DE10230222A1 - Separation of acids from reaction mixtures by means of an auxiliary base that forms a liquid salt with the acid to result in two non-miscible phases with the product or solution of the product in a suitable solvent - Google Patents

Abstract

A process for the separation of acids from reaction mixtures by means of an auxiliary base (I) is characterized by (a) the base (I) forming a salt with the acid that is liquid at temperatures that do not lead to significant decomposition of the product during separation of the liquid salt (b) the salt of the base (I) forming two non-miscible phases with the product or solution of the product in a suitable solvent.

Description

The present invention describes a process for the simplified separation of acids from reaction mixtures using an ionic liquid.

The chemical specialist often does Problem while to trap acids released from a chemical reaction or to release acids Separate reaction mixtures. Examples of reactions in which acids in The course of the reaction is released by the silylation of alcohols or amines with halosilanes, the phosphorylation of amines or alcohols with phosphorus halides, the formation of sulfonic acid esters or amides from alcohols or amines and sulfonic acid chlorides or anhydrides, eliminations or substitutions.

In these reactions, acids are released which is why an auxiliary base is added, which is usually not a reactant takes part in the actual reaction. As a rule, it is necessary the acids released bind with this base with salt formation to side and subsequent reactions to prevent or simply to remove the acid from the desired Remove reaction product and, if necessary, return it to the process. Become the salts of the bases used are not initially separated, so they can in the presence of the product of value, e.g. by adding another, stronger Base, such as aqueous alkalis, e.g. Sodium hydroxide solution or potassium hydroxide solution. This creates the salt of the stronger base added in this step. Besides, will the original used base set free. These two components, i.e. the salt of the stronger Base and the first set free base (auxiliary base) have to usually also be separated from the valuable product. at With this approach, it is often disadvantageous that the product of value, that is present during the work-up, through the added stronger base itself or other substances in this base, e.g. the water in one aqueous Lye that can be decomposed.

The salts of the auxiliary base with the acid are usually in organic solvents not soluble and have high melting points, so that they are in organic media Form suspensions that are more difficult to handle than, for example Liquids. It would be so desirable the salts of the auxiliary bases in liquid To be able to separate the form. In addition, would the known procedural disadvantages of suspensions eliminated. These are e.g. the formation of incrustations, reduction of the Heat transfer, bad Mixing and stirrability as well as the formation of local supervisory or under-concentrations and so-called hot spots.

The state of the art includes for industrial conducted The following disadvantages:

• 1) Add two auxiliary substances, the auxiliary base as well as another strong base and the resulting task, to separate two auxiliary substances from the valuable product and from each other,
• 2) Handling suspensions
• 3) Separation of the salt of the strong base as a solid.

However, the aim is to be a procedural one simple phase separation by means of a liquid-liquid phase separation.

Out DE-A 197 24 884 and DE-A 198 26 936 Processes for the preparation of carbonyldiimidazoles by phosgenation of imidazoles are known, in which the hydrochloride formed of the imidazole used as starting material is separated from the reaction mixture as a melt. In the DE-A 198 26 936 on page 3, line 5, it is pointed out that the hydrochloride of the imidazole is surprisingly liquid at temperatures of 110-130 ° C. and melts well below the melting point of 158-161 ° C. described in the literature. The inventors state that the reason for this is either the formation of a eutectic mixture of the imidazole hydrochloride with the valuable product carbonyldiimidazole or the formation of a ternary mixture of the imidazole hydrochloride, the valuable product carbonyldiimidazole and solvent chlorobenzene. Although the imidazole hydrochloride should not have been in liquid form, this was surprisingly the case in this particular case. The applicability of this concept for reactions other than phosgenation of imidazoles is not described.

So there was the job, too for others chemical reactions or for the separation of acids, contained in mixtures, but not during a chemical reaction split off, a simplified process for separating acids to find, in which one from an inserted auxiliary base and one Acid formed Salt over a process-technically simple liquid-liquid phase separation separated can be.

The object was achieved by a process for the separation of acids from reaction mixtures by means of an auxiliary base in which the auxiliary base

• b) forms a salt with the acid, which at temperatures liquid is where the product of value during the separation of the liquid salt is not significantly decomposed and
• c) the salt of the auxiliary base with the product of value or the solution of Product of value in a suitable solvent two immiscible liquid Phases.

The person skilled in the art is aware that the separation a liquid Phase of a second liquid phase procedurally much easier to design than one Solids separation.

The technical benefit of the method according to the invention is that the Separation of the auxiliary material by a simple liquid-liquid phase separation can be done so that the procedurally complex handling of solids is eliminated.

Processing the auxiliary materials can take place in the absence of the valuable product, so that the latter is less burdened.

The task is defined by the Invention described here solved. This happens because of auxiliary bases are contained in reaction mixtures or added subsequently, the Salts with cleaved or added in the course of the reaction, i.e. not during acids released from the reaction under the reaction conditions and / or work-up conditions liquid and are immiscible with the product of value that may be dissolved Form phase. Such liquid Salts are often called ionic liquids designated. The acids to be bound can either present freely in the reaction mixture or a complex or an adduct with the product of value or another in the reaction mixture form the present substance. Lewis acids in particular tend to work with substances how to form ketones complexes. These complexes can be broken up by the auxiliary base be, the salt from the auxiliary base in the sense of this invention and the Lewis acid to be separated forms.

The auxiliary bases can be inorganic or organic Be bases, preferably organic.

Mixtures or solutions of Auxiliary bases are used to fulfill the task.

Immiscible means that at least two, through a phase interface separate liquid phases form.

If the pure product of value with the Salt from the auxiliary base and the acid completely or to a greater extent is miscible, an auxiliary, e.g. on solvent can be added to achieve segregation or solubility reduction. This is useful, for example, if the solubility of the salt in the product of value or vice versa is 20% by weight or more, is preferred 15% by weight or more, particularly preferably 10% by weight or more and is very particularly preferably 5% by weight or more. The solubility is determined under the conditions of the respective separation. Solubility is preferred determined at a temperature above the melting point of the Salt is below the lowest of the following temperatures, particularly preferably 10 ° C. below the lowest and most preferably 20 ° C below the lowest:

• - boiling point of the product of value
• - boiling point of the solvent
• - temperature the significant decomposition of the product of value

The solvent is then suitable to look at when the mixture of product of value and solvent the salt or the salt the product of value or a mixture of product of value and solvents can solve less than the amounts specified above. As a solvent Usable are, for example, benzene, toluene, o-, m- or p-xylene, cyclohexane, Cyclopentane, pentane, hexane, heptane, octane, petroleum ether, acetone, Isobutyl methyl ketone, diethyl ketone, diethyl ether, tert-butyl methyl ether, tert-butyl ethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl acetate, Dimethylformamide, dimethyl sulfoxide, acetonitrile or mixtures thereof.

The product of value is usually around non-polar organic or inorganic compounds.

As chemical reactions that the On the basis of the invention, all reactions are possible in which acids are released, with the exception of phosgenation, particularly preferred with the exception of acylations, i.e. Reactions of acid halides and carboxylic anhydrides.

Reactions in which the inventive method can be applied, for example

• - alkylations with alkyl or aralkyl halides, e.g. Methyl chloride, methyl iodide, Benzyl chloride, 1,2-dichloroethane or 2-chloroethanol,
• Silylations, ie reactions with compounds which contain at least one Si-Hal bond, such as SiCl ₄ , (H ₃ C) ₂ SiCl ₂ or trimethylsilyl chloride,
• Phosphorylations, ie reactions with compounds which contain at least one P-Hal bond, such as, for example, PCl ₃ , PCl ₅ , POCl ₃ , POBr ₃ , dichlorophenylphosphine or diphenylchlorophosphine, as also described, for example, by Chojnowski et al., Loc. Cit.
• - Sulfurizations, ie sulfidations, sulfonations, sulfonations and sulfations, with for example sulfuryl chloride (SO ₂ Cl ₂ ), thionyl chloride (SOCl ₂ ), chlorosulfonic acid (ClSO ₃ H), sulfonic acid halides, such as p-toluenesulfonic acid chloride, methanesulfonic acid chloride or trifluoromethanesulfonic acid chloride, or sulfonic acid anhydride, or sulfonic acid anhydride, as described, for example, by Dobrynin, VN et al. Bioorg. Khim. 9 (5), 1983, 706-10,
• - eliminations, in which a C = C double bond is formed with elimination of an acid will or
• - deprotonation, where an acidic hydrogen atom is abstracted from the auxiliary base becomes.

Preferred among the reaction types mentioned are alkylations, silylations, phosphorylations, sulfurizations, Acylations with the exception of phosgenations and eliminations and particularly preferred are silylations, phosphorylations and Sulfurations.

According to the invention, a Acid out Reaction mixtures are separated in which an acid, the not during released to the reaction was added, for example around the Adjust pH or to catalyze a reaction. For example, Lewis acids, which as catalysts for Friedel-Crafts alkylations or acylations were used, can be easily separated.

The acids to be separated for the purposes of this invention can be Bronsted acids and Lewis acids. Which acids are called Brönsted and Lewis acids is described in Hollemann-Wiberg, Textbook of Inorganic Chemistry, 91. – 100. Edition, Walter de Gruyter, Berlin New York 1985, p. 235 and p. 239. The Lewis acids for the purposes of this invention also include the Lewis acids used as Friedel-Crafts catalysts, which are described in George A. Olah, Friedel-Crafts on Related Reactions, Vol. I, 201 and 284-90 (1963). Examples include aluminum trichloride (AlCl ₃ ), iron (III) chloride (FeCl ₃ ), aluminum tribromide (AlBr ₃ ) and zinc chloride (ZnCl ₂ ).

With halogen or hal is in the frame In this document, fluorine (F), chlorine (Cl), bromine (Br) or iodine (I) are preferred Chlorine meant.

Implemented in the sense of a silylation, Phosphorylation or sulfurization are usually compounds which have at least one free O-H, S-H or N-H bond, if necessary after deprotonation by the auxiliary base.

According to the invention, such an auxiliary base can be used Connection used that

• b) a salt with that split off during the reaction Acid forms that liquid at temperatures is where the product of value during the separation of the liquid salt is essentially not decomposed and
• c) the salt of the auxiliary base with the product of value or the solution of Product of value in a suitable solvent two immiscible liquid Phases.

Such auxiliary bases are preferred the

• a) do not participate in the reaction as a reactant.

This auxiliary base may also be preferred additionally

• d) at the same time as a nucleophilic catalyst act in the reaction, i.e. it increases the speed of reaction towards the reaction the implementation without the presence of an auxiliary base by at least 1.5 times, preferably by at least two times, particularly preferably five times, very particularly preferably by at least ten times and in particular at least twenty times.

Such compounds that can be used as bases can Phosphorus-sulfur or contain nitrogen atoms, for example at least one nitrogen atom, preferably one to ten nitrogen atoms, particularly preferably one to five, very particularly preferably one to three and in particular one to two Nitrogen atoms. If necessary, other heteroatoms, such as. Oxygen, sulfur or phosphorus atoms may be included.

Preferred compounds are the at least one five- to six-membered Heterocycle contain at least one nitrogen atom as well optionally has an oxygen or sulfur atom, especially preferably those compounds which have at least one five to contain six-membered heterocycle, one, two or three Has nitrogen atoms and a sulfur or an oxygen atom, very particularly preferably those with two nitrogen atoms.

Particularly preferred compounds are those that have a molecular weight below 1000 g / mol, whole particularly preferably below 500 g / mol and in particular below 250 g / mol.

sowie Oligo- bzw. Polymere, die diese Strukturen enthalten,
worin
R¹, R², R³, R⁴, R⁵ und R⁶ unabhängig voneinander jeweils Wasserstoff, C₁-C₁₈-Alkyl, gegebenenfalls durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbrochenes C₂- C₁₈-Alkyl, C₆-C₁₂-Aryl, C₅-C₁₂-Cycloalkyl oder einen fünf- bis sechsgliedrigen, Sauerstoff-, Stickstoff- und/oder Schwefelatome aufweisenden Heterocyclus bedeuten oder zwei von ihnen gemeinsam einen ungesättigten, gesättigten oder aromatischen und gegebenenfalls durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbrochenen Ring bilden, wobei die genannten Reste jeweils durch funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alky-loxy, Halogen, Heteroatome und/oder Heterocyclen substituiert sein können.Preference is furthermore given to those compounds which can be used as bases and which are selected from the compounds of the formulas (Ia) to (Ir),

and oligomers or polymers that contain these structures,
wherein
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently of one another are hydrogen, C ₁ -C ₁₈ alkyl, optionally by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted Imino groups interrupted C ₂ -C ₁₈ alkyl, C ₆ -C ₁₂ aryl, C ₅ -C ₁₂ cycloalkyl or a five- to six-membered heterocycle having oxygen, nitrogen and / or sulfur atoms or two of them together mean one form an unsaturated, saturated or aromatic ring which may be interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, the radicals mentioned being in each case by functional groups, aryl, alkyl, aryloxy, alkyloxy, Halogen, heteroatoms and / or heterocycles can be substituted.

Mean in it
C ₁ -C ₁₈ alkyl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, hetadecyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1 , 3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α, α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) -ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p -Methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di (methoxycarbonyl) ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl , Diethoxymethyl, diethoxyethyl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2 -yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1,1-dimethyl-2-chloroethyl, 2-methoxyisopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl, 2 -Phenylthioethyl, 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexy 1,2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl and,
C ₂ -C ₁₈ alkyl optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, for example 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6-dioxa- octyl, 11-hydroxy-3,6,9-trioxa-undecyl, 7-hydroxy-4-oxa-heptyl, 11-hydroxy-4,8-dioxa-undecyl, 15-hydroxy-4,8,12-trioxa -pentadecyl, 9-hydroxy-5-oxa-nonyl, 14-hydroxy-5,10-oxa-tetradecyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxa-octyl, 11-methoxy -3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 11-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl, 9-methoxy -5-oxa-nonyl, 14-methoxy-5,10-oxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 11-ethoxy-3,6,9 -trioxa-undecyl, 7-ethoxy-4-oxa-heptyl, 11-ethoxy-4,8-dioxa-undecyl, 15-ethoxy-4,8,12-trioxa-pentadecyl, 9-ethoxy-5-oxa-nonyl or 14-ethoxy-5,10-oxa-tetradecyl.

If two radicals form a ring, these radicals can jointly mean 1,3-propylene, 1,4-butylene, 2-0xa-1,3-propylene, 1-oxa-1,3-propylene, 2-oxa-1, 3-propylene, 1-0xa-1,3-propenylene, 1-aza-1,3-propenylene, 1-C ₁ -C ₄ alkyl-1-aza-1,3-propenylene, 1,4-buta- 1,3-dienylene, 1-aza-1,4-buta-1,3-dienylene or 2-aza-1,4-buta-1,3-dienylene.

The number of oxygen and / or Sulfur atoms and / or imino groups are not limited. In the Rule is they not more than 5 in the rest, preferably not more than 4 and very particularly preferably not more than 3.

Furthermore are between two heteroatoms, as a rule, preferably at least one carbon atom at least two.

Substituted and unsubstituted Imino groups can for example imino, methylimino, iso-propylimino, n-butylimino or be tert-butylimino.

Continue to mean
functional groups carboxy, carboxamide, hydroxy, di (C ₁ -C ₄ alkyl) amino, C ₁ -C ₄ alkyloxycarbonyl, cyano or C ₁ -C ₄ alkyloxy,
C ₆ -C ₁₂ aryl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles, for example phenyl, tolyl, xylyl,? -naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl , Trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, 2-propylnaphthyl, 2-propylnaphthyl, 2-propylnaphthyl, 4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylamino phenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl,
C ₅ -C ₁₂ cycloalkyl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles, for example cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, methylcyclohexohexyl, methylcyclohexohexyl , Dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl,
a five- to six-membered heterocycle containing oxygen, nitrogen and / or sulfur atoms, for example furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimoxypyridyl, dimethylpyridyl, dimethylpyrylyl, Methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl and
C ₁ to C ₄ alkyl, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are preferably, independently of one another, hydrogen, methyl, ethyl, n-butyl, 2-hydroxyethyl, 2-cyanoethyl, 2- (methoxycarbonyl) ethyl, 2- ( Ethoxycarbonyl) ethyl, 2- (n-butoxycarbonyl) ethyl, dimethylamino, diethylamino and chlorine.

Particularly preferred pyridines (Ia) are those in which one of the radicals R ¹ to R ^{5 is} methyl, ethyl or chlorine and all the others are hydrogen, or R ^{3 is} dimethylamino and all the others are hydrogen or all are hydrogen or R ^{2 is} carboxy or carboxamide and all others are hydrogen or R ¹ and R ² or R ² and R ^{3 are} 1,4-buta-l, 3-dienylene and all others are hydrogen.

Particularly preferred pyridazines (Ib) are those in which one of the radicals R1 to R4 is methyl or ethyl and all others are hydrogen or all are hydrogen.

Pyrimidines (Ic), particularly preferred are those in which, to R ⁴ is hydrogen or methyl and R1 is hydrogen, R2 is methyl or ethyl, or R2 and R4 are methyl, R3 is hydrogen and R1 is hydrogen, methyl or ethyl.

Particularly preferred pyrazines (Id) are those in which R1 to R4 are all methyl or all hydrogen.

Particularly preferred imidazoles (Ie) are those where are independent R1 is selected from each other under methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, 2-hydroxyethyl or 2-cyanoethyl and R2 to R4 independently of one another hydrogen, Mean methyl or ethyl.

Particularly preferred 1H-pyrazoles (If) are those in which R1 independently of one another under hydrogen, Methyl or ethyl, R2, R3 and R4 are selected from hydrogen or methyl.

Particularly preferred 3H-pyrazoles (Ig) are those in which, independently of one another, R1 under hydrogen, Methyl or ethyl, R2, R3 and R4 are selected from hydrogen or methyl.

Particularly preferred 4H-pyrazoles (Ih) are those in which R1 to R4 are independent of each other selected from hydrogen or methyl.

Particularly preferred 1-pyrazolines (2i) are those in which R1 to R6 are independent of one another are selected from hydrogen or methyl.

Particularly preferred 2-pyrazolines (Ij) are those in which, independently of one another, R1 under hydrogen, Methyl, ethyl or phenyl and R2 to R6 under hydrogen or methyl selected are.

Particularly preferred 3-pyrazolines (Ik) are those in which R1 or R2 are independent of each other Hydrogen, methyl, ethyl or phenyl and R3 to R6 under hydrogen or selected methyl are.

Particularly preferred imidazolines (I1) are those in which R1 or R2 are independent of each other Hydrogen, methyl, ethyl, n-butyl or phenyl and R3 or R4 under Hydrogen, methyl or ethyl and R5 or R6 under hydrogen or selected methyl are.

Particularly preferred imidazolines (Im) are those in which R1 or R2 are independent of each other Hydrogen, methyl or ethyl and R3 to R6 under hydrogen or Methyl selected are.

Particularly preferred imidazolines (In) are those in which R1, R2 or R3 are independent of one another under hydrogen, methyl or ethyl and R4 to R6 under hydrogen or selected methyl are.

Particularly preferred thiazoles (Io) or oxazoles (Ip) are those in which they are independent of one another
R ¹ under hydrogen, methyl, ethyl or phenyl and
R ² or R3 under hydrogen or methyl
are selected.

Particularly preferred 1,2,4-triazoles (Iq) are those in which are independent of one another
R ¹ or R2 under hydrogen, methyl, ethyl or phenyl and
R ³ under hydrogen, methyl or phenyl
are selected.

Particularly preferred 1,2,3-triazoles (Ir) are those in which are independent of one another
R ¹ under hydrogen, methyl or ethyl and
R ² or R ³ are selected from hydrogen or methyl or
R ² and R ^{3 are} 1,4-buta-1,3-dienylene and all others are hydrogen.

Among these are the pyridines and the imidazoles are preferred.

3-Chloropyridine, 4-dimethylaminopyridine, 2-ethyl-4-aminopyridine, 2-methylpyridine (α-picoline), 3-methylpyridine (β-picoline), 4-methylpyridine (? -Picolin), 2 are very particularly preferred as bases -Ethylpyridine, 2-ethyl-6-methylpyridine, quinoline, isoquinoline, pyridine, 1-C ₁ -C ₄ alkylimidazole, 1-methylimidazole, 1,2-dimethylimidazole, 1-n-butylimidazole, 1,4,5-trimethylimidazole , 1,4-dimethylimidazole, imidazole, 2-methylimidazole, 1-butyl-2-methylimidazole, 4-methylimidazole, 1-n-pentylimidazole, 1-n-hexylimidazole, 1-n-octylimidazole, 1- (2'-aminoethyl ) -imidazole, 2-ethyl-4-methylimidazole, 1-vinylimidazole, 2-ethylimidazole, 1- (2'-cyanoethyl) imidazole and benzotriazole.

Particularly preferred are 1-n-butylimidazole, 1-methylimidazole, 2-methylpyridine and 2-ethylpyridine.

Acids with which the bases can form salts are, for example, hydroiodic acid (HI), hydrogen fluoride (HF), hydrogen chloride (HCl), nitric acid (HNO ₃ ), nitrous acid (HNO ₂ ), hydrobromic acid (HBr), carbonic acid (H ₂ CO ₃₎ ), Hydrogen carbonate (HCO ₃ -), methyl carbonic acid (HO (CO) OCH ₃ ), ethyl carbonic acid (HO (CO) OC ₂ H ₅ ), n-butyl carbonic acid, sulfuric acid (H ₂ SO ₄ ), hydrogen sulfate (HSO ₄ -), Methyl sulfuric acid (HO (SO ₂ ) OCH ₃ ), ethyl sulfuric acid (HO (SO ₂ ) OC ₂ H ₅ ), phosphoric acid (H ₃ PO ₄ ), dihydrogen phosphate (H ₂ PO ₄ ^- ), formic acid (HCOOH), acetic acid (CH ₃ COOH), propionic acid, n- and iso-butyric acid, Pivalic acid, para-toluenesulfonic acid, benzenesulfonic acid, benzoic acid, 2,4,6-trimethylbenzoic acid, mandelic acid, methanesulfonic acid, ethanesulfonic acid or trifluoromethanesulfonic acid, preference is given to hydrogen chloride, acetic acid, p-toluenesulfonic acid, methanesulfonic acid, 2,4,6-trimethylbenzoic acid and trifluoromethanesulfonic acid and particularly preferred is hydrogen chloride.

Such auxiliary bases are preferred their salts from auxiliary bases and acids, have a melting temperature at which in the course of the separation of the salt as a liquid Phase no significant decomposition of the product of value occurs, i.e. less than 10 mol% per hour, preferably less than 5 mol% / h, particularly preferably less than 2 mol% / h and very particularly preferably less than 1 mole% / h.

The melting points of the salts are particularly preferred auxiliary bases are usually below 160 ° C, especially preferably below 100 ° C and most preferably below 80 ° C.

Among the auxiliary bases, those whose salts have an _ET (30) value of> 35, preferably of> 40, particularly preferably of> 42 are very particularly preferred. The _ET (30) value is a measure of the polarity and is described by C. Reichardt in Reichardt, Christian Solvent Effects in Organic Chemistry Weinheim: VCH, 1979. - XI, (Monographs in Modern Chemistry; 3), ISBN 3- 527-25793-4 page 241.

An exceptionally preferred base, which fulfills the task, for example, is 1-methylimidazole. The use of 1-methylimidazole as a base is described, for example, in DE-A 35 02 106 mentioned, but their usability as an ionic liquid is not recognized there.

1-methylimidazole is also still as nucleophilic catalyst effective [Julian Chojnowski, Marek Cypryk, Witold Fortuniak, heteroatom. Chemistry, 1991, 2, 63-70]. Chojnowski et al. have found that 1-methylimidazole compared to triethylamine, the phosphorylation of t-butanol by a factor of 33 and the silylation of pentamethyldisiloxanol accelerated by a factor of 930.

It was also found that the hydrochloride of 1-methylimidazole has a melting point of about 75 ° C and with non-polar organic products of value, e.g. diethoxyphenylphosphine, Triethyl phosphite, ethoxydiphenyl phosphine, alkyl ketene dimer, alkoxysilanes or esters, or solvents is essentially immiscible. So 1-methylimidazole × HCl forms in Contrary to the polar solvent Water, even with acetone, from two immiscible phases. 1-methylimidazole can also serve as an auxiliary base and nucleophilic catalyst and as a liquid Hydrochloride over a process-technically simple liquid-liquid phase separation from organic Media are separated.

Instead of 1-methylimidazole, too 1-Butylimidazole can be used. The hydrochloride of 1-butylimidazole is already liquid at room temperature, so that 1-butylimidazole as an auxiliary base and catalyst for Reactions can be used in which substances are handled, those already decomposable at temperatures above room temperature are. The acetate and formate are also liquid at room temperature of 1-methylimidazole.

Likewise, all derivatives of imidazole can be used, the salts of which have an _ET (30) value of> 35, preferably> 40, particularly preferably> 42 and have a melting temperature at which, in the course of the removal of the salt, as a liquid phase no significant decomposition of the product of value occurs. As mentioned above, the polar salts of these imidazoles form two immiscible phases with less polar organic media.

Another exceptionally preferred base that fulfills the task is 2-ethylpyridine. The use of various pyridines as an auxiliary base is described, for example, in DE 198 50 624 described, but their usability as an ionic liquid is not recognized there.

Pyridine itself and derivatives of pyridine are the expert as nucleophilic catalysts known [Jerry March, "Advanced Organic Chemistry, ^3rd Edition, John Wiley & Sons, New York 1985, pp 294, 334, 347] It was further found that the Hydrochloride of 2-ethylpyridine has a melting point of about 55 ° C and is not miscible with non-polar organic products of value (see above) or solvents.2-Ethylpyridine can thus serve as an auxiliary base and nucleophilic catalyst at the same time and as a liquid hydrochloride via a process-technically simple liquid-liquid -Phase separation from organic media to be separated.

Likewise, all derivatives of pyridine can be used, the salts of which have an _ET (30) value of> 35, preferably> 40, particularly preferably> 42 and have a melting temperature at which, in the course of the removal of the salt, as a liquid phase no significant decomposition of the product of value occurs. The polar salts of these pyridines form two immiscible phases with less polar organic media.

The implementation of the reaction is not limited and can according to the invention under Intercept the released or added acids, if necessary under nucleophilic catalysis, discontinuous or continuous and be carried out in air or under a protective gas atmosphere.

For temperature-sensitive valuable products it may be sufficient to use the salt from the auxiliary base and acid solid salt during let the reaction fail and only melt for workup. The This means that the product is subjected to less thermal stress.

Another object of the invention is a method for separating the above-mentioned auxiliary bases or auxiliary bases which are used as nucleophilic catalysts, from a reaction mixture by adding at least one mol of acid to the reaction mixture per mol of auxiliary base. This makes it possible to separate such auxiliary bases as ionic liquids with the aid of a liquid-liquid separation.

From that separated from the valuable product Salt of the auxiliary base can be prepared in a manner known to those skilled in the art the free base is recovered and returned to the process.

This can be done, for example, by salting the auxiliary base with a strong base, for example NaOH, KOH, Ca (OH) ₂ , milk of lime, Na ₂ CO ₃ , NaHCO ₃ , K ₂ CO ₃ , or KHCO ₃ , optionally in a solvent , such as water, methanol, ethanol, n- or iso-propanol, n-butanol, n-pentanol or butanol or pentanol isomer mixtures or acetone. The auxiliary base released in this way, if it forms its own phase, or if it is miscible with the salt of the stronger base or the solution of the salt of the stronger base, can be removed from the mixture by distillation. If necessary, the liberated auxiliary base can also be separated from the salt of the stronger base or the solution of the salt of the stronger base by extraction with an extracting agent. Extraction agents are, for example, solvents, alcohols or amines.

If necessary, the auxiliary base can be washed with water or aqueous NaCl or Na ₂ SO ₄ solution and then dried, for example by separating off any water which may be present using an azeotropic distillation with benzene, toluene, xylene butanol or cyclohexane.

If necessary, the base be distilled before reuse.

Another possibility of recycling is to distill the salt of the auxiliary base, the salt being thermally split into its starting materials, ie the free base and the acid trapped. The lower-boiling part of the salt is distilled off, while the higher-boiling part remains in the swamp. The free auxiliary base is either the low or high boiler. In this way, for example, 1-butylimidazole formate can be separated by distillation into formic acid (top product) and 1-butylimidazole (bottom product), as in the EP-A 181 078 described.

Preferred with the method according to the invention feasible Phosphorylations are reactions in which phosphorus compounds, for example phosphines, phosphinic acid esters, phosphinous acid esters (Phosphinites), phosphonic acid esters, phosphonic acid halides, phosphonic, phosphonous (Phosphonites), phosphonous acid amides, Phosphonigsäurehalogenide, Phosphoric acid esters, phosphoric acid diester halides, Phosphorsäurediesteramide, Phosphorsäureesterdihalogenide, Phosphorsäureesterdiamide, phosphorous (Phosphites), phosphorous diester halides, Phosphorigsäurediesteramide, Phosphorigsäureesterdihalogenide or phosphoric acid ester diamides are formed and an acid is split off in the course of the reaction, which with the auxiliary base forms a salt as described above.

In it, R, R 'and R' 'stand for any Residues, X and X 'for halogen or pseudohalogen, such as F, Cl, Br, I, CN, OCN or SCN or unsubstituted, mono- or disubstituted amino groups and Z for oxygen, Sulfur or an unsubstituted or monosubstituted nitrogen atom.

These can be phosphorus compounds act one or more, for example two, three or four, preferably two or three, particularly preferably two phosphorus atoms exhibit. In such compounds, the phosphorus atoms are typical through a bridge connected.

For example, such bridged compounds with two phosphorus atoms can be:
diphosphites (RO) (R'O) POZOP (OR '') (OR ''') (Formula II) , Diphosphonites (RO) R'POZO-PR '' (OR ''') (Formula III) , Diphosphinites (R) (R ') POZOP (R'')(R''') (Formula IV) , Phosphite-phosphonites (RO) (R'O) POZOP (OR '') (R ''') (Formula V) , Phosphite-phosphinites (RO) (R'O) POZOP (R '') (R ''') (Formula VI) , Phosphonite phosphinites (R) (R'O) POZOP (R '') (R ''') (Formula VII) In this, R, R ', R''andR''' can be any organic radicals and Z can be any bivalent bridge.

In each case and independently of one another, it can be, for example, one to 20 carbon atoms, linear or branched, substituted or unsubstituted, aromatic or aliphatic radicals, such as C ₁ -C ₁₈ -alkyl, optionally by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted C ₂ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, C ₆ -C ₁₂ aryl, C ₅ -C ₁₂ cycloalkyl or a five- to six-membered, oxygen- , Nitrogen and / or sulfur atoms having a heterocycle, where the radicals mentioned are each aryl, alkyl, aryloxy, alkoxy, He teroatoms and / or heterocycles can be substituted.

The compounds mentioned can each be substituted symmetrically or asymmetrically.

Phosphorus compounds with a phosphorus atom are, for example, those of the formula (VIII) P (X ¹ R ⁷ ) (X ² R ⁸ ) (X ³ R ⁹ ) (VIII) With
X ¹ , X ² , X ³ independently of one another oxygen, sulfur, NR ¹⁰ or single bond
R ⁷ , R ⁸ , R ⁹ , R ¹⁰ independently of one another the same or different organic radicals.

mit
X¹¹, X¹², X¹³, X²¹, X²², X²³ unabhängig voneinander Sauerstoff, Schwefel, NR¹⁰ oder Einzelbindung
R¹¹, R¹² unabhängig voneinander gleiche oder unterschiedliche, einzelne oder verbrückte organische Reste
R²¹, R²² unabhängig voneinander gleiche oder unterschiedliche, einzelne oder verbrückte organische Reste,
Y Brückengruppe.Phosphorus compounds with two phosphorus atoms are, for example, those of the formula (IX)

With
X ¹¹ , X ¹² , X ¹³ , X ²¹ , X ²² , X ²³ independently of one another oxygen, sulfur, NR ¹⁰ or single bond
R ¹¹ , R ¹² independently of one another the same or different, individual or bridged organic radicals
R ²¹ , R ²² independently of one another are identical or different, individual or bridged organic radicals,
Y bridge group.

The described phosphorus compounds are, for example, as ligands for catalysts for hydrocyanation of butadiene to a mixture of isomeric pentenenitriles. Next the hydrocyanation of 1,3-butadiene-containing hydrocarbon mixtures the catalysts are generally suitable for all common hydrocyanation processes. In particular, the hydrocyanation of unactivated olefins, z. B. of styrene and 3-pentenenitrile. Furthermore, the Use for hydrogenation, hydroformylation, hydrocarboxylation, Hydroamidation, hydroesterification and aldol condensation are conceivable.

Such catalysts can have one or more of the phosphorus compounds as ligands. In addition to the phosphorus compounds as ligands, they can also contain at least one further ligand, which is selected from cyanide, halides, amines, carboxylates, acetylacetone, aryl or alkyl sulfonates, hydride, CO, olefins, dienes, cycloolefins, nitriles, N-containing heterocycles, aromatics and Heteroaromatics, ethers, PF ₃ and monodentate and multidentate phosphine, phosphinite, phosphonite and phosphite ligands. These further ligands can also be monodentate or multidentate and coordinate with the metal. Suitable further phosphorus-containing ligands are e.g. B. the phosphine, phosphinite and phosphite ligands previously described as prior art.

It is preferably the Metal around one of subgroup VIII, particularly preferably around cobalt, Rhodium, ruthenium, palladium or nickel atoms in any Oxidation states. Are the catalysts for hydrocyanation used, it is the metal of subgroup VIII especially nickel.

If you use nickel, it can in different valences, such as 0, +1, +2, +3. Prefers here is Nikkel (0) and nickel (+2), especially nickel (0).

For catalysts for hydroformylations are generally derived from the hydroformylation conditions catalysts or catalyst precursors used in each case catalytically active species formed.

For this, metal is preferred Cobalt, ruthenium, rhodium, palladium, platinum, osmium or iridium and in particular cobalt, rhodium and ruthenium in any oxidation state used.

The production of these catalyst systems is technically complex and expensive. This is especially true as that the catalyst systems gradually as they are used be decomposed and thus removed and replaced by a new catalyst need to be replaced.

Processes for the preparation of the phosphorus compounds and the corresponding catalysts are known per se, for example from US 3,903,120 . US 5,523,453 . US 5,981,772 . US 6,127,567 . US 5,693,843 . US 5,847,191 . WO 01/14392 . WO 99/13983 and WO 99/64155 ,

To manufacture the in the catalysts Phosphorus compounds used as ligands can be used, for example first a dihalophosphorus (III) compound with a monoalcohol Implement diester. If desired, this compound can be known before further implementation Processes are isolated and / or cleaned, e.g. B. by distillation. This diester is then, for example, with a diol to the bidentate phosphonite ligands implemented. For the case that symmetrical ligands are to be obtained can be two equivalents of the diester in a one-step reaction with one equivalent of the diol are implemented. Otherwise, an equivalent of the diester is used first an equivalent implemented the diol and after formation of the monocondensation product a second diol is added and further to the phosphorus compound implemented.

The released in the reaction Acid can according to the invention with a said auxiliary base with the formation of a liquid salt be intercepted so this Synthesis can be simplified considerably.

Organodiphosphonites of the formula III and catalyst systems which contain such organodiphosphonites are known, for example from WO 99/64155 , For the preparation of such organodiphosphonites of formula III describes WO 99/64155 the reaction of R'PCl ₂ with one mole of ROH and the subsequent reaction of the (RO) R'PCl obtained with half a mole, based on one mole (RO) R'PC1, of a compound HO-Z-OH at a temperature in Range from 40 to about 200 ° C. In the first step, the hydrogen halide should preferably be split off purely thermally. In addition, both steps should be able to be carried out in the presence of a base.

According to the invention, the methods known in the prior art, such as that from WO 99/64155 Known, carried out analogously to the preparation of the phosphorus compounds mentioned, with the difference that, according to the invention, an auxiliary base is used as described above and the acid liberated is separated from the reaction mixture by means of the auxiliary base, the auxiliary base forming a salt with the acid as above, which at Temperatures is liquid at which the phosphorus compound is not significantly decomposed during the separation of the liquid salt and the salt of the auxiliary base with the phosphorus compound or the solution of the phosphorus compound in a suitable solvent forms two immiscible liquid phases.

In general, the phosphorus compounds mentioned can be prepared, for example, as follows:
The starting materials are mixed with one another in the desired stoichiometry, optionally dissolved or dispersed in a solvent, ie suspended or emulsified. It may make sense to divide the starting materials into one or more compositions, ie separate streams, so that the reaction does not take place before the mixing. The auxiliary base, which forms a liquid salt with the acid according to the invention, can be admixed to one or more of these streams or fed separately from the streams to the reaction as a separate stream. It is also possible, although less preferred, to add the auxiliary base only after the reaction to remove the acid.

The starting materials or the compositions mentioned are fed to a reactor and reacted with each other under reaction conditions, leading to the reaction the starting materials lead to the product. Such reaction conditions depend on the starting materials used and the one you want Products and in the state of the art mentioned in this document specified.

^I The reaction can be carried out continuously, semi-continuously or batchwise. The temperature generally ranges from 40 ° C. to 200 ° C., the pressure is not essential according to the invention and can be under, over or normal pressure, for example from 10 mbar to 10 bar, preferably 20 mbar to 5 bar, particularly preferably 50 mbar to 2 bar and in particular 100 mbar to 1.5 bar. The residence time of the reaction mixture in the reactor can be from a few seconds to several hours and is dependent on the reaction temperature and, as a rule to a lesser extent, on the pressure applied.

The residence time is preferred at a continuous reaction with one sufficient for the reaction high temperature selected briefly, i.e. from a few seconds to about 2 hours, preferably from 1 second up to 2 hours, particularly preferably from 1 second to 1 hour, entirely particularly preferably from 1 second to 30 minutes, in particular from 1 second to 15 minutes and exceptionally preferred from 1 second to 5 minutes.

In a particularly preferred embodiment is the production of phosphorus compounds, preferably such with several phosphorus atoms, particularly preferably those with 2 or 3 and very particularly preferably those with 2 phosphorus atoms the respective starting materials continuously at a temperature of 60 ° C to 150 ° C, preferred at a temperature above the melting point of the salt used auxiliary base with the released acid up to 130 ° C, with a residence time below 1 hour, preferably less than 30 minutes, particularly preferably less than 15 minutes, very particularly preferably from 1 second to 5 minutes, in particular from 1 second to 1 minute and exceptionally preferably from 1 to 30 seconds.

Such an embodiment suppresses the exchange of substituents on the phosphorus atoms and it is thus possible, under predominantly kinetic control, to use compounds with a plurality of phosphorus atoms, such as, for example, compounds of the formula (IX), and phosphorus compounds with mixed substituents, for example compounds of the formula (VIII) with different radicals R ⁷ , R ⁸ and / or R ⁹ , without the substituents being replaced as a result of equilibration on the phosphorus atom / on the phosphorus atoms.

While the reaction is for to ensure thorough mixing, for example by stirring or pumping with static mixers or nozzles.

Reactors known per se can be used as reactors Apparatus are used, for example one or more cascaded Stirred or tubular reactors with inside and / or outside Heaters and preferably reaction mixing pumps.

The reaction discharge is fed into an apparatus in which was formed during the reaction Can separate phases from each other, for example phase separators or mixer-settlers. In this apparatus, at a temperature at which the salt of the auxiliary base is liquid with the acid, the phase, which predominantly contains ionic liquid, is separated from the phase which predominantly contains the desired reaction product. If necessary, solvent can be added to accelerate phase separation.

From the phase that predominantly ionic liquid contains the auxiliary base can be recovered as described above.

From the phase that the desired reaction product contains can isolate the reaction product using methods known per se and / or cleaned, for example by distillation, rectification, Extraction, fractional or simple crystallization, membrane separation process, Chromatography or combinations thereof.

The one used in the reaction solvent can be the ones listed above solvent act.

The auxiliary base used in the reaction usually becomes stoichiometric based on the expected amount of acid Amount or slight excess used, for example 100 to 200 mol% based on the expected amount Acid, preferably 100 to 150 and particularly preferably 105 to 125 mol%.

The starting materials for the production of the desired Phosphorus compounds are known per se to the person skilled in the art or are easy deducible and are for example in the state mentioned in this document the technology, as well as the stoichiometric conditions, to react the reactants with each other.

The starting materials are as possible as liquids or melting, if necessary, they are used in one solvent solved or dispersed. Of course but it is also possible to use the starting materials at least partially as solids.

They are made with a solvent is added, so the solvent usually used in such an amount that the mixture liquid is, for example, as a solution or dispersion. Typical concentrations of the starting materials based on the total amount of solution or dispersion are 5 to 95% by weight, preferably 10 to 90% by weight, particularly preferably 25 to 90% by weight and very particularly preferably 50 to 90% by weight.

Compounds (VIII) have the formula P (X ¹ R ⁷ ) (X ² R ⁸ ) (X ³ R ⁹ ) (VIII) on.

Under compound (VIII) in the sense of the present invention, a single compound or a mixture understood various compounds of the aforementioned formula.

According to the invention, X ¹ , X ² , X ^{3 are} independently oxygen, sulfur, NR ¹⁰ or single bond.

R ^{10 here} represents hydrogen or an organic radical having 1 -10 carbon atoms, preferably hydrogen, phenyl or C ₁ -C ₄ -alkyl, including in this document methyl, ethyl, isopropyl, n-propyl, n-butyl, Isobutyl, sec-butyl and tert-butyl is understood.

If all of the groups X ¹ , X ² and X ^{3 are} individual bonds, compound (VIII) is a phosphine of the formula P (R ⁷ R ⁸ R ⁹ ) with those for R ⁷ , R ⁸ and R ^{9 mentioned} in this description Meanings.

If two of the groups X ¹ , X ² and X ^{3 are} individual bonds and one is oxygen, compound (VIII) is a phosphinite of the formula P (OR ⁷ ) (R ⁸ ) (R ⁹ ) or P (R ⁷ ) ( OR ⁸ ) (R ⁹ ) or P (R ⁷ ) (R ⁸ ) (OR ⁹ ) with the meanings given for R ⁷ , R ⁸ and R ⁹ in this description.

If one of the groups X ¹ , X ² and X ^{3 represents} a single bond and two represent oxygen, compound (VIII) represents a phosphonite of the formula P (OR ⁷ ) (OR ⁸ ) (R ⁹ ) or P (R ⁷ ) (OR ⁸ ) (OR ⁹ ) or P (OR ⁷ ) (R ⁸ ) (OR ⁹ ) with the meanings given for R ⁷ , R ⁸ and R ⁹ in this description.

In a preferred embodiment, all of the groups X ¹ , X ² and X ^{3 should} stand for oxygen, so that compound (VIII) advantageously a phosphite of the formula P (OR ⁷ ) (OR ⁸ ) (OR ⁹ ) with those for R ⁷ , R ⁸ and R ⁹ represent meanings mentioned in this description.

According to the invention, R ⁷ , R ⁸ , R ⁹ independently of one another represent identical or different organic radicals.

R ⁷ , R ⁸ and R ⁹ are, independently of one another, alkyl radicals, advantageously having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t- Butyl, aryl groups, such as phenyl, o-tolyl, m-tolyl, p-tolyl, p-fluorophenyl, 1-naphthyl, 2-naphthyl, or hydrocarbyl, advantageously with 1 to 20 C atoms, such as 1, 1'-biphenol, 1,1'-binaphthol.

The groups R ⁷ , R ⁸ and R ⁹ can be connected to one another directly, that is to say not only via the central phosphorus atom. The groups R ⁷ , R ⁸ and R ⁹ are preferably not directly connected to one another.

In a preferred embodiment, groups R ⁷ , R ⁸ and R ⁹ are selected from the group consisting of phenyl, o-tolyl, m-tolyl and p-tolyl.

In a particularly preferred embodiment, a maximum of two of the groups R ⁷ , R ⁸ and R ^{9 should be} phenyl groups.

In another preferred embodiment, a maximum of two of the groups R ⁷ , R ⁸ and R ^{9 should be} o-tolyl groups.

Particularly preferred compounds (VIII) are those of the formula (o-tolyl-O-) _w (m-tolyl-O-) _x (p-tolyl-O-) _y (phenyl-O-) _z P with w, x, y, z a natural number
with w + x + y + z = 3 and
w, z less than or equal to 2
are used, such as (p-tolyl-O -) (phenyl) ₂ P, (m-tolyl-O -) (phenyl) ₂ P, (o-tolyl-O -) (phenyl) ₂ P, (p-tolyl -O-) ₂ (phenyl) P, (m-to-lyl-O-) ₂ (phenyl) P, (o-tolyl-O-) ₂ (phenyl) P, (m-tolyl-O -) (p -To-lyl-O -) (phenyl) P, (o-tolyl-O -) (p-tolyl-O -) (phenyl) P, (o-To-lyl-O -) (m-tolyl-O -) (Phenyl) P, (p-tolyl-O-) ₃ P, (m-tolyl-O -) (p-tolyl-O-) ₂ P, (o-tolyl-O -) (p-tolyl- O-) ₂ P, (m-tolyl-O-) ₂ (p-tolyl-O-) P, (o-tolyl-O-) ₂ (p-tolyl-O-) P, (o-tolyl-O -) (m-tolyl-O -) (p-tolyl-O-) P, (m-tolyl-O-) ₃ P, (o-tolyl-O -) (m-tolyl-O-) ₂ P ( o-tolyl-O-) ₂ (m-to-lyl-O-) P or mixtures of such compounds can be used.

For example, mixtures containing (m-tolyl-O-) ₃ P, (m-tolyl-O-) ₂ (p-tolyl-O-) P, (m-tolyl-O -) (p-tolyl-O- ) ₂ P and (p-tolyl-O-) ₃ P by reacting a mixture containing m-cresol and p-cresol, in particular in a molar ratio of 2: 1, as is obtained in the working up of petroleum by distillation, with a phosphorus trihalide, such as phosphorus trichloride , can be obtained.

Such compounds (VIII) and their Manufacturing are known per se.

mit
X¹¹, X¹², X¹³, X²¹, X²², X²³ unabhängig voneinander Sauerstoff, Schwefel, NR¹⁰ oder Einzelbindung
R¹¹, R¹² unabhängig voneinander gleiche oder unterschiedliche, einzelne oder verbrückte organische Reste
R²¹, R²² unabhängig voneinander gleiche oder unterschiedliche, einzelne oder verbrückte organische Reste,
Y Brückengruppe
auf.Compounds (IX) have the formula

With
X ¹¹ , X ¹² , X ¹³ , X ²¹ , X ²² , X ²³ independently of one another oxygen, sulfur, NR ¹⁰ or single bond
R ¹¹ , R ¹² independently of one another the same or different, individual or bridged organic radicals
R ²¹ , R ²² independently of one another are identical or different, individual or bridged organic radicals,
Y bridge group
on.

Under compound (IX) in the sense of the present invention, a single compound or a mixture understood various compounds of the aforementioned formula.

In a preferred embodiment, X ¹¹ X ¹² , X ¹³ X ²¹ X ²² , X ²³ can represent oxygen. In such a case, the bridging group Y is linked to phosphite groups.

In another preferred embodiment, X ¹¹ and X ¹² oxygen and X ^{13 may be} a single bond or X ¹¹ and X ¹³ oxygen and X ^{12 may be} a single bond, so that the phosphorus atom surrounded by X ¹¹ , X ¹² and X ^{13 is the} central atom of a phosphonite. In such a case, X ²¹ , X ²² and X ²³ oxygen or X ²¹ and X ²² oxygen and X ²³ a single bond or X ²¹ and X ²³ oxygen and X ²² a single bond or X ²³ oxygen and X ²¹ and X ²² a single bond or X ²¹ oxygen and X ²² and X ^{23 represent} a single bond or X ²¹ , X ²² and X ^{23 represent} a single bond, so that the phosphorus atom surrounded by X ²¹ , X ²² and X ^{23 is} preferably a central atom of a phosphite, phosphonite, phosphinite or phosphine a phosphonite.

In another preferred embodiment, X ¹³ oxygen and X ¹¹ and X ^{12 can be} a single bond or X ¹¹ oxygen and X ¹² and X ^{13 can be} a single bond, so that the phosphorus atom surrounded by X ¹¹ , X ¹² and X ^{13 is the} central atom of a phosphinite. In such a case, X ²¹ , X ²² and X ²³ oxygen or X23 oxygen and X ²¹ and X ²² a single bond or X ²¹ oxygen and X22 and X ²³ a single bond or X ²¹ , X ²² and X ²³ a single bond, so that the phosphorus atom surrounded by X ²¹ , X ²² and X ^{23 can be the} central atom of a phosphite, phosphinite or phosphine, preferably a phosphinite.

In another preferred embodiment, X ¹¹ X ¹² and X ^{13 can represent} a single bond, so that the phosphorus atom surrounded by X ¹¹ X ¹² and X ^{13 is the} central atom of a phosphine. In such a case, X ²¹ , X ²² and X ²³ oxygen or X ²¹ , X ²² and X ^{23 may represent} a single bond, so that the phosphorus atom surrounded by X ²¹ , X ²² and X ^{23 is the} central atom of a phosphite or phosphine, preferably a phosphine , can be.

Suitable bridge groups Y are advantageously substituted, for example with C ₁ -C ₄ -alkyl, halogen, such as fluorine, chlorine, bromine, halogenated alkyl, such as trifluoromethyl, aryl, such as phenyl, or unsubstituted aryl groups, preferably those having 6 to 20 Carbon atoms in the aromatic system, in particular pyrocatechol, bis (phenol) or bis (naphthol).

The radicals R ¹¹ and R ¹² can independently represent the same or different organic radicals. R ¹¹ and R ¹² are advantageously aryl radicals, preferably those having 6 to 10 carbon atoms, which may be unsubstituted or mono- or polysubstituted, in particular by C ₁ -C ₄ -alkyl, halogen, such as fluorine, chlorine, bromine halogenated alkyl such as trifluoromethyl, aryl such as phenyl or unsubstituted aryl groups.

The radicals R ²¹ and R ²² can independently of one another represent identical or different organic radicals. Aryl radicals, preferably those having 6 to 10 carbon atoms, which can be unsubstituted or mono- or polysubstituted, in particular by C ₁ -C ₄ -alkyl, halogen, such as fluorine, chlorine, bromine, are advantageously suitable as radicals R ²¹ and R ²² halogenated alkyl such as trifluoromethyl, aryl such as phenyl or unsubstituted aryl groups.

The radicals R ¹¹ and R ¹² can be individually or bridged.

The radicals R ²¹ and R ²² can be individually or bridged.

The radicals R ¹¹ , R ¹² , R ²¹ and R ²² can all be individually, two bridged and two individually or all four bridged in the manner described.

The following particularly preferred embodiments are expressly referred to within the scope of the present disclosure:
In a particularly preferred embodiment, the come in US 3,773,809 compounds mentioned, in particular those described in column 2, line 23 to column 4, line 14 and in the examples.

In a particularly preferred embodiment, the come in US 6,127,567 Compounds mentioned, in particular the compounds used in column 2, line 23 to column 6, line 35, in the formulas I, II, III, IV, V, VI, VII, VIII and IX and in Examples 1 to 29.

In a particularly preferred embodiment, the come in US 6,171,996 compounds mentioned, in particular the compounds used in column 2, line 25 to column 6, line 39, in the formulas I, II, III, IV, V, VI, VII, VIII and IX and in Examples 1 to 29.

In a particularly preferred embodiment, the come in US 6,380,421 compounds mentioned, in particular the compounds used in column 2, line 58 to column 6, line 63, in the formulas I, II and III and in examples 1 to 3.

In a particularly preferred embodiment, the come in US 5,488,129 compounds mentioned, in particular the compounds used in column 3, line 4 to column 4, line 33, in the formula I and in examples 1 to 49.

In a particularly preferred embodiment, the come in US 5,856,555 compounds mentioned, in particular the compounds used in column 2, line 13 to column 5, line 30, in the formulas I and II and in examples 1 to 4.

In a particularly preferred embodiment, the come in WO 99/46044 Compounds mentioned, especially the compounds in page 3, line 7 to page 8, line 27, and in particular the compounds used in the formulas Ia to Ig and in examples 1 to 6.

In a particularly preferred embodiment, the come in US 5,723,641 mentioned compounds of formula I, II, III, IV and V into consideration.

In a particularly preferred embodiment, the come in US 5,512,696 Compounds of the formula I, II, III, IV, V, VI and VII mentioned, in particular the compounds used there in Examples 1 to 31, into consideration.

In a particularly preferred embodiment, the come in US 5,821,378 Compounds of the formula I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV mentioned, in particular the compounds used there in Examples 1 to 73, into consideration.

In a particularly preferred embodiment, the come in US 5,512,695 Compounds of the formula I, II, III, IV, V and VI mentioned, in particular the compounds used there in Examples 1 to 6, into consideration.

In a particularly preferred embodiment, the come in US 5,981,772 Compounds of the formula I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII and XIV mentioned, in particular the compounds used there in Examples 1 to 66, into consideration.

In a particularly preferred embodiment, the come in US 6,020,516 Compounds of the formula I, II, III, IV, V, VI, VII, VIII, IX and X mentioned, in particular the compounds used there in Examples 1 to 33, into consideration.

In a particularly preferred embodiment, the come in US 5,959,135 mentioned compounds and compounds used there in Examples 1 to 13 into consideration.

In a particularly preferred embodiment, the come in US 5,847,191 mentioned compounds of formula I, II and III into consideration.

In a particularly preferred embodiment, the come in US 5,523,453 Compounds mentioned, especially those there in formula 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 12, 13, 14, 15, 16, 17, 18, 19, 20 and 21 connections shown.

In a particularly preferred embodiment, the come in WO 01/14392 Compounds mentioned, preferably the compounds shown there in formula V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XXI, XXII, XXIII.

In a particularly preferred embodiment, the come in WO 98/27054 mentioned compounds into consideration.

In a particularly preferred embodiment, the come in WO 99/13983 compounds mentioned, especially the compounds on page 5, line 1 to page 11, line 45 and in particular the compounds mentioned in the formulas Ia to Ih and examples 1 to 24.

In a particularly preferred embodiment, the come in WO 99/64155 compounds mentioned, especially the compounds on page 4, line 1 to page 12, line 7 and in particular the compounds mentioned in the formulas Ia to Ic and examples 1 to 4.

In a particularly preferred embodiment, those in the German patent application DE 10038037 mentioned compounds into consideration.

In a particularly preferred embodiment, those in the German patent application DE 10046025 mentioned compounds into consideration.

In a particularly preferred embodiment, those in the German patent application come with the file number DE 10156292.6 and the filing dates of 11/19/01, especially the compounds mentioned in the filing on page 1, lines 6 to 19 and from page 2, line 21 to page 2, line 30.

In a particularly preferred embodiment, those in the German patent application come with the file number DE 10150281.8 and the date of filing on October 12, 2001, in particular the compounds mentioned in the submission text on page 1, line 36 to page 5, line 45.

In a particularly preferred embodiment, those in the German patent application come with the file number DE 10150285.0 and the date of filing on October 12, 2001, in particular the compounds mentioned in the submission text on page 1, line 35 to page 5, line 37.

In a particularly preferred embodiment, those in the German patent application come with the file number DE 10150286.9 and the date of filing on October 12, 2001, in particular the compounds mentioned in the submission text on page 1, line 37 to page 6, line 15.

In a particularly preferred embodiment, those in the German patent application come with the file number DE 10148712.6 and the dates mentioned in the filing date 2.10.01, in particular the connections mentioned in the submission text on page 1, lines 6 to 29 and page 2, line 15 to page 4, line 24.

Ppm- used in this document and percentages relate to unless otherwise stated Percentages by weight and - ppm.

Examples

Comparative Example 1 Preparation of Diethoxyphenylphosphin (DEOPP)

101.4 g of ethanol, 543 g of xylene and 232.7 g of triethylamine were placed in a 1000 ml reactor inertized with N ₂ with an impeller stirrer and heated to 50.degree. 181.5 g of 98.6% dichlorophenylphosphine were added dropwise to this mixture in the course of 40 minutes, whereupon a colorless, readily stirrable suspension was formed. The reaction temperature was kept at 50 ° C. by cooling. After the addition of the dichlorophenylphosphine was complete, the mixture was stirred for a further 60 minutes at 75-80 ° C. and then the precipitated hydrochloride was filtered off with suction and washed with cold xylene. The filtrate and washing xylene were combined (859.9 g in total) and examined by GC with an internal standard. The xylene solution contained 11.8% diethoxyphenylphosphine, which corresponds to a yield of 51%.

Comparative Example 2 Preparation of Diethoxyphenylphosphin (DEOPP)

90.9 g of ethanol and 382.2 g of tributylamine were placed in a 1000 ml reactor inertized with N ₂ with an impeller stirrer and heated to 70.degree. 162.7 g of 98.6% dichlorophenylphosphine were added dropwise to this mixture over the course of 40 minutes, whereupon a colorless solution was formed which was liquid when heated and solidified to a colorless, crystalline solid after cooling to ramut temperature. The reaction temperature was kept at 50 ° C. by cooling. After the addition of the dichlorophenylphosphine was complete, the mixture was stirred at 75-80 ° C. for a further 60 minutes. According to GC with an internal standard, the 625.8 g of reaction discharge contained 23.7% diethoxyphenylphosphine, which corresponds to a yield of 82.7%.

Example 1: Production of Diethoxyphenylphosphin (DEOPP)

188.9 g (2.3 mol) of 1-methylimidazole and 101.4 g (2.2 mol) of ethanol were placed in a 1000 ml reactor with an inclined-blade stirrer and inertized with N ₂ . 181.5 g (1.0 mol) of 98.6% dichlorophenylphosphine were then metered in within 90 min. Initially, heating to 60 ° C was permitted (duration: 6 min) and then the temperature was kept at 60 ° C during the further addition. After the end of the feed, the batch was still liquid, but crystallized out in the subsequent stirring time of 45 min. After heating to 80 ° C, the reaction mixture was completely liquid again. After stirring for another hour, the stirrer was switched off. Two well-separated phases quickly developed. After phase separation at 80 ° C., 199.4 g of a clear, colorless upper phase (DEOPP content according to GC: 96.1%; content of 1-methylimidazole 1.7%) and 266.4 g lower phase (“ionic liquid”) receive.

The upper phase was vacuumed over a 40 cm column with 5 mm Raschig rings distilled. Thereby received 15.8 g of a clear, colorless forerunner (GC: 76.9% DEOPP content) and 177.5 g of a colorless main run (GC: 99.4% DEOPP). In the piston only 4.3 g of sump remained, which according to GC still contained 11.1% DEOPP. The DEOPP yield after Distillation was 95.9%.

Example 2

Manufacture of triethyl phosphite (TEP)

425 g of 1-methylimidazole and 228.1 g of ethanol were placed in a 1000 ml reactor inertized with N ₂ with an inclined blade stirrer. 206 g of phosphorus trichloride were then added dropwise within 190 min with ice cooling at an internal temperature of 23-33 ° C. The reaction was exothermic, so cooling was required to maintain this temperature. After about half the addition, the reaction mixture became cloudy, giving two liquid phases. According to GC, the upper one consisted of 90.0% triethyl phosphite, the lower one from the hydrochloride of 1-methylimidazole. The phase was heated to 78 ° C. before the phase separation. 231.4 g of a colorless upper phase and 611.9 g of a clear lower phase were obtained. The upper phase was distilled in vacuo over a 30 cm glass column with a Sulzer DX packing. 177 g of triethyl phosphite with a purity of 99% were obtained. A further 28.3 g of triethyl phosphite were contained in the pre- and post-run. The overall yield was 82.4%.

Example 3

Manufacture of diethoxyphenylphosphine (DEOPP)

In a 250 ml glass flask with a Teflon blade stirrer 85.7 g of 2-methylpyridine and 40.5 g of ethanol presented. Under cooling 71.6 g of dichlorophenylphosphine (98.6%) were added dropwise within 25 minutes, So that the Indoor temperature at 20-29 ° C remained. While the hydrochloride of 2-methylpyridine precipitated out. To complete Addition, the batch was heated, the hydrochloride from about 70 ° C too started melting. Two clear, sharply separated ones were formed liquid Phases out, with 75.5 g of the upper phase and 115.8 g of the lower phase were. The upper phase contained 81.6% DEOPP, so the yield Was 77.7%.

The lower phase was with aqueous sodium hydroxide solution neutralized, a two-phase system formed again, the lower one from an aqueous saline solution and the top consisted of the released 2-methylpyridine, which on can be returned in this way by a simple liquid-liquid phase separation could.

Example 4

Production of ethoxydiphenylphosphine (EODPP)

141.7 g of 1-methylimidazole and 76.0 g of ethanol were placed in a 1000 ml reactor inertized with N ₂ with an inclined blade stirrer, into which 315.8 g of chlorodiphenylphosphine were added dropwise within 30 min, during which two liquid phases formed. The internal temperature was kept below 65 ° C. After the addition was complete, the mixture was heated to 75 ° C., stirred for 45 minutes and the phases were separated, 194.3 g of lower and 332.8 g of upper phase being obtained. According to GC, the upper phase contained 96.6% of the product EODPP. For further purification, the upper phase was distilled in vacuo over a glass column with Raschig rings, 292.5 g of 99.4% EODPP being obtained. Together with the EODPP in the lead, the overall yield was 92.2%.

The lower phase, which consisted of the liquid hydrochloride of 1-methylimidazole, was mixed with 244.1 g of 25% sodium hydroxide solution. In order to completely dissolve the precipitated table salt, a further 94.3 g Water was added until a clear solution was obtained. After the addition of 450 g of n-propanol, salt again precipitated out, which was brought into solution again after the further addition of 69.8 g of water. Two liquid phases were obtained, the 739.3 g upper phase containing 19.99% water and 16.7% 1-methylimidazole. This is 94.9% of the amount of 1-methylimidazole used in the synthesis. In addition to the common salt, the 304.2 g lower phase contained 70.6% water and 2.2% 1-methylimidazole. The content of 1-methylimidazole in the aqueous phase was reduced to 0.4% by renewed extraction with n-propanol. 1-methylimidazole could now be recovered by distilling off the mixture of propanol and water from the upper phase of the first extraction.

Example 5

Continuous manufacturing of ethoxydiphenylphosphine (EODPP)

In a nitrogen inert Reactor with a three-stage inclined blade stirrer continuously at 80 ° C The following feed materials are supplied: 1) Mixture of 110.7 g ethanol and 205.8 g 1-methylimidazole 2) Chlorodiphenylphosphine (99.4%). Stream 1) was at 330 ml / h and stream 2) at 380 ml / h added. Both inlets were submerged. The reactor was equipped with an overflow from which reaction mixture could run continuously. The reactor volume until the overflow was 710 ml. The reaction temperature was kept at 80 ° C. To balance the system, the discharge of the discarded for the first 4 hours. Subsequently the discharge was over collected and accounted for a period of 1 h. The discharge existed from two liquid Phases. Within an hour, 497.2 g of top and 280.8 g Sub-phase collected. The upper phase consisted of 96.8% EODPP. The upper phase was then in a vacuum over one filled with Raschi rings Column distilled to give 438.2 g of 99.74% EODPP. Together with the EODPP in the lead, the overall yield was 96.7%.

Example 6

Continuous manufacturing of ethoxydiphenylphosphine (EODPP)

The following feed streams were continuously mixed in a reaction mixer pump: 1) Mixture of 159.2 g of 1-methylimidazole and 85.4 g of ethanol 2) 372.8 g of chlorodiphenylphosphine (99.1% strength). From stream 1) 1257 g / h were added, from stream 2) 1928 g / h. The volume of the mixing chamber was 3.3 ml. The head of the reaction mixing pump was thermostatted to 120 ° C. The system was equilibrated for 5 minutes. The discharge was then collected over 11 minutes in order to be balanced. During the balance run, the amount of input materials was determined by weighing the templates. 372.8 g of chlorodiphenylphosphine were added. The discharge consisted of two liquid phases. In the 11 min 392.2 g upper and 218.3 g lower phase were collected. The upper phase consisted of 96.5% EODPP, so that the gas chromatographically determined yield was 98.2%. The residence time of the reactants in the mixing chamber was 4 s. This resulted in a space-time yield of 0.69 10 ⁶ kgm ^-3 h ^-1 .

Example 7

Continuous manufacturing of ethoxydiphenylphosphine (EODPP)

In a reaction mixing pump continuously mixed the following feed streams: 1) mixture of 156.7 g of 1-methylimidazole and 84.1 g of ethanol 2) 370.0 g of chlorodiphenylphosphine (99.1%). From stream 1) 167.5 g / h were added, from stream 2) 257.4 g / h. The volume of the mixing chamber was 3.3 ml. The head of the Reaction mixing pump was at 80 ° C thermostatically controlled. The system was equilibrated for 60 minutes. Subsequently the discharge was over 87 min collected to balance. During the balance trip the amount of input materials is determined by weighing the templates. 370.0 g of chlorodiphenylphosphine were added. The discharge existed from two liquid Phases. In the 87 min 389.3 g upper and 219.2 g lower phase collected. The upper phase consisted of 96.8% EODPP, so that the gas chromatography certain yield was 98.5%. The residence time of the reactants. in the mixing chamber was 30 s.

Example 8

Continuous manufacturing of Diethoxyphenylphosphin (DEOPP)

The following feed streams were continuously mixed in a reaction mixing pump: 1) Mixing from 237.1 g of 1-methylimidazole and 127.2 g of ethanol 2) 225.8 g of dichlorophenylphosphine. 385.6 g / h were added from stream 1) and 239.0 g / h from stream 2). The volume of the mixing chamber was 3.3 ml. The head of the reaction mixing pump was thermostatted to 80 ° C. The system was equilibrated for 30 minutes. The discharge was then collected over 58 minutes in order to be balanced. During the balance run, the amount of input materials was determined by weighing the templates. 225.8 g of dichlorophenylphosphine were added. The discharge consisted of two liquid phases. In the 58 min, 249.0 g upper and 335.6 g lower phase were collected. The upper phase consisted of 95.4% DEOPP, so that the gas chromatographically determined yield was 95.5%. The residence time of the reactants in the mixing chamber was 20 s.

Example 9

Continuous manufacturing of Diethoxyphenylphosphin (DEOPP)

The following feed streams were continuously mixed in a reaction mixer pump: 1) mixture of 212.0 g of 1-methylimidazole and 113.7 g of ethanol 2) 201.7 g of dichlorophenylphosphine 3) recycled upper phase of the reaction discharge. 1543.5 g / h were added from stream 1), 955.9 g / h from stream 2) and 2377 ml / h from stream 3). The volume of the mixing chamber was 3.3 ml. The head of the reaction mixing pump was thermostatted to 80 ° C. The system was equilibrated for 5 minutes. The discharge was then collected over 12 minutes in order to be balanced. During the balance run, the amount of input materials was determined by weighing the templates. 201.7 g of dichlorophenylphosphine were added. The discharge consisted of two liquid phases, which were separated in a continuously operated phase separator. Part of the upper phase was returned to the process. 227.0 g of the upper and 300.6 g of the lower phase were collected in a 12 min balance run. The upper phase consisted of 95.2% DEOPP, so that the yield was 97.2%. The residence time of the reactants in the mixing chamber was 2.5 s. This results in a space-time yield of 0.36 10 ⁶ kgm ^-3 h ^-1 .

Example 10

Regeneration of 1-methylimidazole hydrochloride

Analog to Example 1 were made 181.5 g dichlorophenylphosphine, 101.4 g ethanol and 189 g 1-methylimidazole DEOPP produced, with 202.2 g upper phase with a DEOPP content of 93.9% and 265.5 g lower phase. The upper phase also contains 3.7 g more 1-methylimidazole. The lower phase was mixed with 169.6 g paraffin oil. 168 g of 50% sodium hydroxide solution were then dripped into this mixture, being a well stirrable Suspension was obtained. After the addition of 12.9 g of xylene and 78.4 g of recycled xylene from a previous experiment which still contained 3.8 g of 1-methylimidazole, was removed from the water using xylene. Overall, were 132.7 g of water removed. When no more water has been separated, The xylene was distilled out at 30-85 mbar and a head temperature of 57-90 ° C. the reaction mixture over a 30 cm packed column, to obtain 88.4 g of distillate, the 21.8 g of 1-methylimidazole contained. The distillate was returned as xylene in the next test reinserted so that in it contained 1-methylimidazole was repeatedly returned to the process. After the xylene distillation at 30 mbar and 90 ° C head temperature distilled off the 1-methylimidazole. There were 164.0 g of 1-methylimidazole recovered, which has a content of 99.7%. The water content of the distilled 1-methylimidazole was 0.06%.

The distillation sump was now mixed with 350 g of water to add the common salt suspended in the white oil to solve. Two phases developed. The contained 475.7 g lower phase the common salt and 0.3% (1.4 g) 1-methylimidazole. The 161.1 g upper phase consisted of the white oil that as inert suspension aid was also returned to the process. Of the total of 192.8 g of 1-methylimidazole (189.0 g fresh and 3.8 g in the recycled xylene) 164.0 g were recovered as leg material. Another 21.8 g was found in the distilled xylene, which was returned to the process and is therefore retained. A total of 185.8 g (96%) of the 1-methylimidazole could thus be recycled.

Example 11

51 g of acetic acid were dissolved in 120.8 g of cyclohexane. To remove the acid, 69.80 g of 1-methylimidazole were then added to the solution, whereupon a two-phase mixture consisting of 119.4 g of the upper phase (cyclohexane) and 122.5 g of the lower phase (ionic liquid = 1-methylimidazolium acetate) formed. During the addition of 1-methylimidazole, the temperature rose to 40 ° C. due to the salt formation. The temperature was kept at 40 ° C. during the further addition by cooling with an ice bath. After cooling, the acetic acid was almost completely in the form of the ionic liquid formed, which with Cyclo hexane is not miscible, from which solvents are separated via a liquid-liquid phase separation.

Example 12 Continuous Preparation of the Following Chelate Phosphonite:

In a reaction mixing pump continuously mixed the following feed streams:

• 1) Composition: mixture of 11.9 g of 1-methylimidazole, 11.8 g of o-biphenol and 35.1 g of toluene and
• 2) Composition: mixture of 38.4 g (2-tert-butylphenoxy) chlorphenylphosphine and 153.5 g toluene.

From stream 1) 681 ml / h, from Stream 2) metered 2373 ml / h. The volume of the mixing chamber was 3.3 ml. The head of the reaction mixing pump was thermostatted to 120 ° C. The system was balanced for 3 minutes. Then was the discharge over 7 min collected to balance. The temperature of the reaction medium at the outlet of the reaction mixing pump was 100 ° C. The discharge consisted of two liquid Phases collected in a jar and subsequently were separated. In a 7 min balance run, 233.9 g top and 14.0 g Sub-phase collected. The upper phase was a toluene solution Reaction products, the lower phase was the hydrochloride of 1-methylimidazole, that above 75 ° C as an ionic liquid was incurred. The selectivity which he wished Chelate phosphonites the unwanted monodentate phosphonites were determined using 31P NMR spectra. It was 93.8% in favor of the chelate phosphonite. The turnover was Completely.

Example 13

The synthesis of chelate phosphonite from example 12 was carried out as described in Example 12. There were different parameters varied. The head of the reaction mixing pump was thermostated that the final temperatures of the reaction mixture given in the table could be obtained at the outlet of the pump. The results are summarized in the following table.

Sales were with all variants Completely.

Example 14 Continuous Preparation of the Following Chelate Phosphonite:

In a reaction mixing pump continuously mixed the following feed streams:

• 1) Composition: mixture of 28.0 g of 1-methylimidazole, 36.1 g of 2,2 ', 4,4'-tetramethyl-o-biphenol and 116.4 g of toluene and
• 2) Composition: mixture of 88.4 g (2-tert-butylphenoxy) chlorphenylphosphine and 37.9 g of toluene.

From stream 1) 1817 ml / h, from Stream 2) metered 1153 ml / h. The volume of the mixing chamber was 3.3 ml. The system was equilibrated for 2 min. Then was the discharge over 5 min collected to balance. The temperature of the reaction medium at the outlet of the reaction mixing pump was 76.3 ° C. The discharge consisted of two liquid Phases collected in a jar and subsequently were separated. 264.3 g of top and 40.1 g Sub-phase collected. The upper phase was a toluene solution Reaction products, the lower phase was the hydrochloride of 1-methylimidazole, that above 75 ° C as an ionic liquid was incurred. The selectivity of the desired Chelate phosphonites the unwanted monodentate phosphonites were determined using 31P NMR spectra. It was 95.6% in favor of the chelate phosphonite. The turnover was Completely. The Lower phase (ionic liquid) contained only about 300 ppm of phosphorus-containing secondary components.

Example 15 Continuous Preparation of the Following Chelate Phosphonite:

In a reaction mixing pump continuously mixed the following feed streams:

• 1) Composition: mixture of 188.9 g of 1-methylimidazole, 249.1 g of 2,2 ', 4,4'-tetramethyl-o-biphenol and 807.4 g of toluene and
• 2) Composition: mixture of 664.7 g (2-tert-butylphenoxy) -p-fluorophenylchlorophosphine and 284.9 g toluene.

From stream 1) 1781 ml / h, from Stream 2) 1189 ml / h metered. The volume of the mixing chamber was 3.3 ml. The system was equilibrated for 2 min. Then was the discharge over 275 min collected to balance. The temperature of the reaction medium at the outlet of the reaction mixing pump was 69.8 ° C. The discharge consisted of two liquid Phases collected in a jar and subsequently were separated. In a 275 min balance run, 799.6 g top and 98.9 g lower phase collected. The upper phase was a toluene solution of the reaction products, the lower phase was the hydrochloride of 1-methylimidazole, that above 75 ° C as an ionic liquid was incurred. The yield of isolated product of value was 302.9 g (93.4 % d.Th).

Example 16 Continuous Preparation of the Following Chelate Phosphonite:

In a reaction mixing pump continuously mixed the following feed streams:

1) mixture of 188.9 g of 1-methylimidazole, 249.1 g of 2,2`, 4,4`-tetramethyl-o-biphenol and 807.4 g of toluene and

2) Composition: mixture of 696.1 g (2-tert-butyl-6-methylphenoxy) chlorophenylphosphine and 298.3 g To1uo1.

From stream 1) 1730 ml / h, from Stream 2) metered 1238 ml / h. The volume of the mixing chamber was 3.3 ml. The system was equilibrated for 2 min. Then was the discharge over 275 min collected to balance. The temperature of the reaction medium at the outlet of the reaction mixing pump was 69.5 ° C. The discharge consisted of two liquid Phases collected in a jar and subsequently were separated. 798.1 g top and 93.3 g lower phase collected. The upper phase was a toluene solution of the reaction products, the lower phase was the hydrochloride of 1-methylimidazole, that above 75 ° C as an ionic liquid was incurred. The yield of isolated product of value was 298.3 g (95.2 % d.Th).

Example 17 Continuous Preparation of the Following Chelate Phosphite:

In a reaction mixing pump continuously mixed the following feed streams:

• 1) Mixture of 188.9 g of 1-methylimidazole, 249.1 g 2,2 ', 4,4'-tetramethyl-o-biphenol and 807.4 g of toluene and
• 2) Composition: mixture of 660.5 g (di-o-cresyl) chlorophosphine and 283.1 g toluene.

From stream 1) 1793 ml / h, from Stream 2) 1176 ml / h metered. The volume of the mixing chamber was 3.3 ml. The system was equilibrated for 2 min. Then was the discharge over 160 min collected to balance. The temperature of the reaction medium at the outlet of the reaction mixing pump was 70.1 ° C. The discharge consisted of two liquid Phases collected in a jar and subsequently were separated. In 160 min balance run 470.8 g top and 60.8 g lower phase collected. The upper phase was a toluene solution of the reaction products, the lower phase was the hydrochloride of 1-methylimidazole, that above 75 ° C as an ionic liquid was incurred. The yield of isolated product of value was 166.6 g (93.0 % d.Th).

Example 18 Continuous Preparation of the Following Chelate Phosphinite:

In a reaction mixing pump continuously mixed the following feed streams:

• 1) Mixture of 188.9 g of 1-methylimidazole, 249.1 g 2,2 ', 4,4'-tetramethyl-o-biphenol and 807.4 g of toluene and
• 2) Composition: mixture of 445.8 g diphenylchlorophosphine and 191.1 g toluene.

From stream 1) 1991 ml / h, from Stream 2) 906 ml / h metered. The volume of the mixing chamber was 3.3 ml. The system was equilibrated for 2 min. Then was the discharge over 218 min collected to balance. The temperature of the reaction medium at the outlet of the reaction mixing pump was 70.1 ° C. The discharge consisted of two liquid Phases collected in a jar and subsequently were separated. 641.8 g top and 93 g lower phase collected. The upper phase was a toluene solution Reaction products, the lower phase was the hydrochloride of 1-methylimidazole, that above 75 ° C as an ionic liquid was incurred. The yield of isolated product of value was 152.3 g (67.4 % d.Th).

Example 19 Continuous Preparation of the Following Chelate Phosphonite:

In a reaction mixing pump continuously mixed the following feed streams:

• 1) Mixture of 188.9 g of 1-methylimidazole, 249.1 g 2,2`, 4,4`-tetramethyl-o-biphenol and 807.4 g toluene and
• 2) Composition: mixture of 828.1 g) (2,4-di-isoamylphenoxy) chlorphenylphosphine and 354.9 g toluene.

From stream 1) 1532 ml / h, from Stream 2) metered 1395 ml / h. The volume of the mixing chamber was 3.3 ml. The system was equilibrated for 2 min. Then was the discharge over 275 min collected to balance. The temperature of the reaction medium at the outlet of the reaction mixing pump was 69 ° C. The discharge consisted of two liquid Phases collected in a jar and subsequently were separated. 787.9 g of top and bottom 85.3 g lower phase collected. The upper phase was a toluene solution of the reaction products, the lower phase was the hydrochloride of 1-methylimidazole, that above 75 ° C as an ionic liquid was incurred. The yield of isolated product of value was 304 g (89.6 % d.Th).

Example 20 Continuous Preparation of the Following Chelate Phosphonite:

In a reaction mixing pump continuously mixed the following feed streams:

• 1) Mixture of 188.9 g of 1-methylimidazole, 249.1 g 2,2 ', 4,4'-tetramethyl-o-biphenol and 807.4 g of toluene and
• 2) Composition: mixture of 738.3 g (2,4-di-tert-butylphenoxy) chlorophenylphosphine and 316.4 g of toluene.

From stream 1) 1664 ml / h, from Stream 2) metered 1308 ml / h. The volume of the mixing chamber was 3.3 ml. The system was equilibrated for 2 min. Then was the discharge over 233 min collected to balance. The temperature of the reaction medium at the outlet of the reaction mixing pump was 75.8 ° C. The discharge consisted of two liquid Phases collected in a jar and subsequently were separated. In 233 min balance run 663.9 g top and 79.8 g lower phase collected. The upper phase was a toluene solution of the reaction products, the lower phase was the hydrochloride of 1-methylimidazole, that above 75 ° C as an ionic liquid was incurred. The yield of isolated product of value was 267 g (94.7% d.Th).

Claims (16)

Process for the separation of acids from reaction mixtures by means of an auxiliary base, characterized in that the auxiliary base b) forms a salt with the acid which is liquid at temperatures at which the product of value is not significantly decomposed during the separation of the liquid salt and c) the salt the auxiliary base forms two immiscible liquid phases with the product of value or the solution of the product of value in a suitable solvent. A method according to claim 1, characterized in that the acid in the course of the reaction a phosphorylation, silylation, sulfurization, acylation with Exception of phosgenation, elimination or substitution released becomes. Method according to claim 1 or 2, characterized in that the auxiliary base additionally d) also acts as a nucleophilic catalyst. Method according to one of claims 1 to 3, characterized in that that this Salt of the auxiliary base has a melting point below 160 ° C. A method according to any one of claims 1 to 4, characterized in that the salt of the auxiliary base has an E _T (30) value of more than 35th Method according to one of claims 1 to 5, characterized in that that the Base contains at least one nitrogen atom. Method according to one of claims 1 to 6, characterized in that a base is used selected from the formula (Ia) to (Ir),

wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R6 independently of one another hydrogen, C ₁ -C ₁₈ alkyl, optionally by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted C ₂ -C ₁₈ alkyl, C ₆ -C ₁₂ aryl, C ₅ -C ₁₂ cycloalkyl or a five- to six-membered heterocycle containing oxygen, nitrogen and / or sulfur atoms, the radicals mentioned in each case by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles can be substituted. Method according to one of claims 1 to 7, characterized in that that the Auxiliary base 1-n-butylimidazole, 1-methylimidazole, 2-methylpyridine or Is 2-ethyl pyridine. Method according to one of claims 1 to 8, characterized in that that the Acid hydrochloric acid, acetic acid, p-toluenesulfonic acid, methanesulfonic acid or trifluoromethanesulfonic is. Method according to one of claims 1 to 9, characterized in that that this Salt of the auxiliary base in the product of value or in the solution of the Product of value in a suitable solvent less than 20% by weight soluble is. Method according to one of claims 1 or 3 to 10, characterized characterized that the Do not acid during the Reaction was released. Method according to one of the preceding claims, characterized in that that phosphines, phosphinic, phosphinous (Phosphinites), phosphonic acid esters, phosphonic acid halides, phosphonic, phosphonous (Phosphonites), phosphonous acid amides, Phosphonigsäurehalogenide, organophosphate, Phosphorsäurediesterhalogenide, Phosphorsäurediesteramide, Phosphorsäureesterdihalogenide, Phosphorsäureesterdiamide, phosphorous (Phosphites), phosphorous diester halides, Phosphorigsäurediesteramide, Phosphorigsäureesterdihalogenide or phosphoric acid ester diamides getting produced. Process for the preparation of phosphorus compounds from the respective Educts according to claim 12, characterized in that one the production continuously at a temperature of 60 ° C to 150 ° C and one Dwell time less than 1 hour. Use of a phosphine, phosphinic acid ester, phosphinous acid ester (phosphinite), phosphonic acid ester, phosphonic acid halide, phosphonic acid amide, phosphonous acid ester (phosphonite), phosphonous acid amide, phosphonous acid halide, phosphoric acid ester, phosphoric acid diester halide, phosphoric acid diester amide, phosphoric acid ester dihalide halide, phosphite acid amide ester phosphate acid, Acid ester dihalide or phosphoric acid ester diamide obtainable by a process according to claim 12 or 13 as a ligand for catalysts. Use of a ligand according to claim 14 as a ligand for cobalt, Rhodium, ruthenium, palladium, platinum, osmium, iridium or Nickel-containing catalysts. Use of a catalyst according to claim 15 in a hydrocyanation, Hydrogenation or hydroformylation.