WO2001087900A1 - Phosphonium salts - Google Patents

Phosphonium salts Download PDF

Info

Publication number
WO2001087900A1
WO2001087900A1 PCT/US2001/012780 US0112780W WO0187900A1 WO 2001087900 A1 WO2001087900 A1 WO 2001087900A1 US 0112780 W US0112780 W US 0112780W WO 0187900 A1 WO0187900 A1 WO 0187900A1
Authority
WO
WIPO (PCT)
Prior art keywords
phosphonium
salt according
salt
salts
groups
Prior art date
Application number
PCT/US2001/012780
Other languages
French (fr)
Inventor
Allan James Robertson
Original Assignee
Cytec Technology Corp.
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 Cytec Technology Corp. filed Critical Cytec Technology Corp.
Priority to EP01928671A priority Critical patent/EP1287007A1/en
Priority to AU2001255504A priority patent/AU2001255504A1/en
Publication of WO2001087900A1 publication Critical patent/WO2001087900A1/en

Links

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
    • C07F9/54—Quaternary phosphonium compounds
    • C07F9/5407—Acyclic saturated phosphonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
    • C07C309/30—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings of six-membered aromatic rings substituted by alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/46—Friedel-Crafts reactions

Definitions

  • This invention relates to phosphonium salts and particularly to such salts in the form of ionic liquids.
  • Ionic liquids are salts that are liquid over a broad range of temperatures. Ionic liquids are useful for many purposes, including as catalysts, solvents, and electrolytes (for a general review, see Olivier, H. (1998), “Nonaqueous Ionic Liquids (NAILs)", in Aqueous Phase Organometallic Catalysis Concepts and Applications, eiley-VCH, Chapter 7.3, pp. 554-563) .
  • Known ionic liquids are generally nitrogen-based systems. For example, U.S. Patent No.
  • compositions comprising mixtures of a metal halide, such as aluminum trichloride (AICI3) , and an alkyl-containing amine hydrohalide salt, such as trimethylamine hydrochloride salt ((01-13)3 NH + C1 ⁇ ) to form an ionic liquid, such as (CH3) 3NH + Al2 ⁇ l7N Pyridiniu salts are described by Chum et al ( J. Am . Chem . Soc . , 97, 3264 (1975)).
  • AICI3 aluminum trichloride
  • alkyl-containing amine hydrohalide salt such as trimethylamine hydrochloride salt ((01-13)3 NH + C1 ⁇ )
  • ionic liquids include l-ethyl-3- methylimidazolium tetrachloroaluminate and 1-butylpyridinium nitrate (Chemical & Engineering News, March 30, 1998, pages 32 to 37), and dialkylimidazolium chloroaluminates ( ilkes, J.S. et al. "Dialkylimidazolium chloroaluminate melts: A New Class of Room-Temperature Ionic Liquids for Eletrochemistry, Spectroscopy, and Synthesis" Inorg. Chem . , 21, 1263-1264 (1982) ) .
  • Phosphonium salts have been previously described.
  • U.S. Patent No. 5,310,853, (May 10, 1994; Pham et al) describes phosphonium catalysts for use in fast cures of epoxy resins.
  • the phosphonium salts of the examples are not ionic liquids.
  • the invention provides a phosphonium salt of formula I:
  • R1, R2, R3, and R 4 each independently represents a c l-20 hydrocarbyl group, provided that (i) Rl, R2, R3, and R 4 are not all the same; and (ii) no more than two of R 1 , R 2 , R 3 , and R 4 are aryl, and
  • X " is an anion, excluding halide.
  • R 1 , R2, R3, R , and X " are preferably chosen to obtain low melting salts. If the salt is to be used as a polar solvent for an organic reaction, then there should be chosen a salt whose melting point is below the temperature at which the reaction is to be carried out.
  • the phosphonium salt of the invention is a liquid below 100°C, more preferably a liquid below 50°C, most preferably a liquid below 35°C.
  • the melting point of the phosphonium salt depends mostly upon the particular hydrocarbyl groups that are attached to the phosphorus atom. For instance, a higher number of carbon atoms present tends to result in a lower melting product. Branching also tends to result in a lower melting product, so it is preferred that alkyl groups are branched, for example, ⁇ -branched or ⁇ -branched. Steric considerations may limit this, for instance, and may prohibit salts in which all of R! to R 4 are ⁇ -branched. Branching is especially preferred when the anion is a tosylate. Choosing R ⁇ , R-2, R3 an d R4 such that they are not all the same also tends to lower the melting point of the salt.
  • the hydrocarbyl groups R! to R 4 are preferably alkyl groups but they may be, or contain, aryl groups such as phenyl, tolyl, or naphthyl groups. They may be alicyclic groups such as cyclopentyl or cyclohexyl groups. They are preferably free of ethylenic unsaturation. Further, the hydrocarbyl groups may be substituted. Suitable substituents include hydroxyl and halides .
  • the hydrocarbyl groups can be interrupted by heteroatoms that do not interfere with the utility of the phosphonium salts, or the carbon chain can bear non-interfering substituents. Which heteroatoms or which substituents interfere, of course, depends on the intended utility of the phosphonium salt and will therefore vary from case to case. Oxygen is mentioned as a heteroatom that can be present in a carbon chain.
  • R3, and R 4 is chosen with many factors in mind but is usually 7 to 30, preferably 22 to 26 and more preferably 24.
  • one of R 1 , R 2 , R3, and R 4 is a Cg_20 alkyl group, more preferably a C]_Q-16 alkyl group.
  • At least one of R! to R 4 is a long chain alkyl group containing a straight chain of at least 14 carbon atoms.
  • X is tosylate
  • at least one of R ⁇ is tosylate
  • R2, R , and R 4 is a branched alkyl group, and two, three, or all four can be branched.
  • Partially fluorinated ethers are one class of R groups which can be particularly useful in certain applications. Phosphonium salts comprising one or more of such R groups tend to have high densities (for example, 1.3 to 1.5), making them well suited for phase separation.
  • the partially fluorinated ethers may also be further substituted.
  • An example of a partially fluorinated ether is - (CH2) m -0-CH2 (CF2) n CF 3 wherein n represents a number from 0 to 9, preferably 4, 6, or 8, and m represents a number from 1 to 6, preferably 3.
  • R groups include hydroxyalkyl groups, such as 3-hydroxypropyl .
  • the miscibility of the phosphonium salts with organic compounds can be extensively varied, particularly by altering the chain lengths of the R groups.
  • This feature can be quite useful in carrying out a chemical reaction.
  • the salt may be selected because it is miscible with a product of the reaction at elevated temperature but immiscible at a lower temperature.
  • the reaction mixture upon termination of the reaction, can be cooled to the lower temperature to result in two liquid phases and the product phase simply decanted off. This lower temperature is preferably ambient temperature.
  • the salt is miscible with the product at the lower temperature
  • one possibility to separate the product from the salt is to boil off the product, leaving the solvent ready 'to be used again.
  • the longer the hydrocarbyl groups are the greater the miscibility with organic reactants and products. With shorter hydrocarbyl groups, the product and/or reactant may become miscible with the phosphonium salt upon heating.
  • the phosphonium salt can be selected with the required properties as a solvent in ' mind.
  • the phosphonium salts display a high degree of flexibility that assists in selecting particular properties of the salt, such as the melting point. This contrasts, for instance, with the known imidazolium salts mentioned above, which have only two groups that can be varied. It also contrasts with ammonium salts. Although ammonium salts bear four groups attached to one nitrogen atom, in practice the ammonium salts are made from tertiary- amine precursors, and it is difficult to make mixed tertiary amines. Hence the ammonium salts that are practically available are confined to those which have three identical and one different group attached to the nitrogen atom, so their flexibility is limited.
  • Tertiary phosphines can be prepared by reacting phosphine with an olefin or a mixture of olefins. For example, if phosphine is reacted with a mixture of hexene and octene there is obtained a mixture of four tertiary phosphines, namely, trihexyl, trioctyl, dihexyloctyl and dioctylhexyl phosphines. This provides additional flexibility in tailoring the tertiary phosphine and, subsequently, the phosphonium salt to have particular selected properties.
  • Suitable anions, X include phosphate, nitrate, hexafluorophosphate * (PFg-, SbFg-) , tetrafluoroborate, (BF4 ⁇ ) tetrachloroaluminate (AIC4 "" ) , Al2Cl7 ⁇ , carboxylates, and sulfonates.
  • sulfonates include tosylate, esylate, benzenesulfonate, and triflate.
  • carboxylates include acetate, propionate, and trifluoroethanoate.
  • Preferred anions are sulfonates, tetrafluoroborate, hexafluorophosphate, SbFg-, AICI4- and AI2CI7-. Especially preferred are tosylate, tetrafluoroborate, and hexafluorophosphate .
  • the anion, X also affects the properties of the phosphonium salt, including the melting point. Many anions are available but the required properties of the phosphonium salt should be borne in mind when selecting the anion.
  • liquid phosphonium salts there are mentioned triisobutylmethylphosphonium tosylate and diisobutyl- n-octylmethylphosphonium tosylate, both of which are liquids at room temperature.
  • the compound tri-n-butylmethyl-phosphonium tosylate is a high melting solid.
  • the distinction in melting point between the tri-n-butyl compound and the corresponding triisobutyl compound is a clear demonstration of the effect of branching on the melting point of the compound.
  • Ionic liquids of the invention are also suitably formed from mixtures of phosphonium salts of formula I.
  • the phosphonium sulfonates of the invention can readily be prepared by reacting a tertiary phosphine R!R2R P with a sulfonate ester R 4 X, where R ⁇ , R 2 , R and R 4 are as defined above, and X is a sulfonate.
  • R 4 X a sulfonate ester
  • a mixture of different tertiary phosphines can be used. The reaction proceeds readily at elevated temperature, say 60 to 100°C, and is often complete in about 4 to 5 hours.
  • phosphonium tosylates are readily prepared by heating a tertiary phosphine with a tosylate ester, suitably a lower alkyl tosylate ester, to form a phosphonium tosylate.
  • a tertiary phosphine R!R2R3P with an alkyl halide under conditions similar to those given above for tosylates.
  • a phosphonium chloride by reaction of a tertiary phosphine with a lower alkyl chloride.
  • Phosphonium hexafluorophosphates and tetrafluoroborates are typically prepared through an anion exchange process from a halide salt such as the chloride or bromide salt.
  • the phosphonium halide by anion exchange, to the desired phosphonium salt.
  • an anion exchange is done with the corresponding phosphonium chloride and hexafluorophosphoric acid, e.g. in a 60% aqueous solution in water as solvent, or sodium tetrafluoroborate in acetone as solvent.
  • the corresponding phosphonium chloride is mixed with sodium hyroxide in methanol. Sodium chloride falls out of solution.
  • the resulting phosphonium hydroxide is mixed with the acid corresponding to the desired salt (i.e. a carboxylic acid is used to form a phosphonium carboxylate) to obtain the desired product.
  • a phosphine is mixed with trichloroaluminum.
  • halide ions such as chloride ions coordinate with group VIII metals such as palladium and platinum. If the phosphonium salt is to be used as a solvent for a reaction that is catalysed by a palladium or platinum catalyst the phosphonium salt must be totally free of halide anion. Sulfonates would be preferred in such cases.
  • Halide ions do not coordinate with nickel, so if the phosphonium salt is to be used as a solvent for a nickel- catalysed reaction it is acceptable that trace levels of halide ion remain.
  • the phosphonium salts of the invention are very thermally stable. They have extremely low vapour pressure and may decompose rather than boil. The temperature at which this occurs will vary from compound to compound, but substantially all are stable up to about 200°C, many are stable up to about 300°C and some are stable even up to about 450°C. These properties render them useful for many purposes, but particularly for use as a solvent for various reactions including carbonylation, hydrogenation, hydroformylation, olefin dimerization, olefin oligomerization, olefin polymerization, acylation, alkylation, reduction and oxidation reactions.
  • reaction of carbon monoxide, ethylene and methanol or ethanol in the presence of a palladium catalyst to form methyl acetate or ethyl acetate, respectively can be carried out in a phosphonium salt of the invention as solvent, and the product ester distilled off thereafter.
  • Example 1 The invention is further illustrated in the following examples .
  • Example 1 The invention is further illustrated in the following examples .
  • Example 1
  • the triisobutylethylphosphonium tosylate product was a solid (mp 28-29°C) but it could be supercooled and thus remain a liquid at 10-12°C. Above 30°C, it was a viscous liquid and its viscosity decreased rapidly with increasing temperature. It was more dense than water (approximately 1.06 g/cc at 30°C) .
  • Example 1 The procedure of Example 1 was followed, except that methyl tosylate was used in place of ethyl tosylate.
  • the triisobutylmethylphosphonium tosylate product that was obtained from the vacuum stripping was a viscous liquid at room temperature but its viscosity decreased rapidly with increasing temperature. Its density was approximately 1.065/cc at 30°C. Examples 3 to 12
  • Alkylphosphonium tosylates listed in Table 1 were synthesized in a manner similar to that described for Examples 1 and 2.
  • the phosphonium salts were prepared from a mixture of phosphines (R!R 2 R P) , wherein R1, R 2 , and R3 are each hexyl or octyl.
  • Example 21 was provided for the purpose of comparison.
  • the phosphonium salts were prepared from a mixture of phosphines (R ⁇ R 2 R 3 P), wherein R 1 , R 2 , and R 3 are each one of the two components listed.
  • the final conditions were 140°C at 0.3 mmHg pressure.
  • the product was slightly viscous pale yellow oil which had a melting point of 30°C.
  • the chloride content was 0.16%. This represents approximately 98% conversion of the chloride to tetrafluoroborate.
  • Alkylphosphonium tetrafluoroborates listed in Table 3 were synthesized in a manner similar to that described for Example 22.
  • the phosphonium salts were prepared from a mixture of phosphines (R ⁇ R 2 R ⁇ P), wherein R1 , R 2 , and R 3 are each butyl or hexyl.
  • the miscibility of phosphonium iodides with dodecane as a function of number of carbons in a series of phosphonium iodides was determined. While phosphonium iodides are not part of the claimed invention, this example is provided here to demonstrate how miscibility may be affected by carbon number for phosphonium salts.
  • the first column of Table 4 identifies the tertiary phosphine, most of which have R groups which are a mixture of different lengths. Column 2 identifies the alkyl iodide with which the tertiary phosphine has been reacted to form a phosphonium iodide.
  • the phosphonium salts were prepared from a mixture of phosphines (R-*- R 2 R3p) , wherein Rl, R 2 , and R are each one of the two components listed. 2 At Room Temperature

Landscapes

  • 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)
  • Chemical Kinetics & Catalysis (AREA)

Abstract

The invention provides a phosphonium salt of formula I wherein R?1, R2, R3, and R4¿ are C¿1-20? hydrocarbyl groups and X is an anion, except halide, provided that (i) R?1, R2, R3, and R4¿ are not all the same; and (ii) not more than two of R?1, R2, R3, and R4¿ are aryl. Such phosphonium salts may be useful as catalysts, solvents, and electrolytes.

Description

Phosphonium Salts
Field of the Invention
This invention relates to phosphonium salts and particularly to such salts in the form of ionic liquids.
Background of the Invention
Ionic liquids are salts that are liquid over a broad range of temperatures. Ionic liquids are useful for many purposes, including as catalysts, solvents, and electrolytes (for a general review, see Olivier, H. (1998), "Nonaqueous Ionic Liquids (NAILs)", in Aqueous Phase Organometallic Catalysis Concepts and Applications, eiley-VCH, Chapter 7.3, pp. 554-563) . Known ionic liquids are generally nitrogen-based systems. For example, U.S. Patent No. 5,731,101 (March 24, 1998; Sherif et al.) describes compositions comprising mixtures of a metal halide, such as aluminum trichloride (AICI3) , and an alkyl-containing amine hydrohalide salt, such as trimethylamine hydrochloride salt ((01-13)3 NH+C1~) to form an ionic liquid, such as (CH3) 3NH+Al2θl7N Pyridiniu salts are described by Chum et al ( J. Am . Chem . Soc . , 97, 3264 (1975)).
Other examples of ionic liquids include l-ethyl-3- methylimidazolium tetrachloroaluminate and 1-butylpyridinium nitrate (Chemical & Engineering News, March 30, 1998, pages 32 to 37), and dialkylimidazolium chloroaluminates ( ilkes, J.S. et al. "Dialkylimidazolium chloroaluminate melts: A New Class of Room-Temperature Ionic Liquids for Eletrochemistry, Spectroscopy, and Synthesis" Inorg. Chem . , 21, 1263-1264 (1982) ) .
Phosphonium salts have been previously described. For example, U.S. Patent No. 5,310,853, (May 10, 1994; Pham et al) describes phosphonium catalysts for use in fast cures of epoxy resins. However, the phosphonium salts of the examples are not ionic liquids.
Summary of the Invention
In one aspect, the invention provides a phosphonium salt of formula I:
R1R2R3R4 P+X" I
wherein
R1, R2, R3, and R4 each independently represents a cl-20 hydrocarbyl group, provided that (i) Rl, R2, R3, and R4 are not all the same; and (ii) no more than two of R1, R2, R3, and R4 are aryl, and
X" is an anion, excluding halide.
Description of the Preferred Embodiments of the Invention
R1, R2, R3, R , and X" are preferably chosen to obtain low melting salts. If the salt is to be used as a polar solvent for an organic reaction, then there should be chosen a salt whose melting point is below the temperature at which the reaction is to be carried out.
In general it is preferred that the phosphonium salt of the invention is a liquid below 100°C, more preferably a liquid below 50°C, most preferably a liquid below 35°C.
The melting point of the phosphonium salt depends mostly upon the particular hydrocarbyl groups that are attached to the phosphorus atom. For instance, a higher number of carbon atoms present tends to result in a lower melting product. Branching also tends to result in a lower melting product, so it is preferred that alkyl groups are branched, for example, α-branched or β-branched. Steric considerations may limit this, for instance, and may prohibit salts in which all of R! to R4 are α-branched. Branching is especially preferred when the anion is a tosylate. Choosing R^, R-2, R3 and R4 such that they are not all the same also tends to lower the melting point of the salt.
The hydrocarbyl groups R! to R4 are preferably alkyl groups but they may be, or contain, aryl groups such as phenyl, tolyl, or naphthyl groups. They may be alicyclic groups such as cyclopentyl or cyclohexyl groups. They are preferably free of ethylenic unsaturation. Further, the hydrocarbyl groups may be substituted. Suitable substituents include hydroxyl and halides .
The hydrocarbyl groups can be interrupted by heteroatoms that do not interfere with the utility of the phosphonium salts, or the carbon chain can bear non-interfering substituents. Which heteroatoms or which substituents interfere, of course, depends on the intended utility of the phosphonium salt and will therefore vary from case to case. Oxygen is mentioned as a heteroatom that can be present in a carbon chain.
The total number of carbon atoms present in R^, R2,
R3, and R4 is chosen with many factors in mind but is usually 7 to 30, preferably 22 to 26 and more preferably 24.
Preferably, one of R1, R2, R3, and R4 is a Cg_20 alkyl group, more preferably a C]_Q-16 alkyl group.
For some purposes, it is desirable that at least one of R! to R4 is a long chain alkyl group containing a straight chain of at least 14 carbon atoms. Preferably, when X is tosylate, at least one of R^,
R2, R , and R4 is a branched alkyl group, and two, three, or all four can be branched.
Partially fluorinated ethers are one class of R groups which can be particularly useful in certain applications. Phosphonium salts comprising one or more of such R groups tend to have high densities (for example, 1.3 to 1.5), making them well suited for phase separation. The partially fluorinated ethers may also be further substituted. An example of a partially fluorinated ether is - (CH2)m-0-CH2 (CF2) n CF3 wherein n represents a number from 0 to 9, preferably 4, 6, or 8, and m represents a number from 1 to 6, preferably 3.
Other specific examples of suitable R groups include hydroxyalkyl groups, such as 3-hydroxypropyl .
As well as a being able to vary the melting points of the phosphonium salts of the invention to suit various purposes, the miscibility of the phosphonium salts with organic compounds can be extensively varied, particularly by altering the chain lengths of the R groups. This feature can be quite useful in carrying out a chemical reaction. For instance, in a reaction where the salt is used as a polar solvent, the salt may be selected because it is miscible with a product of the reaction at elevated temperature but immiscible at a lower temperature. In this example, upon termination of the reaction, the reaction mixture can be cooled to the lower temperature to result in two liquid phases and the product phase simply decanted off. This lower temperature is preferably ambient temperature. Alternatively, if the salt is miscible with the product at the lower temperature, one possibility to separate the product from the salt is to boil off the product, leaving the solvent ready 'to be used again. In general, the longer the hydrocarbyl groups are, the greater the miscibility with organic reactants and products. With shorter hydrocarbyl groups, the product and/or reactant may become miscible with the phosphonium salt upon heating.
The phosphonium salt can be selected with the required properties as a solvent in' mind.
As there are four groups, R***-, R2, R3 and R4, that can be varied, the phosphonium salts display a high degree of flexibility that assists in selecting particular properties of the salt, such as the melting point. This contrasts, for instance, with the known imidazolium salts mentioned above, which have only two groups that can be varied. It also contrasts with ammonium salts. Although ammonium salts bear four groups attached to one nitrogen atom, in practice the ammonium salts are made from tertiary- amine precursors, and it is difficult to make mixed tertiary amines. Hence the ammonium salts that are practically available are confined to those which have three identical and one different group attached to the nitrogen atom, so their flexibility is limited.
It is not difficult to prepare phosphonium salts bearing different groups, giving a higher degree of flexibility. Tertiary phosphines can be prepared by reacting phosphine with an olefin or a mixture of olefins. For example, if phosphine is reacted with a mixture of hexene and octene there is obtained a mixture of four tertiary phosphines, namely, trihexyl, trioctyl, dihexyloctyl and dioctylhexyl phosphines. This provides additional flexibility in tailoring the tertiary phosphine and, subsequently, the phosphonium salt to have particular selected properties.
Suitable anions, X, include phosphate, nitrate, hexafluorophosphate* (PFg-, SbFg-) , tetrafluoroborate, (BF4~) tetrachloroaluminate (AIC4"") , Al2Cl7~, carboxylates, and sulfonates. Examples of sulfonates include tosylate, esylate, benzenesulfonate, and triflate. Examples of carboxylates include acetate, propionate, and trifluoroethanoate. Preferred anions are sulfonates, tetrafluoroborate, hexafluorophosphate, SbFg-, AICI4- and AI2CI7-. Especially preferred are tosylate, tetrafluoroborate, and hexafluorophosphate .
The anion, X, also affects the properties of the phosphonium salt, including the melting point. Many anions are available but the required properties of the phosphonium salt should be borne in mind when selecting the anion.
As examples of liquid phosphonium salts there are mentioned triisobutylmethylphosphonium tosylate and diisobutyl- n-octylmethylphosphonium tosylate, both of which are liquids at room temperature. The compound tri-n-butylmethyl-phosphonium tosylate is a high melting solid. The distinction in melting point between the tri-n-butyl compound and the corresponding triisobutyl compound is a clear demonstration of the effect of branching on the melting point of the compound.
Ionic liquids of the invention are also suitably formed from mixtures of phosphonium salts of formula I.
The phosphonium sulfonates of the invention can readily be prepared by reacting a tertiary phosphine R!R2R P with a sulfonate ester R4X, where R^, R2, R and R4 are as defined above, and X is a sulfonate. A mixture of different tertiary phosphines can be used. The reaction proceeds readily at elevated temperature, say 60 to 100°C, and is often complete in about 4 to 5 hours. For instance, phosphonium tosylates are readily prepared by heating a tertiary phosphine with a tosylate ester, suitably a lower alkyl tosylate ester, to form a phosphonium tosylate. In cases where the anion is other than a sulfonate, it is convenient to first prepare the corresponding halide salt, by combining a tertiary phosphine R!R2R3P with an alkyl halide under conditions similar to those given above for tosylates. For instance, there may readily be prepared a phosphonium chloride, by reaction of a tertiary phosphine with a lower alkyl chloride.
Phosphonium hexafluorophosphates and tetrafluoroborates are typically prepared through an anion exchange process from a halide salt such as the chloride or bromide salt.
In some instances it is convenient to then convert the phosphonium halide, by anion exchange, to the desired phosphonium salt. For instance, to prepare phosphonium hexafluorophosphate or tetrafluoroborate from the phosphonium chloride, an anion exchange is done with the corresponding phosphonium chloride and hexafluorophosphoric acid, e.g. in a 60% aqueous solution in water as solvent, or sodium tetrafluoroborate in acetone as solvent. To make the carboxylate, phosphate, sulfate, nitrate, or acetate salts, the corresponding phosphonium chloride is mixed with sodium hyroxide in methanol. Sodium chloride falls out of solution. The resulting phosphonium hydroxide is mixed with the acid corresponding to the desired salt (i.e. a carboxylic acid is used to form a phosphonium carboxylate) to obtain the desired product.
To form the tetrachloroaluminate, a phosphine is mixed with trichloroaluminum.
Trace levels of halide ion usually remain in the phosphonium salt when converting a phosphonium halide to another salt. If such converted salts are to be used in an environment where halide ions are unacceptable, even at low levels, phosphonium halides should not be used as starting materials, or a process must be used which ensures complete removal of halide ions. For instance, halide ions such as chloride ions coordinate with group VIII metals such as palladium and platinum. If the phosphonium salt is to be used as a solvent for a reaction that is catalysed by a palladium or platinum catalyst the phosphonium salt must be totally free of halide anion. Sulfonates would be preferred in such cases. Halide ions do not coordinate with nickel, so if the phosphonium salt is to be used as a solvent for a nickel- catalysed reaction it is acceptable that trace levels of halide ion remain.
The phosphonium salts of the invention are very thermally stable. They have extremely low vapour pressure and may decompose rather than boil. The temperature at which this occurs will vary from compound to compound, but substantially all are stable up to about 200°C, many are stable up to about 300°C and some are stable even up to about 450°C. These properties render them useful for many purposes, but particularly for use as a solvent for various reactions including carbonylation, hydrogenation, hydroformylation, olefin dimerization, olefin oligomerization, olefin polymerization, acylation, alkylation, reduction and oxidation reactions. For instance the reaction of carbon monoxide, ethylene and methanol or ethanol in the presence of a palladium catalyst to form methyl acetate or ethyl acetate, respectively, can be carried out in a phosphonium salt of the invention as solvent, and the product ester distilled off thereafter.
The invention is further illustrated in the following examples . Example 1
Preparation of triisobutylethylphosphonium tosylate: An inerted reactor was charged with ethyl tosylate. After heating the tosylate ester to 100-110°C, a 2-3% molar excess of triisobutylphosphine was added slowly over 1-2 hours. The reaction was exothermic and the temperature of the reaction was controlled by regulating the addition rate and by removing the source of heat. After a two hour digestion period the mixture was cooled to 50 °C at which point enough dilute aqueous hydrogen peroxide was added to convert the excess triisobutylphosphine (less than 0.5%) to the corresponding phosphine oxide. The product mixture was then vacuum stripped to remove the water. The triisobutylethylphosphonium tosylate product was a solid (mp 28-29°C) but it could be supercooled and thus remain a liquid at 10-12°C. Above 30°C, it was a viscous liquid and its viscosity decreased rapidly with increasing temperature. It was more dense than water (approximately 1.06 g/cc at 30°C) .
Example 2
Preparation of triisobutylmethylphosphonium tosylate:
The procedure of Example 1 was followed, except that methyl tosylate was used in place of ethyl tosylate. The triisobutylmethylphosphonium tosylate product that was obtained from the vacuum stripping was a viscous liquid at room temperature but its viscosity decreased rapidly with increasing temperature. Its density was approximately 1.065/cc at 30°C. Examples 3 to 12
Alkylphosphonium tosylates listed in Table 1 were synthesized in a manner similar to that described for Examples 1 and 2.
Table 1: Alkyl Phosphonium Tosylates
Density (g/mL)
Example _ Rl R —2 R —3 — R4 m (.cp). 30°C 60°C
8 Et Et Et Et 68- 69
9 n-Pr n-Pr n-Pr Me 50-52 0.9974 0.9802
10 n-Pr n-Pr n-Pr Et 52-53
11 n-Bu n-Bu n-Bu Me 72-73
12 n-Bu n-Bu n-Bu Et 71.5-
73.5
2 iBu iBu iBu Me liquid2 1-0664 1.0486 1 iBu iBu iBu Et 28-29 1.0593 1.0416
3 iBu iBu octyl Me <40 1.0229 1.0036
4 iBu iBu octyl Et liquid2 1-0148 0.9955
5 iBu iBu tetrade Me <40 0.9885 0.9681 cyl
6 iBu iBu tetrade Et liquid2 0.9821 0.9619 cyl
7 Mixed Hexyl/Octyll Me <40 0.9853 0.9661
^The phosphonium salts were prepared from a mixture of phosphines (R!R2R P) , wherein R1, R2, and R3 are each hexyl or octyl.
At Room Temperature. Example 13
Preparation of tri-hexyl (tetradecyl) phosphonium hexafluorophosphate : 202 g of tri-hexyl (tetradecyl) phosphonium chloride was dissolved in 293 g of distilled water. To this solution 99.4 g of 60% aqueous hexafluorophosphoric acid was added with stirring at room temperature. A waxy immiscible solid formed. After two hours of stirring, the mixture was warmed to 45°C. At this point there were two liquid layers. The aqueous layer was decanted and the organic phase was washed two times with two volumes of distilled water at 45 °C to remove residual HC1. Finally the organic phase was heated to 100°C under 20 mmHg pressure to remove the last traces of water. 238 g of a low melting (29-33°C) product was recovered.
Examples 14 to 21
Alkylphosphonium hexafluorophosphates listed in Table
2 were synthesized in a manner similar to that described for Example 13. Example 21 is provided for the purpose of comparison.
Table 2: Alkyl Phosphonium Hexafluorophosphates
P NMR (ppm) F NMR (ppm)
Example R1 R2 R3 R4 m.p. (C) E4E EEβ PF6
16 Propyl Propyl Propyl Tetradecyl 44.5-45.5 32.46 -143.67 -69.22 -73.02
15 Butyl Butyl Butyl Tetradecyl 38.0-39.0 33.75 -143.54 -69.83 -73.61
14 Pentyl Pentyl Pentyl Tetradecyl 35.5-37.0 33.55 -143.68 -69.18 -72.97
13 Hexyl Hexyl Hexyl Tetradecyl 29-33 33.53 -143.68 -69.93 -73.7
21 Butyl Butyl Butyl Butyl 161-163 34.47 -143.32 -70.47 -74.25
17 Dodecyl Dodecyl Dodecyl Dodecyl 72-78 33.2 143.47 -69.5 -73.28
18 Mixed Butyl/H( 3xy|1 Tetradecyl liquid/solid^ 33.4 -143.75 -69.89 -73.67
19 Mixed Butyl/Octyl1 Butyl <30 34.36 -143.36 -70.45 -74.21
20 Mixed Hexyl/Octyl'' Octyl 55.5-64.0 33.45 -143.85 -70.11 -73.39
1The phosphonium salts were prepared from a mixture of phosphines (R^ R2 R3P), wherein R1 , R2, and R3 are each one of the two components listed.
2At Room Temperature.
Example 22
Preparation of tri-hexyl (tetradecyl) phosphonium tetrafluoroborate : A stirred reactor was charged with two parts of acetone and one part by weight of tri-hexyl (tetradecyl) phosphonium chloride. To this solution was added a 50% molar excess of sodium tetrafluoroborate. The mixture was stirred vigorously for 10 minutes at room temperature. Afterwards, it was filtered to remove the excess sodium tetrafluoroborate and precipitated sodium chloride. The clear acetone solution containing tri-hexyl (tetradecyl) hosphonium tetrafluoroborate was then heated under reduced pressure to remove the acetone. The final conditions were 140°C at 0.3 mmHg pressure. The product was slightly viscous pale yellow oil which had a melting point of 30°C. The chloride content was 0.16%. This represents approximately 98% conversion of the chloride to tetrafluoroborate.
Examples 23 and 24
Alkylphosphonium tetrafluoroborates listed in Table 3 were synthesized in a manner similar to that described for Example 22.
Table 3: Alkyl Phosphonium Tetrafluoroborates
P NMR (ppm) F NMR (ppm) B NMR (ppm) Examples Rj. R? R£ R£ m.p. (C) R4P BF4 BF4
23 Butyl Butyl Butyl Tetradecyl 32-35 33.83 -153.74 -0.7224 22 Hexyl Hexyl Hexyl Tetradecyl liquid2 33.32 -149.09 -1.021
24 Mixed Butyl/Hexyl"! Tetradecyl liquid 33.45 -1.1602
1The phosphonium salts were prepared from a mixture of phosphines (R^ R2 R^P), wherein R1 , R2, and R3 are each butyl or hexyl.
At Room Temperature.
Example 25
Preparation of diisobutyl (methyl) (3- (1, 1- dihydroperfluorooctoxy) propyl) phosphonium tosylate : A stirred reactor was charged with one equivalent of methyltosylate . After heating the tosylate ester to 100 °C, one equivalent of diisobutyl (3- (1, 1-dihydroperfluorooctoxy) propyl) phosphine was added over 2 hours. The mixture was held for an additional 6 hours at 100 °C. The product was a viscous liquid at room temperature, with a density and viscosity of 1.34 g/cc and 5.8 cps, respectively, at 60°C.
Example 26
Preparation of bis (3- (1, 1-dihydroperfluorooctoxy) propyl) (isobutyl) (methyl) phosphonium tosylate: A stirred reactor was charged with one equivalent of methyltosylate. After heating the tosylate ester to 100 °C, one equivalent of bis (3- (1, 1-dihydroperfluorooctoxy) propyl) (isobutyl) phosphine was added over 2 hours. The mixture was held for an additional 6 hours at 100 °C. The product was a viscous liquid at room temperature, with a density and viscosity of 1.5 g/cc and 50 cps, respectively, at 60°C.
Example 27
The miscibility of phosphonium iodides with dodecane as a function of number of carbons in a series of phosphonium iodides was determined. While phosphonium iodides are not part of the claimed invention, this example is provided here to demonstrate how miscibility may be affected by carbon number for phosphonium salts. The first column of Table 4 identifies the tertiary phosphine, most of which have R groups which are a mixture of different lengths. Column 2 identifies the alkyl iodide with which the tertiary phosphine has been reacted to form a phosphonium iodide. Column 3 shows the average number of carbon atoms per phosphonium iodide molecule and column 4 shows the average molecular weight of the phosphonium iodide products. The last column shows the temperature at which the phosphonium iodide became miscible with dodecane. This Table demonstrates that the miscibility of the phosphonium iodides with dodecane decreases as the number of carbon atoms in the phosphonium iodide increases.
Figure imgf000018_0001
^The phosphonium salts were prepared from a mixture of phosphines (R-*- R2 R3p) , wherein Rl, R2, and R are each one of the two components listed. 2At Room Temperature

Claims

CLAIMS :
1. A phosphonium salt of formula I
R1R2R3R4P+ -
wherein R1, R2, R3 and R4 are C-]__20 hydrocarbyl groups and X is
an anion, excluding halide, provided that
(i) R1, R2, R3 and R4 are not all the same; and
(ii) not more than two of R1, R2, R3 and R4 are aryl.
2. The salt according to claim 1, wherein the sum total of the carbon atoms present in R1, R2, R and R4 is from 7 to 30 inclusive.
3. The salt according to claim 1 or 2, wherein at least two of R-*-, R2, R3 and R4 are different from the others of R^, R2, R3 and R4.
4. The salt according to claim 1, 2, or 3, wherein one of R1, R2, R3 and R4 includes a straight chain of 14 or more carbon atoms.
5. The salt according to any one of claims 1 to 4, wherein R^, R2, R and R4 are all saturated acyclic groups.
6. The salt according to any one of claims 1 to 5, wherein at least one of R*--, R2, R3, and R4 is a partially fluorinated ether.
7. The salt according to claim 6, wherein at least one of R1, R2, R3, and R4 is -CH2CH2CH -0-CH2 (CF2) nCF3' wherein n is 4, 6, or 8.
8. The salt according to any one of claims 1 to 7, wherein at least one of R^, R2, R , and R4 is a hydroxyalkyl group.
9. The salt according to claim 8, wherein at least one of Rl, R2, R , and R4 is 3-hydroxypropyl .
10. The salt according to any one of claims 1 to 5, wherein the anion is selected from the group consisting of sulfonates, tetrafluoroborate, hexafluoroborate, SbFg-, AICI4-, and AI2CI7"".
11. The salt according to any one of claims 1 to 10 having a melting point below 100°C.
12. The salt according to any one of claims 1 to 10 having a melting point below 50 °C.
13. The salt according to any one of claims 1 to 10 having a melting point below 35°C.
14. Use of a phosphonium salt according to any one of claims 1 to 13 as a reaction solvent.
PCT/US2001/012780 2000-05-18 2001-04-19 Phosphonium salts WO2001087900A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP01928671A EP1287007A1 (en) 2000-05-18 2001-04-19 Phosphonium salts
AU2001255504A AU2001255504A1 (en) 2000-05-18 2001-04-19 Phosphonium salts

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CA 2308896 CA2308896A1 (en) 2000-05-18 2000-05-18 Phosphonium salts
CA2,308,896 2000-05-18

Publications (1)

Publication Number Publication Date
WO2001087900A1 true WO2001087900A1 (en) 2001-11-22

Family

ID=4166192

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2001/012780 WO2001087900A1 (en) 2000-05-18 2001-04-19 Phosphonium salts

Country Status (4)

Country Link
EP (1) EP1287007A1 (en)
AU (1) AU2001255504A1 (en)
CA (1) CA2308896A1 (en)
WO (1) WO2001087900A1 (en)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002079212A1 (en) * 2001-03-30 2002-10-10 Cytec Canada Inc. Phosphonium phosphinate compounds and their preparation
WO2002092608A2 (en) * 2001-05-17 2002-11-21 Rhodia Chimie Use of a composition of an ionic nature as a substrate reagent, a composition constituting a fluorination reagent and a method using same
WO2003051894A1 (en) * 2001-12-14 2003-06-26 Cytec Canada Inc. Preparation of ionic liquids
FR2839716A1 (en) * 2002-05-15 2003-11-21 Rhodia Chimie Sa Process for enabling nucleophilic substitution reactions, uses an ionic liquid or fused salt as a fluorinating medium
WO2004016631A1 (en) * 2002-08-16 2004-02-26 Cytec Canada Inc. Phosphonium and imidazolium salts and methods of their preparation
WO2004094438A1 (en) * 2003-03-31 2004-11-04 Cytec Canada Inc. Phosphonium salts and methods of their preparation
JP2005521750A (en) * 2002-04-05 2005-07-21 ユニバーシティ オブ サウス アラバマ Functionalized ionic liquids and methods of use thereof
EP1574548A1 (en) * 2002-12-19 2005-09-14 Nippon Chemical Industrial Co., Ltd. Antistatic agents for resins, antistatic resin compositions, and moldings of antistatic resins
EP1773785A2 (en) * 2004-07-23 2007-04-18 Sigma-Aldrich Co. High stability diionic liquid salts
US20100068604A1 (en) * 2008-07-14 2010-03-18 Hawkins J Adrian Phosphonium Ionic Liquids, Compositions, Methods of Making and Electrolytic Films Formed There From
US8907133B2 (en) 2008-07-14 2014-12-09 Esionic Es, Inc. Electrolyte compositions and electrochemical double layer capacitors formed there from
US8927775B2 (en) 2008-07-14 2015-01-06 Esionic Es, Inc. Phosphonium ionic liquids, salts, compositions, methods of making and devices formed there from
US8956445B2 (en) 2004-07-23 2015-02-17 Sigma-Aldrich Co. High stability diionic liquid salts
US9694021B2 (en) 2010-04-28 2017-07-04 Alcon Research, Ltd Pharmaceutical compositions with phosphonium antimicrobial agents
WO2020047210A1 (en) * 2018-08-30 2020-03-05 HYDRO-QUéBEC Rechargeable battery with ionic liquid electrolyte and electrode pressure

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1778705A4 (en) * 2004-07-16 2008-12-31 Univ Fraser Simon Phosphonium ionic liquids as recyclable solvents for solution phase chemistry
EP2791099B1 (en) 2011-12-16 2017-02-01 Celanese International Corporation Production of acetic acid with enhanced catalyst stability

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976566A (en) * 1975-04-23 1976-08-24 Vojislav Petrovich Froth flotation method for the recovery of minerals by means of quaternary phosphonium nitrites and ternary phosphine dinitrites
EP0161128A1 (en) * 1984-03-23 1985-11-13 EASTMAN KODAK COMPANY (a New Jersey corporation) Two-component dry electrostatic developer composition
JPS63119490A (en) * 1986-11-05 1988-05-24 Dai Ichi Kogyo Seiyaku Co Ltd Production of quaternary phosphonium compound
US4837394A (en) * 1988-08-05 1989-06-06 Eastman Kodak Company electrostatographic toner particle comprising a polyester containing a covalently bound quaternary phosphonium salt
US4867790A (en) * 1987-01-27 1989-09-19 Espe Stiftung & Co. Produktions- Und Vertriebs Kg Dental composition containing an aziridine compound and method of preparation
EP0455257A2 (en) * 1990-05-04 1991-11-06 Union Carbide Chemicals And Plastics Company, Inc. Catalysts for producing 1,3-diols and/or 3-hydroxy-aldehydes, and processes for making and using same
EP0640646A1 (en) * 1993-08-26 1995-03-01 Teijin Limited Process for production of stabilized polycarnonate

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976566A (en) * 1975-04-23 1976-08-24 Vojislav Petrovich Froth flotation method for the recovery of minerals by means of quaternary phosphonium nitrites and ternary phosphine dinitrites
EP0161128A1 (en) * 1984-03-23 1985-11-13 EASTMAN KODAK COMPANY (a New Jersey corporation) Two-component dry electrostatic developer composition
JPS63119490A (en) * 1986-11-05 1988-05-24 Dai Ichi Kogyo Seiyaku Co Ltd Production of quaternary phosphonium compound
US4867790A (en) * 1987-01-27 1989-09-19 Espe Stiftung & Co. Produktions- Und Vertriebs Kg Dental composition containing an aziridine compound and method of preparation
US4837394A (en) * 1988-08-05 1989-06-06 Eastman Kodak Company electrostatographic toner particle comprising a polyester containing a covalently bound quaternary phosphonium salt
EP0455257A2 (en) * 1990-05-04 1991-11-06 Union Carbide Chemicals And Plastics Company, Inc. Catalysts for producing 1,3-diols and/or 3-hydroxy-aldehydes, and processes for making and using same
EP0640646A1 (en) * 1993-08-26 1995-03-01 Teijin Limited Process for production of stabilized polycarnonate

Non-Patent Citations (24)

* Cited by examiner, † Cited by third party
Title
ABDALLAH, DAVID J. ET AL: "Smectic Liquid-Crystalline Phases of Quaternary Group VA (Especially Phosphonium) Salts with Three Equivalent Long n-Alkyl Chains. How Do Layered Assemblies Form in Liquid-Crystalline and Crystalline Phases?", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 122, no. 13, 5 April 2000 (2000-04-05), pages 3053 - 3062, XP002172924, ISSN: 0002-7863 *
ADAMS ET AL: "Friedel-Crafts reactions in room temperature ionic liquids", CHEMICAL COMMUNICATIONS, no. 19, 1998, pages 2097 - 2098, XP002172928, ISSN: 1359-7345 *
ALBANESE D ET AL: "Synthesis of Pentacoordinated Tetraalkylammonium and Tetraalkylphosphonium Difluorosilicates", TETRAHEDRON LETTERS, vol. 36, no. 48, 27 November 1995 (1995-11-27), pages 8865 - 8866, XP004026854, ISSN: 0040-4039 *
BARRAUD A ET AL: "A NOVEL HIGHLY CONDUCTING PHOSPHONIUM TETRACYANOQUINODIMETHANE LANGMUIR-BLODGETT FILM", THIN SOLID FILMS, vol. 160, no. 1 + INDEX, 1 June 1988 (1988-06-01), pages 81 - 85, XP000024752, ISSN: 0040-6090 *
BOHM, VOLKER P. W. ET AL: "Coordination chemistry and mechanisms of metal-catalyzed C-C coupling reactions;Part 12 nonaqueous ionic liquids: superior reaction media for the catalytic Heck -vinylation of chloroarenes", CHEMISTRY - A EUROPEAN JOURNAL, vol. 6, no. 6, 17 March 2000 (2000-03-17), pages 1017 - 1025, XP002172926, ISSN: 0947-6539 *
BOY CORNILS (EDITOR), WOLFGANG A. HERMANN (EDITOR): "Aqueous Phase Organometallic Catalysis, Concelts and Applications", 28 May 1998, WILEY-VCH, ISBN: 3527294783, XP001007486 *
CERICHELLI ET AL: "Role of Counterions in the Catalytic Activity and Phase Equilibria of Phosphonium Salts in Water", LANGMUIR, vol. 16, no. 1, 11 January 2000 (2000-01-11), pages 166 - 171, XP002172929, ISSN: 0743-7463 *
CHAUVIN Y ET AL: "OLIGOMERIZATION OF N-BUTENES CATALYZED BY NICKEL COMPLEXES DISSOLVED IN ORGANOCHLOROALUMINATE IONIC LIQUIDS", JOURNAL OF CATALYSIS,US,ACADEMIC PRESS, DULUTH, MN, vol. 165, 1997, pages 275 - 278, XP002070945, ISSN: 0021-9517 *
CHAUVIN, YVES ET AL: "Catalytic dimerization of alkenes by nickel complexes in organochloroaluminate molten salts", JOURNAL OF THE CHEMICAL SOCIETY, CHEMICAL COMMUNICATIONS, no. 23, 1990, pages 1715 - 1716, XP001007301, ISSN: 0022-4936 *
CHAUVIN, YVES ET AL: "Catalytic dimerization of olefins by nickel complexes in organochloroaluminate molten salts", ELECTROCHEMICAL SOCIETY PROCEEDINGS, PROCEEDINGS OF THE 7TH INTERNATIONAL SYMPOSIUM ON MOLTEN SALTS, vol. 90, no. 17, 1990, pages 822 - 832, XP001008355, ISSN: 0161-6374 *
COMYNS, CLAIRE ET AL: "Clean catalysis with clean solvents - phosphonium tosylates for transfer hydrogenation reactions", CATALYSIS LETTERS, vol. 67, no. 2-4, 2000, pages 113 - 115, XP001008262, ISSN: 1011-372X *
DEMA, ANNE C. ET AL: "Transformation of alkynylphosphine oxides and alkynylphosphonium cations to 2-alkylidene-1,2-dihydro-3-phosphete ligands by platinum-hydrogen addition and rearrangement reactions", ORGANOMETALLICS, vol. 10, no. 4, 1991, pages 1197 - 1200, XP001007321, ISSN: 0276-7333 *
ESTERUELAS, MIGUEL A. ET AL: "Reductive Elimination of [Ph2C:C:CHPR3]BF4 from the Rhodium(III)-Allenyl Derivatives [Rh(acac){CH:C:CPh2}(PR3)2]BF4 (PR3 = PCy3, PiPr3)", ORGANOMETALLICS, vol. 16, no. 21, 14 October 1997 (1997-10-14), pages 4572 - 4580, XP002172925, ISSN: 0276-7333 *
FISCHER T ET AL: "Diels-Alder Reactions in Room-Temperature Ionic Liquids", TETRAHEDRON LETTERS,NL,ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, vol. 40, no. 4, 22 January 1999 (1999-01-22), pages 793 - 796, XP004151448, ISSN: 0040-4039 *
IMRIE, C. ET AL: "Photolysis of (arylmethyl)triphenylphosphonium salts. Substituent, counterion, and solvent effects on reaction products", JOURNAL OF ORGANIC CHEMISTRY, vol. 58, no. 21, 1993, pages 5643 - 5649, XP001007323, ISSN: 0022-3263 *
JONES, RICHARD A. ET AL: "Synthesis and x-ray crystal structure of (triphenylmethyl)trimethylphosph nium tetrafluoroborate", JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS II, no. 1, 1980, pages 117 - 120, XP001007320 *
KANAZAWA, AKIHIKO ET AL: "Polymeric phosphonium salts as a novel class of cationic biocides. II. Effects of counter anion and molecular weight on antibacterial activity o polymeric phosphonium salts", JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY, vol. 31, no. 6, 1993, pages 1441 - 1447, XP001007322, ISSN: 0887-624X *
KARODIA ET AL: "Clean catalysis with ionic solvents - phosphonium tosylates for hydroformylation", CHEMICAL COMMUNICATIONS, no. 21, 1998, pages 2341 - 2342, XP002172927, ISSN: 1359-7345 *
KHASKIN ET AL: "Organic insectofungicides. Thione-thiol isomerisation of quaternary phosphonium O,O-dialkyldithiophosphates", ZHURNAL OBSHCHEI KHIMII, vol. 38, no. 12, 1968, pages 2652 - 2658, XP001008399, ISSN: 0044-460X *
LUDLEY P ET AL: "Phosphonium tosylates as solvents for the Diels-Alder reaction", TETRAHEDRON LETTERS, vol. 42, no. 10, 4 March 2001 (2001-03-04), pages 2011 - 2014, XP004238666, ISSN: 0040-4039 *
MASATSUGU OGATA ET AL: "EFFECTS OF CROSSLINKING ON PHYSICAL PROPERTIES OF PHENOL-FORMALDEHYDE NOVOLAC CURED EPOXY RESINS", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 48, no. 4, 20 April 1993 (1993-04-20), pages 583 - 601, XP000455203, ISSN: 0021-8995 *
PATENT ABSTRACTS OF JAPAN vol. 012, no. 365 (C - 532) 29 September 1988 (1988-09-29) *
VANMAELE L: "Non-polymeric phosphonium mordanting agents", RESEARCH DISCLOSURE, no. 287, 1988, pages 133 - 134, XP001008612, ISSN: 0374-4353 *
WESSOLOWSKI, HOLGER ET AL: "Novel perfluoroalkenylphosphonates and iodoperfluoroalkenes from 3,3-bis(trifluoromethyl)-1,2,2,4,4,4-hexafluoro-1-butylene and nonafluoro-n-butoxy-1,1,2-trifluoroethylene", JOURNAL OF FLUORINE CHEMISTRY, vol. 80, no. 2, 1996, pages 149 - 152, XP004071323, ISSN: 0022-1139 *

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002079212A1 (en) * 2001-03-30 2002-10-10 Cytec Canada Inc. Phosphonium phosphinate compounds and their preparation
WO2002092608A2 (en) * 2001-05-17 2002-11-21 Rhodia Chimie Use of a composition of an ionic nature as a substrate reagent, a composition constituting a fluorination reagent and a method using same
US7393980B2 (en) 2001-05-17 2008-07-01 Rhodia Chimie Use of a composition of an ionic nature as a substrate reagent, a composition constituting a fluorination reagent and a method using same
WO2002092608A3 (en) * 2001-05-17 2003-12-24 Rhodia Chimie Sa Use of a composition of an ionic nature as a substrate reagent, a composition constituting a fluorination reagent and a method using same
WO2003051894A1 (en) * 2001-12-14 2003-06-26 Cytec Canada Inc. Preparation of ionic liquids
JP2010100630A (en) * 2002-04-05 2010-05-06 Univ Of South Alabama Functionalized ionic liquid and method of using the same
US7744838B2 (en) 2002-04-05 2010-06-29 University Of South Alabama Functionalized ionic liquids, and methods of use thereof
JP2005521750A (en) * 2002-04-05 2005-07-21 ユニバーシティ オブ サウス アラバマ Functionalized ionic liquids and methods of use thereof
EP1556390A2 (en) * 2002-04-05 2005-07-27 University Of South Alabama Functionalized ionic liquids, and methods of use thereof
JP4886967B2 (en) * 2002-04-05 2012-02-29 ユニバーシティ オブ サウス アラバマ Functionalized ionic liquids and methods of use thereof
AU2003237797B2 (en) * 2002-04-05 2009-02-26 University Of South Alabama Functionalized ionic liquids, and methods of use thereof
US8674135B2 (en) 2002-04-05 2014-03-18 University Of South Alabama Functionalized ionic liquids, and methods of use thereof
EP1556390A4 (en) * 2002-04-05 2007-12-26 Univ South Alabama Functionalized ionic liquids, and methods of use thereof
FR2839716A1 (en) * 2002-05-15 2003-11-21 Rhodia Chimie Sa Process for enabling nucleophilic substitution reactions, uses an ionic liquid or fused salt as a fluorinating medium
WO2004016631A1 (en) * 2002-08-16 2004-02-26 Cytec Canada Inc. Phosphonium and imidazolium salts and methods of their preparation
US7638636B2 (en) 2002-08-16 2009-12-29 Cytec Technology Corp. Phosphonium and imidazolium salts and methods of their preparation
KR101014087B1 (en) * 2002-08-16 2011-02-14 사이텍 캐나다 인코포레이티드 Phosphonium and imidazolium salts and methods of their preparation
EP1574548A4 (en) * 2002-12-19 2006-12-06 Nippon Chemical Ind Antistatic agents for resins, antistatic resin compositions, and moldings of antistatic resins
JPWO2004056917A1 (en) * 2002-12-19 2006-04-20 日本化学工業株式会社 Antistatic agent for resin, antistatic resin composition and antistatic resin molded product
EP1574548A1 (en) * 2002-12-19 2005-09-14 Nippon Chemical Industrial Co., Ltd. Antistatic agents for resins, antistatic resin compositions, and moldings of antistatic resins
US8748668B2 (en) 2003-03-31 2014-06-10 Cytec Technology Corp. Phosphonium salts and methods of their preparation
US8901339B2 (en) 2003-03-31 2014-12-02 Cytec Technology Corp. Phosphonium salts and methods of their preparation
US20110021838A1 (en) * 2003-03-31 2011-01-27 Cytec Canada Inc. Phosphonium salts and methods of their preparation
US7829744B2 (en) 2003-03-31 2010-11-09 Cytec Technology Corp Phosphonium salts and their method of preparation
US8901338B2 (en) 2003-03-31 2014-12-02 Cytec Technology Corp. Phosphonium salts and methods of their preparation
WO2004094438A1 (en) * 2003-03-31 2004-11-04 Cytec Canada Inc. Phosphonium salts and methods of their preparation
CN103694275A (en) * 2003-03-31 2014-04-02 Cytec加拿大股份有限公司 Phosphonium salts and methods of their preparation
EP1773785A2 (en) * 2004-07-23 2007-04-18 Sigma-Aldrich Co. High stability diionic liquid salts
EP1773785A4 (en) * 2004-07-23 2009-07-22 Sigma Aldrich Co High stability diionic liquid salts
US8956445B2 (en) 2004-07-23 2015-02-17 Sigma-Aldrich Co. High stability diionic liquid salts
US8846246B2 (en) * 2008-07-14 2014-09-30 Esionic Es, Inc. Phosphonium ionic liquids, compositions, methods of making and electrolytic films formed there from
US20100068604A1 (en) * 2008-07-14 2010-03-18 Hawkins J Adrian Phosphonium Ionic Liquids, Compositions, Methods of Making and Electrolytic Films Formed There From
US8907133B2 (en) 2008-07-14 2014-12-09 Esionic Es, Inc. Electrolyte compositions and electrochemical double layer capacitors formed there from
US8927775B2 (en) 2008-07-14 2015-01-06 Esionic Es, Inc. Phosphonium ionic liquids, salts, compositions, methods of making and devices formed there from
US9694021B2 (en) 2010-04-28 2017-07-04 Alcon Research, Ltd Pharmaceutical compositions with phosphonium antimicrobial agents
WO2020047210A1 (en) * 2018-08-30 2020-03-05 HYDRO-QUéBEC Rechargeable battery with ionic liquid electrolyte and electrode pressure

Also Published As

Publication number Publication date
EP1287007A1 (en) 2003-03-05
CA2308896A1 (en) 2001-11-18
AU2001255504A1 (en) 2001-11-26

Similar Documents

Publication Publication Date Title
WO2001087900A1 (en) Phosphonium salts
CA2398682C (en) Phosphonium and imidazolium salts and methods of their preparation
KR840000517B1 (en) Preparation of fluorocarbon ethers having substituted halogen site(s)
US8049026B2 (en) Synthesis of ionic liquids
EP1233936B1 (en) Process for preparing ambient temperature ionic liquids
EP1308449B1 (en) Process for synthesizing ionic metal complex
KR20070101301A (en) Base stable ionic liquids
WO2000016902A1 (en) Ionic liquids
US8680307B2 (en) Complexes and method for synthesis of group 6 organometallics grafted on anions, and use thereof in an olefin metathesis method
JP2007501313A (en) Flame retardant phosphonate additives for thermoplastics
KR20030093282A (en) Phosphonium phosphinate compounds and their preparation
KR100458793B1 (en) The synthetic method of glycidylether without solvent and water
US4673535A (en) Quaternary ammonium salts of sulfonated triarylphosphines and process for the production thereof
CA1142947A (en) Optically active 1,2-bis-(diphenyl-phosphino) compounds and metal complexes containing them as chiral ligands as well as their use
DE69931165T2 (en) Preparation of Organolithium and Organophosphorus Derivatives
US20040106823A1 (en) Novel phosphonium phosphinate compounds and their methods of preparation
US7208626B2 (en) Method for the production of perfluoroalkyl phosphines and the use thereof as perfluoroalkylating reactants
US5250736A (en) Method of preparing a phosphine compound
US3133949A (en) Novel preparation of organic sulfates
JPH032855B2 (en)
CA2086285A1 (en) Process for the preparation of vicinally-disubstituted bis(diorganophosphino) compounds
US2904588A (en) Fluorophosphoranes and their preparation
US2765333A (en) Bis(cyanopentenoxy) alkanes and their preparation
KR20050123129A (en) Phosphonium salts and methods of their preparation
JP7304554B2 (en) Silyl ether containing sulfonate

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2001928671

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2001928671

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 2001928671

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: JP