EP0453484A4 - Fluorinated phosphonic sulfonic acids and derivatives thereof - Google Patents

Fluorinated phosphonic sulfonic acids and derivatives thereof

Info

Publication number
EP0453484A4
EP0453484A4 EP19900902058 EP90902058A EP0453484A4 EP 0453484 A4 EP0453484 A4 EP 0453484A4 EP 19900902058 EP19900902058 EP 19900902058 EP 90902058 A EP90902058 A EP 90902058A EP 0453484 A4 EP0453484 A4 EP 0453484A4
Authority
EP
European Patent Office
Prior art keywords
reaction product
general formula
yield
represented
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP19900902058
Other languages
English (en)
French (fr)
Other versions
EP0453484A1 (en
Inventor
Donald J. Burton
Ramil Guneratne
Wenbiao Cen
Robert L. Kirchmeier
Anil S. Modak
William Anthony Sanderson
Jean'ne M. Shreeve
Debao Su
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GTI Energy
Original Assignee
Gas Research Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Gas Research Institute filed Critical Gas Research Institute
Publication of EP0453484A1 publication Critical patent/EP0453484A1/en
Publication of EP0453484A4 publication Critical patent/EP0453484A4/en
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
    • C07F9/4012—Esters of acyclic acids which can have further substituents on alkyl substituted by B, Si, P or a metal
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl

Definitions

  • the present invention relates to fluorinated organic compounds having at least one phosphono substituent and at least one sulfo substituent. These compounds are useful as an electrolyte in hydrocarbon/air fuel cell or as an additive to phosphoric acid electroytes in such fuel cells.
  • Multifunctional acids wherein one acid group comprises sulfonic acid and another acid group comprises phosphonic acid are known as useful esterification catalysts. See U.S. Patent 2,776,985. In all of the acid compounds disclosed in this patent, the sulfonic acid and the phosphonic acid moieties are covalently bound to an aryl group. Moreover, there is no indication that these compounds are contemplated as fluorinated derivatives.
  • the present invention provides compounds comprising one or more fluorine atoms, sulfo radicals and phosphono radicals, each such radical being bonded to the same or different carbon atom, with the proviso that at least one sulfo radical and at least one phosphono radical are bonded to such carbon atoms through the sulfur atom and the phosphorus atom, respectively.
  • These compounds are preferably non-polymeric, i.e. they have a molecular weight of about 5000 or less.
  • R is an organo radical having at least one covalent carbon-fluorine bond
  • R 1 is selected from the group consisting of alkali metals, cadmium, zinc and hydrogen
  • R 2 is a hydrocarbyl radical, having up to 20 carbon atoms, e.g. a lower alkyl radical or is hydrogen
  • r is 2 or 3
  • y is an integer of from 1 to 3
  • x is an integer of from 1 to 3, with the proviso that the phosphorus and the sulfur are covalently bonded to a carbon atom and when x is 1, then cadmium and zinc are 1/2.
  • the above fluorinated phosphono sulfo compounds may be prepared by reacting a first reactant represented by the general formula (R 4 0) 3 P with a second reactant represented by the general formula R 3 X 2 to yield a first reaction product represented by the general formula
  • R 4 may be a lower alkyl radical having up to six carbon atoms, e.g. methyl, ethyl, n- propyl or i-propyl, and preferably i-propyl or ethyl;
  • R 3 is an organo radical having at least one covalent fluorine bond;
  • X is bromine or iodine and
  • z is an integer of 2 or 3.
  • the first reaction product may be synthesized in high yield merely by combining the first and second reactant in a sealed vessel at a temperature of from -50°C to 200°C, e.g. from 0 to 120°C, i.e. conveniently from 0°C to about 25°C.
  • Reaction time may vary from 1 to 100 hours, e.g. 48 hours. Of course, increasing the reaction temperature can lower the reaction time to 2 to 10 hours, e.g. about 3 hours.
  • the reaction can be carried out neat or in the presence of an inert solvent.
  • an ether solvent may be used.
  • diethylether is useful as a solvent for this reaction.
  • the first reaction product is recovered by methods known in the art, e.g. distillation at a reduced pressure.
  • the first reaction product may be reacted with (R 5 ) 2 S 2°4' wherein R 5 is an alkali metal ion, e.g. a sodium ion, to yield a second reaction product represented by the general formula
  • reaction is conveniently carried out by combining the first reaction product and the above dithionite in a basic aqueous solution comprising, as a cosolvent, acetonitrile or the like.
  • the reaction may be effected at an elevated temperature of from 50 to 100°C, e.g. about 80°C, and a reaction time of from 1 to 20 hours, e.g. 2 to 12 hours.
  • the second reaction product may be recovered by evaporation of the excess solvent and purified by extraction with acetonitrile or a like solvent.
  • Suitable fluorinated organo radicals (R 3 ) for the above reaction scheme include alkylene radicals, both cyclic and acyclic radicals, which may be interrupted with hetero atoms such as nitrogen, oxygen and sulfur, alkenylene radicals, both cyclic and acyclic, which may also be interrupted with heteroatoms such as nitrogen, oxygen and sulfur, and arylene radicals, including heteroaryl, e.g. nitrogen, sulfur and oxygen-containing heteroarylene radicals, mono and poly arylene radicals, e.g. condensed arylene radicals having from 2 to 5 aryl rings, biphenyl, etc.
  • the above fluorinated organo radicals may comprise from one to about 100 carbon atoms, e.g.
  • radicals will comprise one or more covalently bonded fluorine and may be perfluorinated, i.e. all of the carbon bonds, other than the sulfur or phosphorus bonds, may be filled by fluorine radicals.
  • the above fluorinated organo radicals may also be substituted with inert substituents such as halo, nitro, amino, oxy, hydroxy, carboxy, thio, etc.
  • the fluorinated organo radicals will be either halo substituted or unsubstituted, i.e. all the carbon bonds other than the bonds to the fluoro, sulfo or phosphono radicals, as required by the, above general formula, will be filled by hydrogen radicals or halo radicals (other than fluoro radicals) .
  • fluorinated organo radicals are chloro or bromo-substituted or unsubstituted alkylene radicals having from 1 to 6 carbon atoms and chloro or bromo-substituted or unsubstituted arylene radicals having from 6 to 10 carbon atoms.
  • alkyleneoxyalkylene radicals wherein the alkylene moieties comprise from 2 to 4 carbon atoms.
  • lower alkylene radicals including alkyleneoxyalkylene radicals such as methylene, ethylene, propylene, butylene, methyleneoxymethylene, ethyleneoxyethylene, butyleneoxyethylene radicals, etc.
  • R 3 may be * ⁇ CF 2 , ⁇ CF, ⁇ CHF, ⁇ CFBr,
  • the second reaction product may be oxidized to yield a third reaction product having the general formula
  • H 2 0 2 or similar oxidizing agent may be provided in molar excess directly to the second reaction product or to an aqueous solution thereof.
  • a sufficient amount of a 30% aqueous H 2 0 solution may be combined with the second reaction product to provide an aqueous solution, H 2 0 2 comprising from 1.1 to 5 moles of per mole of the second reaction product, at a temperature of from 0° to 25°C and such aqueous solution allowed to react for 1 to 10 hours, e.g. about 4 to 5 hours.
  • the third reaction product is conveniently recovered by evaporation of the excess solvent. In this manner
  • ( R 4 O ) 2 P (O ) CHF ( S0 2 R 5 ) is reacted to (R 4 0) 2 P(0)CHF(S0 3 R 5 ) .
  • (R 4 0 ) P (0) CFBr ( SO3R 5 ) may be reduced to (R 0) 2 P(0)CHF(S0 3 R 5 ) by a reducing agent, for example metallic zinc, in a suitable inert solvent, for example tetrahydrofuran.
  • a reducing agent for example metallic zinc
  • a suitable inert solvent for example tetrahydrofuran.
  • Such reduction may be effected at an elevated temperature, e.g. about 60°C and a ratio of Zn to the bromo product of about 1 to about 2, e.g. about 1.1 and the reduced product recovered by extraction with water.
  • the third reaction product may be reacted, e.g. hydrolyzed, to yield the corresponding phosphonic acid.
  • the third reaction product may be hydrolyzed in an aqueous solution of a strong acid, e.g. concentrated hydrochloric acid, wherein said hydrolysis is effected at an elevated temperature, e.g. at reflux, in the presence of excess strong acid, e.g. from about 1.1 to 10 moles, i.e. 3 moles of strong acid per equivalent of R 4 .
  • a strong acid e.g. concentrated hydrochloric acid
  • excess strong acid e.g. from about 1.1 to 10 moles, i.e. 3 moles of strong acid per equivalent of R 4 .
  • the hydrolysis product or the fourth reaction product may be recovered by evaporation of excess solvent.
  • the fourth reaction product may be further reacted to exchange hydrogen ions for R 5 .
  • the fourth reaction product may be passed through an ion exchange column, e.g. a strong acid such as an acidified sulfonated polystyrene resin such as Amberlite 1R-120 to exchange hydrogen ions for the alkali ions.
  • a strong acid such as an acidified sulfonated polystyrene resin such as Amberlite 1R-120 to exchange hydrogen ions for the alkali ions.
  • R 5 may be Cd or Zn, (represented by M, below) may be prepared according to the following scheme:
  • Step (1) is carried out as described above.
  • Step (2) may be carried out by dissolving or suspending the reactants in an anhydrous solvent, e.g. dimethylformamide (DMF) under nonoxidizing conditions, i.e. N 2 atmosphere, and agitating while allowing the reaction to occur.
  • an anhydrous solvent e.g. dimethylformamide (DMF)
  • Step (3) may thus be effected.
  • the remaining reaction product may be recovered by washing with water and filtering. Recrystallization from hot isopropanol yields the product of Step (3) .
  • Step (4) may also be carried out as described above.
  • the resulting reaction product of Step (4) may be converted into an alkali salt by reaction with the appropriate aqueous alkali solution, e.g. an aqueous NaOH solution, and the metal, M, removed as an insoluble hydroxide, M(OH) .
  • sulfate ion contamination may be removed by reacting an aqueous solution thereof with an excess of barium ions to precipitate barium sulfate.
  • the filtrate, comprising the acid-exchanged reaction product and sodium and barium ions is then passed through the acid form of an ion exchange column, to remove such ions and a purified solution of such acid-exchanged reaction product is recovered.
  • phosphate contaminants can also be removed as an insoluble product.
  • the acid-exchanged reaction product may be converted to the corresponding phosphonylsulfonyl chloride by reaction with sufficient PC1 5 to yield such phosphonylsulfonyl chloride which can be recovered by distillation.
  • Any or all of the sulfonic acid and phosphonic acid moieties of the acid-exchanged reaction product may be converted into the corresponding acid chloride by reaction with an amount of PCI5 equivalent to from 1 to all of the acid moieties in the acid-exchanged reaction product.
  • reaction scheme utilizes a monophosphono reactant.
  • Compounds within the scope of the present invention, wherein polyphosphono functionality are desired, e.g. wherein y is 2 or 3, may be prepared by reacting supra molar amounts of (R 4 0) 3 P with R 3 X Z wherein z is from 3 to 6 and proceeding according to the above illustrative reaction scheme.
  • An alternate method for making certain of the fluorinated phosphonosulfo compounds of the present invention comprises reacting a first reactant having the general formula
  • the first reactant may be prepared by reacting
  • CF 2 CF 2 in the presence of KF and IC1
  • the second reaction product may be treated as described above to yield the corresponding third and fourth reaction product, as well as the hydrogen ion- exchanged reaction product.
  • fluorinated phosphonosulfo compounds of this invention may be prepared according to the following scheme: (R 2 0) 2 P(0)CF 2 Br + Na 2 S0 3
  • CF 2 may be any other fluorinated organo radical disclosed, herein. That is, CF 2 may be R as defined above.
  • This reaction is effected in water or aqueous ethanol at reflux and provides a third reaction product which can be subsequently treated as described above.
  • the fluorinated phosphonosulfono compounds of the present invention may be utilized as electrolytes, e.g. in fuel cells, in the same manner as perfluorosulfonic acids are now used. See for example. Fuel Cell Reactions in Super Acid Electrolytes. (Annual Rept. 1 June '82 - 31 May 83) . Prepared in cooperation with Brookhaven National Lab. , Upton, New York; Fuel Cell Reactions in Super Acid Electrolytes. Final Report June 1982 - December 1985, sponsored by Gas Research Inst. , Chicago, IL. and New Catalysts and New Electrolytes for Acid Fuel Cells 188. Meeting of the American Chemical Society, Philadelphia, PA, USA, 26 August 1984, all available from NTIS and hereby incorporated in their entirety by this reference.
  • Example 1(e) containing sulfate ions, was dissolved in water and an aqueous BaCl 2 solution was added thereto with stirring, until an excess was present, i.e. until additions caused no further precipitation of BaS0 . After centrifugation, a supernatant was decanted, concentrated, and passed through a 4.5cm by 50 cm packed column of DOWEX M-31 (Dow Chemical Company) , a styrenesulfonic acid resin, to recover an eluate containing no detectable sulfate.
  • DOWEX M-31 DOWEX M-31
  • Ba(0H) 2 may be used in place of BaCl 2 to obtain a similarly purified solution. Moreover, if the pH of said purification was adjusted to 11 or greater, by addition of Ba(0H) 2 , the inorganic phosphate ion was reduced to a level undetectable by 31 P NMR.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fuel Cell (AREA)
EP19900902058 1989-01-03 1990-01-03 Fluorinated phosphonic sulfonic acids and derivatives thereof Ceased EP0453484A4 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US29039489A 1989-01-03 1989-01-03
US290394 1989-01-03

Publications (2)

Publication Number Publication Date
EP0453484A1 EP0453484A1 (en) 1991-10-30
EP0453484A4 true EP0453484A4 (en) 1991-12-11

Family

ID=23115797

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900902058 Ceased EP0453484A4 (en) 1989-01-03 1990-01-03 Fluorinated phosphonic sulfonic acids and derivatives thereof

Country Status (6)

Country Link
EP (1) EP0453484A4 (ko)
JP (1) JPH02184693A (ko)
KR (1) KR900011782A (ko)
AU (1) AU4842190A (ko)
CA (1) CA2045151A1 (ko)
WO (1) WO1990007513A1 (ko)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK167946B1 (da) * 1991-06-28 1994-01-03 Topsoe Haldor As Fosforsyrebraendelsescelle med forbedret elektrisk effektivitet
DK0642518T3 (da) * 1992-05-29 1998-12-14 Procter & Gamble Pharma Phosphonosulfonat-forbindelser til behandling af abnormt calcium- og phosphatstofskifte
US5731299A (en) * 1992-05-29 1998-03-24 The Procter & Gamble Company Phosphonosulfonate compounds, pharmaceutical compositions, and methods for treating abnormal calcium and phosphate metabolism
NZ248852A (en) * 1992-10-28 1997-06-24 Squibb & Sons Inc Alpha-phosphono and phosphinosulphonates and medicaments thereof
US5470845A (en) * 1992-10-28 1995-11-28 Bristol-Myers Squibb Company Methods of using α-phosphonosulfonate squalene synthetase inhibitors including the treatment of atherosclerosis and hypercholesterolemia
US5447922A (en) * 1994-08-24 1995-09-05 Bristol-Myers Squibb Company α-phosphonosulfinic squalene synthetase inhibitors
CN103875117B (zh) * 2011-10-21 2016-08-17 三井化学株式会社 含有膦酰基磺酸化合物的非水电解液及锂二次电池
JP6629529B2 (ja) * 2015-06-19 2020-01-15 旭化成株式会社 含フッ素エーテルの製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
INORGANIC CHEMISTRY, vol. 25, no. 18, 27th August 1986, pages 3128-3131, American Chemical Society; T. MAHMOOD et al.: "New perfluoroalkylphosphonic and bis(perfluoroalkyl)phosphinic acids and their precursors" *
See also references of WO9007513A1 *

Also Published As

Publication number Publication date
AU4842190A (en) 1990-08-01
JPH02184693A (ja) 1990-07-19
KR900011782A (ko) 1990-08-02
CA2045151A1 (en) 1990-07-04
WO1990007513A1 (en) 1990-07-12
EP0453484A1 (en) 1991-10-30

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