US20040029723A1 - Novel aminophosphonium compounds - Google Patents

Novel aminophosphonium compounds Download PDF

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US20040029723A1
US20040029723A1 US10/632,396 US63239603A US2004029723A1 US 20040029723 A1 US20040029723 A1 US 20040029723A1 US 63239603 A US63239603 A US 63239603A US 2004029723 A1 US2004029723 A1 US 2004029723A1
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Berthold Schiemenz
Thomas Wessel
Ralf Pfirmann
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Clariant Produkte Deutschland GmbH
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
    • B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0237—Amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B39/00—Halogenation
    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/572—Five-membered rings
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/59—Hydrogenated pyridine rings
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6509—Six-membered rings
    • C07F9/650952—Six-membered rings having the nitrogen atoms in the positions 1 and 4
    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07F9/6533—Six-membered rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
    • B01J2531/98—Phase-transfer catalysis in a mixed solvent system containing at least 2 immiscible solvents or solvent phases
    • B01J2531/985—Phase-transfer catalysis in a mixed solvent system containing at least 2 immiscible solvents or solvent phases in a water / organic solvent system

Definitions

  • the present invention relates to novel aminophosphonium compounds, to substance mixtures containing them, and to the preparation and use thereof.
  • Aminophosphonium compounds are used, as is evident from WO 98/32532 and WO 98/22413, as catalysts for preparing fluorine-containing compounds by a halogen/fluorine exchange reaction (halex reaction).
  • halex reaction halogen/fluorine exchange reaction
  • the tetrakis-(diethylamino)phosphonium bromide used in WO 98/32532 and WO 98/22413 gives good results, it has a very high dermal toxicity which stands in the way of industrial use, however.
  • the object is to provide novel compounds which are suitable as catalyst or component of catalyst systems for phase-transfer reactions, in particular for halogen-fluorine exchange reactions, have a lower dermal toxicity and achieve or even exceed the results obtainable on use of tetrakis(diethylamino)phosphonium bromide.
  • R 5 , R 6 R 7 and R 8 are, independently of one another, identical or different and are a straight-chain or branched alkyl radical having 1 to 10 carbon atoms, and the remaining radical(s) R 1 to R 4 are
  • R 9 and R 10 are identical or different and are a straight-chain or branched alkyl radical having 1 to 10 carbon atoms, and X ⁇ is an inorganic or organic anion or an equivalent of a multiply charged inorganic or organic anion.
  • Importance further attaches to compounds of the formula (1) in which m and n are an integer from 1 to 6, and R 5 , R 6 , R 7 , R 1 , R 9 and R 10 are identical or different and are a straight-chain or branched alkyl radical having 1 to 4 carbon atoms.
  • X ⁇ is F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , ClO 4 ⁇ , BF 4 ⁇ , PF 6 ⁇ , NO 3 ⁇ , HSO 4 ⁇ , 1 ⁇ 2 SO 4 2 ⁇ , H 2 PO 4 ⁇ , 1 ⁇ 2 HPO 4 2 ⁇ , 1 ⁇ 3 PO 4 3 ⁇ , R′—COO ⁇ , where R′ is an alkyl radical having 1 to 9 carbon atoms, a phenyl radical, benzyl radical or naphthyl radical, R′′—SO 3 ⁇ , where R′′ is an alkyl radical having 1 to 18 carbon atoms, a phenyl radical, tolyl radical or naphthyl radical, HCO 3 ⁇ , 1 ⁇ 2 CO 3 2 ⁇ or 1 ⁇ 2 C 6 H 4 (COO ⁇ ) 2 .
  • X ⁇ is, in particular, F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , BF 4 ⁇ , PF 6 ⁇ or 1 ⁇ 2 SO 4 2 ⁇ , preferably F ⁇ , Cl ⁇ , or Br ⁇ , particularly preferably Cl ⁇ .
  • aminophosphonium compounds aminophosphonium salts
  • aminophosphonium salts aminophosphonium salts
  • the present invention also relates to mixtures of substances comprising at least one compound of the formula
  • R 1 , R 2 , R 3 , R 4 and X ⁇ have the above meaning, and at least one compound selected from the group of quaternary ammonium compounds of the formula
  • R 11 , R 12 and R 13 are identical or different and are a linear or branched radical of the formula —(C p H 2p O) r R 15 in which R 15 is hydrogen or a linear or branched alkyl radical having 1 to 16 carbon atoms, p is an integer from 1 to 10 and r is an integer from 1 to 15;
  • R 14 is a linear or branched radical of the formula —(C p H 2p O) r R 15 and
  • Y ⁇ is an inorganic anion
  • R 16 , R 17 , R 18 and R 19 are identical or different and are a linear or branched alkyl radical having 1 to 22 carbon atoms; or an unsubstituted or substituted aryl radical or a C 1 -C 4 -alkylaryl radical, where aryl has the meaning of phenyl or naphthyl, and said substituents are halogen,
  • R 20 and R 21 are identical or different and are a linear or branched alkyl radical having 1 to 16 carbon atoms;
  • x is an integer from 2 to 6 and
  • s is an integer from 1 to 60;
  • one of the radicals R 20 and R 21 is hydrogen and the other one of the radicals is a linear or branched alkyl radical having 1 to 16 carbon atoms,
  • x is an integer from 2 to 6 and s is an integer from 2 to 50, or the radicals R 20 and R 21 are hydrogen, x is an integer from 2 to 6 and s is an integer from 3 to 5.
  • the present invention relates in particular to mixtures of substances which comprise at least one compound of the formula (1) and at least one compound selected from the group of quaternary ammonium compounds of the formula (2), quaternary ammonium salts and phosphonium salts of the formula (3), polyethers of the formula (4) and crown ethers, in which in formula (2) R 11 , R 12 and R 13 are identical or different and are a linear or branched radical of the formula —(C p H 2p O) r R 15 in-which R 15 is hydrogen or a linear or branched alkyl radical having 1 to 8 carbon atoms, p is an integer from 1 to 5 and r is an integer from 2 to 10; or a linear or branched alkyl radical having 1 to 18 carbon atoms; or an unsubstituted phenyl or naphthyl radical; R 14 is a linear or branched radical of the formula —(C p H 2p O) r R 15 , in which R 15 is
  • Mixtures of substances of particular interest are those comprising at least one compound of the formula (1) and at least one compound from the group of quaternary ammonium compounds of the formula (2).
  • R 16 , R 17 , R 18 and R 19 are identical or different and are a linear or branched alkyl radical having 1 to 16 carbon atoms; or an unsubstituted or substituted aryl radical or a C 1 -C 4 -alkylaryl radical, where aryl has the meaning of phenyl or naphthyl, and said substituents are halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, nitro or cyano.
  • the mixtures of substances normally comprise from 5 to 95% by weight, in particular 20 to 80% by weight, preferably 25 to 75% by weight, of at least one compound of the formula (1).
  • the residual 95 to 5% by weight, in particular 80 to 20% by weight, preferably 75 to 25% by weight, of the mixtures of substances account for the remainder, namely at least one compound selected from the group of quaternary ammonium compounds of the formula (2) of quaternary ammonium or phosphonium salts of the formula (3), polyethers of the formula (4) and crown ethers, in particular at least one compound from the group of quaternary ammonium compounds of the formula (2).
  • the present invention further relates to a process for preparing compounds of the formula
  • It comprises reacting a phosphorus pentahalide in the presence of an inert solvent at ⁇ 70 to 140° C., in particular ⁇ 30 to 120° C., preferably ⁇ 15 to 60° C., with from 1 to 6 mol, in particular 1 to 2.5 mol, of
  • the phosphorus pentahalide employed is PCl 5 or PBr 5 , in particular PCl 5 .
  • the inert solvent employed is an aliphatic, cycloaliphatic or aromatic hydrocarbon or a mono- or polychlorinated aliphatic, cycloaliphatic or aromatic hydrocarbon.
  • Very suitable inert solvents are, for example, hexane, cyclohexane, methylcyclohexane, toluene, ethylbenzene, mesitylene, o-xylene, m-xylene, p-xylene, technical mixtures of isomeric xylenes, methylene chloride, tetrachloroethane, chlorobenzene, dichlorobenzene or chlorotoluene. It is also possible to use mixtures of solvents.
  • the phosphorus pentahalide is suspended or dissolved in the inert solvent and the reaction is carried out with the addition of the aforementioned nitrogen-containing compounds.
  • the invention further relates to the use of the compounds of the formula (1) as catalyst and cocatalyst for phase-transfer reactions, nucleophilic substitutions and halogen-fluorine exchange reactions.
  • the invention further relates to the use of the mixtures of substances comprising at least one compound of the formula (1) and at least one compound selected from the group of quaternary ammonium compounds of the formula (2), quaternary ammonium salts or phosphonium salts of the formula (3), polyethers of the formula (4) and crown ethers as catalyst for phase-transfer reactions, nucleophilic substitutions and halogen-fluorine exchange reactions.
  • Dioctylamino-tris(pyrrolidino)phosphonium chloride is prepared in analogy to Example 1 from 41.65 g (0.2 mol) of phosphorus pentachloride, 48.3 g (0.2 mol) of dioctylamine and 99.6 g (1.4 mol) of pyrrolidine.
  • Morpholino-tris(pyrrolidino)phosphonium chloride is prepared in analogy to Example 1 from 104.12 g (0.5 mol) of phosphorus pentachloride, 43.6 g (0.5 mol) of morpholine and 214.6 g (3.0 mol) of pyrrolidine.
  • Bis(2-methoxyethyl)amino-tris(piperidino)phosphonium chloride is prepared in analogy to Example 2 from 104.12 g (0.5 mol) of phosphorus pentachloride, 66.9 g (0.5 mol) of bis-(2-methoxyethyl)amine and 255.4 g (3.0 mol) of piperidine.
  • Tris(dibutylamino)-(diethylamino)phosphonium bromide is prepared in analogy to Comparative Example A from 41.65 g (0.2 mol) of phosphorus pentachloride, 77.50 g (0.6 mol) of dibutylamine, an excess of ammonia and 47.9 g (0.44 mol) of ethyl bromide.
  • the reaction mixture is dried by azeotropic distillation of the chlorobenzene under reduced pressure. After 20 hours at 170° C., the formation of 2,6-difluorobenzaldehyde (DFBAL) and the conversion in the reaction are determined by gas chromatography.
  • DFBAL 2,6-difluorobenzaldehyde
  • the reaction mixture is dried by azeotropic distillation of the chlorobenzene under reduced pressure. After 20 hours at 165° C., the formation of 2-chloro-6-fluorobenzaldehyde (CFBAL) and 2,6-difluorobenzaldehyde (DFBAL) and the conversion in the reaction are determined by gas chromatography.
  • CFBAL 2-chloro-6-fluorobenzaldehyde
  • DFBAL 2,6-difluorobenzaldehyde

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Abstract

The present invention relates to compounds of the formula
Figure US20040029723A1-20040212-C00001
in which one, two or three of the radicals R1, R2, R3 and R4 are
Figure US20040029723A1-20040212-C00002
—N{(CH2—CH2—O)mR5}2,
Figure US20040029723A1-20040212-C00003
or —N{(CH2—CH2—N(R7))nR8}2
where m and n are an integer from 1 to 10, R5, R6, R7 and R8 are, independently of one another, identical or different and are a straight-chain or branched alkyl radical having 1 to 10 carbon atoms, and the remaining radical(s) R1 to R4 are
Figure US20040029723A1-20040212-C00004
or —NR9R10, where R9 and R10 are identical or different and are a straight-chain or branched alkyl radical having 1 to 10 carbon atoms,
and X− is an inorganic or organic anion or an equivalent of a multiply charged inorganic or organic anion. The invention further relates to mixtures of substances comprising compounds of the formula (1), to a process for preparing the compounds of the formula (1) and to the use thereof.

Description

    BACKGROUND OF THE INVENTION
  • The present invention relates to novel aminophosphonium compounds, to substance mixtures containing them, and to the preparation and use thereof. [0001]
  • Aminophosphonium compounds are used, as is evident from WO 98/32532 and WO 98/22413, as catalysts for preparing fluorine-containing compounds by a halogen/fluorine exchange reaction (halex reaction). Although the tetrakis-(diethylamino)phosphonium bromide used in WO 98/32532 and WO 98/22413 gives good results, it has a very high dermal toxicity which stands in the way of industrial use, however. [0002]
    • SUMMARY OF THE INVENTION
  • The object is to provide novel compounds which are suitable as catalyst or component of catalyst systems for phase-transfer reactions, in particular for halogen-fluorine exchange reactions, have a lower dermal toxicity and achieve or even exceed the results obtainable on use of tetrakis(diethylamino)phosphonium bromide. [0003]
    • DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • This object is achieved by compounds of the formula [0004]
    Figure US20040029723A1-20040212-C00005
  • in which one, two or three of the radicals R[0005] 1, R2, R3 and R4 are
    Figure US20040029723A1-20040212-C00006
  • —N{(CH[0006] 2—CH2—O)mR5}2,
    Figure US20040029723A1-20040212-C00007
  • or —N{(CH[0007] 2—CH2—N(R7))nR8}2
  • where m and n are an integer from 1 to 10, R[0008] 5, R6 R7 and R8 are, independently of one another, identical or different and are a straight-chain or branched alkyl radical having 1 to 10 carbon atoms, and the remaining radical(s) R1 to R4 are
    Figure US20040029723A1-20040212-C00008
  • or —NR[0009] 9R10, where R9 and R10 are identical or different and are a straight-chain or branched alkyl radical having 1 to 10 carbon atoms, and X− is an inorganic or organic anion or an equivalent of a multiply charged inorganic or organic anion.
  • Compounds of interest are those of the formula (1) in which one or two of the radicals R[0010] 1, R2, R3 and R4 are
    Figure US20040029723A1-20040212-C00009
  • —N{(CH[0011] 2—CH2—O)mR5}2,
    Figure US20040029723A1-20040212-C00010
  • or —N{(CH[0012] 2—CH2—N(R7))nR8}2
  • and the remaining radicals R[0013] 1 to R4 are
    Figure US20040029723A1-20040212-C00011
  • or —NR[0014] 9R10.
  • Importance further attaches to compounds of the formula (1) in which m and n are an integer from 1 to 6, and R[0015] 5, R6, R7, R1, R9 and R10 are identical or different and are a straight-chain or branched alkyl radical having 1 to 4 carbon atoms.
  • The aforementioned radicals R[0016] 1, R2 R3 and R4 are, in particular,
    Figure US20040029723A1-20040212-C00012
  • —N{(CH[0017] 2—CH2—O)mR5}2 or —N{(CH2—CH2—N(R7))nR8}2
  • preferably —N{(CH[0018] 2—CH2—O)mR5}2 or —N{(CH2—CH2—N(R7))nR8}2, particularly preferably —N{(CH2—CH2—O)mR5}2.
  • The aforementioned remaining radical(s) R[0019] 1 to R4 are, in particular,
    Figure US20040029723A1-20040212-C00013
  • In the compounds of the formula (1), X[0020] − is F−, Cl−, Br−, I−, ClO4 −, BF4 −, PF6 −, NO3 −, HSO4 −, ½ SO4 2−, H2PO4 −, ½ HPO4 2−, ⅓ PO4 3−, R′—COO−, where R′ is an alkyl radical having 1 to 9 carbon atoms, a phenyl radical, benzyl radical or naphthyl radical, R″—SO3 −, where R″ is an alkyl radical having 1 to 18 carbon atoms, a phenyl radical, tolyl radical or naphthyl radical, HCO3 −, ½ CO3 2− or ½ C6H4(COO−)2.
  • X[0021] − is, in particular, F−, Cl−, Br−, I−, BF4 −, PF6 − or ½ SO4 2−, preferably F−, Cl−, or Br−, particularly preferably Cl−.
  • The following aminophosphonium compounds (aminophosphonium salts) may be mentioned as examples without claiming completeness. [0022]
  • Bis(2-methoxyethyl)amino-tris(pyrrolidino)phosphonium chloride [0023]
  • Di(bis(2-methoxyethyl)amino)-bis(pyrrolidino)phosphonium chloride [0024]
  • Tri(bis(2-methoxyethyl)amino)-(pyrrolidino)phosphonium chloride [0025]
  • Bis(methyl-diethoxyethylene)amino-tris(pyrrolidino)phosphonium chloride [0026]
  • Di(bis(methyl-diethoxyethylene)amino)-bis(pyrrolidino)phosphonium chloride [0027]
  • Tri(bis(methyl-diethoxyethylene)amino)-(pyrrolidino)phosphonium chloride [0028]
  • Bis(methyl-tetraethoxyethylene)amino-tris(pyrrolidino)phosphonium chloride [0029]
  • Di(bis(methyl-tetraethoxyethylene)amino)-bis(pyrrolidino)phosphonium chloride [0030]
  • Tri(bis(methyl-tetraethoxyethylene)amino)-(pyrrolidino)phosphonium chloride [0031]
  • Morpholino-tris(pyrrolidino)phosphonium chloride [0032]
  • Dimorpholino-bis(pyrrolidino)phosphonium chloride [0033]
  • Trimorpholino-(pyrrolidino)phosphonium chloride [0034]
  • Bis(2-methoxyethyl)amino-tris(piperidino)phosphonium chloride [0035]
  • Di(bis(2-methoxyethyl)amino)-bis(piperidino)phosphonium chloride [0036]
  • Tri(bis(2-methoxyethyl)amino)-(piperidino)phosphonium chloride [0037]
  • Bis(methyl-diethoxyethylene)amino-tris(piperidino)phosphonium chloride [0038]
  • Di(bis(methyl-diethoxyethylene)amino)-bis(piperidino)phosphonium chloride [0039]
  • Tri(bis(methyl-diethoxyethylene)amino)-(piperidino)phosphonium chloride [0040]
  • Bis(methyl-tetraethoxyethylene)amino-tris(piperidino)phosphonium chloride [0041]
  • Di(bis(methyl-tetraethoxyethylene)amino)-bis(piperidino)phosphonium chloride [0042]
  • Tri(bis(methyl-tetraethoxyethylene)amino)-(piperidino)phosphonium chloride [0043]
  • Morpholino-tris(piperidino)phosphonium chloride [0044]
  • Dimorpholino-bis(piperidino)phosphonium chloride [0045]
  • Bis(2-methoxyethyl)amino-tris(diethylamino)phosphonium chloride [0046]
  • Di(bis(2-methoxyethyl)amino)-bis(diethylamino)phosphonium chloride [0047]
  • Tri(bis(2-methoxyethyl)amino)-(diethylamino)phosphonium chloride [0048]
  • Bis(methyl-tetraethoxyethylene)amino-tris(diethylamino)phosphonium chloride [0049]
  • Di(bis(methyl-tetraethoxyethylene)amino)-bis(diethylamino)phosphonium chloride [0050]
  • Tri(bis(methyl-tetraethoxyethylene)amino)-(diethylamino)phosphonium chloride [0051]
  • Morpholino-tris(diethylamino)phosphonium chloride [0052]
  • Dimorpholino-bis(diethylamino)phosphonium chloride [0053]
  • Trimorpholino-(diethylamino)phosphonium chloride [0054]
  • Bis(2-methoxyethyl)amino-tris(dimethylamino)phosphonium chloride [0055]
  • Di(bis(2-methoxyethyl)amino)-bis(dimethylamino)phosphonium chloride [0056]
  • Tri(bis(2-methoxyethyl)amino)-(dimethylamino)phosphonium chloride [0057]
  • Bis(methyl-bisethoxyethylene)amino-tris(dimethylamino)phosphonium chloride [0058]
  • Di(bis(methyl-bisethoxyethylene)amino)-bis(dimethylamino)phosphonium chloride [0059]
  • Tri(bis(methyl-bisethoxyethylene)amino)-(dimethylamino)phosphonium chloride [0060]
  • Bis(methyl-tetraethoxyethylene)amino-tris(dimethylamino)phosphonium chloride [0061]
  • Di(bis(methyl-tetraethoxyethylene)amino)-bis(dimethylamino)phosphonium chloride [0062]
  • Tri(bis(methyl-tetraethoxyethylene)amino)-(dimethylamino)phosphonium chloride [0063]
  • Tris(dimethylamino)-morpholino-phosphonium chloride [0064]
  • Bis(dimethylamino)-dimorpholino-phosphonium chloride [0065]
  • Dimethylamino-trimorpholino-phosphonium chloride [0066]
  • Bis(2-methoxyethyl)amino-tris(butyl-ethylamino)phosphonium chloride [0067]
  • Di(bis(2-methoxyethyl)amino)-bis(butyl-ethylamino)phosphonium chloride [0068]
  • Tri(bis(2-methoxyethyl)amino)-(butyl-ethylamino)phosphonium chloride [0069]
  • Bis(methyl-tetraethoxyethylene)amino-tris(butyl-ethylamino)phosphonium chloride [0070]
  • Di (bis(methyl-tetraethoxyethylene)amino)-bis(butyl-ethylamino)phosphonium chloride [0071]
  • Tri(bis(methyl-tetraethoxyethylene)amino)-(butyl-ethylamino)phosphonium chloride [0072]
  • Tris(butyl-ethylamino)-morpholino-phosphonium chloride [0073]
  • Bis(butyl-ethylamino)-dimorpholino-phosphonium chloride [0074]
  • (Butyl-ethylamino)-trimorpholino-phosphonium chloride [0075]
  • N-Methylpiperazino-tris(pyrrolidino)phosphonium chloride [0076]
  • Bis(N-methylpiperazino)-bis(pyrrolidino)phosphonium chloride [0077]
  • Tris(N-methylpiperazino)-(pyrrolidino)phosphonium chloride [0078]
  • N-Methylpiperazino-tris(diethylamino)phosphonium chloride [0079]
  • Bis(N-methylpiperazino)-bis(diethylamino)phosphonium chloride [0080]
  • Tris(N-methylpiperazino)-(diethylamino)phosphonium chloride [0081]
  • N-Methylpiperazino-tris(dimethylamino)phosphonium chloride [0082]
  • Bis(N-methylpiperazino)-bis(dimethylamino)phosphonium chloride [0083]
  • Tris(N-methylpiperazino)-(dimethylamino)phosphonium chloride [0084]
  • N-Methylpiperazino-tris(butyl-ethylamino)phosphonium chloride [0085]
  • Bis(N-methylpiperazino)-bis(butyl-ethylamino)phosphonium chloride [0086]
  • Tris(N-methylpiperazino)-(butyl-ethylamino)phosphonium chloride [0087]
  • In place of the listed aminophosphonium chlorides it is also possible to employ, for example, the corresponding bromides, iodides, fluorides, sulfates, hydrogen sulfates, acetates or phthalates. [0088]
  • The present invention also relates to mixtures of substances comprising at least one compound of the formula [0089]
    Figure US20040029723A1-20040212-C00014
  • in which R[0090] 1, R2, R3, R4 and X− have the above meaning, and at least one compound selected from the group of quaternary ammonium compounds of the formula
    Figure US20040029723A1-20040212-C00015
  • quaternary ammonium salts or phosphonium salts of the formula [0091]
    Figure US20040029723A1-20040212-C00016
  • polyethers of the formula R[0092] 20—(O—CxH2x)s—OR21 (4) and crown ethers,
  • in which in formula (2) R[0093] 11, R12 and R13 are identical or different and are a linear or branched radical of the formula —(CpH2pO)rR15 in which R15 is hydrogen or a linear or branched alkyl radical having 1 to 16 carbon atoms, p is an integer from 1 to 10 and r is an integer from 1 to 15;
  • or a linear or branched alkyl radical having 1 to 30 carbon atoms; [0094]
  • or an unsubstituted phenyl or naphthyl radical, or a substituted phenyl or naphthyl radical, where the substituents have the meaning of halogen, C[0095] 1-C4-alkyl, C1-C4-alkoxy, nitro or cyano;
  • R[0096] 14 is a linear or branched radical of the formula —(CpH2pO)rR15 and
  • Y[0097] − is an inorganic anion;
  • and in formula (3) [0098]
  • R[0099] 16, R17, R18 and R19 are identical or different and are a linear or branched alkyl radical having 1 to 22 carbon atoms; or an unsubstituted or substituted aryl radical or a C1-C4-alkylaryl radical, where aryl has the meaning of phenyl or naphthyl, and said substituents are halogen,
  • C[0100] 1-C4-alkyl, C1-C4-alkoxy, nitro or cyano; Z has the meaning of N or P, and Y− is an inorganic anion;
  • and in formula (4) [0101]
  • R[0102] 20 and R21 are identical or different and are a linear or branched alkyl radical having 1 to 16 carbon atoms;
  • x is an integer from 2 to 6 and [0103]
  • s is an integer from 1 to 60; [0104]
  • or one of the radicals R[0105] 20 and R21 is hydrogen and the other one of the radicals is a linear or branched alkyl radical having 1 to 16 carbon atoms,
  • x is an integer from 2 to 6 and s is an integer from 2 to 50, or the radicals R[0106] 20 and R21 are hydrogen, x is an integer from 2 to 6 and s is an integer from 3 to 5.
  • The present invention relates in particular to mixtures of substances which comprise at least one compound of the formula (1) and at least one compound selected from the group of quaternary ammonium compounds of the formula (2), quaternary ammonium salts and phosphonium salts of the formula (3), polyethers of the formula (4) and crown ethers, in which in formula (2) R[0107] 11, R12 and R13 are identical or different and are a linear or branched radical of the formula —(CpH2pO)rR15 in-which R15 is hydrogen or a linear or branched alkyl radical having 1 to 8 carbon atoms, p is an integer from 1 to 5 and r is an integer from 2 to 10; or a linear or branched alkyl radical having 1 to 18 carbon atoms; or an unsubstituted phenyl or naphthyl radical; R14 is a linear or branched radical of the formula —(CpH2pO)rR15, in which R15 is hydrogen or a linear or branched alkyl radical having 1 to 8 carbon atoms, p is an integer from 1 to 5 and r is an integer from 2 to 10; and X− is fluoride, chloride, bromide, SO4 2−/2 or hydrogen sulfate.
  • Mixtures of substances of particular interest are those comprising at least one compound of the formula (1) and at least one compound from the group of quaternary ammonium compounds of the formula (2). [0108]
  • Mention should also be made of mixtures of substances of the above type comprising at least one ammonium salt or phosphonium salt of the formula (3), in which in formula (3) R[0109] 16, R17, R18 and R19 are identical or different and are a linear or branched alkyl radical having 1 to 16 carbon atoms; or an unsubstituted or substituted aryl radical or a C1-C4-alkylaryl radical, where aryl has the meaning of phenyl or naphthyl, and said substituents are halogen, C1-C4-alkyl, C1-C4-alkoxy, nitro or cyano.
  • Mixtures of substances of the above type comprising at least one polyether of the formula (4) or crown ether, in which in formula (4) R[0110] 20 and R21 are identical or different and are hydrogen or a linear or branched alkyl radical having 1 to 8.1carbon atoms, x is an integer from 2 to 3 and s is an integer from 4 to 50, are likewise of interest.
  • The mixtures of substances normally comprise from 5 to 95% by weight, in particular 20 to 80% by weight, preferably 25 to 75% by weight, of at least one compound of the formula (1). The residual 95 to 5% by weight, in particular 80 to 20% by weight, preferably 75 to 25% by weight, of the mixtures of substances account for the remainder, namely at least one compound selected from the group of quaternary ammonium compounds of the formula (2) of quaternary ammonium or phosphonium salts of the formula (3), polyethers of the formula (4) and crown ethers, in particular at least one compound from the group of quaternary ammonium compounds of the formula (2). [0111]
  • The present invention further relates to a process for preparing compounds of the formula [0112]
    Figure US20040029723A1-20040212-C00017
  • It comprises reacting a phosphorus pentahalide in the presence of an inert solvent at −70 to 140° C., in particular −30 to 120° C., preferably −15 to 60° C., with from 1 to 6 mol, in particular 1 to 2.5 mol, of [0113]
    Figure US20040029723A1-20040212-C00018
  • HN{(CH[0114] 2—CH2—O)mR5}2
    Figure US20040029723A1-20040212-C00019
  • or HN{(CH[0115] 2—CH2—N(R7))nR8}, per halogen equivalent to be exchanged, and subsequently reacting the reaction product with from 1 to 10 mol, in particular 1 to 3 mol, of
    Figure US20040029723A1-20040212-C00020
  • or HNR[0116] 9R10 per halogen equivalent still to be exchanged. This reaction of the reaction product takes place at −15 to 140° C., in particular 0 to 130° C., preferably 20 to 130° C.
  • The phosphorus pentahalide employed is PCl[0117] 5 or PBr5, in particular PCl5.
  • The inert solvent employed is an aliphatic, cycloaliphatic or aromatic hydrocarbon or a mono- or polychlorinated aliphatic, cycloaliphatic or aromatic hydrocarbon. [0118]
  • Very suitable inert solvents are, for example, hexane, cyclohexane, methylcyclohexane, toluene, ethylbenzene, mesitylene, o-xylene, m-xylene, p-xylene, technical mixtures of isomeric xylenes, methylene chloride, tetrachloroethane, chlorobenzene, dichlorobenzene or chlorotoluene. It is also possible to use mixtures of solvents. [0119]
  • The phosphorus pentahalide is suspended or dissolved in the inert solvent and the reaction is carried out with the addition of the aforementioned nitrogen-containing compounds. [0120]
  • This results in compounds of the formula (1) in which X[0121] − is a halide. If required, the halide can be exchanged for another one of the aforementioned anions by metathesis.
  • The invention further relates to the use of the compounds of the formula (1) as catalyst and cocatalyst for phase-transfer reactions, nucleophilic substitutions and halogen-fluorine exchange reactions. [0122]
  • The invention further relates to the use of the mixtures of substances comprising at least one compound of the formula (1) and at least one compound selected from the group of quaternary ammonium compounds of the formula (2), quaternary ammonium salts or phosphonium salts of the formula (3), polyethers of the formula (4) and crown ethers as catalyst for phase-transfer reactions, nucleophilic substitutions and halogen-fluorine exchange reactions.[0123]
    • EXAMPLES
  • The following examples describe the present invention further without restricting it. [0124]
  • Experimental Section [0125]
  • Preparation of the aminophosphonium compounds (aminophosphonium salts) [0126]
    • Example 1 Bis(2-methoxyethyl)amino-tris(pyrrolidino)phosphonium Chloride
  • 104.12 g (0.5 mol) of phosphorus pentachloride are introduced into 400 g of chlorobenzene and cooled to −20 to −10° C. At this temperature, 66.89 g (0.5 mol) of bis-(2-methoxyethyl)amine are added dropwise in such a way that the internal temperature does not exceed 0° C. After the addition, the mixture is allowed to warm slowly to 30° C. and is then heated at 90-100° C. for one hour. [0127]
  • It is then cooled again to 10° C., and 214.5 g (3.0 mol) of pyrrolidine are added dropwise in such a way that the internal temperature does not exceed 15° C. After the addition, the mixture is heated to reflux for two hours. [0128]
  • After cooling to 0° C., 779.94 g (3.9 mol) of 20% strength sodium hydroxide solution are cautiously used to make alkaline. The aqueous phase is separated off and discarded. Excess amine is then distilled out of the organic phase. After the end of the distillation, HCl is used to acidify to pH=6-7 and, after filtration, the chloro-benzene is stripped off in a rotary evaporator. [0129]
  • Elemental analysis: C=55.2%, H=8.9%, N=12.9%, P=7.0%, Cl=8.2% [0130]
    • Example 2 Bis(bis(2-methoxyethyl)amino)-bis(pyrrolidino)phosphonium Bromide
  • 104, 12 g (0.5 mol) of phosphorus pentachloride are introduced into 400 g of chlorobenzene and cooled to −20 tol ° C. At this temperature, 133.78 g (1 mol) of bis-(2-methoxyethyl)amine are added dropwise in such a way that the internal temperature does not exceed 0° C. After the addition, the mixture is heated at 100° C. for one hour. [0131]
  • It is then cooled again to 10° C., and 214.55 g (3.0 mol) of pyrrolidine are added dropwise in such a way that the internal temperature does not exceed 15° C. After the addition, the mixture is heated to reflux for two hours. After cooling to 0° C., 779.94 g (3.9 mol) of 20% strength sodium hydroxide solution (equivalent to 155.99 g of NaOH) are cautiously used to make alkaline. The aqueous phase is separated off and discarded. After addition of 71.93 g (0.6 mol) of potassium bromide, excess free amine is distilled out of the organic phase. After the end of the distillation, HBr is used to acidify to pH=6-7 and, after filtration, the chlorobenzene is stripped off in a rotary evaporator. [0132]
  • Elemental analysis: C=46.9%, H=8.8%, N=10.6%, P=5.9%, Br=15.2%, Cl=0.14% [0133]
    • Example 3 (n-Butyl-ethylamino)-tris-(pyrrolidino)phosphonium Bromide
  • 42.7 g (0.6 mol) of pyrrolidine are added dropwise to 20.8 g (0.1 mol) of PCl[0134] 5 in 100 ml of chlorobenzene in 1 hour so that the internal temperature does not exceed 15° C. After the addition, the mixture is stirred at 50° C. for one hour and then, at a reaction temperature of 25° C., 16 g (0.22 mol) of n-butylamine are added.
  • After 1 hour under reflux, the mixture is again cooled to 25° C. and hydrolyzed with 200 ml of ice-water, and the aqueous phase is separated off. After the excess amine has been distilled off, 19.9 g (0.5 mol) of NaOH in 20 ml of water are introduced. At 50° C., 12.0 g (0.11 mol) of ethyl bromide are added dropwise. After stirring at 70° C. for 3 hours, the mixture is cooled to 25° C. and diluted with 200 ml of water. The organic phase is separated off and acidified to pH=6-7 with 60% strength hydro-bromic acid. After all the volatile constituents have been distilled off, 33.6 g (n-butyl-ethylamino)-tris-(pyrrolidino)phosphonium bromide are obtained as a pale brownish oil. [0135]
    • Example 4 Bis(methyl-tetraethoxyethylene)amino-tris(pyrrolidino)phosphonium Chloride
  • Bis(methyl-tetraethoxyethylene)amino-tris(pyrrolidino)phosphonium chloride is prepared in analogy to Example 1 from 104.12 g (0.5 mol) of phosphorus penta-chloride, 198.75 g (0.5 mol) of bis-(methyl-tetraethoxyethylene)amine (═HN{(CH[0136] 2—CH2—O)4CH3}2) and 214.55 g (3.0 mol) of pyrrolidine.
  • Elemental analysis: C=53.6%, H=9.6%, N=8.1%, P=4.3%, Cl=5.6% [0137]
    • Example 5 Bis(bis(methyl-tetraethoxyethylene)amino)-bis(pyrrolidino)-phosphonium Chloride
  • Bis(bis(methyl-tetraethoxyethylene)amino)-bis(pyrrolidino)phosphonium chloride is prepared in analogy to Example 2 from 104.12 g (0.5 mol) of phosphorus penta-chloride, 397.51 g (1 mol) of bis-(methyl-tetraethoxyethylene)amine (═HN{(CH[0138] 2—CH2—O)4CH3}2) and 214.55 g (3.0 mol) of pyrrolidine.
  • Elemental analysis: C=44.7%, H=8.3%, N=6.5%, P=3.7%, Cl=4.5% [0139]
    • Example 6 Tris(2-methoxyethyl)amino-(diethylamino)phosphonium Bromide
  • 104.12 g (0.5 mol) of phosphorus pentachloride are introduced into 400 g of chlorobenzene and cooled to −20 to −10° C. At a reaction temperature of <5° C., 401.34 g (3 mol) of bis-(2-methoxyethyl)amine are added dropwise. After the addition, the mixture is slowly allowed to warm to 30° C. and is then heated at 100° C. for one hour. [0140]
  • At 20° C., 36 g (2.1 mol) of ammonia are passed in. After hydrolysis with 850 g of 20% strength aqueous sodium hydroxide solution, the chlorobenzene and the excess bis(2-methoxyethyl)amine are distilled out of the organic phase (120° C., 10 mbar). The oily residue is taken up in 300 ml of chlorobenzene, and 340 g of 50% strength aqueous sodium hydroxide solution are added. At 50° C., 119 g (1.1 mol) of ethyl bromide are added dropwise, and the mixture is then stirred at 70° C. for three hours to complete the reaction. Then, at 20° C., 350 ml of water are added and, after phase separation, the organic phase is neutralized with 24 g of 36% strength hydrobromic acid. Removal of all volatile constituents by distillation results in 33.6 g of tris(2-methoxyethyl)amino-(diethylamino)phosphonium bromide as a brownish oil: [0141]
  • Elemental analysis: C=36.1%, H=7.9%, N=7.5%, P=4.15%, Br=9.8%, Cl=0.5%. [0142]
    • Example 7 N-Methylpiperazino-tris(pyrrolidino)phosphonium Chloride
  • 41.65 g (0.2 mol) of phosphorus pentachloride are introduced into 200 g of toluene and cooled to −20° C. Then 20.03 g (0.2 mol) of N-methylpiperazine are added dropwise in such a way that the internal temperature does not exceed 5° C. After the addition, the mixture is heated at 100° C. for one hour. [0143]
  • At 10° C., 56.9 g (0.8 mol) of pyrrolidine are added dropwise. After the addition, the mixture is allowed to warm slowly to 20° C. After a further 30 min, it is heated to reflux for two hours. [0144]
  • After hydrolysis with 20% strength aqueous sodium hydroxide solution, the toluene and the excess amine are distilled out of the organic phase (120° C., 10 mbar). 69.6 g of N-methylpiperazino-tris(pyrrolidino)phosphonium chloride are obtained as a brownish oil. [0145]
  • Elemental analysis: C=54.3%, H=9.6%, N=18.5%, P=8.15%, Cl=9.7% [0146]
    • Example 8 Dioctylamino-tris(pyrrolidino)phosphonium Chloride
  • Dioctylamino-tris(pyrrolidino)phosphonium chloride is prepared in analogy to Example 1 from 41.65 g (0.2 mol) of phosphorus pentachloride, 48.3 g (0.2 mol) of dioctylamine and 99.6 g (1.4 mol) of pyrrolidine. [0147]
  • Elemental analysis: C=65.3%, H=11.6%, N=10.5%, P=5.9%, Cl=7.0% [0148]
    • Example 9 Morpholino-tris(pyrrolidino)phosphonium Chloride
  • Morpholino-tris(pyrrolidino)phosphonium chloride is prepared in analogy to Example 1 from 104.12 g (0.5 mol) of phosphorus pentachloride, 43.6 g (0.5 mol) of morpholine and 214.6 g (3.0 mol) of pyrrolidine. [0149]
  • Elemental analysis: C=52.8%, H=9.0%, N=15.3%, P=8.4%, Cl=10.1% [0150]
  • The corresponding bromide is obtained by salts metathesis in analogy to Example 2. [0151]
    • Example 10 Bis(morpholino)-bis(pyrrolidino)phosphonium Chloride
  • Bis(morpholino)-bis(pyrrolidino)phosphonium chloride is prepared in analogy to Example 2 from 104.12 g (0.5 mol) of phosphorus pentachloride, 87.12 g (1 mol) of morpholine and 214.55 g (3.0 mol) of pyrrolidine. [0152]
  • Elemental analysis: C=50.6%, H=8.7%, N=14.6%, P=8.0%, Cl=9.5% [0153]
  • The corresponding bromide is obtained by salt metathesis in analogy to Example 2. [0154]
    • Example 11 Bis(2-methoxyethyl)amino-tris(piperidino)phosphonium Chloride
  • Bis(2-methoxyethyl)amino-tris(piperidino)phosphonium chloride is prepared in analogy to Example 2 from 104.12 g (0.5 mol) of phosphorus pentachloride, 66.9 g (0.5 mol) of bis-(2-methoxyethyl)amine and 255.4 g (3.0 mol) of piperidine. [0155]
    • Example 12 Bis(bis(2-methoxyethyl)amino)-bis(piperidino)phosphonium Chloride
  • Bis(bis(2-methoxyethyl)amino)-bis(piperidino)phosphonium chloride is prepared in analogy to Example 1 from 104.12 g (0.5 mol) of phosphorus pentachloride, 133.2 g (1 mol) of bis-(2-methoxyethyl)amine and 212.9 g (2.5 mol) of piperidine. [0156]
    • Comparative Example A: Tetrakis(diethylamino)phosphonium Bromide
  • (Comparison Substance) [0157]
  • 109.7 g (1.5 mol) of diethylamine are added dropwise to a 52.1 g (0.25 mol) of PCl[0158] 5 in 220 ml of chlorobenzene in 1 hour so that the internal temperature does not exceed 5° C. After the addition, the mixture is stirred at 30° C. for one hour and then, at T=15° C., 30 g of ammonia are passed in:
  • After 1 hour, 340 g of 20% strength sodium hydroxide solution are added, and the aqueous phase is separated off. The excess diethylamine is distilled out of the organic phase. Then 170 g of 50% strength sodium hydroxide solution and 60 g (0.55 mol) of ethyl bromide are added, and the mixture is heated at 50° C. for 4 hours. After phase separation, the organic phase is acidified to pH=6-7 with 60% strength hydrobromic acid. Removal of all the volatile constituents by distillation results in 83.9 g of tetrakis(diethylamino)phosphonium bromide as a pale brownish oil. [0159]
    • Comparative Example B: Tris(dibutylamino)-(diethylamino)phosphonium Bromide
  • (Comparison Substance) [0160]
  • Tris(dibutylamino)-(diethylamino)phosphonium bromide is prepared in analogy to Comparative Example A from 41.65 g (0.2 mol) of phosphorus pentachloride, 77.50 g (0.6 mol) of dibutylamine, an excess of ammonia and 47.9 g (0.44 mol) of ethyl bromide. [0161]
  • Elemental analysis: C=53.2%, H=10.9%, N=12.3%, P=6.75%, Br=16.3%, Cl=0.7% [0162]
  • Testing of the Catalytic Activity: [0163]
  • Preparation of 2,6-difluorobenzaldehyde (DFBAL) from 2-chloro-6-fluorobenzaldehyde (CFBAL) by chlorine-fluorine exchange reaction [0164]
    • Comparative Example 1A and 1 B
  • At 60° C., 4.4 g (0.01 mol) of tetrakis(diethylamino)phosphonium bromide (Comparative Example 1A) or 5.7 g (0.01 mol) of tris(dibutylamino)-(diethylamino)-phosphonium bromide (Comparative Example 1B) and, in each case, 17.6 g (0.03 mol) of methyl-tris(methyltetraethoxy)ammonium chloride [{CH[0165] 3—(O—C2H4)4}3NCH3]Cl, 58.3 g (1 mol) of potassium fluoride and 10 ml of chlorobenzene are successively added to 158.6 g (1 mol) of 2-chloro-6-fluorobenzaldehyde (CFBAL). The reaction mixture is dried by azeotropic distillation of the chlorobenzene under reduced pressure. After 20 hours at 170° C., the formation of 2,6-difluorobenzaldehyde (DFBAL) and the conversion in the reaction are determined by gas chromatography.
    • EXAMPLES
  • In the following examples identified by an * in Table 1, in place of tetrakis(diethylamino)phosphonium bromide there is used an equivalent molar quantity of the aminophosphonium salt indicated in each case in Table 1 (0.01 mol in each case) and 0.03 mol of methyl-tris(methyltetraethoxy)ammonium chloride. The procedure is otherwise analogous to Comparative Example 1A. [0166]
  • The numerical data in Table 1 correspond to GC percentage areas. The difference from 100% (remainder) which is likewise indicated in Table 1 is a measure of side reactions and decomposition. [0167]
    TABLE 1
    Yields of 2,6-difluorobenzaldehyde (DFBAL)
    from the halex reaction of 2-chloro-6-
    fluorobenzaldehyde (CFBAL) in GC % areas
    Re-
    Aminophosphonium salt DFBAL CFBAL mainder
    No catalysts 16.2 72.1 11.7
    [(Et2N)4P]Br 56.1 24.7 19.2
    [(Bu2N) 3(Et2N)P]Br 63.0 20.1 16.9
    [(Me(OCH2CH2)2N)(pyrrolidino)3P]Br * 68.9 15.0 16.1
    [(Me(OCH2CH2)2N)(pyrrolidino)3P]Cl * 67.7 17.8 14.5
    [(Me(OCH2CH2)2N)2(pyrrolidino)2P]Br * 70.2 12.3 17.5
    [{(Et)(Bu)N}(pyrrolidino)3P]Br * 64.4 22.6 13.0
    [{(Me(O—C2H4)4)2N}(pyrrolidino)3P]Br * 71.5 18.4 10.1
    [{(Me(O—C2H4)4)2N}2(pyrrolidino)2P]Br * 70.8 17.2 12.0
    [(N-Me(piperazino)(pyrrolidino)3P]Cl * 68.2 18.2 13.6
    [(Morpholino)(pyrrolidino)3P]Br * 68.5 18.1 13.4
    [(Morpholino)(pyrrolidino)3P]Cl * 68.2 17.1 14.7
    [(Morpholino)2(pyrrolidino)2P]Br * 66.3 19.7 14.0
    [(Morpholino)2(pyrrolidino)2P]Cl * 65.8 20.1 14.1
    [(Me(OCH2CH2)2N)(piperidino)3P]Cl * 71.2 16.8 12.0
    [(Me(OCH2CH2)2N)2(piperidino)2P]Cl * 70.4 18.2 11.4
  • Testing of the Catalytic Activity: [0168]
  • Preparation of 2,6-difluorobenzaldehyde (DFBAL) and 2-chloro-6-fluorobenzaldehyde (CFBAL) from 2,6-dichlorobenzaldehyde (DCBAL) by chlorine-fluorine exchange reaction. [0169]
    • Comparative Example 2A and 2 B
  • At 60° C., 8.8 g (0.02 mol) of tetrakis(diethylamino)phosphonium bromide (Comparative Example 2A) or 11.35 g (0.02 mol) of tris(dibutylamino)(diethylamino)phosphonium bromide (Comparison Example 2B) and, in each case, 35.2 g (0.06 mol) of methyl-tris(methyltetraethoxy)ammonium chloride, 116.2 g (2 mol) of potassium fluoride and 10 ml of chlorobenzene are successfully added to 175.0 g (1 mol) of 2,6-dichlorobenzaldehyde (DCBAL). The reaction mixture is dried by azeotropic distillation of the chlorobenzene under reduced pressure. After 20 hours at 165° C., the formation of 2-chloro-6-fluorobenzaldehyde (CFBAL) and 2,6-difluorobenzaldehyde (DFBAL) and the conversion in the reaction are determined by gas chromatography. [0170]
    • EXAMPLES
  • In the following examples identified by an * in Table 2, in place of tetrakis-(diethylamino)phosphonium bromide there is used an equivalent molar quantity of the aminophosphonium salt indicated in each case (0.02 mol in each case) and 0.06 mol of methyl-tris(methyltetraethoxy)ammonium chloride. The procedure is otherwise analogous to Comparative Example 2A. [0171]
  • The numerical data in Table 2 correspond to GC percentage areas. The difference from 100% (remainder) which is likewise indicated in Table 2 is a measure of side reactions and decomposition. [0172]
    TABLE 2
    Yields of 2,6-difluorobenzaldehyde (DFBAL) and 2-chloro-6-fluorobenzaldehyde
    (CFBAL) from the halex reaction of 2,6-dichlorobenzaldehyde (DCBAL) in GC %
    areas
    Aminophosphonium salt DFBAL CFBAL DCBAL Remainder
    no catalyst 1.2 11.4 71.5 15.9
    [(Et2N)4P]Br 40.2 26.9 11.2 21.7
    [(Bu2N)3(Et2N)P]Br 41.1 27.5 10.4 21.0
    [(Me(OCH2CH2)2N)(pyrrolidino)3P]Br * 51.1 36.1 1.8 11.0
    [(Me(OCH2CH2)2N)(pyrrolidino)3P]Cl * 50.7 37.8 2.1 9.4
    [(Me(OCH2CH2)2N)2(pyrrolidino)2P]Br * 50.6 37.3 1.4 10.7
    [{(Et)(Bu)N}(pyrrolidino)3P]Br * 43.6 31.2 8.6 16.6
    [(Octyl2N)(pyrrolidino)3P]Br * 41.6 33.5 8.1 16.8
    [{(Me(O—C2H4)4)2N}(pyrrolidino)3P]Br * 53.8 31.4 3.9 10.9
    [{(Me(O—C2H4)4)2N}2(pyrrolidino)2P]Br * 50.4 36.8 2.1 10.7
    [(N-Me(piperazino)(pyrrolidino)3P]Cl * 46.9 38.2 4.4 10.5
    [(Morpholino)(pyrrolidino)3P]Br * 46.9 32.3 5.1 15.7
    [(Morpholino)(pyrrolidino)3P]Cl * 47.2 34.8 5.4 12.6
    [(Morpholino)2(pyrrolidino)2P]Br * 47.8 35.6 5.2 11.4
    [(Morpholino)2(pyrrolidino)2P]Cl * 49.6 31.9 4.8 13.7
    [(Me(OCH2CH2)2N)(piperidino)3P]Cl * 54.2 34.4 1.7 9.7
    [(Me(OCH2CH2)2N)2(piperidino)2P]Cl * 53.1 35.5 1.5 9.9
  • In Tables 1 and 2, Me stands for methyl, Et for ethyl and Bu for butyl, Me(O—C[0173] 2H4)4 for methyl-tetraethoxyethylene
    Figure US20040029723A1-20040212-C00021

Claims (12)

1. A compound of the formula
Figure US20040029723A1-20040212-C00022
in which one, two or three of the radicals R1, R2, R3 and R4 are
Figure US20040029723A1-20040212-C00023
—N{(CH2—CH2—O)mR5}2,
Figure US20040029723A1-20040212-C00024
or —N{(CH2—CH2—N(R7))nR8}2
where m and n are an integer from 1 to 10, R5, R6, R7 and R8 are, independently of one another, identical or different and are a straight-chain or branched alkyl radical having 1 to 10 carbon atoms, and the remaining radical(s) R1 to R4 are
Figure US20040029723A1-20040212-C00025
or —NR9R10, where R9 and R10 are identical or different and are a straight-chain or branched alkyl radical having 1 to 10 carbon atoms,
and X− is an inorganic or organic anion or an equivalent of a multiply charged inorganic or organic anion.
2. A compound as claimed in claim 1, wherein one or two of the radicals R1, R2,
Figure US20040029723A1-20040212-C00026
—N{(CH2—CH2—O)mR5}2,
Figure US20040029723A1-20040212-C00027
or —N{(CH2—CH2—N(R7))nR8}2
and the remaining radicals R1 to R4 are
Figure US20040029723A1-20040212-C00028
or —NR9R10.
3. A compound as claimed in claim 1, wherein m and n are an integer from 1 to 6, and R5, R6, R7, R8, R9 and R10 are identical or different and are a straight-chain or branched alkyl radical having 1 to 4 carbon atoms.
4. A compound as claimed in claim 1, wherein X− is F−, Cl−, Br−, I−, ClO4 −, BF4 −, PF6 −, NO3 −, HSO4 −, ½ SO4 2−, H2PO4 −, ½ HPO4 2−, ⅓ PO4 3−, R′—COO−, where R′ is an alkyl radical having 1 to 9 carbon atoms, a phenyl radical, benzyl radical or naphthyl radical, R″—SO3 −, where R″ is an alkyl radical having 1 to 18 carbon atoms, a phenyl radical, tolyl radical or naphthyl radical, HCO3 −, ½ CO3 2− or ½ C6H4(COO−)2.
5. A mixture of substances comprising at least one compound of the formula
Figure US20040029723A1-20040212-C00029
in which R1, R2, R3, R4 and X have the above meaning, and at least one compound selected from the group of quaternary ammonium compounds of the formula
Figure US20040029723A1-20040212-C00030
quaternary ammonium salts or phosphonium salts of the formula
Figure US20040029723A1-20040212-C00031
polyethers of the formula R20—(O—CxH2x)s—OR21 (4) and crown ethers,
in which in formula (2) R11, R12 and R13 are identical or different and are a linear or branched radical of the formula —(CpH2pO)rR15 in which R15 is hydrogen or a linear or branched alkyl radical having 1 to 16 carbon atoms, p is an integer from 1 to 10 and r is an integer from 1 to 15;
or a linear or branched alkyl radical having 1 to 30 carbon atoms;
or an unsubstituted phenyl or naphthyl radical, or a substituted phenyl or naphthyl radical, where the substituents have the meaning of halogen, C1-C4-alkyl, C1-C4-alkoxy, nitro or cyano;
R14 is a linear or branched radical of the formula —(CpH 2pO)rR15 and
Y− is an inorganic anion;
and in formula (3)
R16, R17, R18 and R19 are identical or different and are a linear or branched alkyl radical having 1 to 22 carbon atoms; or an unsubstituted or substituted aryl radical or a C1-C4-alkylaryl radical, where aryl has the meaning of phenyl or naphthyl, and said substituents are halogen,
C1-C4-alkyl, C1-C4-alkoxy, nitro or cyano; Z has the meaning of N or P, and Y− is an inorganic anion;
and in formula (4)
R20 and R21 are identical or different and are a linear or branched alkyl radical having 1 to 16 carbon atoms;
x is an integer from 2 to 6 and
s is an integer from 1 to 60;
or one of the radicals R20 and R21 is hydrogen and the other one of the radicals is a linear or branched alkyl radical having 1 to 16 carbon atoms,
x is an integer from 2 to 6 and s is an integer from 2 to 50, or the radicals R20 and R21 are hydrogen, x is an integer from 2 to 6 and s is an integer from 3 to 5.
6. A mixture of substances as claimed in claim 5, which comprise at least one compound of the formula (1) and at least one compound selected from the group of quaternary ammonium compounds of the formula (2), quaternary ammonium salts and phosphonium salts of the formula (3), polyethers of the formula (4) and crown ethers, in which in formula (2) R11, R12 and R13 are identical or different and are a linear or branched radical of the formula —(CpH2pO)rR5 in which R15 is hydrogen or a linear or branched alkyl radical having 1 to 8 carbon atoms, p is an integer from 1 to 5 and r is an integer from 2 to 10; or a linear or branched alkyl radical having 1 to 18 carbon atoms; or an unsubstituted phenyl or naphthyl radical; R14 is a linear or branched radical of the formula —(CpH 2pO)rR15, in which R15 is hydrogen or a linear or branched alkyl radical having 1 to 8 carbon atoms, p is an integer from 1 to 5 and r is an integer from 2 to 10; and X− is fluoride, chloride, bromide, SO4 2−/2 or hydrogen sulfate.
7. A mixture of substances as claimed in claim 5, which comprises at least one compound of the formula (1) and at least one compound from the group of quaternary ammonium compounds of the formula (2).
8. A process for preparing compounds of the formula
Figure US20040029723A1-20040212-C00032
which comprises reacting a phosphorus pentahalide in the presence of an inert solvent at from −70 to 140° C. with from 1 to 6 mol of
Figure US20040029723A1-20040212-C00033
HN{(CH2—CH2—O)mR5}2,
Figure US20040029723A1-20040212-C00034
or HN{(CH2—CH2—N(R7))nR8}, per halogen equivalent to be exchanged, and subsequently reacting the reaction product with from 1 to 10 mol of
Figure US20040029723A1-20040212-C00035
or HNR9R10 per halogen equivalent still to be exchanged.
9. The process as claimed in claim 8, wherein PCl5 or PBr5 is employed as phosphorus pentahalide.
10. The process as claimed in claim 8, wherein an aliphatic, cycloaliphatic or aromatic hydrocarbon or a mono- or polychlorinated aliphatic, cycloaliphatic or aromatic hydrocarbon is employed as inert solvent.
11. The use of a compound of the formula (1) as catalyst and cocatalyst for phase-transfer reactions, nucleophilic substitutions and halogen-fluorine exchange reactions.
12. The use of a mixture of substances comprising at least one compound of the formula (1) and at least one compound selected from the group of quaternary ammonium compounds of the formula (2), quaternary ammonium salts or phosphonium salts of the formula (3), polyethers of the formula (4) and crown ethers as catalyst for phase-transfer reactions, nucleophilic substitutions and halogen-fluorine exchange reactions.
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US20060069291A1 (en) * 2004-09-24 2006-03-30 General Electric Company Phosphazenium salt phase transfer catalysts
US7138551B2 (en) 2004-11-05 2006-11-21 E. I. Du Pont De Nemours And Company Purification of fluorinated alcohols
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US20060241300A1 (en) * 2003-02-21 2006-10-26 Thomas Wessel Phosphazenium salt mixtures containing hexakis(amino)diphosphazenium, tetrakis(amino)-phosphonium and polyaminophosphazenium salts
US9269998B2 (en) 2013-03-13 2016-02-23 Fluidic, Inc. Concave gas vent for electrochemical cell
US9325037B2 (en) 2013-03-13 2016-04-26 Fluidic, Inc. Hetero-ionic aromatic additives for electrochemical cells comprising a metal fuel
US11664547B2 (en) 2016-07-22 2023-05-30 Form Energy, Inc. Moisture and carbon dioxide management system in electrochemical cells

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