EP1597220A2

EP1597220A2 - Phosphazenium salt mixtures containing hexakis(amino)diphosphazenium, tetrakis(amino)-phosphonium and polyaminophospazenium salts

Info

Publication number: EP1597220A2
Application number: EP04709990A
Authority: EP
Inventors: Thomas Wessel; Daniel Decker; Thomas Sommer; Hagen HÜNIG; Reinhard Schwesinger
Original assignee: Clariant Produkte Deutschland GmbH; Clariant GmbH
Current assignee: Clariant Produkte Deutschland GmbH
Priority date: 2003-02-21
Filing date: 2004-02-11
Publication date: 2005-11-23
Also published as: DE10307558A1; WO2004074296A2; WO2004074296A3; JP2006518273A; US20060241300A1

Abstract

The invention relates to mixtures containing 5 99.5 wt. % of a compound of formula (I), 95 0.5 wt. % of a compound of formula (II) and a maximum of 10 wt. % of one of several compounds of general formula (III a), wherein A<1> - A<32> which are independent from each other are equal or different and represent a straight-chained or branched alkyl or alkenyl having 1 - 12 carbon atoms, cycloalkyl having 4 8 carbon atoms, an aryl having 6 -12 carbon atoms, an aralkyl having 7 - 12 carbon atoms, or A<1>-A<2>, A<3>-A<4>, A<5>-A<6> etc. - A<31>-A<32> which are independent from each other and are equal or different and are connected together directly or via O or N-A<33> to a ring having 3 - 7 ring members, A<33> represents an alkyl having 1 - 4 carbon atoms. X1 and/or X2 and/or X3 which are independent from each other represent a radical of formula (III b), or the radical X1 and/or X2 and/or X3 as well as a straight-chained or branched alkyl or alkenyl having 1 - 12 carbon atoms, cycloalkyl having 4 - 8 carbon atoms represent an aryl having 6 - 12 carbon atoms, an aralkyl having 7 - 12 carbon atoms, or respectively the radicals which are disposed on an identically bound nitrogen atom, e.g. A<1> and A<2>, A<3> and A<4>, A<5> and A<6> etc. - A<31> and A<32> which are independent from each other are equal or different and are connected together directly or via O or N-A<33> to a ring having 3 - 7 ring members and A<33> represents an alkyl having 1 - 4 carbon atoms and B<-> represents a single-valent organic or inorganic acid radical or the equivalent of a multi-valent acid radical. The mixtures can be used as catalysts and co-catalysts for phase transfer reactions, nucleophilic substitution reactions or halogen-fluoro-exchange reactions.

Description

description

Phosphazenium salt mixtures containing hexakis (amino) diphosphazenium, tetrakis (amino) phosphonium and polyaminophospazenium salts

The present invention relates to aminophosphazenium salt mixtures, a process for their preparation and their use as catalysts for phase transfer reactions, nucleophilic substitution reactions or halogen-fluorine exchange reactions.

Find aminophosphonium salts and polyaminophosphazenium salts, e.g. in US-A-5,824,827, EP-A-1 070 723, EP-A-1 070 724 and EP-A-1 266 904, use as catalysts in the preparation of fluorine-containing compounds by means of a halogen exchange reaction (Halogen Exchange = Halex reaction).

The aminophosphonium salts mentioned in US Pat. No. 5,824,827, EP-A-1 070 723 and mixtures containing them (EP-A-1 070 724) provide good results in the catalysis of Halex reactions, but are compared to those Polyaminophosphazenium salts less active catalysts. The previously known syntheses of polyamino-phosphazenium compounds are, however, very complex and associated with disadvantages, so that their large-scale use has so far been out of the question.

The preparation and isolation of pure hexakis (amino) diphosphazenium salts according to R. Schwesinger et al., Liebigs Ann. 1996, 1055-1081 is carried out, for example, by first producing a chlorotetrisaminophosphonium salt from phosphorus pentachloride with a secondary amine and then reacting it with a tris (amino) phosphorus imine to form hexakis (amino) diphosphazenium chloride. The phosphorus imine must first be prepared by reacting the chlorotisaminophosphonium salt with ammonia and then treating it with potassium methylate in methanol. A simpler one by R. Schwesinger et al. The variant described relates to the synthesis of hexakis (dimethylamino) diphosphazenium tetrafluoroborate (Angew. Chem. 103 (1991), 1376 or Angew. Chem. 104 (1992), 864) and includes the reaction of phosphorus pentachloride with ammonium chloride and subsequent reaction with dimethylamine and sodium tetrafluoroborate in nitromethane (CH ₃ NO ₂ ) or phosphorus oxychloride (POCI ₃ ).

The higher homologous polyaminophosphazenium salts are produced via multi-stage syntheses (cf. R. Schwesinger et al., Liebigs Ann. 1996, 1055-1081), for example by converting from phosphorus pentachloride with a secondary amine, adding ammonia and subsequent treatment with Potassium methylate in methanol first synthesized an iminotrisaminophosphorane and then reacted it with an alkyliminophosphorus trichloride, which was previously prepared from the corresponding alkylammonium chloride with a mixture of PCI ₅ and PCI ₃ .

These synthesis instructions are associated with a number of disadvantages: When nitromethane is used as a solvent, explosive nitromethane-amine mixtures are formed during the synthesis, so that nitromethane is eliminated as a solvent for the synthesis of the aminophosphazenium salts for safety reasons. The use of phosphorus oxychloride (POCI ₃ ) as a solvent for the synthesis of the hexakis (dimethylamino) diphosphazenium tetrafluoroborate has the disadvantage that it reacts with the dimethylamine to form hexamethylphosphoric acid triamide (HMPT) as an undesired carcinogenic by-product.

Furthermore, the large-scale use of POCI ₃ as a solvent is severely restricted due to its toxicity (classification T +) and requires additional requirements for industrial hygiene measures and the design of technical systems.

In view of the limitations and disadvantages of the aminophosphazenium syntheses described, there is a great need for a simple and inexpensive process for the preparation of Polyaminophosphazenium salts or mixtures containing them, which reduces the use of toxic solvents and starting materials to what is necessary, avoids the formation of carcinogenic by-products as far as possible and leads to catalysts for the Halex reaction which have a comparable catalytic activity to the pure polyaminophosphazenium salts and Eliminates the need to separate the individual components.

The object is achieved by a process for the preparation of aminophosphazenium mixtures which contain 5 to 99.5% by weight, in particular 10 to 95% by weight, preferably 20 to 80% by weight of a compound of the formula (I) 95 to 0.5% by weight, in particular 90 to 5% by weight, preferably 80 to 20% by weight of a compound of the formula (II) and at most 10% by weight, preferably at most 8% by weight, particularly preferably contain at most 5% by weight of one or more compounds of the general formula (III a),

I II

purple

wherein A ¹ to A ^{32 are,} independently of one another, the same or different, and are a straight-chain or branched alkyl or alkenyl having 1 to 12 carbon atoms, cycloalkyl having 4-8 carbon atoms, an aryl having 6 to 12 carbon atoms Aralkyl having 7-12 carbon atoms, or A ¹ -A ² , A ³ -A ⁴ , A ⁵ -A ⁶ etc. to A ³¹ - A ^{32 are} independently of one another, identical or different and directly or via O or NA ³³ with one another are connected to a ring having 3 to 7 ring members and A ^{33 represents} an alkyl having 1 to 4 carbon atoms, where Xi and / or X ₂ and / or X ₃ independently of one another are radicals of the formula (III b), or the radicals Xi and / or X ₂ and / or X ₃ also represent a straight-chain or branched alkyl or alkenyl having 1 to 12 carbon atoms, cycloalkyl having 4 to 8 carbon atoms, an aryl having 6 to 12 carbon atoms, an aralkyl having 7 to 12 carbon atoms, or in each case the radicals which are located on an identically bound nitrogen atom, for example A ¹ and A ² , A ³ and A ⁴ ,

A ⁵ and A ⁶ etc. to A ³¹ and A ^{32 are} independently of one another, identical or different and are bonded to one another directly or via O or NA ³³ to form a ring having 3 to 7 ring members, A ³³ for an alkyl having 1 to 4 carbon atoms and B ^"represents a monovalent organic or inorganic acid residue or the equivalent of a polyvalent acid residue,

wherein a phosphorus pentahalide is first reacted with ammonia or an ammonium halide in an inert solvent with removal of hydrogen halide and then with one or more amines of the general formula HNA ¹ A ² , HNA ³ A ⁴ , etc. to HNA ³¹ A ³² , in which A ¹ to A ^{32 means} the above-mentioned radicals are reacted, the reaction product obtained is adjusted to pH 7 to 15 with aqueous alkali, the organic and aqueous phases are separated and the organic phase is concentrated by distillation or the reaction product is isolated as a solid by completely removing the solvent becomes.

The present invention further relates to the mixtures themselves and their use as catalysts and co-catalysts for phase transfer reactions, nucleophilic substitution reactions or halogen-fluorine exchange reactions.

In the process according to the invention, phosphorus pentahalide (PHal ₅ ) with ammonia or a Implemented ammonium halide, the ratio PHals to ammonia or ammonium halide being 0.5: 1 to 5: 1. The reaction is carried out at a temperature around the range of 25 ° C to 200 ° C in an inert solvent with removal of hydrogen halide. The reaction mixture obtained is then in a second reaction step with one or more amines of the general formula HNA ¹ A ² , HNA ³ A ⁴ , etc. to HNA ³¹ A ³² , in which A ¹ to A ^{32 are} the radicals mentioned above, in a ratio of 6 : 1 to 50: 1, based on the phosphorus pentahalide reacted at -20 to 200 ° C, the reaction product obtained at 0 to 80 ° C with aqueous alkali to a pH of 7 to 15, the organic and the aqueous Phase separated and the organic phase concentrated by distillation. The product obtained is used directly as a solution or isolated as a solid by completely distilling off the solvent. If desired, the composition of the reaction product can be changed with respect to the individual components by recrystallization.

In the reaction of phosphorus pentahalide with ammonia or the ammonium halide, the primary reaction product is a dispersion of various intermediates, to which the amine is usually metered in. The reverse order of addition is also possible.

The ratio of the individual phosphazene structures can be determined by choosing the ratio of phosphorus pentahalide to ammonia or ammonium halide. A low ratio leads to an increased proportion of the components of the formulas purple in the product mixture. Height

Temperatures favor the formation of the more condensed phosphazenium compounds, short reaction times lead to incomplete reactions and the formation of by-products in the subsequent steps.

In the reaction of those obtained in the first reaction step

Intermediates with the amine or amines are used to heat the reaction to bring the reaction mixture to the reaction temperature heat. To complete the reaction, the reaction mixture is stirred at the respective final temperature.

After the second reaction step has ended, the reaction product is treated at 0 to 80 ° C. with aqueous alkali. The lye is used in such amounts that a pH of 7 to 15 is maintained during the treatment. By treatment with the aqueous alkali, hydrolyzable constituents of the reaction product are released and the amine used in excess is released from the hydrohalides of the amine formed during the reaction. The recovered amine can be used again in the reaction.

The aqueous phase is separated from the organic phase, which contains the desired reaction product, the solvent, excess and the amine liberated from the hydrohalides of the amine. The organic phase is then concentrated, e.g. by vacuum distillation and uses the residue directly or completely distills off the solvent and isolates the product as a solid. Precipitation with a second solvent and filtering the precipitate gives a product that is different

Product composition has as a product which is obtained by completely distilling off the solvent. The solvent used for the precipitation is used in an amount of 500 to 5% by weight. If desired, the ratio of the individual components I, II and purple in the mixtures can be changed by recrystallizing the reaction product with a further solvent.

In view of the fact that according to Schwesinger et al. the reaction of the hexachlorodiphosphazenium salt obtained from POCI _{3 is} only described with the sterically less demanding dimethylamine, it is surprising for the experts that this reaction also with sterically demanding amines such as piperidine and pyrrolidine (compare examples 1 to 3) in high selectivity and excellent yields is possible. It is also noteworthy that, with regard to the syntheses described in the literature, the mixtures obtained have a defined composition, ie consist predominantly of two compounds of the formula I and II. A person skilled in the art would have expected that a large number of products would form in the manner of production described.

It is also impressive and to be regarded as unexpected that the mixtures obtained can be used directly as catalysts or cocatalysts in Halex reactions and have a comparable activity or in many cases even have a higher activity than e.g. aminophosphonium salts used in US Pat. No. 5,824,827 and the pure polyaminophosphazenium salts used in DE-A-102 32 811.0.

Chemical reactions at high temperatures and long reaction times usually lead to reaction products with a large number of

By-products that prevent use as a catalyst - without having to carry out complex additional cleaning. As the person skilled in the art knows, catalyst poisons work in very small amounts.

Due to the partly Increased activity of the mixtures as catalysts can lower the reaction temperatures in Halex reactions and thereby higher

Selectivities and yields can be achieved.

The reaction of the phosphorus pentahalide with ammonia or the ammonium halide is carried out at 25 ° C. to 200 ° C., preferably at 50 to 150 ° C., the hydrogen halide formed being removed during the reaction. The halides used are preferably phosphorus pentachloride, phosphorus pentabromide, ammonium chloride and ammonium bromide. It is also possible to produce the phosphorus pentahalide in a preceding reaction step from the corresponding phosphorus trihalide with the halogen.

In a large number of cases, the phosphorus pentahalide is reacted with ammonia or the ammonium halide in a ratio of 0.5: 1 to 5: 1, in particular 1: 1 to 4: 1, preferably 1.5: 1 to 3: 1. The inert solvent used is phosphorus oxychloride (POCI ₃ ), an aliphatic, cycloaliphatic or aromatic hydrocarbon or a single or multiply chlorinated aliphatic, cycloaliphatic or aromatic hydrocarbon. Suitable as solvents are, for example, phosphorus oxychloride, methylcyclohexane, heptane, octane, toluene, ethylbenzene, mesitylene, o-xylene, m-xylene, p-xylene, industrial mixtures of isomeric xylenes, tetrachloroethane, chlorobenzene, chlorotoluene, dichlorobenzene, dichlorotoluene, especially POCl ₃ , Toluene, chlorobenzene and dichlorobenzene. Mixtures of solvents can also be used. For the second reaction stage, the implementation of the reaction product

Phosphorus penta-halide with ammonia or ammonium halide with the amine or amines, the solvents mentioned above are suitable with the exception of phosphorus oxychloride, which is not stable under these conditions.

The hydrogen halide formed during the reaction is continuously removed by letting it escape from the apparatus, supporting the removal of the hydrogen halide through the apparatus with an inert gas stream or by applying a slight vacuum.

After the reaction of the phosphorus pentahalide with ammonia or the ammonium halide has ended, the reaction product with the amine is reacted in a ratio of 6: 1 to 50: 1, in particular 7: 1 to 30: 1, preferably 8: 1 to 25: 1, based on the phosphorus pentahalide used ,

In particular, the following amines, for example, can be used successfully:

Dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, dipentylamine, bis (3-methylbutyl) amine, dihexylamine, bis (2-ethylhexyl) amine, diallylamine, bis (cyclopropylmethyl) amine, dicyclopentylamine, dicyclohex Bis (4-methylcyclohexyl) amine, bis (4-tert-butylcyclohexyl) amine, pyrrolidine, piperidine, N-methylpiperazine, N-ethylpiperazine, morpholine, The amine is added and the reaction is continued at from -20 to 200 ° C., in particular at 0 to 180 ° C., preferably at 20 to 160 ° C.

Continuing the reaction is particularly easy if you go under

Reflux conditions works and chooses a solvent which one

Has boiling point in the desired temperature range.

The reaction is usually operated without pressure, but the reaction can take place under

Pressure are carried out so that solvents can be used whose boiling point is below the temperature range mentioned above.

When the reaction has ended, the reaction product, as already mentioned, is treated at 0 to 80 ° C., in particular 10 to 70 ° C., preferably 25 to 50 ° C., with aqueous alkali, so that a pH of 7 to 15, in particular of 8 to 14.5, preferably 9 to 14. Suitable aqueous lye is, for example, 5 to 50, in particular 15 to 30, preferably 20 to 25% by weight alkali metal or alkaline earth metal hydroxide solution. It is particularly easy to use an appropriate aqueous NaOH or KOH solution.

Following the treatment of the reaction product with the alkali, the aqueous phase is separated from the organic phase. The mixtures of the compounds of the formulas I, II and lilac are in the organic phase.

Partial or complete removal of the volatile constituents, which includes the solvent, excess and the amine released from the hydrohalides of the amine, gives solutions of the mixtures or

Mixture in the form of a solid. By adding a second solvent in which one or more components I, II, lilac have a lower solubility, part of the product mixture can be precipitated and a product with a different product composition can be obtained compared to the starting mixture. If desired, the relative proportions of the individual components in the mixtures can be changed further by recrystallizing the product. It is also possible to exchange the anion B ^" = CI ^" or Br ^" for other monovalent organic or inorganic acid residues or equivalents of a polyvalent acid residue. B ^" in this case stands for F ^" , J ^" , CIO ₄ ^" , BF ₄ ^" , PF ₆ ^", NO _^3", HSO ₄ ^{^_'1/2} S0 ₄ ^2', H ₂ PO ₄ ^{^_"1/2} HPO ₄ ^2", 1/3 PO ₄ ^{3, "R} ¹ ^-COO", wherein R ¹ is an alkyl radical having 1 to 9 carbon atoms, a phenyl radical, benzyl radical or naphthyl radical, R ² -SO ₃ ^", wherein R ² is an alkyl radical having 1 to 18 carbon atoms, a phenyl radical, tolyl radical or naphthyl radical, HCO _^3" "A CO3 ^2" , AC ₆ H ₄ (COO ^" ) 2, CN ^" , R ¹ O ^" , where R ^{1 has} the meaning given above.

B ^" in particular means F ^" , CI ^" , Br ^" , J ^" , BF ₄ ^" , PF ₆ ^" or ^Λ SO ^2" , preferably F ^' , CI ^" , Br ^" for use as Halex catalysts.

The invention further relates to the use of the abovementioned mixtures, which contain the compounds of the formulas I, II and lilac, as catalysts or cocatalysts for phase transfer reactions, nucleophilic substitutions or halex reactions, in particular for phase transfer reactions and halex reactions, preferably for halex reactions.

Example 1 :

750 ml of chlorobenzene are placed in a 41 flat-bottomed flask under argon and 208.3 g (1.0 mol) PCI ₅ and 36.0 g (0.67 mol) NH ₄ CI are introduced in succession. The reaction mixture is slowly heated to 105 ° C and held at 105 ° C until no gas evolution can be detected. The hydrogen chloride released during the reaction is continuously removed via an exhaust pipe and absorbed in water.

The mixture is then cooled to 20 ° C. and 1920 g (22.5 mol) of piperidine are metered in with cooling so that the internal temperature does not exceed 50 ° C. When the addition is complete, the mixture is heated to reflux and followed for 22 hours.

When the reaction has ended, the mixture is cooled to 40 ° C. and 700 g of a 20% strength aqueous sodium hydroxide solution are added. The organic phase is separated off and evaporated to dryness on a rotary evaporator. Piperidine is redistilled from the distillate and used again. The isolated solid is dried and examined by ³¹ P NMR spectroscopy. After this, the mixture consists of 1, 1, 1, 3,3,3-hexakis (piperidino) diphosphazenium chloride (P ₂ PipCI) and tetrakis (piperidino) phosphonium chloride (PiPipCI) in a ratio of 1: 8.

Example 2:

250 ml of toluene are placed in a 21 flat-bottomed flask under argon and 104.5 g (0.5 mol) of PCI ₅ and 9.5 g (0.18 mol) of NH ₄ CI are introduced in succession. The reaction mixture is slowly heated to reflux and stirred until the evolution of gas has ended. The hydrogen chloride released during the reaction is continuously removed via an exhaust pipe.

It is then cooled to 20 ° C. and 355.5 g (5 mol) pyrrolidine are metered in with cooling so that the internal temperature does not exceed 40 ° C. When the addition is complete, the mixture is heated to reflux and followed up for 22 h. When the reaction has ended, the mixture is cooled to 40 ° C. and 350 g of a 20% strength aqueous sodium hydroxide solution are added. The organic phase is separated off and evaporated to dryness on a rotary evaporator. The solid obtained is recrystallized in a mixture of toluene and THF in a ratio of 5: 1. 81g of a 1.7: 1 mixture of 1, 1, 1,3,3,3- Hexakis (pyrrolidino) diphosphazenium chloride (P ₂ PyrCI) and tetrakis (pyrrolidino) phosphonium chloride (PiPyrCI) obtained.

Example 3: 1000 ml of POCI ₃ are placed in a 41 flat-bottomed flask under argon and 208.3 g (1 mol) of PCI ₅ and 17.65 g (0.33 mol) of NH ₄ CI are introduced in succession. The reaction mixture is slowly heated to reflux and stirred until the evolution of gas has ended. The hydrogen chloride released during the reaction is continuously removed via an exhaust pipe. The POCI3 used is then distilled off as completely as possible and replaced by 2000 ml of chlorobenzene. The reaction mixture is cooled to 20 ° C., 1277 g (15 mol) of piperidine are added while cooling with ice and the mixture is stirred at 40 ° C. for 4.5 days. When the reaction has ended, excess piperidine is distilled off and the concentrated reaction mixture is hydrolyzed with 900 g of 22.5% sodium hydroxide solution. The phases are separated and the organic phase is concentrated by distillation. The addition of 500 ml of tetrahydrofuran gives a precipitate which is filtered off with suction and dried in vacuo. 270 g of a mixture of 1, 1, 1, 3,3, 3-hexakis (piperidino) diphosphazenium chloride (P ₂ PipCI) and tetrakis (piperidino) phosphonium chloride (PiPipCI) in a ratio of 1: 1 are obtained.

Example 4:

Preparation of 2,6-difluorobenzaldehyde from 2-chloro-6-fluorobenzaldehyde by means of a chlorine-fluorine exchange reaction using a 1: 1 mixture of 1, 1, 1, 3,3,3-hexakis (piperidino) diphosphazenium chloride (P ₂ PipCI) and tetrakis (piperidino) phosphonium chloride (Pi PipCI)

To 277.5 g of 2-chloro-6-fluorobenzaldehyde (1.75 mol) are added in succession 4.63 g of a 1: 1 mixture (corresponding to 9.5 mmol of catalyst) from 1, 1, 1, 3,3,3 -Hexakis (piperidino) -diphosphazenium chloride and

Tetrakis (piperidino) phosphonium chloride, 92.1 g of potassium fluoride (1.57 mol) and 39.5 g of chlorobenzene were added. The reaction mixture is dried azeotropically by distillation at reduced pressure. Then bring to 190 ° C and Held for 24 hours. Gas chromatographic analysis of the reaction mixture shows 24.6% 2-chloro-6-fluorobenzaldehyde and 75.2% 2,6-difluorobenzaldehyde.

Comparative Example 4a: Preparation of 2,6-difluorobenzaldehyde from 2-chloro-6-fluorobenzaldehyde by means of a chlorine-fluorine exchange reaction using tetrakis (piperidino) phosphonium chloride (PiPipCI) or 1, 1, 1, 3,3,3-hexakis (piperidino) diphosphazenium chloride (P ₂ PipCI) as catalyst:

9.5 mmol of catalyst, 92.1 g of potassium fluoride (1.57 mol) and 39.5 g of chlorobenzene are successively added to 277.5 g of 2-chloro-6-fluorobenzaldehyde (1.75 mol). The reaction mixture is dried azeotropically by distillation at reduced pressure. The mixture is then brought to 190 ° C. and held for 24 hours. The reaction mixture is analyzed by gas chromatography. The following sales were received:

Comparative Example 5:

Preparation of 2,3,4,5,6-pentafluoropyridine from 3,5-dichloro-2,4,6-trifluoropyridine by chlorine-fluorine exchange reaction using tetrakis (piperidino) phosphonium chloride (PiPipCI), 1.1.1 , 3,3,3-Hexakis (pyrrolidino) diphosphazenium chloride (P2PyrCI) or a 1: 1 mixture of PiPipCI and P ₂ PipCI as phase transfer catalysts:

sulfolane

DCTFPy CTFPy PFPy 11 mmol of catalyst, 38.3 g of potassium fluoride (0.66 mol) and 50 g of chlorobenzene are successively added to 135 g of molten sulfolane. The reaction mixture is dried azeotropically by distillation at reduced pressure. Then 44.4 g of 3,5-dichloro-2,4,6-trifluoropyridine are added and the mixture is heated to 190 ° C. in a closed stirred autoclave and held for 24 hours in this reaction. The reaction mixture is analyzed by gas chromatography. The following sales were obtained

Claims

claims:

1. Mixtures containing 5 to 99.5% by weight of a compound of the formula I, 95 to 0.5% by weight of a compound of the formula II and at most 10% by weight of one or more compounds of the general formula III a,

I II

purple

wherein A ¹ to A ^{32 are} independently of one another, identical or different and for a straight-chain or branched alkyl or alkenyl having 1 to 12 carbon atoms, cycloalkyl having 4 to 8 carbon atoms, an aryl having 6 to 12 carbon atoms, an aralkyl having 7 to 12 carbon atoms stand, or A ¹ -A ² , A ³ -A ⁴ , A ⁵ -A ⁶ etc. to A ³¹ -A ³² independently of one another, are the same or different and directly or via O or NA ³³ together to form a ring with 3 to 7 ring members are connected, A ^{33 represents} an alkyl having 1 to 4 carbon atoms, where Xi and / or X ₂ and / or X3 independently of one another are radicals of the formula III b, or the radicals Xi and / or X ₂ and / or X ₃ likewise represent a straight-chain or branched alkyl or alkenyl having 1 to 12 carbon atoms, cycloalkyl having 4 to 8 carbon atoms, an aryl having 6 to 12 carbon atoms, an aralkyl having 7 to 12 carbon atoms, or the radicals which are attached to one there are identically bound nitrogen atoms, for example A ¹ and A ² , A ³ and A ⁴ , A ⁵ and A ⁶ etc. to A ³¹ and A ^{32 are} independently of one another, identical or different and directly or via O or NA ³³ to form a ring are connected to 3 to 7 ring members and A ^{33 stands} for an alkyl with 1 to 4 carbon atoms and B ^"stands for a monovalent organic or inorganic acid residue or the equivalent of a polyvalent acid residue.

2. Mixtures according to claim 1, containing 10 to 95 wt .-% of a compound of formula I, 90 to 5 wt .-% of a compound of formula II and at most 8 wt .-% of compounds of general formula III a.

3. Mixtures according to claim 1, containing 20 to 80 wt .-% of a compound of formula I, 80 to 20 wt .-% of a compound of formula II and at most 5 wt .-% of compounds of general formula III a.

4. A process for the preparation of mixtures according to any one of claims 1 to 3, characterized in that a phosphorus pentahalide is initially inert with ammonia or an ammonium halide in a ratio of 0.5: 1 to 5: 1 at 25 ° C to 200 ° C Reacting solvent with removal of hydrogen halide and then with one or more amines of the general formula HNA ¹ A ² , HNA ³ A ⁴ , etc. to HNA ³¹ A ³² , in which A ¹ to A ^{32 are} the radicals mentioned above, in a ratio of 6: 1 to 50: 1, based on the phosphorus pentahalide used at -20 to 200 ° C to react, the reaction product obtained at 0 to 80 ° C with aqueous alkali to a pH of 7 to 15, the organic and the aqueous phase separates and the organic phase concentrated by distillation.

5. The method according to claim 4, characterized in that one uses for the first reaction stage phosphorus oxychloride, an aliphatic, cycloaliphatic or aromatic hydrocarbon or a single or multiple chlorinated aliphatic, cycloaliphatic or aromatic hydrocarbon as a solvent.

6. The method according to claim 4 or 5, characterized in that an aliphatic, cycloaliphatic or aromatic hydrocarbon or a singly or multiply chlorinated aliphatic, cycloaliphatic or aromatic hydrocarbon is used as the solvent for the second reaction stage.

7. The method according to at least one of claims 4 to 6, characterized in that the phosphorus pentahalide and ammonia or. Ammonium halide in a ratio of 1: 1 to 4: 1.

8. The method according to at least one of claims 4 to 7, characterized in that the reaction product of phosphorus pentahalide and ammonia or ammonium halide is reacted with an amine in a ratio of 7: 1 to 30: 1.

9. Use of the mixtures according to one of claims 1 to 3 as a catalyst and co-catalyst for phase transfer reactions, nucleophilic substitution reactions or halogen-fluorine exchange reactions.