Trivalent Phosphorus Converted Into Pentavalent Phosphorus Patents (Class 558/122)
  • Patent number: 8426629
    Abstract: Disclosed is a process for producing a phosphine derivative from a phosphine oxide derivative, which comprises the following steps: (I) mixing a phosphine oxide derivative represented by formula (1) with a chlorinating agent in a polar organic solvent to cause the reaction between these components; and (II-1) adding a salt of a metal having an ionization tendency equal to or lower than that of aluminum to the reaction mixture and carrying out the reductive reaction in the presence of aluminum or (II-2) subjecting the reaction mixture to electrolytic reduction, thereby producing a phosphine derivative represented by formula (2). ArnR3-nP?O (1) ArnR3-nP (2) In formulae (1) and (2), Ar represents an aryl group such as a phenyl group, a phenyl group having a substituent, a heteroaromatic ring group, and a heteroaromatic ring group having a substituent; R represents an aliphatic hydrocarbon group or an aliphatic hydrocarbon group having a substituent; and n represents an integer of 0 to 3.
    Type: Grant
    Filed: May 14, 2009
    Date of Patent: April 23, 2013
    Assignees: National University Corporation Okayama University, Asahi Kasei Chemicals Corporation, Hokko Chemical Industry Co., Ltd.
    Inventors: Hideo Tanaka, Manabu Kuroboshi, Tomotake Yano, Masakatsu Hoshino, Hiromu Kawakubo
  • Patent number: 7964750
    Abstract: A method for synthesizing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or its derivatives has a step of introducing 6-chloro-6H-dibenz[c,e][1,2]oxaphosphorin or its derivative, an acid compound and water into a reacting chamber to form an organic layer having 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or its derivative and an aqueous layer. Because the acid compound is from an external source and has a catalyzing effect, employing the method can prevent side reaction from occurring and increase yield of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or its derivative. Furthermore, the method is a one-pot operation of hydrolysis, dehydration and cyclization, so the method does not require purification of intermediates. Therefore, the method is time- and cost-saving and requires less organic solvent, resulting in less pollution to the environment.
    Type: Grant
    Filed: August 5, 2009
    Date of Patent: June 21, 2011
    Assignee: UFC Corporation
    Inventors: Ling Lu, Kai-Chiang Huang, Kuan-Chieh Tseng, Chung-Ning Fan, Yu-Cheng Lee, Tien-Wen Lo, Yu-Chin Lee
  • Publication number: 20110015384
    Abstract: The use of a sulfurizing agent of formula A: or a salt, hydrate, solvate, or a mixture thereof, in which all R groups, independently, represent H or an organic group, in sulfurization. The sulfurizing agent is preferably a formamidine disulfide. It is found a particularly suitable alternative to existing sulfurizing agents, since it is easy to synthesize from readily available, cheap starting materials.
    Type: Application
    Filed: February 6, 2009
    Publication date: January 20, 2011
    Applicant: PROSENSA HOLDING BV
    Inventors: Peter Christian De Visser, Gerardus Johannes Platenburg
  • Publication number: 20100179342
    Abstract: This invention provides a process for the preparation of a dihydrocarbyl hydrocarbonphosphonate. The process comprises forming a reaction mixture from components comprising (i) at least one dihydrocarbyl phosphite, (ii) at least one alkali metal hydrocarbyloxide, and (iii) at least one alcohol, so that a dihydrocarbyl hydrocarbonphosphonate is formed.
    Type: Application
    Filed: June 5, 2008
    Publication date: July 15, 2010
    Applicant: ALBEMARLE CORPORATION
    Inventors: Anne M. Sauer, Techen Tsao, Arthur G. Mack, William J. Layman, Jr.
  • Patent number: 6245880
    Abstract: A polyester having a good color tone can be obtained by using, as an ester-forming component, a compound derived from an organophosphorous composition comprising an organophosphorous compound represented by the general formula (1): wherein R1 and R2 represent an organic group or a halogen atom, and m and n represent an integer of 0 to 4, provided that R1 and R2 may be the same or different when m or n is an integer of 2 to 4, and a divalent metallic compound in an amount more than 30 ppm and not more than 2300 ppm in terms of a divalent metal based on the organophosphorous compound.
    Type: Grant
    Filed: October 4, 2000
    Date of Patent: June 12, 2001
    Assignee: Toyo Boseki Kabushiki Kaisha
    Inventors: Hideo Takeuchi, Maki Sato, Shoichi Gyobu
  • Patent number: 5973179
    Abstract: The present invention describes novel phosphonate reagent compositions of the formula: ##STR1## wherein R and R'=C.sub.1 -C.sub.4 alkyl groups, or R, R'=(CH.sub.2).sub.n (n=2 or 3) or [CH.sub.2 C(CH.sub.3).sub.2 CH.sub.2 ].The invention also describes allylic C-15 phosphonate compounds of the formula: ##STR2## wherein R and R'=C.sub.1 -C.sub.4 alkyl groups. The invention also describes methods of preparing phosphonate reagent compositions (4), allylic phosphonate compounds (5), and lycopene.
    Type: Grant
    Filed: November 19, 1998
    Date of Patent: October 26, 1999
    Assignee: Loyola University of Chicago
    Inventors: James H. Babler, Harvey W. Posvic
  • Patent number: 5929226
    Abstract: The invention provides improved oligonucleotides having greater resistance to nucleolytic degradation by virtue of having alkylphosphonothioate or arylphosphonothioate internucleotide linkages.
    Type: Grant
    Filed: May 8, 1995
    Date of Patent: July 27, 1999
    Assignee: Hybridon, Inc.
    Inventors: A. Padmapriya, Sudhir Agrawal
  • Patent number: 5922897
    Abstract: A process for the preparation of surfactants is described comprising reacting a phosphorus acid ester of the following Formula (IV) ##STR1## wherein R.sup.t is aryl, R.sup.2 is alkyl or aryl, with a hydrophilic polyoxyalkylene of the following Formulas (VIII), or (IX) ##STR2## wherein R.sup.3 is alkyl and A is a hydrophilic polyoxyalkylene chain, and which reaction results in an intermediate compound Formulas (XI), (XII), or (XIII); ##STR3## reacting the intermediate compound selected from the group consisting of Formulas (XI) through (XIII), with a hydroxylic compound R.sup.1 -OH (X) to yield surfactant precursors comprised of Formulas (V), (VI), and (VII), respectively: ##STR4## and, oxidizing said phosphorus ester-linked surfactant precursors selected from the group consisting of Formulas (V), (VI) and (VII), with an oxidizing agent to produce the surfactants.
    Type: Grant
    Filed: May 29, 1998
    Date of Patent: July 13, 1999
    Assignee: Xerox Corporation
    Inventors: Nan-Xing Hu, H. Bruce Goodbrand
  • Patent number: 5919967
    Abstract: A process for preparing a phosphodiester of the formula: ##STR1## is described that involves (1) reaction of a first alcohol with phosphorous trichloride to form a phosphorodichlorodite, (2) reaction of the phosphorodichlorodite with an amine to form a phosphorodiamidite, (3) reaction with a second alcohol (which may be the same as the first alcohol) to form a phosphoramidite diester, and finally, (4) hydrolysis and oxidation of the phosphoramidite to form the phosphodiester. R and R1 may represent aliphatic, aromatic, heterocyclic, peptidic, peptoid, deoxyribo- or ribonucleotidic or nucleosidic, or organic chelating moieties.
    Type: Grant
    Filed: April 11, 1997
    Date of Patent: July 6, 1999
    Assignee: EPIX Medical, Inc.
    Inventors: John C. Amedio, Paul J. Bernard, Mark Fountain
  • Patent number: 5919968
    Abstract: A process for preparing an organic pentavalent phosphorus compound comprising oxidizing an organic trivalent phosphorus compound with an aqueous hydrogen peroxide solution in the presence of an inorganic or organic base at a temperature of 0.degree. C. to 50.degree. C. to obtain the corresponding organic pentavalent phosphorus compound.
    Type: Grant
    Filed: November 10, 1997
    Date of Patent: July 6, 1999
    Assignee: Daihachi Chemical Industry Co., Ltd.
    Inventors: Kozo Kitamura, Tsuyoshi Kihara, Yoshinori Tanaka, Yoshimi Yano
  • Patent number: 5852168
    Abstract: The present invention provides a method for sulfurizing a phosphorus-containing compound, such as a trivalent phosphorus compound, using a disulfide-containing five-membered heterocycle.
    Type: Grant
    Filed: April 30, 1996
    Date of Patent: December 22, 1998
    Assignees: Regents of the University of Minesota, The Board of Supervisors of LA State University
    Inventors: George Barany, Robert P. Hammer, Karin Musier-Forsyth, Qinghong Xu, Lin Chen
  • Patent number: 5618963
    Abstract: A process is described for the preparation of hydroxybenzylphosphonates of the formula I ##STR1## which involves A) reacting a phenol of the formula II ##STR2## with an amine of the formula III ##STR3## formaldehyde or paraformaldehyde and a protonic acid H.sub.n A to give a salt of the formula IV ##STR4## B) distilling off the water of reaction which forms, and C) reacting the reaction mixture, or the salt IV isolated therefrom, with a trialkyl phosphite of the formula ##STR5## in which H.sub.n A is an organic or inorganic acid having n protons,n is 1, 2, 3 or 4,R.sub.1 and R.sub.2 independently of one another are C.sub.1 -C.sub.12 alkyl or C.sub.5 -C.sub.7 cycloalkyl,R.sub.3 and R.sub.4 independently of one another are C.sub.1 -C.sub.12 alkyl or form, together with the nitrogen atom attached to them, a piperidyl or morpholinyl radical, and R.sub.5, R.sub.6 and R.sub.7 independently of one another are C.sub.1 -C.sub.
    Type: Grant
    Filed: June 22, 1995
    Date of Patent: April 8, 1997
    Assignee: Ciba-Geigy Corporation
    Inventors: Thomas Engert, Hans Stephan, Walter Wolf
  • Patent number: 5606093
    Abstract: A process for the manufacture of an acid salt of an alkyl ester of N-phosphonomethylglycinonitrile is described which comprises reacting methyleneaminoacetonitrile trimer with a trialkylphosphite. The process is carried out under anhydrous conditions and in the presence of an anhydrous acid and an inert solvent in which methyleneaminoacetonitrile trimer is at least partially soluble and the acid salt of the alkyl ester of N-phosphonomethylglycinonitrile product is substantially insoluble. This is followed by recovering the precipitated acid salt of the alkyl ester of N-phosphonomethylglycinonitrile.
    Type: Grant
    Filed: October 5, 1995
    Date of Patent: February 25, 1997
    Assignee: Zeneca Limited
    Inventor: Ian Hodgkinson
  • Patent number: 5481017
    Abstract: Process for the preparation of 6H-dibenzo [c,e][1,2]oxaphosphorin-6-one of the formula ##STR1## in which R.sup.1 and R.sup.2 are identical or different and are halogen or an alkyl or alkoxy group having from 1 to 6 carbon atoms and a and b are identical or different and are 0, 1, 2 or 3, which involves reacting a 6-chloro-(6H)-dibenzo[c,e][1,2]oxaphosphorin of the formula ##STR2## in which R.sup.1, R.sup.2, a and b are as defined above, with water in a molar ratio of 1:1 at from 50.degree. to 250.degree. C., in the presence if desired of a solvent, and separating off gaseous hydrogen chloride at the rate at which it is formed.
    Type: Grant
    Filed: June 30, 1994
    Date of Patent: January 2, 1996
    Assignee: Hoechst Aktiengesellschaft
    Inventor: Hans-Jerg Kleiner
  • Patent number: 5466852
    Abstract: S,S,S-tributylphosphorotrithioite is oxidized with a perborate or percarbonate at a pH of from about 6 to about 12 and at a temperature of from about 40.degree. to about 65.degree. C. Sodium perborate is a particularly preferred oxidizing agent. The product S,S,S-tributylphosphorotrithioate may be recovered by simple phase separation.
    Type: Grant
    Filed: August 30, 1994
    Date of Patent: November 14, 1995
    Assignee: Bayer Corporation
    Inventors: Vidyanatha A. Prasad, Peter E. Newallis
  • Patent number: 5430169
    Abstract: The present invention provides a series of non-toxic compounds which function to inhibit the activity of S-1-P aldolase in respect to its cleavage of S-1-P. These inhibitors are described by the compounds of formula I ##STR1## wherein R is a radical containing 1 to 15 carbon atoms, a halogen, or hydrocarbon, R' is an organic radical or hydrogen, and R" is --NH.sub.3.sup.+ or --NH--NH .sup.+, with the proviso that, when R is CH.sub.3 (CH).sub.12 (CH.dbd.CH) and R' is hydrogen, R" is --NH--NH.sub.3.sup.+.A method for preparing such compounds, which may generally be described as 1-phosphate derivatives of compounds which include a 2-amino-1,3-alcohol radical is also disclosed.
    Type: Grant
    Filed: February 14, 1994
    Date of Patent: July 4, 1995
    Assignee: The United States of America represented by the Department of Health and Human Services
    Inventors: Ahcene Boumendjel, Stephen P. F. Miller
  • Patent number: 5362899
    Abstract: A stereospecific method of preparing alpha-aminophosphonic acids and derivatives thereof is provided. A protected amino acid is converted to a acyl aroyl or diacyl peroxide which spontaneously rearranges to form an alpha-amino ester. This rearrangement occurs stereospecifically with retention of configuration. The ester is subsequently converted to an appropriate leaving group and displaced with a phosphite yielding a chiral alpha-aminophosphonic acid or derivative.Alpha-aminophosphonic acids are useful for the synthesis of peptide analogs that possess a phosphonate linkage in the place of an amide linkage. This substitution can impart protease resistance in therapeutic peptides thereby increasing the serum half-life.
    Type: Grant
    Filed: September 9, 1993
    Date of Patent: November 8, 1994
    Assignee: Affymax Technologies, N.V.
    Inventor: David A. Campbell
  • Patent number: 5292875
    Abstract: A method for synthesizing sulfurized oligonucleotide analogs, such as phosphorothioate and phosphorodithioate analogs, is provided that employs a thiophosphorus compound, such as a thiophosphoric, dithiophosphoric, thiophosphinic, or dithiophosphinic acid disulfide or polysulfide, as a sulfurizing agent. The method of the invention may be used to sulfurize any phosphorous(III)containing intermediate. Preferably, the method is practiced on a commercial DNA synthesizer using phosophoramidite and/or phosphorthioamidite intermediates.
    Type: Grant
    Filed: August 27, 1993
    Date of Patent: March 8, 1994
    Assignee: Lynx Therapeutics, Inc.
    Inventors: Wojciech J. Stec, Bogdan Uznanski, B. John Bergot, Bernard L. Hirschbein, Karen L. Fearson
  • Patent number: 5290935
    Abstract: A process for producing phosphonate esters containing the 2-(pyridyl)ethyl group by reacting a vinylpyridine with a di- or trihydrocarbylphosphite in the presence of a selected silane, protic acid, or Lewis acid is disclosed. Also disclosed are novel silylphosphonate esters containing the 2-(pyridyl)ethyl group. All of the compounds produced herein are useful as catalysts for increasing the molecular weight of polyamides.
    Type: Grant
    Filed: July 29, 1993
    Date of Patent: March 1, 1994
    Assignee: E. I. Du Pont De Nemours and Company
    Inventors: David L. Thorn, Owen W. Webster, Robert C. Wheland
  • Patent number: 5264605
    Abstract: A process for preparing myoinositol polyphosphoric acid from myoinositol via a polyacylmyoinositol, a process for preparing a polysilyl-polyacylmyoinositol from a polyacylmyoinositol, and a process for preparing an optically active myoinositol polyphosphoric acid from the above product or a polysilylmyoinositol.
    Type: Grant
    Filed: February 20, 1991
    Date of Patent: November 23, 1993
    Assignee: Mitsui Toatsu Chemicals, Incorporated
    Inventors: Shoichiro Ozaki, Yutaka Watanabe
  • Patent number: 5171873
    Abstract: A process for the preparation of hydroxybenzylphosphonates of forula ##STR1## by reacting Mannich base of formula ##STR2## with as trialkyl phosphite of formula ##STR3## wherein R.sub.1 and R.sub.2 are each independently of the other C.sub.1 -C.sub.12 alkyl or, when taken together form a piperidinyl or morpholinyl radical, and R.sub.5, R.sub.6 and R.sub.7 are each independently of one another C.sub.1 -C.sub.4 alkyl, which reaction is carried out in the presence of a carboxylic anhydride (IV).The compounds of formula I may suitably be used as processing stabilizers for plastics.
    Type: Grant
    Filed: April 1, 1992
    Date of Patent: December 15, 1992
    Assignee: Ciba-Geigy Corporation
    Inventors: Thomas Kainmuller, Rudolf Maul
  • Patent number: 5157141
    Abstract: A process for the preparation of compounds of the general formula I ##STR1## in which R.sub.1 is hydrogen or methyl, R.sub.2 and R.sub.3 independently of one another are C.sub.1 -C.sub.18 alkyl, C.sub.5 -C.sub.8 cycloalkyl, phenyl, C.sub.7 -C.sub.9 phenylalkyl or halogen, R.sub.2 is additionally hydrogen and R.sub.7 and R.sub.8 independently of one another are C.sub.1 -C.sub.18 alkyl, phenyl or C.sub.7 -C.sub.18 alkylphenyl, which comprises reacting a phenol of the formula II ##STR2## in which R.sub.1 to R.sub.3 have the meaning described above, with formaldehyde or paraformaldehyde, an amine of the formula IIINR.sub.4 R.sub.5 R.sub.6 IIIin which R.sub.4 is C.sub.1 -C.sub.4 alkyl and R.sub.5 and R.sub.6 independently of one another are hydrogen or C.sub.1 -C.sub.4 alkyl, and a phosphite of the formula IV ##STR3## in which R.sub.7 and R.sub.8 have the meaning described above and R.sub.9 has the meaning given for R.sub.7 and R.sub.8, at a temperature of 0.degree.-200.degree. C.
    Type: Grant
    Filed: November 21, 1990
    Date of Patent: October 20, 1992
    Assignee: Ciba-Geigy Corporation
    Inventors: Paul Dubs, Werner Stegmann, Reto Luisoli, Roger Martin
  • Patent number: 5099056
    Abstract: A process for the production of N-substituted aminoethylphosphonic acid derivatives represented by the formula (I) is disclosed ##STR1## wherein R.sub.1 is an alkyl having 1-18 carbon atoms or a cycloolkyl having 3-18 carbon atoms and R.sub.2 is hydrogen, methyl or ethyl. This process comprises the steps of: reacting N-alkyl and N-cycloalkylhexahydro-s-triazine of formula ##STR2## with trialkylphosphites of formulaP(OR.sub.2).sub.3in the presence of titanium tetrahydrochloride at -20.degree.-10.degree. C. to yield N-substituted aminomethylphosphonic acid dialkylesters, followed by hydrolysis to yield N-substituted aminomethylphosphonic acid.
    Type: Grant
    Filed: July 31, 1990
    Date of Patent: March 24, 1992
    Assignee: Korea Institute of Science and Technology
    Inventors: Hyun-Joon Ha, Gong-Sil Nam
  • Patent number: 4774349
    Abstract: A process for the preparation of (meth)acrylamidomethylphosphonic acid diesters of formula I:H.sub.2 C.dbd.C(R.sub.1)--CO--N(R.sub.2)--CH.sub.2 --P(O)(OR.sub.3)(OR.sub.4) (I)is disclosed. In the above formula, R.sub.1 is a hydrogen atom or methyl group. R.sub.2 is a hydrogen atom, a C.sub.1 -C.sub.4 alkyl group (which can be substituted) or a C.sub.3 -C.sub.4 alkenyl group. R.sub.3 and R.sub.4 are each independently a phenyl group, or an alkyl group (which can be substituted) having 1-4 C atoms. Or R.sub.3 and R.sub.4 together form an alkylene group which forms a 5- or 7-membered ring with the oxygen atoms and the phosphorus atoms.The process is based on reacting a N-methylol derivative of (meth)acrylamide with a phosphorous acid triester, in which a N-methylol ether of a (meth)acrylamide is used. The reaction can be advantageously catalyzed by Lewis acids.
    Type: Grant
    Filed: October 14, 1986
    Date of Patent: September 27, 1988
    Assignee: Rohm GmbH Chemische Fabrik
    Inventors: Klaus Langerbeins, Werner Ude
  • Patent number: 4587362
    Abstract: A process is provided for the preparation of diaryl methylphosphonates through the reaction of triaryl phosphites with methanol in the presence of a catalytic quantity of methyl iodide. The reaction is conducted at a temperature of from about 170.degree. C. to about 250.degree. C. New and useful derivatives are produced by reaction of the diaryl methylphosphonates with polyols or amines.
    Type: Grant
    Filed: March 5, 1984
    Date of Patent: May 6, 1986
    Assignee: Stauffer Chemical Company
    Inventors: Milton L. Honig, Edward D. Weil