Facile synthesis of symmetric esters of...

Organic compounds -- part of the class 532-570 series – Organic compounds – Phosphorus esters

Reexamination Certificate

Rate now

  [ 0.00 ] – not rated yet Voters 0   Comments 0


C558S087000, C558S089000, C558S090000, C558S092000, C562S020000, C562S021000, C562S022000, C548S250000, C548S255000

Reexamination Certificate



A facile synthesis of symmetric esters of C1-C10alkylenebisphopsphonic acids is disclosed in which a C1-C10alkylenebis(phosphonic dichloride) is reacted with an alcohol in the presence of a catalytic amount of 1H-tetrazole and a base in an aprotic solvent to form a first reaction mixture. The first reaction mixture is maintained for a time period sufficient to form a C1-C10alkylenebis(chloro ester phosphonate) that is reacted under basic conditions with an excess of a hydroxylated compound to form a second reaction mixture that is itself maintained for a time period sufficient to form a C1-C10alkylenebis(ester phosphonate) partial ester, homoleptic tetraester or mixed tetraester. The material so formed can be recovered or used as is.

patent: 3156739 (1964-11-01), Klink et al.
patent: 4548790 (1985-10-01), Horwitz et al.
patent: 4574072 (1986-03-01), Horwitz et al.
patent: 4835107 (1989-05-01), Horwitz et al.
patent: 5651883 (1997-07-01), Horwitz et al.
patent: 5851401 (1998-12-01), Horwitz et al.
Raskina et al (1968): STN CAS International CAPLUS database, Columbus, Ohio, document No. 69:86266.
Horwitz, et al., “DIPEX: A New Extraction Chromatographic Material for the Separation and Preconcentration of Actinides from Aqueous Solution,”Reactive and Functional Polymers33: 25-36 (1997).
Chiarizia, et al., “Metal Extraction by Alkyl Substituted Diphosphonic Acids, Part 1. P, P′-DI (2-Ethylhexyl) Methanediphosphonic Acid,”Solvent Extr. Ion Exchange14: 773-792 (1996).
J. March,Advanced Organic Chemistry: Reactions, Mechanisms and Structure,4th Edition, John Wiley & Sons, New York (1992) pp. 348-352.
Stepinski, et al., “Facile high yielding synthesis of symmetric esters of methylenebisphosphonic acid,”Tetrahedron52: 8637-8645 (2001).
Griffith-Dzielawa, et al., “Synthesis and Characterization of DI[3-(Trimethylsilyl)-1-Propylene] Alkylenediphosphonic Acids,”Synth. Commun.,30: 2121-2132 (2000).
Zhao, et al., “Tetrazole Catalyzed Synthesis of Phosphonate Esters,”Tetrahedron49:(2) 363-368 (1993).
McKenna, et al., “Functional Selectivity in Phosphonate Ester Dealkylation with Bromotrimethylsilane,”J. Chem. Soc. Chem. Commun.,739 (1979).
McKenna, et al., “The Facile Dealkylation of Phosphonic Acid Dialkyl Esters by Bromotrimethylsilane ,”Tetrahedron Letter2: 155-158 (1977).
Lesiak, et al., “2-(4-Nitrophenyl)ethyl Methylenebis(Phosphonate): A Versatile Reagent for the Synthesis of Nucleoside 5′-Methylenebis(Phosphonate)s,”J. Org. Chem.63: 1906-1909 (1998).
Vepsalainen, et al., “An Improved Synthetic Method and the First Crystal Structures for (Dihalomethylene)bisphosphonate Partial Esters,”Tetrahedron51: 6805-6818 (1995).
Vepsalainen, et al., “Bisphosphonic Compounds VIII. A Facile and Selective One-Pot Synthesis of P,P-Dialkyl (Dichloromethylene)bisphosphonate Partial Esters,”Tetrahedron Lett.37: 3533-3536 (1996).
Vepsalainen, et al., “Bisphosphonic Compounds V. Selective Preparation of (Dichloromethylene)bisphosphonate Partial Esters,”Tetrahedron Lett.34: 4551-4554 (1993).
Morita, et al., “ Dealkylation Reaction of Acetals, Phosphonate, and Phosphate Esters with Chlorotrimethylsilane/Metal Halide Reagant in Acetonitrile, and Its Application to the Synthesis of Phosphonic Acids and Vinyl Phosphates,”Bull. Chem. Soc., Japan,54: 267-273 (1981).
Petrow, et al., “Cyclohexyl Alkylenediphosphonates and Some of Their Properties,”J. Gen. Chem. USSR39: 809-811 (1969).
Krawczyk, “A Convenient Route for Monodealkylation of Diethyl Phosphonates,”Synthetic Communications27: 3151-3161 (1977).
Lang, et al., “Synthese von Phenoxygruppenhaltige Derivate der Methandiphosphonsaure,”Z. Anorg. Allg. Chem.,56: 187-196 (1986).
Sober, et al., Eds., “Physical and Chemical Data—Ionization Constants of Acids and Bases (Continued) and Nitrogen Compounds (Continued),”CRC Handbook of Biochemistry,Second Edition, The Chemical Rubber Company, Cleveland, OH (1970) pp. 209-220.
McKenna, et al., “Fluorination of Methanediphosphonate Esters by Perchloryl Fluoride. Synthesis of Fluoromethanediphosphonic Acid and Difluoromethanediphosphonic Acid,”J. Org. Chem.,46: 4573-4576 (1981).
Morita, et al., “A Convenient Dealkylation of Dialkyl Phosphonates by Chlorotrimethylsilane in the Presence of Sodium Iodide,”Tetrahedron Letters28: 2523-2526 (1978).
CRC Handbook of Chemistry and Physics, 3rd Electronic Edition,CRC Press LLC(2001).


Say what you really think

Search LandOfFree.com for the USA inventors and patents. Rate them and share your experience with other people.


Facile synthesis of symmetric esters of... does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Facile synthesis of symmetric esters of..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Facile synthesis of symmetric esters of... will most certainly appreciate the feedback.

Rate now


Profile ID: LFUS-PAI-O-3500984

All data on this website is collected from public sources. Our data reflects the most accurate information available at the time of publication.