup.6 ; a method of preparing a phosphorus ylide of the formula R.sup.1 R.sup.2 R.sup.3 P.dbd.CR.sup.4 R.sup.5, comprising ball-milling a phosphonium salt of the formula [R.sup.1 R.sup.2 R.sup.3 P--HCR.sup.4 R.sup.5 ]X in the presence of a base; and a method of preparing an olefin of the formula R.sup.4 R.sup.5 C.dbd.CR.sup.7 H or R.sup.4 R.sup.5 C.dbd.CR.sup.7 R.sup.8, comprising ball-milling a phosphorus ylide of the formula R.sup.1 R.sup.2 R.sup.3 P.dbd.CR.sup.4 R.sup.5 with a compound of the formula R.sup.7 C(O)H or R.sup.7 C(O)R.sup.8. 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.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Tue May 04 00:00:00 EDT 2004},
month = {Tue May 04 00:00:00 EDT 2004}
}
Works referenced in this record:
Mechanically Induced Solid-State Generation of Phosphorus Ylides and the Solvent-Free Wittig Reaction
journal, June 2002
- Balema, Viktor P.; Wiench, Jerzy W.; Pruski, Marek
- Journal of the American Chemical Society, Vol. 124, Issue 22
Kumulierte Ylide; XIII 1 : Diethoxyvinylidentriphenylphosphoran als Reagenz zur Herstellung von Carbonsäure-ethylestern in aprotischen Lösungsmitteln
journal, January 1981
- Bestmann, Hans Jürgen; Roth, Kurt
- Synthesis, Vol. 1981, Issue 12