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  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
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  • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
  • C07F9/4808—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the acid moiety containing a substituent or structure which is considered as characteristic
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  • C07F9/6584—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
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Definitions

• the present invention describes a process for the simplified separation of acids from reaction mixtures using an ionic liquid.
• the chemical specialist often has the problem of trapping acids released during a chemical reaction or of separating acids from reaction mixtures.
• Examples of reactions in which acids are released in the course of the reaction are 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.
• auxiliary base which usually does not participate in the actual reaction as a reactant.
• the salts of the bases used are not initially separated off, they can also be used in the presence of the valuable product, e.g. by adding another, stronger base, such as aqueous bases, e.g. Sodium hydroxide solution or potassium hydroxide solution. This creates the salt of the stronger base added in this step.
• the base originally used is set free.
• the salt of the stronger base and the first set free base must usually also be separated from the product of value.
• the product of value which is present during the work-up is added by the added stronger base itself or other substances in this base, e.g. the water in an aqueous alkali can be decomposed.
• the salts of the auxiliary base with the acid are generally not soluble in organic solvents and have high melting points, so that they form suspensions in organic media which are more difficult to handle than liquids, for example. It would therefore be desirable to be able to separate the salts of the auxiliary bases in liquid form.
• the known procedural disadvantages of suspensions would be eliminated. These are, for example, the formation of incrustations, reduction heat transfer, poor mixing and stirrability as well as the formation of local over or under concentrations and so-called hot spots.
• the aim should be a phase separation that is simple in terms of process technology by means of a liquid-liquid phase separation.
• the inventors give the reason for this 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.
• the imidazole hydrochloride should not have been liquid, this was surprisingly the case in this particular case. The applicability of this concept for reactions other than phosgenation of imidazoles is not described.
• the object was achieved according to the invention by a process for separating acids from reaction mixtures by means of an auxiliary base, in which the auxiliary base
• the salt of 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.
• the technical benefit of the process according to the invention is that the auxiliary can be separated off by a simple liquid-liquid phase separation, so that the process-related handling of solids is eliminated.
• the auxiliaries can be worked up in the absence of the valuable product, so that the latter is less burdened.
• auxiliary bases are present in reaction mixtures or are added subsequently, the salts of which are liquid under the reaction conditions and / or working-up conditions with acids which have been split off or added in the course of the reaction, ie which have not been split off during the reaction, and one which may be dissolved with the latter Form product of value immiscible phase.
• Such liquid salts are often referred to as ionic liquids.
• the acids to be bound can either be present freely in the reaction mixture or form a complex or an adduct with the product of value or another substance present in the reaction mixture.
• Lewis acids in particular tend to work with substances like ketones To form complexes. These complexes can be broken up by the auxiliary base, the salt being formed from the auxiliary base and the Lewis acid to be separated off for the purposes of this invention.
• the auxiliary bases can be inorganic or organic bases, preferably organic.
• Mixtures or solutions from auxiliary bases can also be used to fulfill the task.
• Immiscible means that at least two liquid phases separated by a phase interface form.
• an auxiliary e.g. a solvent can be added to achieve segregation or a reduction in solubility.
• a solubility of the salt in the product of value or vice versa is 20% by weight or more, preferably 15% by weight or more, particularly preferably 10% by weight or more and very particularly preferably 5% by weight or more.
• the solubility is determined under the conditions of the respective separation.
• the solubility is preferably determined at a temperature which is above the melting point of the salt and below the lowest of the following temperatures, particularly preferably 10 ° C. below the lowest and very particularly preferably 20 ° C. below the lowest:
• the solvent is to be regarded as suitable if the mixture of the product of value and the solvent is able to dissolve the salt or the salt the product of value or a mixture of the product of value and the solvent less than the amounts specified above.
• solvents which can be used are benzene, toluene, o-, m- or p-xylene, mesitylene, cyclohexane, cyclopentane, pentane, hexane, heptane, octane, petroleum ether, acetone, isobutyl methyl ketone, diethyl ketone, diethyl ether, tert-butyl methyl ether, terf.-butyl ethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl acetate, dimethylfor mamide, dimethyl sulfoxide, acetonitrile, chloroform, dichlorome
• the product of value is usually a non-polar organic or inorganic compound.
• the chemical reactions on which the invention is based are all reactions in which acids are released, with the exception of phosgenations, particularly preferably with the exception of acylations, i.e. Reactions of acid halides and carboxylic anhydrides.
• 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,
• an acid can also be separated off from reaction mixtures in which an acid which has not been released during the reaction has been added, for example in order to adjust the pH or to catalyze a reaction.
• Lewis acids which have been used as catalysts for Friedel-Crafts alkylations or acylations can be removed in a simple manner.
• 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 also include the Friedel-Crafts
• Catalysts used Lewis acids, which are described in George A. Olah, Friedel-Crafts and Related Reactions, Vol. 1, 191 to 197, 201 and 284-90 (1963). Examples include aluminum trichloride (AICI 3 ), iron (III) chloride (FeCI 3 ), aluminum tribromide (AIBr 3 ) and zinc chloride (ZnCl 2 ).
• AICI 3 aluminum trichloride
• FeCI 3 iron (III) chloride
• AIBr 3 aluminum tribromide
• ZnCl 2 zinc chloride
• the Lewis acids which can be separated off according to the invention contain cationic forms of the metals from groups Ib, IIb, lilac, IIIb, IVa, IVb, Va, Vb, Vlb, Vllb and VIII of the periodic table of the elements and of rare earths, such as, for example, lanthanum, cerium, Praseodymium, Neodymium, Samarium, Europium, Gadolinium, Terbium, Dysprosium, Holmium, Erbium, Thulium, Ytterbium or Lutetium.
• rare earths such as, for example, lanthanum, cerium, Praseodymium, Neodymium, Samarium, Europium, Gadolinium, Terbium, Dysprosium, Holmium, Erbium, Thulium, Ytterbium or Lutetium.
• Possible counterions of the Lewis acid are F, CI “ , CIO “ , CIO 3 ⁇ , CIO 4 " , Br “ , J ⁇ JO 3 “ , CN “ , OCN “ , SCN “ , NO 2 “ , NO 3 “ , HCO 3 “ , CO 3 2” , S 2_ , SH “ HSO 3 “ , SO 3 2 ⁇ , HSO 4 " , SO 4 2_ , S 2 O 2 2_ , S 2 O 4 2 ⁇ , s 2 o 5 2 -, S 2 O 6 2_ , s 2 o 7 2 -, S 2 O 8 2 " , H 2 PO 2 -, H 2 PO 4 " , HPO 4 2_ , PO, 3- , PaO ?
• n stands for the numbers 1 to 20, methanesulfonate (CH 3 SO 3 ' ), trifluoromethanesulfonate (CF 3 SO 3 ' ), toluenesulfonate (CH 3 C 6 H 4 SO 3 ' ), benzenesulfonate (CeHsSOg ' ), hydroxide (OH ' ), Anions of aromatic acids such as benzoic acid, phthalic acid, and the like and 1, 3-dicarbonyl compounds.
• Carboxylates may also be mentioned, in particular formate, acetate, trifluoroacetate, propionate, hexanoate and 2-ethylhexanoate, stearate and oxalate, acetylacetonate, tartrate, acrylate and methacrylate, preferably formate, acetate, propionate, oxalate, acetylacetonate, acrylate and methacrylate.
• borohydrides and organoboron compounds of the general formula BR "" 3 and B (OR “") 3 come into consideration, in which R “" each independently of one another is hydrogen, d - Ci ⁇ -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 8 alkyl, C 6 -C 2 aryl, C 5 -C 2 cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or Heterocycle having sulfur atoms mean or two of them together 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.
• Lewis acids are BeCI 2 , ZnBr 2 , Znl 2 , ZnSO 4 , CuCI 2l CuCI, Cu (O 3 SCF 3 ) 2 , CoCI 2 , Col 2 , Fel 2 , FeCI 2 , FeCI 2 (THF) 2 , TiCI 4 (THF) 2 , TiCI 4 , TiCI 3 , CITi (OiPr) 3 , SnCI 2 , SnCI 4 , Sn (SO 4 ), Sn (SO 4 ) 2 , MnCI 2 , MnBr 2 , ScCI 3 , BPh 3 , BCI 3 , BBr 3 , BF 3 « OEt 2 , BF 3 » OMe 2 , BF 3 » MeOH, BF 3 « CH 3 COOH, BF 3 -CH 3 CN, B (CF 3 COO) 3 ,
• the Lewis acids can be stabilized by alkali or alkaline earth metal halides, for example LiCl or NaCl.
• the (earth) alkali metal halides are mixed to the Lewis acid in a molar ratio of 0-100: 1.
• halogen or shark means fluorine (F), chlorine (Cl), bromine (Br) or iodine (I), preferably chlorine.
• such a compound can be used as the auxiliary base, the
• This auxiliary base can furthermore preferably be used
• d) at the same time act as a nucleophilic catalyst in the reaction, ie it increases the reaction rate of the reaction by at least 1.5 times, preferably by at least two times, particularly preferably five times, especially in the absence of an auxiliary base preferably at least ten times and in particular at least twenty times.
• Such compounds which can be used as bases can contain phosphorus sulfur or 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, further heteroatoms, e.g. Oxygen, sulfur or phosphorus atoms may be included.
• those compounds which contain at least one five- to six-membered heterocycle which has at least one nitrogen atom and optionally an oxygen or sulfur atom particularly preferred those compounds which contain at least one five- to six-membered heterocycle which has one, two or three nitrogen atoms and has a sulfur or an oxygen atom, very particularly preferably those having two nitrogen atoms.
• Particularly preferred compounds are those which have a molecular weight below 1000 g / mol, very particularly preferably below 500 g / mol and in particular below 250 g / mol.
• R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently of one another are hydrogen, C 1 -C 8 -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 ⁇ 2 cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur atoms having heterocycle or two of them together represent an unsaturated , saturated or aromatic and optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, the radicals mentioned being each by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles can be substituted.
• Ci - Ci 8 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, ⁇ , ⁇ -dimethylbenzyl, benzhydryl, p-tolyl
• 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 13 -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-undecyi, 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-oxatetradecyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxa-octyl, 11-methoxy-3 , 6,9-trioxa-undecyl, 7-methoxy-4-oxa-
• the number of oxygen and / or sulfur atoms and / or imino groups is not restricted. As a rule it is not more than 5 in the rest, preferably not more than 4 and very particularly preferably not more than 3.
• Substituted and unsubstituted imino groups can be, for example, imino, methyl limino, / so propylimino, n-butylimino or tert-butylimino.
• C 5 -C 2 -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, diethyl , Methoxycyclohexyl, 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, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyridyl, dimethylpyridyl Difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl and
• Ci 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 other hydrogen or R and R 2 or R 2 and R 3 1, 4-buta- 1, 3-dienylene and all others are hydrogen.
• Particularly preferred pyridazines (Ib) are those in which one of the radicals R 1 to R 4 is methyl or ethyl and all the others are hydrogen or all hydrogen.
• Particularly preferred pyrimidines (Ic) are those in which R 2 to R 4 are hydrogen or methyl and R 1 is hydrogen, methyl or ethyl, or R 2 and R 4 are methyl, R 3 is hydrogen and R 1 is hydrogen, methyl or ethyl.
• Particularly preferred pyrazines (Id) are those in which R 1 to R 4 are all methyl or all hydrogen.
• Particularly preferred imidazoles (le) are those in which are independent of one another
• R 1 is selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, 2-hydroxyethyl or 2-cyanoethyl and
• R to R independently of one another denote hydrogen, methyl or ethyl.
• Particularly preferred 1H-pyrazoles (If) are those in which they are independent of one another
• R 1 under hydrogen, methyl or ethyl
• Particularly preferred 3H-pyrazoles (Ig) are those in which they are independent of one another
• R 1 under hydrogen, methyl or ethyl
• R 2 , R 3 and R 4 under hydrogen or methyl
• Particularly preferred 4H-pyrazoles (Ih) are those in which are independent of one another
• R 1 to R 4 under hydrogen or methyl
• Particularly preferred 1-pyrazolines are those in which are independent of one another
• Particularly preferred 2-pyrazolines (Ij) are those in which are independent of one another
• R 1 under hydrogen, methyl, ethyl or phenyl
• Particularly preferred 3-pyrazolines (Ik) are those in which are independent of one another
• R 1 or R 2 under hydrogen, methyl, ethyl or phenyl
• R 3 to R 6 under hydrogen or methyl are selected.
• Particularly preferred imidazolines (II) are those in which are independent of one another
• R 1 or R 2 under hydrogen, methyl, ethyl, n-butyl or phenyl and
• R 3 or R 4 under hydrogen, methyl or ethyl
• Particularly preferred imidazolines (Im) are those in which are independent of one another
• R 1 or R 2 under hydrogen, methyl or ethyl
• Particularly preferred imidazolines (In) are those in which are independent of one another
• R 1 , R 2 or R 3 under hydrogen, methyl or ethyl
• Particularly preferred thiazoles (lo) or oxazoles (Ip) are those in which are independent of one another R 1 under hydrogen, methyl, ethyl or phenyl and
• Particularly preferred 1,2,4-triazoles (Iq) are those in which they are independent of one another
• R 1 or R 2 under hydrogen, methyl, ethyl or phenyl
• R 3 under hydrogen, methyl or phenyl
• Particularly preferred 1, 2,3-triazoles (Ir) are those in which are independent of one another
• R 1 under hydrogen, methyl or ethyl
• 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.
• the pyridines and the imidazoles are preferred.
• 3-Chloropyridine, 4-dimethylaminopyridine, 2-ethyl-4-aminopyridine, 2-methylpyridine ( ⁇ -picoline), 3-methylpyridine (ß-picoline), 4-methylpyridine ( ⁇ -picoline), 2 are very particularly preferred as bases -Ethylpyridine, 2-ethyl-6-methylpyridine, quinoline, isoquinoline, 1-CrC 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
• R a , R b and R independently of one another each Ci - C 18 alkyl, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, C 2 - C 18 alkyl, C 6 - C 12 aryl or C 5 -C 2 -cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur atom-containing heterocycle or two of them together represent an unsaturated, saturated or aromatic and optionally by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups form an interrupted ring, where the radicals mentioned can each be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles with which Provided that
• At least two of the three radicals R a , R b and R c are different and
• the radicals R a , R b and R c together have at least 8, preferably at least 10, particularly preferably at least 12 and very particularly preferably at least 13 carbon atoms.
• R a , R b and R ° are each independently of one another Ci - C 18 alkyl, C 6 - C 2 ⁇ aryl or C 5 - C 12 cycloalkyl and particularly preferably d - C 8 alkyl, the said Residues can each be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles.
• R a , R b and R c are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl (n-amyl), 2- Pentyl (sec-amyl), 3- Pentyl, 2,2-dimethyl-prop-1-yl (neo-pentyl), n-hexyl, n-heptyl, n-octyl, iso-octyl, 2-ethylhexyl, 1,1-dimethylpropyl, 1, 1-dimethylbutyl , Benzyl, 1-phenylethyl, 2-phenylethyl, ⁇ , ⁇ -dimethylbenzyl, phenyl, tolyl, xylyl, ⁇ -naphthyl, ⁇ -naphthyl, cycl
• radicals R a , R and R c form a chain, this can be, for example, 1,4-butylene or 1,5-pentylene.
• tertiary amines of the formula (XI) are diethyl-n-butylamine, diethyl-tert-butylamine, diethyl-n-pentylamine, diethyl-hexylamine, diethyl-octylamine, diethyl- (2-ethyl-hexyl) -amine, Di -n-propyl-butylamine, di-n-propyl-n-pentylamine, di-n-propyl-hexylamine, di-n-propyl-octylamine, di-n-propyl- (2-ethylhexyl) amine, di-iso -propyl-ethylamine, di-isopropyl-n-propylamine, di-iso-propyl-butylamine, di-iso-propyl-pentylamine, di-iso-propyl-hexyl
• Preferred tertiary amines (XI) are di-iso-propyl-ethylamine, diethyl-tert-butylamine, di-iso-propyl-butylamine, di-n-butyl-n-pentylamine, N, N-di-n-butylcyclohexylamine and tertiary Amines from pentyl isomers.
• tertiary amines are di-n-butyl-n-pentylamine and tertiary amines from pentyl isomers.
• a tertiary amine which is also preferred and can be used according to the invention, but in contrast to the three identical radicals mentioned above, is triallylamine.
• Tertiary amines preferably of the formula (XI) are generally preferred over heterocyclic compounds, for example of the formulas (Ia) to (Ir), when the basicity of the latter auxiliary bases is not sufficient for the reaction, for example for eliminations.
• Acids with which the bases can form salts are, for example, hydroiodic acid (Hl), 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 s ), n-butyl carbonic acid, sulfuric acid (H 2 SO 4 ), hydrogen sulfate (HSO 4 ' ), methylsulfuric acid (HO (SO 2 ) OCH 3 ), ethylsulfuric acid (HO (S ⁇ 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 is
• the separation of Bronsted acids are separated from Lewis acids without large proportions, i.e. in the separated salt of the acid with the auxiliary base, the molar ratio of Bronsted acids to Lewis acids is greater than 4: 1, preferably greater than 5: 1, particularly preferably greater than 7: 1, very particularly preferably greater than 9: 1 and especially larger than 20: 1.
• Preferred auxiliary bases are those whose salts of auxiliary bases and acids have a melting temperature at which no significant decomposition of the product of value occurs in the course of the removal of the salt as the liquid phase, 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 mol% / h.
• the melting points of the salts of the particularly preferred auxiliary bases are generally below 160 ° C., particularly preferably below 100 ° C. and very particularly preferably below 80 ° C.
• auxiliary bases those whose salts have an E ⁇ (30) value of> 35, preferably of> 40, particularly preferably of> 42 are very particularly preferred.
• the E ⁇ (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 e.g. is 1-methylimidazole.
• the use of 1-methylimidazole as the base is e.g. mentioned in DE-A 35 02 106, but their usability as an ionic liquid is not recognized there.
• 1-Methylimidazole is also effective as a nucleophilic catalyst [Julian Chojnowski, Marek Cypryk, Witold Fortuniak, heteroatom. Chemistry, 1991, 2, 63-70]. Chojnowski et al. have found that 1-methylimidazole accelerates the phosphorylation of t-butanol by a factor of 33 and the silylation of pentamethyldisiloxanol by a factor of 930 compared to triethylamine.
• 1-butylimidazole can also be used.
• the hydrochloride of 1-butylimidazole is already liquid at room temperature, so that 1-butylimidazole can be used as an auxiliary base and catalyst for reactions in which substances are handled which are already decomposable at temperatures above room temperature.
• the acetate and formate of 1-methylimidazole is also liquid at room temperature.
• all derivatives of imidazole can be used, the salts of which have an E ⁇ (30) value of> 35, preferably of> 40, particularly preferably of> 42 and have a melting temperature at which in the course of the removal of the salt as liquid phase no significant decomposition of the product of value occurs.
• 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 e.g. in
• hydrochloride of 2-ethylpyridine has a melting point of about 55 ° C. and is immiscible with non-polar organic products of value (see above) or solvents.
• 2-Ethylpyridine can thus also serve as an auxiliary base and nucleophilic catalyst and can be separated off from organic media as liquid hydrochloride via a process-technically simple liquid-liquid phase separation.
• all derivatives of pyridine can be used, the salts of which have an E ⁇ (30) value of> 35, preferably of> 40, particularly preferably of> 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 valuable product occurs.
• the polar salts of these pyridines form two immiscible phases with less polar organic media.
• reaction is not restricted and can be carried out according to the invention intercepting the liberated or added acids, if appropriate with nucleophilic catalysis, batchwise or continuously and in air or under a protective gas atmosphere.
• Another object of the invention is a process 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 auxiliary bases rather than ionic liquids with the aid of liquid-liquid separation.
• the free base can be recovered from the salt of the auxiliary base separated from the product of value in a manner known to the person skilled in the art and returned to the process.
• 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 / so-propanol, n-butanol, n-pentanol or butanol or pentanol isomer mixtures or acetone.
• 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.
• 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.
• 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 with the aid of azeotropic distillation with benzene, toluene, xylene butanol or cyclohexane.
• the base can be distilled before reuse.
• auxiliary base 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 trapped acid.
• 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.
• 1-butylimidazole formate can be separated by distillation into formic acid (top product) and 1-butylimidazole (bottom product), as described in EP-A 181 078.
• a preferred embodiment consists in distilling off the product of value from a reaction mixture in the presence of the auxiliary base in the protonated form and then, after the product of value has been largely removed, releasing the auxiliary base with a strong base and then distilling the released auxiliary base.
• the reaction mixture it can be the product of a chemical reaction or a stream from a distillation or rectification, for example an azeotropic mixture, to which an ionic liquid has been added as entrainer.
• the separation can also be carried out in reverse order by first releasing the auxiliary base with a strong base and then the auxiliary base is distilled in the presence of the valuable product, and only then is the valuable product distilled. This is particularly advantageous if the product of value is not decomposed by the strong base used.
• the same principle can also be used if the protonated form of the auxiliary base is used as an acid catalyst, i.e. instead of an acid, e.g. Hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, trifluoromethanesulfonic acid, toluenesulfonic acid, acetic acid or formic acid, their salt is used in an reaction with an auxiliary base as an ionic liquid.
• an acid e.g. Hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, trifluoromethanesulfonic acid, toluenesulfonic acid, acetic acid or formic acid
• their salt is used in an reaction with an auxiliary base as an ionic liquid.
• the advantage here is that the protonated auxiliary base forms a liquid phase during the reaction. The catalytic effect of the protonated auxiliary base can then be stopped at any time by adding a strong base.
• an acidic catalyst is neutralized in a chemical reaction with an auxiliary base which forms a liquid salt with the acidic catalyst used, so that the catalyst deactivated in this way can be separated off in a light liquid-liquid separation.
• the distillation of an ionic liquid can also take place in the absence of the product of value, for example by distilling the ionic liquid from a phase separation or a liquid-liquid extraction.
• the ionic liquid that is to say the auxiliary base in protonated form, can also contain a proportion of product of value or optionally solvent, generally less than 10% by weight, preferably less than 5% by weight, particularly preferably less than 3% by weight.
• product residues and solvent residues can first be removed from the ionic liquid, for example by vacuum distillation or stripping with an inert gas such as nitrogen, and then, after the auxiliary base has been released with a strong base, the auxiliary base can be purified by distillation or rectification.
• an inert gas such as nitrogen
• a cleaned base can then be returned to the process at any time.
• auxiliary base in protonated form as a solvent for organic reactions. After the reaction products have been separated off, the auxiliary base can be recovered and recycled as described above by liberation with a strong base and distillation.
• Preferred phosphorylations which can be carried out using the process according to the invention are reactions in which phosphorus compounds, for example phosphines, phosphinic esters, phosphinous esters (phosphinites), phosphonic esters,
• Phosphonic acid halides phosphonic acid amides, phosphonous acid esters (phosphonites), phosphonous acid amides, phosphonous acid halides, phosphoric acid esters, phosphoric acid diester halides, phosphoric acid diester amides, phosphoric acid ester dihalides, phosphoric acid ester diamides and phosphoric acid amide ester estershalophosphate, which forms a salt with the auxiliary base as described above.
• Phosphinic acid ester phosphinic acid ester phosphinite
• Phosphonous esters phosphonic esters phosphonite
• halogen or pseudo-halogen such as F, CI, Br, I, CN, OCN or SCN or un-, mono- or disubstituted amino groups
• Z represents oxygen, sulfur or an unsubstituted or monosubstituted nitrogen atom.
• the phosphorus atoms are typically connected by a bridge.
• bridged compounds with two phosphorus atoms can be:
• R, R ', R "and R"' can be any organic radical and Z can be any divalent bridge.
• It can be, in each case and independently of one another, for example one to 20 carbon atoms, linear or branched, substituted or unsubstituted, aromatic or aliphatic radicals, such as C 1 -C 8 -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, Heterocycle containing nitrogen and / or sulfur atoms, where the radicals mentioned can each be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles.
• aromatic or aliphatic radicals such as C 1 -C 8 -alkyl
• the compounds mentioned can each be substituted symmetrically or asymmetrically.
• Phosphorus compounds with a phosphorus atom are, for example, those of the formula (VIII)
• R 7 , R 8 , R 9 , R 10 independently of one another the same or different organic radicals.
• Phosphorus compounds with two phosphorus atoms are, for example, those of the formula (IX)
• 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,
• the phosphorus compounds described are suitable, for example, as ligands for catalysts for the hydrocyanation of butadiene to give a mixture of isomeric pentonitriles.
• the catalysts are generally suitable for all common hydrocyanation processes.
• the hydrocyanation of unactivated olefins e.g. B. of styrene and 3-pentenenitrile.
• 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.
• 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.
• Suitable other phosphorus-containing ligands are e.g. B. the phosphine, phosphinite and phosphite ligands previously described as prior art.
• the metal is preferably one of the VIII.
• Subgroup particularly preferably cobalt, rhodium, ruthenium, palladium or nickel atoms in any oxidation state. If the catalysts according to the invention are used for hydrocyanation, the metal of subgroup VIII is in particular nickel.
• nickel it can have different valences, such as 0, +1, +2, +3.
• Nickel (O) and nickel (+2), in particular nickel (O), are preferred.
• catalytically active species are generally formed from the catalysts or catalyst precursors used in each case under hydroformylation conditions.
• the metal used is preferably cobalt, ruthenium, rhodium, palladium, platinum, osmium or iridium and in particular cobalt, rhodium and ruthenium in any oxidation state.
• a dihalophosphorus (III) compound can first be reacted with a monoalcohol to give a diester. If desired, this compound can be isolated and / or purified by known methods prior to further reaction, e.g. B. by distillation. This diester is then reacted, for example, with a diol to give the bidentate phosphonite ligands. In the event that symmetrical ligands are to be obtained, two equivalents of the diester can be reacted with one equivalent of the diol in a one-step reaction. Otherwise, one equivalent of the diester is first reacted with one equivalent of the diol and after formation of the monocondensation product, a second diol is added and further converted to the phosphorus compound.
• a dihalophosphorus (III) compound can first be reacted with a monoalcohol to give a diester. If desired, this compound can be isolated and / or purified by known methods prior to further reaction, e.g. B. by
• the acid released in the reaction can be trapped with one of the auxiliary bases mentioned to form a liquid salt, so that this synthesis can be considerably simplified.
• Organodiphosphonites of the formula III and catalyst systems which contain such organodiphosphonites are known, for example from WO 99/64155.
• WO 99/64155 describes the reaction of R'PCI 2 with one mole of ROH and the subsequent reaction of the (RO) R'PCI obtained with half a mole, based on one mole of (RO) R'PCI , a compound HO-Z-OH at a temperature in the range of 40 to about 200 ° C.
• the hydrogen halide should preferably be split off purely thermally.
• both steps should be able to be carried out in the presence of a base.
• the processes known in the prior art such as, for example, that known from WO 99/64155, are carried out analogously for the preparation of the phosphorus compounds mentioned, with the difference that, according to the invention, an auxiliary base as described above is used and the acid released from the Reaction mixture is separated by means of the auxiliary base, the auxiliary base forming a salt with the acid as above, which is liquid at temperatures 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.
• phosphorus compounds mentioned can be prepared, for example, as follows:
• the starting materials are dissolved or dispersed in the desired stoichiometry, if appropriate in a solvent, i.e. suspended or emulsified, mixed together. It may make sense to divide the starting materials into one or more compositions, i.e. separate streams, so that the reaction does not take place before 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 one another under reaction conditions which lead to the reaction of the starting materials to the product.
• reaction conditions depend on the starting materials used and the desired products and are specified in the prior art mentioned in this document.
• 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, above 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 preferably chosen to be short in the case of a continuous reaction at a temperature which is sufficiently high for the reaction, ie from a few seconds to about 2 hours, preferably from 1 second to 2 hours, particularly preferably from 1 second to 1 hour, very particularly preferably from 1 second to 30 minutes ten, in particular from 1 second to 15 minutes and exceptionally preferably from 1 second to 5 minutes.
• the preparation of the phosphorus compounds is carried out continuously from the respective starting materials at a temperature of from 60 ° C. to 150 ° C. preferably at a temperature above the melting point of the salt of the auxiliary base used with the released acid to 130 ° C., with a residence time of less than 1 hour, preferably less than 30 minutes, particularly preferably less than 15 minutes, very particularly preferably 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 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 exchanged as a result of equilibration on the phosphorus atom / on the phosphorus atoms.
• reactors for example one or more cascaded stirred or tube reactors with internal and / or external heaters and preferably jet nozzle reactors or reaction mixing pumps.
• the reaction discharge is fed into an apparatus in which phases formed during the reaction can separate from one another, for example phase separators or mixer-settlers.
• the phase which mainly contains ionic liquid
• solvent can be added to accelerate phase separation.
• the auxiliary base as described above, can be recovered from the phase which contains predominantly ionic liquid.
• the reaction product can be isolated and / or purified from the phase which contains the desired reaction product using methods known per se, for example by distillation, rectification, extraction, fractional or simple crystallization, membrane separation processes, chromatography or combinations thereof.
• the solvent used in the reaction can be the solvents listed above.
• the auxiliary base used in the reaction is generally used in, based on the expected amount of acid, stoichiometric amount or a slight excess, for example 100 to 200 mol% based on the expected amount of acid, preferably 100 to 150 and particularly preferably 105 up 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 easily accessible and are given, for example, in the prior art mentioned in this document, as are the stoichiometric ratios in order to react the starting materials with one another.
• the starting materials are used as possible as liquids or melts, if necessary they are dissolved or dispersed in a solvent. Of course, it is also possible to use the starting materials at least partially as solids.
• the solvent is generally used in an amount such that the mixture is liquid, for example as a solution or dispersion.
• concentrations of the starting materials based on the total amount of the 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
• compound (VIII) is understood to mean a single compound or a mixture of different compounds of the abovementioned formula.
• X 1 , X 2 , X 3 are independently oxygen, sulfur, NR 10 or single bond.
• R 10 represents hydrogen or an organic radical with 1-10 carbon atoms, preferably hydrogen, phenyl or C 1 -C 4 -alkyl, including methyl, ethyl, / so-propyl, n-propyl, n- Butyl, / so-butyl, se-butyl and te / f-butyl is understood.
• compound (VIII) provides a phosphine of the formula P (R 7 R 8 R 9 ) with those for R 7 , R 8 and R 9 in this case Meanings of spelling.
• 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.
• compound (VIII) is 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.
• all of the groups X 1 , X 2 and X 3 should stand for oxygen, so that compound (VIII) is advantageously a phosphite of the formula P (OR 7 ) (OR 8 ) (OR 9 ) with the meanings given for R 7 , R 8 and R 9 in this description.
• 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.
• alkyl radicals advantageously having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t- Buty
• 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.
• the groups R 7 , R 8 and R 9 are radicals selected from the group consisting of phenyl, o-tolyl, m-tolyl and p-tolyl.
• a maximum of two of the groups R 7 , R 8 and R 9 should be phenyl groups.
• a maximum of two of the groups R 7 , R 8 and R 9 should be o-tolyl groups.
• 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-tolyl-O-) 2 (phenyl) P, (o-tolyl-O-) 2 (phenyl)
• 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.
• a phosphorus trihalide such as phosphorus trichloride
• 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
• compound (IX) is understood to mean a single compound or a mixture of different compounds of the abovementioned formula.
• X 11 , X 12 , X 13 , X 21 , X 22 , X 23 can represent oxygen.
• the bridging group Y is linked to phosphite groups.
• X 11 and X 12 oxygen and X 13 can be a single bond or X 11 and X 13 oxygen and X 12 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 phosphite is.
• 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 the central atom of a phosphite, phosphonite, phosphinite or phosphine of a phosphonite.
• 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.
• 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.
• X 21 , X 22 and X 23 can represent oxygen or X 21 , X 22 and X 23 a single bond, so that X 21 , X 22 and X 23 Surrounded phosphorus atom can be the central atom of a phosphite or phosphine, preferably a phosphine.
• 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).
• halogen such as fluorine, chlorine, bromine
• halogenated alkyl such as trifluoromethyl
• aryl such as phenyl
• unsubstituted aryl groups, preferably those having 6 to 20 Carbon atoms in the aromatic system, in particular pyrocatechol, bis (phenol) or bis (naphthol).
• R 11 and R 12 can independently represent the same or different organic radicals.
• R 1 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.
• radicals R 21 and R 22 can independently represent the same or different organic radicals.
• 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 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 compounds mentioned in US Pat. No. 3,773,809 come into consideration, in particular those described in column 2, line 23 to column 4, line 14 and in the examples.
• the compounds mentioned in US Pat. No. 6,127,567 come into consideration, in particular those in column 2, line 23 to column 6, line 35, in the formulas I, II, III, IV, V, VI, VII, VIII and IX and compounds used in Examples 1 to 29.
• the compounds mentioned in US Pat. No. 6,171,996 come into consideration, in particular those in column 2, line 25 to column 6, line 39, in the formulas I, II, III, IV, V, VI, VII, VIII and IX and the compounds used in Examples 1 to 29.
• the compounds mentioned in US Pat. No. 6,380,421 are suitable, 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.
• the compounds mentioned in US Pat. No. 5,488,129 are suitable, 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.
• the compounds mentioned in US Pat. No. 5,856,555 are suitable, 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.
• the compounds mentioned in WO 99/46044 are suitable, in particular the compounds used 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 ,
• the compounds of the formula I, II, III, IV, V, VI and VII mentioned in US Pat. No. 5,512,696, in particular the compounds used there in Examples 1 to 31, are suitable.
• the compounds mentioned in WO 01/14392 preferably those there in the formulas V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XXI, XXII, XXIII compounds shown.
• the compounds mentioned in WO 98/27054 are suitable.
• the compounds mentioned in WO 99/13983 are suitable, in particular the compounds mentioned 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.
• the compounds mentioned in WO 99/64155 are suitable, in particular 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.
• German patent application DE 10038037 come into consideration.
• German patent application DE 10046025 come into consideration.
• the compounds mentioned in the German patent application with the file number DE 10156292.6 and the filing date 19.11.01 come into consideration, in particular the compounds in the filing text on page 1, lines 6 to 19 and from page 2, line 21 to page 2, Line 30 called connections.
• the compounds mentioned in the German patent application with the file number DE 10150281.8 and the filing date 12.10.01 are suitable, in particular the compounds mentioned in the filing text on page 1, line 36 to page 5, line 45.
• the compounds mentioned in the German patent application with the file number DE 10150285.0 and the filing date 12.10.01 come into consideration, in particular the compounds mentioned in the filing text on page 1, line 35 to page 5, line 37.
• the compounds mentioned in the German patent application with the file number DE 10150286.9 and the filing date 12.10.01 come into consideration, in particular the compounds mentioned in the filing text on page 1, line 37 to page 6, line 15.
• the compounds mentioned in the German patent application with the file number DE 10148712.6 and the filing date 2.10.01 come into consideration, in particular those in the filing text on page 1, lines 6 to 29 and page 2, line 15 to page 4, line 24 mentioned connections.
• auxiliary base and Lewis acid are liquid at the temperatures concerned and forms a phase which is immiscible with the product of value.
• CI 3 PO «AICI 3 complex fails and can be separated, for example, by filtration (WT Dye, J. Am. Chem. Soc, 1948, 70, 2595). Furthermore, it is known from the same document to add a precisely determined amount of water to the product in order to form the hydrate of aluminum trichloride, which can also be separated from the product by filtration.
• AICI 3 can also be precipitated by complex formation with pyridine and thus separated off.
• DE 32 48483 discloses a process for separating AICI 3 using NaCI.
• EP 838447 describes the formation of liquid clathrates which are insoluble in the respective Friedel-Crafts product and e.g. are separable via phase separation.
• EP-A1 1 142 898 describes phosphorylations for the preparation of biphenylphosphonites in which phases of eutectic pyridine-hydrochloride / pyridine-aluminum chloride mixtures are separated from product-containing solvent phases.
• the disadvantage is that the liquid separation of such mixtures from the product is not possible without the formation of a eutectic.
• the process described above for separating Lewis acids from reaction mixtures is carried out by means of an auxiliary base in which the auxiliary base
• the reaction with the Lewis acid to prepare the product is generally carried out in the customary manner and, after the reaction has ended, the auxiliary base is added to the reaction mixture in order to separate off the Lewis acid.
• the reaction mixture can also be added to the auxiliary base. It is important to mix the reaction mixture with the auxiliary base, the auxiliary base and Lewis acid generally forming a complex.
• at least one mol of auxiliary base is used per mol of Lewis acid to be separated off in the reaction mixture, preferably 1.0 to 1.5 mol / mol, particularly preferably 1.0 to 1.3 mol / mol, very particularly preferably 1.0 to 1, 3 and in particular 1, 0 to 1, 25 mol / mol.
• the mixture can be worked up further immediately, but stirring can also continue for a few minutes to several hours are preferably 5 to 120, particularly preferably 10 to 60 and very particularly preferably 15 to 45 minutes.
• the reaction mixture can advantageously be kept at a temperature at which the complex of auxiliary base and Lewis acid is liquid, but no significant decomposition occurs yet, but it can also be kept below the melting temperature of the complex.
• phase separation takes place under conditions as already described above.
• the melting point is approximately 60 ° C., so that the separation, for example by phase separation, from the product of value can follow at relatively low temperatures.
• the separation according to the invention can be used wherever Lewis acids have to be separated from a product of value, preferably in Friedel-Crafts alkylations or acylations, phosphorylations or sulfurizations of aromatics and particularly preferably in phosphorylation of aromatics.
• Preferred examples of phosphorylations of aromatics are the Lewis acid-catalyzed reaction of aromatics with phosphoryl halides, for example PCI 3 , PCI 5 , POCI 3 or PBr 3 .
• Aromatics which can be used are, for example, those of the formula (X)
• Z is a single bond or any bivalent bridge
• R 31 , R 32 , R 33 , R 34 , R 35 and R 36 independently of one another
• Functional groups mean, for example, nitro- (-NO 2 ), nitroso- (-NO), carboxyl- (-COOH), halogen- (-F, -CI, -Br, -I), amino- (-NH 2 , -NH (-C-C 4 alkyl), -N (CC 4 -alkyl) 2 ), carboxamide- (-CONH 2 , -CONH (C r C 4 -alkyl), -CON (C ⁇ -C 4 -alkyl) 2 ), nitrile (- CN), thiol (-SH) or thioether functions (-S (-C-alkyl)).
• the radicals R 31 , R 32 , R 33 , R 34 , R 35 and R 36 are, independently of one another, hydrogen, CrC 4 -alkyl, dC-alkyloxy, C 1 -C -alkyloxycarbonyl or halogen.
• radicals R 31 , R 32 , R 33 , R 34 , R 35 and R 36 independently of one another are particularly preferably hydrogen, methyl, tert-butyl, ethyl, methoxy, fluorine or chlorine.
• Z are a single bond, methylene, 1, 2-ethylene, 1, 1-ethylene, 1, 1, - propylene, 2,2-propylene, 1, 2-phenylene, 1, 4-dimethyl-2,3- phenylene, oxygen (-O-), unsubstituted or monosubstituted nitrogen (-NH- or -N (dC 4 -alkyl) -) or sulfur (-S-).
• Z is preferably a single bond, oxygen or methylene.
• aromatics are benzene, toluene, o-, m- or p-xylene, 2,4,6-trimethylbenzene, ethylbenzene, 1-ethyl-3-methylbenzene, 1-ethyl-4-methylbenzene, / so-propyl - benzene, 1, 3-di-so-propylbenzene, tert-butylbenzene, 1, 3-di-tert-butylbenzene, 1-tert-butyl -3-methylbenzene, 1-tert-butyl-3,5-dimethylbenzene, n -Propylbenzene, styrene, indene, fluorene, dimethylaniline, fluorobenzene, chlorobenzene, bromobenzene, 1, 2-, 1, 3- or 1, 4-dichlorobenzene, 1, 2-, 1, 3- or 1, 4 -Difluorobenzene, 1,1'-
• Aromade is benzene, toluene, o-, m- or p-xylene, 2,4,6-trimethylbenzene, / so-propylbenzene, tert-butylbenzene, fluorobenzene, chlorobenzene, naphthalene and binaphthyl.
• Examples of valuable products which can be obtained by phosphorylation or sulfurization of aromatics, Friedel-Crafts alkylations or acylations are ethylbenzene, acetophenone, 4-methylacetophenone, 4-methoxyacetophenone, propiophenone, benzophenone, dichlorophenylphosphine, diphenylchlorophosphine, tosino 2-, 1, 3- and 1, 4-diethylbenzene, 1, 2,3-, 1, 2,4- and 1, 3,5-triethylbenzene, cumene (/ so-propylbenzene), tert-butylbenzene, 1, 3- and 1,4-methyl-so-propylbenzene, 9,10-dihydroanthracene, indane, cresol, 2,6-xylenol, 2-sec-butylphenol, 4-tert-butylphenol, octylphenol, nonylphenol, dodecylphenol,
• the acid is treated with a nonionic, i.e. unloaded auxiliary base, separated.
• auxiliary bases of the formulas (la) to (Ir) listed above are particularly suitable for this.
• these are separated off without predominant proportions of Bronsted acids (protonic acids), ie the molar ratio of in the separated salt of the acid with the auxiliary base is Bronsted acids to Lewis acids not larger than 1: 1, preferably not larger than 0.75: 1, particularly preferably not larger than 0.5: 1, very particularly preferably not larger than 0.3: 1 and in particular not larger than 0.2: 1.
• aminodihalophosphines, diaminohalophosphines, triaminophosphines, phosphoric acid ester diamides, aminophosphines, diaminophosphines, phosphoric acid ester amide halides and aminophosphine halides can be prepared using the process according to the invention.
• Van der Slot et al. describe in Organometallics 2002, 21, 3873 the synthesis of aminochlorophosphines, aminophosphines and phosphoramidites using triethylamine as an auxiliary base.
• the insoluble salts formed during the reaction must also be removed by filtration.
• WO 02/83695 describes the synthesis of phosphoramidites and their use in the hydroformylation of terminal and internal olefins.
• phosphorus halides and chelating phosphoramidite ligands can be handled in a technically simpler manner (no solid separation of the salts of the auxiliary base) and can be prepared with a higher space-time yield in the reaction with high selectivity.
• R, R 'and R stand for any organic radicals, which can each be the same or different, X and X' for halogen or pseudohalogen, such as F, CI, Br, I, CN, OCN or SCN, preferably around CI , which can each be the same or different, and [N], [N 1 ] and [N "] for unsubstituted, mono- or disubstituted amino groups, which can each be the same or different.
• halogen or pseudohalogen such as F, CI, Br, I, CN, OCN or SCN, preferably around CI , which can each be the same or different
• [N], [N 1 ] and [N "] for unsubstituted, mono- or disubstituted amino groups, which can each be the same or different.
• the phosphorus atoms are typically connected by a bridge.
• bridged compounds with two phosphorus atoms can be:
• R, R ', R "and R"' can contain any organic radicals, which may be the same or different, [N], [N 1 ], [N “], [IM”'], [N “”] and [N '””] for unsubstituted, mono- or disubstituted amino groups, which can each be the same or different and Z is any divalent bridge.
• R, R ', R “and R'” can each be, independently of one another, for example, one to 20 carbon atoms, linear or branched, substituted or unsubstituted, aromatic or aliphatic radicals, such as C 1 -C 8 -alkyl, if appropriate one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted C 2 -C 8 -alkyl, C 2 - Ci ⁇ -alkenyl, C 6 - C 2 -aryl, C s - C 2 -cycloalkyl or a five- to six-membered heterocycle containing oxygen, nitrogen and / or sulfur atoms, where the radicals mentioned can each be substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles.
• the bivalent bridge Z can, for example, be unsubstituted or with halogen, -CC 8 -
• Alkyl, C 2 -C 8 alkenyl, carboxy, carboxy-dC 8 -alkyl, -C-C 20 -acyl, C ⁇ -C 8 -alkoxy, C 6 -d 2 - aryl, hydroxyl or hydroxy-substituted dC 8 -alkyl substituted C 6 -C ⁇ 2 aryls, C 3 - Ci 2 -cycloalkylene, C ⁇ -C 2 o-alkylene or by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups and / or by one or more - (CO) -, -O ( CO) O-, - (NH) (CO) O-, - O (CO) (NH) -, -O (CO) - or - (CO) O groups mean interrupted C 2 -C 20 alkylene.
• a 1 and A 2 independently of one another represent O, S, SiR s1 R 52 , NR 53 or CR ⁇ R 55 , wherein
• R 51 , R 52 and R 53 independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
• R 54 and R 55 independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl or the group R 54 together with another group R 54 or the group R 55 together with another group R ss an intramolecular bridging group D.
• a 1 additionally represents a C 2 or C 3 alkylene bridge which have a double bond and / or an alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl substituent can, or which can be interrupted by O, S, SiR 51 R 52 or NR 53 ,
• R 61 and R 62 independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylate or cyano or are connected to one another to form a C 3 -C 4 -alkylene bridge,
• R 63 , R 64 , R 65 and R 66 independently of one another for hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, COOH, carboxylate, cyano, alkoxy, SO 3 H, sulfonate, NE 1 E 2 , alkylene-NE 1 E 2 E 3+ X " , acyl or nitro,
• R 56 , E 1 , E 2 and E 3 each represent the same or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl,
• R 57 represents hydrogen, methyl or ethyl
• w represents an integer from 1 to 120
• those bridge groups Z are preferred in which A 1 is different from A 2 , where A 1 is preferably a CR d R e group and A 2 is preferably an O or S group, particularly preferably an oxa group O.
• Particularly preferred bridging groups Z are therefore those which like from a triptycene or xanthene type (A 1: CR d R e, A 2: O) backbone are constructed.
• R 1 , R “, R 1 ", R ⁇ , R V , R VI , R v “, R v ⁇ “, R ⁇ x , R x , R x ⁇ and R x " are preferably selected from hydrogen, alkyl, alkoxy , Cycloalkyl, heterocycloalkyl, aryl and hetaryl. According to a first preferred embodiment, R 1 , R “, R 1 “, R IV , R V , R v ⁇ , R “, R ⁇ “, R , x , R x , R X1 and R x "for hydrogen.
• R 1 and R v ⁇ are independently in Xlll.p and Xlll.q. for CC 4 alkyl or CC alkoxy.
• R 1 and R v are preferably selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.
• R 11 , R 1 ′′ R 1 and R preferably represent hydrogen.
• R 1 , R 1 ", R v ⁇ and R v ⁇ " independently of one another are C 1 -C 4 -alkyl or C 1 -C 4 alkoxy.
• R 1 , R 1 ", R v ⁇ and R v ⁇ " are preferably selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.
• R ", R ⁇ , R V and R v " are preferably hydrogen.
• R 1 , R 1 ", R ⁇ v , R v , R v ⁇ and R v ⁇ " independently of one another are C 1 -C 4 -alkyl or CC 4 - alkoxy.
• R 1 , R 1 ", R lv , R v , R ⁇ and R v ⁇ " are preferably selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.
• R 11 and R v "in these compounds are preferably hydrogen.
• R 1 and R x independently of one another are CC 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -carboalkoxy or C 1 -C -trialkylsilyl.
• R 1 and R x selected from methyl, ethyl, isopropyl, tert-butyl, methoxy, carbomethoxy and trimethylsilyl.
• R ", R 1 ", R IV , R V , R VI , R v ", R v ⁇ ", R ⁇ x , R x and R x ⁇ are preferably hydrogen.
• Fused benzene rings are preferably unsubstituted or have 1, 2 or 3, in particular 1 or 2 sub- substituents which are selected from alkyl, alkoxy, halogen, SO 3 H, sulfonate, NE 1 E 2 , alkylene-NE 1 E 2 , trifluoromethyl, nitro, COOR f , alkoxycarbonyl, acyl and cyano.
• Fused naphthalene rings are preferably unsubstituted or have a total of 1, 2 or 3, in particular 1 or 2, of the substituents previously mentioned for the fused benzene rings in the non-fused ring and / or in the fused ring.
• groups Xlll.a to Xlll.t groups Xlll.a to Xlll.e are preferred, groups Xlll.b and Xlll.d. are particularly preferred.
• [N] can independently of one another in each case be groups -NR 41 R 42 , in which
• R 41 and R 42 independently of one another Ci - C ⁇ 8 alkyl, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups C 2 - C 8 alkyl, C 2 - C 8 - Alkenyl, C 6 -C 2 aryl, C 5 -C 2 cycloalkyl or a five- to six-membered heterocycle having oxygen, nitrogen and / or sulfur atoms, the radicals mentioned being each aryl, alkyl, aryloxy, Alkyloxy, heteroatoms and / or heterocycles can be substituted, where R 41 and R 42 can also form a ring together.
• Preferred groups -NR 41 R 42 in which R 41 and R 42 form a ring, are such groups of the formulas XlV.a to XlV.k.
• Alk is a CrC 4 alkyl group
• R °, R p , R q and R r independently of one another represent hydrogen, C 1 -C 4 -alkyl, dC 4 -alkoxy, acyl, halogen, trifluoromethyl, dC 4 -alkoxycarbonyl or carboxyl.
• the 3-methylindolyl group (skatolyl group) of the formula XIV.f1 is particularly advantageous.
• a 3 is a single bond, O, S, SiR 51 R 52 , NR 53 , CR ⁇ R 55 or a C 2 or C 10 alkylene bridge which has a double bond and / or an alkyl, cycloalkyl, heterocycloalkyl, Aryl or hetaryl substituents, or which can be interrupted by O, S, SiR 51 R 52 or NR 53 , where R 51 , R 52 , R 53 , R 54 and R 55 have the meaning given above, and
• R 71 , R 72 , R 73 , R 74 , R 75 and R 76 independently of one another for hydrogen, alkyl, alkoxy, cycloalkyl, heterocycloalkyl, aryl, hetaryl, halogen, COOR 56 , COO " M + , SO 3 R 56 , SO " 3 M + , NE 1 E 2 , NE 1 E 2 E 3+ X " , alkylene NE 1 E 2 , alkylene NE 1 E 2 E 3+ X " , OR 58 , SR 56 , (CHR ⁇ CHsOJ w R 56 , (CH 2 N (E 1 )) W R 56 , (CH 2 CH 2 N (E 1 )) W R 56 , halogen, trifluoromethyl, nitro, acyl or cyano, where R 56 , E 1 , E 2 , E 3 and X 'are as defined above.
• the groups R 71 and R 72 and or R 75 and R 76 can also together form a five-, six- or seven-membered ring by combining together a chain which is optionally substituted by alkyl, alkoxy, cycloalkyl, heterocycloalkyl, aryl, hetaryl or halogen form which contains three, four or five carbon atoms in the chain, for example 1,3-propylene, 1,4-butylene, 1,5-pentylene and preferably 1,4-buta-1,3-dienylene.
• the compounds mentioned can each be substituted symmetrically or asymmetrically.
• the phosphorus compounds described are suitable, for example, as ligands for catalysts for the hydroformylation of terminal and internal olefins. Use for hydrocyanation, hydrogenation, hydrocarboxylation, hydroamidation, hydroesterification and aldol condensation is also conceivable.
• Such catalysts can have one or more of the phosphorus compounds as ligands.
• they can also contain at least one further ligand, which is selected from hydride, alkyl, cyanide, halides, amines, carboxylates, acetylacetone, aryl or alkyl sulfonates, hydride, CO, olefins, dienes, cycloolefins, nitriles, N -containing heterocycles, aromas and heteroaromatics, ethers, PF 3 and one, bidentate and multidentate phosphine, phosphinite, phosphonite and phosphite ligands.
• Suitable other phosphorus-containing ligands are e.g. B. the phosphine, phosphinite and phosphite ligands previously described as prior art.
• the metal is preferably one of the VIII.
• Subgroup particularly preferably cobalt, rhodium, ruthenium, palladium or nickel atoms in any oxidation state. If the catalysts of the invention are used for hydroformylation, the metal from subgroup VIII is in particular rhodium.
• catalytically active species are generally formed from the catalysts or catalyst precursors used in each case under hydroformylation conditions.
• the metal used is preferably cobalt, ruthenium, rhodium, palladium, platinum, osmium or iridium and in particular cobalt, rhodium and ruthenium in any oxidation state.
• phosphorus compounds used as ligands in the catalysts for example, phosphorus trichloride with two equivalents of a pyrrole the compound are reacted, whereby a diaminochlorophosphine is formed.
• diaminochlorophosphine prepared according to the invention can be reacted with a diol to form a bidentate ligand.
• z. B. reacted diaminochlorophosphine with the diol and then added the further coupling component z. B. an aryldichlorophosphine.
• the starting materials are dissolved or dispersed in the desired stoichiometry, if appropriate in a solvent, i.e. suspended or emulsified, mixed together. It may make sense to divide the starting materials into one or more compositions, i.e. separate streams, so that the reaction does not take place before 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 one another under reaction conditions which lead to the reaction of the starting materials to the product.
• reaction conditions depend on the starting materials used and the desired products and are specified in the prior art mentioned in this document.
• the reaction can be carried out continuously, semi-continuously or batchwise.
• the temperature usually ranges from 30 ° C to 190 ° C, preferably 70 to 120 ° 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 in a continuous reaction at a temperature which is sufficiently high for the reaction is preferably chosen to be short, ie from a few seconds to about 2 hours, preferably from 1 second up to 2 hours, particularly preferably from 1 second to 1 hour, very particularly preferably from 1 second to 30 minutes, in particular from 1 Seconds to 15 minutes and exceptionally preferred from 1 second to 5 minutes.
• the preparation of the phosphorus compounds is carried out continuously from the respective starting materials at a temperature of from 60 ° C. to 150 ° C. preferably at a temperature above the melting point of the salt of the auxiliary base used with the released acid to 130 ° C., with a residence time of less than 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.
• reactors for example one or more cascaded stirred or tube reactors with internal and / or external heaters and preferably jet nozzle reactors or reaction mixing pumps.
• the reaction discharge is fed into an apparatus in which phases formed during the reaction can separate from one another, for example phase separators or mixer-settlers.
• the phase which predominantly contains ionic liquid, is phase-separated from the phase which predominantly contains the desired reaction product. If necessary, solvent can be added to accelerate phase separation.
• the auxiliary base as described above, can be recovered from the phase which contains predominantly ionic liquid.
• the reaction product can be isolated and / or purified from the phase which contains the desired reaction product using methods known per se, for example by distillation, rectification, extraction, fractional or simple crystallization, membrane separation processes, chromatography or combinations thereof.
• the solvent used in the reaction can be the solvents listed above.
• the auxiliary base used in the reaction is generally used in, based on the expected amount of acid, stoichiometric amount or a slight excess, for example 100 to 200 mol% based on the expected amount of acid, preferably 100 to 150 and particularly preferably 105 up to 125 mol%. If the auxiliary base used serves as a solubilizer, larger amounts of auxiliary base can also be added, for example up to 1000 mol% or more.
• the starting materials for the production of the desired phosphorus compounds are known per se to the person skilled in the art or are easily accessible and are given, for example, in the prior art mentioned in this document, as are the stoichiometric ratios in order to react the starting materials with one another.
• the starting materials are used as possible as liquids or melts, if necessary they are dissolved or dispersed in a solvent. Of course, it is also possible to use the starting materials at least partially as solids.
• the solvent is generally used in an amount such that the mixture is liquid, for example as a solution or dispersion.
• concentrations of the starting materials based on the total amount of the solution or dispersion are 5 to 95% by weight, preferably 10 to 90% by weight.
• the acid released in the reaction can be trapped with one of the auxiliary bases mentioned to form a liquid salt, so that the synthesis can be considerably simplified.
• Preferred is the preparation according to the invention of phosphoric acid ester diamides of the formula (RO) P [N] [N '], in which R, [N] and [N 1 ] are as defined above.
• diphosphoric acid ester diamides of the formula [N] [N '] POZOP [N “] [N'”] is particularly preferred, in which Z, [N], [IM '], [N "] and [N' "] are as defined above.
• the compounds mentioned in US 4,668,651 are suitable, in particular the compounds described in column 9, line 25 to column 16, line 53 and in examples 1 to 11, and also ligand A to Q.
• the compounds mentioned in US Pat. No. 4,748,261 are suitable, in particular the compounds described in column 14, line 26 to column 62, line 48 and in examples 1 to 14, and ligand 1 to 8.
• the compounds mentioned in US Pat. No. 4,769,498 are suitable, in particular the compounds described in column 9, line 27 to column 18, line 14 and in examples 1 to 14, and also ligand A to Q.
• the compounds mentioned in US Pat. No. 4,885,401 are suitable, in particular the compounds described in column 12, line 43 to column 30, including and in Examples 1 to 14, and ligand 1 to 8.
• the compounds mentioned in US Pat. No. 5,235,113 are suitable, in particular the compounds described in column 7 to column 40, line 11 and in examples 1 to 22.
• the compounds mentioned in US Pat. No. 5,391,801 come into consideration, in particular the compounds described in column 7 to column 40, line 38 and in examples 1 to 22.
• the compounds mentioned in US Pat. No. 5,663,403 are suitable, in particular the compounds described in column 5, line 23 to column 26, line 33 and in examples 1 to 13.
• the compounds mentioned in US Pat. No. 5,728,861 are suitable, in particular the compounds described in column 5, line 23 to column 26, line 23 and in examples 1 to 13, and ligand 1 to 11.
• the compounds mentioned in US Pat. No. 6,172,267 are suitable, in particular the compounds described in column 11 to column 40, line 48 and in examples 1 and 2, and ligand 1 to 11.
• the compounds mentioned in JP2002-47294 come into consideration.
• the filtrate and washing xylene were combined (in total 859.9 g) and examined by means of GC with an internal standard.
• the xylene solution contained 11.8% diethoxyphenylphosphine, which corresponds to a yield of 51%.
• TEP triethyl phosphite
• EODPP ethoxydiphenylphosphine
• 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 of water were added until a clear solution was obtained. After the addition of 450 g of n-propanol, common salt precipitated again, which was brought back into solution 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.
• 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.
• feedstocks were fed continuously into a nitrogen-inertized reactor with a three-stage inclined-blade stirrer at 80 ° C.: 1) mixture of 110.7 g of ethanol and 205.8 g of 1-methylimidazole 2) chlorodiphenylphosphine (99.4%).
• Stream 1) was added at 330 ml / h and stream 2) at 380 ml / h. Both inlets were made dipped.
• the reactor was equipped with an overflow from which the reaction mixture could run off continuously.
• the reactor volume to the overflow was 710 ml.
• the reaction temperature was kept at 80 ° C. To balance the system, the discharge of the first 4 hours was discarded. The discharge was then collected over a period of 1 h and balanced.
• the discharge consisted of two liquid phases. 497.2 g of upper phase and 280.8 g of lower phase were collected within one hour.
• the upper phase consisted of 96.8% EODPP.
• the upper phase was then distilled in vacuo over a column filled with Raschig rings, 438.2 g of 99.74% EODPP being obtained. Together with the pre-EODPP, the overall yield was 96.7%.
• 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.
• the following feed streams were continuously mixed in a reaction mixer pump: 1) Mixture of 156.7 g of 1-methylimidazole and 84.1 g of ethanol 2) 370.0 g of chlorodiphenylphosphine (99.1% strength). 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. Mixing pump was thermostatted to 80 ° C. The system was equilibrated for 60 minutes. The discharge was then collected over 87 minutes in order to be balanced. During the balance run, the amount of input materials was determined by weighing the templates. 370.0 g of chlorodiphenylphosphine were added. The discharge consisted of two liquid phases.
• the following feed streams were continuously mixed in a reaction mixing pump: 1) mixture of 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.
• 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.
• the following feed streams were continuously mixed in a reaction mixing 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. While During the balance trip, the amount of feed materials was determined by weighing the templates.
• Example 2 Analogously to Example 1, 181.5 g of dichlorophenylphosphine, 101.4 g of ethanol and 189 g of 1-methylimidazole were used to produce DEOPP, 202.2 g of the upper phase having a DE-OPP content of 93.9% and 265.5 g of the lower phase attack. The upper phase also contains 3.7 g of 1-methylimidazole. The lower phase was mixed with 169.6 g paraff in oil. 168 g of 50% strength sodium hydroxide solution were then added dropwise to this mixture, an easily stirrable suspension being obtained.
• the 1-methylimidazole was distilled off at 30 mbar and a top temperature of 90 ° C. 164.0 g of 1-methylimidazole were recovered, which has a content of 99.7%.
• the water content of the distilled 1-methylimidazole was 0.06%.
• the distillation bottoms were then mixed with 350 g of water in order to dissolve the common salt suspended in the white oil.
• Two phases developed.
• the 475.7 g sub-phase contained the common salt and 0.3% (1.4 g) 1-methylimidazole.
• the 161.1 g upper phase consisted of the white oil, which was also returned to the process as an inert suspending aid.
• 164.0 g of the total of 192.8 g of 1-methylimidazole (189.0 g fresh and 3.8 g in the recycled xylene) used were recovered as pure substance.
• a further 21.8 g were in the distilled xylene, the was brought back into the process and is therefore preserved.
• a total of 185.8 g (96%) of the 1-methylimidazole could thus be recycled.
• composition mixture of 11.9 g of 1-methylimidazole, 11.8 g of o-biphenol and 35.1 g of toluene and
• Example 12 The synthesis of the chelate phosphonite from Example 12 was carried out as described under Example 12. Different parameters were varied. The head of the reaction mixing pump was thermostatted in such a way that the end temperatures of the reaction mixture given in the table at the outlet of the pump could be obtained. The results are summarized in the following table.
• MIA 1 -methylimidazole
• TBCP (2-tert-butylphenoxy) chlorphenylphosphine
• 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
• 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
• Composition mixture of 445.8 g diphenylchlorophosphine and 191.1 g toluene.
• Composition mixture of 738.3 g (2,4-di-tert-butylphenoxy) chlorophenylphosphine and 316.4 g toluene.
• Example 23 the reaction was chosen analogously to Example 21, but AICI 3 of a higher purity (> 99%) was used.
• Stream I was fed in at 1767 ml / h, stream II at 1203 ml / h.
• the volume of the mixing chamber was 3.3 ml, the residence time correspondingly about 4 s.
• the system was brought into equilibrium for 3 minutes, after which the discharge was collected.
• the discharge consists of two liquid phases (N-methylimidazolium hydrochloride and solvent / product).
• the upper phase which contains the product, was decanted off and concentrated in vacuo.
• the residue was heated under reflux in ethanol and the clear, yellow solution was then cooled to room temperature, a solid precipitating out, which was filtered off with suction, then washed with ethanol and then dried in vacuo. 27.3 g (41% of theory) of a colorless solid were obtained.
• 31 P NMR (CDCI 3 , 298K): ⁇ 106.
• traces of N-methylimidazole influence the catalysis, they can be removed by washing a solution of the ligand in an organic solvent with water.
• Stream I was fed in at 589 ml / h, stream II at 401 ml / h.
• the volume of the mixing chamber was 3.3 ml, the dwell time accordingly approx. 12 s.
• the system was equilibrated for 3 minutes, then the discharge was collected.
• the discharge consists of two liquid phases (N-methylimidazolium hydrochloride and solvent / product).
• the upper phase which contains the product, was decanted off and concentrated in vacuo.
• the residue was heated under reflux in ethanol and the clear, yellow solution was then cooled to room temperature, a solid precipitating out, which was filtered off with suction, then washed with ethanol and then dried in vacuo. 30.5 g (46% of theory) of a colorless solid were obtained.
• 31 P NMR (CDCI 3 , 298K): ⁇ 106.
• Example 49 (comparison): Hydroformylation of 1-butene from conventional synthesis (Example 45)
• solution I mesitylene
• solution II consisting of 121.6 g (0.66 mol) dichlorophenylphosphine
• solution II was fed in at 1507.9 ml / h.
• the head of the reaction mixing pump was heated to 100 ° C. in an oil bath.
• the volume of the mixing chamber was 3.3 ml, so the residence time was approx. 2 s.
• the system was equilibrated for 3 minutes and then the discharge was collected.
• the discharge consists of two liquid phases (product / solvent and 1-methylimidazolium hydrochloride).
• the upper, product-containing phase was decanted off.
• GC 2-tert-butylphenoxyphenyl chlorophosphine: 60 area%.

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