IL93838A - Process for the preparation of phosphino compounds - Google Patents

Abstract

Phosphorus-containing compounds of the formula (I> (R<1>)(R<2>)P(O)-CR<3>R<4>-CHR<5>R<6> (I> in which R<1> and R<2> represent alkyl, alkoxy or optionally substituted phenyl, R<3> and R<5> represent H, R, optionally substituted phenyl, ROCO-, RO-CO-RO-, halogen, CN, RO-, RO-RO-R-CO-, H2NCO-, RNHCO- or RRNCO-, where R represents alkyl, R<4> and R<6> are defined as R<1> and R<2> or represent a bivalent radical -CO-R<7>-CO in which R<7> represents oxygen, NR* or sulphur and R* represents H, optionally substituted phenyl or alkyl, are precursors for crop protection agents and flameproofing agents. They can be prepared in high yields and high purity by reacting a compound of the formula (R<1>)(R<2>)P-OR<8>, in which R<8> represents alkyl or optionally substituted phenyl, with an alkene of the formula R<3>R<4>C=CR<5>R<6> and an at least equimolar amount of a protic organic substance such as alcohols, amines, phenols, thiophenols or anilines.

Description

Hoe 89/F 100 PROCESS FOR THE PREPARATION OF PHOSPHINO COMPOUNDS HOECHST A TIENGESELLSCHAFT HOE 89/F 100 Dr. E/PP .· ' ' ■/ Description Process for the preparation of phosphlno compounds , The invention relates to a process for the preparation of 5 phosphlno compounds of the formula (I) in which R1 and R2 independently of one another are alkyl, alkoxy where underlined or optionally substituted phenyl, 21.3.90 R3 and R5 independently of one another are hydrogen, alkyl, unsubstituted phenyl or phenyl mono- or multisubstituted by halogen or mono- or disubstituted by alkoxy; or are alkoxycarbonyl, alkoxycarbonylalkoxy, halogen, cyano, alkoxy, 15 alkoxyalkoxy, alkylcarbonyl, alkoxycarbonyl- alkyl, carbamoyl, alkylaminocarbonyl or dialkylaminocarbonyl, R* and R6 independently of one another are hydrogen, alkyl, unsubstituted phenyl or phenyl mono- or 20 multisubstituted by halogen or mono- or disub- stituted by alkoxy; or are halogen, alkoxycarbonyl, alkoxycarbonylalkoxy, cyano, alkoxy, alkoxyalkoxy, alkylcarbonyl, alkoxycarbonyl- alkyl, carbamoyl, alkylaminocarbonyl or di- 25 alkylaminocarbonyl; or jointly are a divalent radical of the formula - CO - R7 - CO -, in which R7 is oxygen, a radical of the formula NR*, in 30 which R* represents hydrogen, Ci-Ce-alk l, - 2 - 93838/2 unsubstituted phenyl or phenyl mono- or multi- substituted by halogen; or is sulfur, which comprises reacting a compound. of the formula (II) in which R1 and R2 have the meanings defined above and R8 is alkyl or optionally substituted phenyl, together with a compound of the formula (III) in which R3, R*f R5f R8 and R7 have the meanings defined above, and with at least an equimolar amount of a protic organic substance selected from: alcohols, mercaptans, amines, phenols, thiophenols or anilines or mixtures of these substances.

The term 'alkyl' denotes, for example, a straight-chain, branched or cyclic alkyl such as methyl, ethyl, n- and i-propyl, n-, i-, t- and 2-butyl, pentyl isomers, hexyl isomers, cyclopentyl, cyclohexyl, heptyl and octyl-isomers . The terra 'alkoxy' denotes an alkyloxy radical comprising l "_jE¾ 'alky 1 j)a^^th¥^e¥nlngs" cited abpve_ as examples " of alkylT Tne term Optionally substituted phenyl' denotes an unsubstituted phenyl or a phenyl substituted, for example, by halogen, lower alkoxy or lower alkyl. The term 'halogen' denotes fluorine, chlorine, bromine and/or iodine, preferably chlorine.

Of particular interest is a process according to the invention, in which R1 and R2 independently of one another are Cj-Ce-alkyl, phenyl or Cj-Ce-alkoxy, preferably methyl, ethyl, phenyl, methoxy, ethoxy, propoxy or butoxy, in particular methyl, ethyl, phenyl, methoxy or ethoxy, R3 and R5 independently of one another are hydrogen, C1-C8-alkyl, unsubstituted phenyl or phenyl mono- or multisubstituted by halogen; or are C2-C6-alkoxycarbonyl , C2-Ce-alkylcarbonyl , (Ci-C^-alkyl)carbonyl-Cj-Cuj-alkyl, halogen, cyano, Cj-Ce-alkoxy, (Cj-C^-alkoxyJ-C^C^-alkoxy, carbamoyl, N- ( C1-C^-alkyl)aminocarbonyl, N,N- 1-(C1-C4-alkoxy)- 1-hydroxymethyl or 1,1-bis(Cx-C^-alkoxy)methyl, R4 and R6 independently of one another are hydrogen, Ci-Cg-alkyl, unsubstituted phenyl or phenyl mono- or multisubstituted by halogen; or are C2-C6-alkoxycarbonyl , C2-C6-alkylcarbonyl, ( C1-C^-alkyl)carbonyl-Ci-Cio-alkyl, halogen, cyano, Cj-Ce-alkoxy, carbamoyl, N-(C!-C4-alkyl)aminocarbonyl, N,N- di(Ci-C-alkyl)aminocarbonyl, 1-(C^-C^-alkoxy)- 1-hydroxymethyl or l,l-bis(C1-C4-alkoxy)methyl; or jointly are a divalent radical of the formula - CO - R7 - CO -, in which R7 is oxygen, a radical of the formula NR*, in which R* represents hydrogen, (Cj-CeJ-alkyl, unsubstituted phenyl or phenyl mono- to trisub- stituted by halogen; or is sulfur.

The process according to the invention, in which R1 and R2 independently of one another are methyl, ethyl/ methoxy, ethoxy or phenyl, R3 is hydrogen, R* is hydrogen or (Cj-C^-alkoxyJcarbonyl, R5 is hydrogen, R6 is hydrogen, halogen, cyano, (C^C^-alkoxy)car- bony1 or carbamoyl, preferably (Ci-Ca-alkoxy)- carbonyl or cyano is particularly preferred.

The compounds of the formula (I) are useful intermediates in the preparation of plant protection agents (see for example EP-A-30,424, US-A-4 , 399 , 287 and IL 61633 and fire retardants (Angewandte Makromolekulare Chemie 105 , pp.203-215 (1982) and literature cited therein). It is known that a few representatives of the compounds of the formula (I) are obtainable, for example, by reacting the compounds of the formula (II) with unsaturated fatty acids (see Houben-Weyl, Methoden der org. Chemie, volume 12/1, pp. 259-260 (1963) and literature cited therein). However, this process gives yields of only 10 - 50 % which, because of the high amounts of effluent gases and waste products formed, represents a serious drawback both technically and ecologically. The unreacted phosphorus component (I) must undergo a costly process of disposal, since these compounds represent a fire and toxic hazard and have an objectionable smell (see Houben-Weyl, Method-en der org. Chemie, Vol. 12/1, p. 14). In addition, because of the poor yields, costly purification operations are needed at the end of the reaction.

In comparison with the known processes, the present invention relates to a highly selective, inexpensive and simple process which furnishes the phosphino compounds of the formula (I) in almost quantitative yields and in high purity.

The crude products obtained in an almost quantitative yield are usually so pure that they can be directly used for further chemical reactions.

For a number of reasons the process according to the invention is to be regarded as surprising. Thus, for example, the reactions of the phosphorus components (II) with the alkenes (III) do not give rise, according to examples in the literature, to the products (I) without resorting to a protic organic substance. Only highly viscous polymeric products are obtained (see Anionische Polymerisation, B. Vollmert, Grundriss der Makromoleku-laren Chemie, Springer-Verlag 1962, p. 107 ff and 159, see Comparison Example I) . The low yields of up to a maximum of 50 % in the examples described in the literature are likewise due to competing polymerization reactions as secondary reactions. The desired reactions are in some cases so slow that the polymerization becomes the main reaction. (Houben-Weyl, Methoden der org. Chemie, vol. 12/1, pp. 259 - 260). Surprisingly, the addition according to the invention of protic organic substances succeeds in substantially suppressing the polymerization and in forming the ltl adducts of the formula (I) in almost quantitative yields.

The process according to the invention is furthermore to be regarded as surprising inasmuch as it is precisely by the addition of protic organic substances to the reactions described in the literature in which phosphorus compounds of the formula (II) are reacted with unsaturat-ed fatty acids that yields of less than 30 % and hence even worse yields of the desired 1:1 adducts are obtained (see Comparison Example II).

The preferred protic organic substances are alcohols, in particular C^Ce-alcohols, for example, methanol, ethanol, propanol, isopropanol, n-, i-, t- and 2-butanol, further polyhydric alcohols such as ethanediol and glycerol, C1-Ce-mercaptans, for example methylmercaptan, ethylmer-captan, propylmercaptan and 1,2-ethanedithiol, amines, in particular mono- or di(C!-C6-alkyl)amines, for example methylamine, ethylamine, dimethylamine and propylamine, phenols, thiophenols, anilines and similar compounds. Because the above substances can be generally regarded as "derivatives" of water on account of their protic properties, the process according to the invention cannot be carried out in the presence of water, in contrast to the organic protic compounds described, since water rapidly hydrolyzes the phosphorus components of the formula (II) (Sander, Chem. Ber. £1 (I960) 1223). Since it is quite impossible to obtain products of the formula (I) with water as the protic substance because of hydrolytic reactions taking place (see also Comparison Example III), it was unexpected for the protic organic substances to be used according to the invention to be suitable for achieving high selectivity and yields.

The protic organic substances R-H employed in the process according to the invention in at least eguimolar amounts serve as reactants and, if appropriate, as solvents, and are converted, depending on the course. of .the reaction-, at least in part, for example, to ethers, thioethers, amines, phenetoles, thiophenetoles or substituted anilines of the formula R-R8, R8 having the meaning defined above. The products R-R8 are preferably removed from the reaction mixture during or at the end of the reaction, for example by distillation. Excess reactant or solvent R-H is preferably removed at the end of the reaction by vacuum distillation.

Car oxylie acids are likewise excluded from the process according to the invention. When in the process according to the invention organic acids, for example formic acid or acetic acid, are used as protic substances, virtually no products of the formula (I) are obtained (see Comparison Example IV) . It follows that the protic organic substance must not possess too acidic characteristics. Whether a substance is suitable in the sense of the invention can be readily established in a preliminary experiment.

The procedure of the process according to the invention is for example such that the compounds of the formula (II) are dissolved in the protic organic substance and the alkenes (III) are added to the reaction mixture at temperatures between -20°C and 150"C, preferably between 0 and 100"C. It is also possible to add the components (II) and (III) to the protic organic substance at the same time.

It is equally possible to start with a mixture of the alkene component (III) and the protic organic substance and add the phosphorus component (II) to this solution.

The protic organic substances are used in at least eguimolar amounts. In amounts greater than eguimolar they can be additionally employed in the sense of an organic solvent .

The process may be carried out without solvent or with excess protic organic substance as solvent and/or in the presence of customary organic solvents which are inert under the reaction conditions. Examples of the last-named solvents are solvents such as optionally halogenated, aliphatic, cycloaliphatic, aromatic or araliphatic hydrocarbons, aliphatic or cycloaliphatic ethers, for example polyglycol dialkyl ethers, as well as ketones and esters. It is expedient to perform the process in an inert gas atmosphere, for example under nitrogen, in order to prevent oxygen interfering with the reaction.

The process according to the invention may be continuous or discontinuous.

The process according to the invention is elucidated in greater detail by the - examples below.

EXAMPLE 1: Methyl 3- (methoxy-methylphosphln^lJjJroP-lonate . 80 g of methanol are mixed at room temperature under nitrogen with 216 g of dimethyl methanephosphonate and the mixture is treated dropwise at room temperature with 172 g of methyl aerylate, the temperature rising to 70°C. At the end of the dropwise addition the mixture is further stirred for 1 hour, at the end of which period about 90 g of dimethyl ether have separated in a fitted cooling trap. Excess methanol used as solvent is then removed by vacuum distillation. The crude product is obtained in a yield of 365 g with a 96.4 % purity, which represents a theoretical yield of 97.7 %. The boiling point of a distilled sample is 96 °C at 0.027 mbar. The XH-NMR spectrum and the CHP analysis of the product correspond to those of a comparison sample, synthesized by an independent route.

EXAMPLE 2: Ethy1 3- (methoxy-methylphosphinyl) propionate" __' _ A flask filled with nitrogen and fitted with a cooling trap is charged with 216 g of dimethyl methanephosphonate; the contents are heated to 60°C and a mixture of 200 g of ethyl aerylate and 100 g of methanol is added dropwise in the course of 1 hour, the temperature rising to 65 °C. The reaction mixture is further stirred for 1 hour, during which period a total of 91 g of dimethyl ether are collected in the cooling trap. Excess methanol is removed by vacuum distillation. The crude product is obtained in a yield of 362 g with a 97.3 % purity, which corresponds to a theoretical yield of 97.9 %. The boiling point of a sample is 100 - 102°C at 0.013 mbar.

EXAMPLE 3: Methyl' ~3~- rmet^xy"-me€h^y Ros^inyl propj-oiate _" A mixture of 86 g of methyl acrylate and 80 g of ethanol is added dropwise in the course of 30 minutes at 60°C under nitrogen to a solution of 108 g of dimethyl meth-anephosphonate . The reaction mixture is then stirred at 60eC for one hour. A total of 55 g of methyl ethyl ether are collected in the cooling trap. Excess ethanol is then removed by vacuum distillation. The crude product is obtained in a yield of 184 g with a 95.4 % purity, which corresponds to a theoretical yield of 97.5 %.

EXAMPLE 4: 3- (Methoxy-ethylphospinyl) piogJ^namide 71 g of acrylamide and 120 g of n-propylamine are mixed at room temperature under nitrogen and the mixture is heated to 50°C. 122 g of dimethyl ethanephosphonate are added dropwise to the reaction solution in the course of 30 minutes. The reaction mixture is then stirred for 5 hours at reflux temperature and the solvent (low-boiling solvent such as excess propylamine + -methyl-N-propylamine) is removed by vacuum distillation. The crude product is obtained in a yield of 175 g with a 94.4 % purity, which corresponds to a theoretical yield of 92.3 %.

The ^- MR spectrum and the CHP analysis of the product are in agreement with the corresponding data of a comparison sample, synthesized by an independent route.

EXAMPLE 5: 3- (Ethoxy-propylphospKinyl) prop cnltrile 53 g of acrylonitrile are added dropwise under nitrogen at a reaction temperature of 70*C to a mixture of 160 g of diethyl propanephosphonate In 100 g of n-propylmer-captan in the course of 2 hours. After a further 3 hours the solvent (low-boiling solvent such as C3H7SC2H3 and excess C3H7SH) is removed by vacuum distillation; the crude product is obtained in a yield of 173 g with a 95.4 % purity, which corresponds to a theoretical yield of 94.4 %. The boiling point of the product is 117 -118eC at 0.027 mbar.

EXAMPLE 6: "Et y1 3-T^hoxycarbony!)__- 3- (ethoxy-ethylphosphinyl) propionate 172 g of diethyl fumarate are slowly added at 65 - 70°C under nitrogen to a mixture of 140 g of diethyl ethane-phosphonate in 46 g of ethanol. After a further 3 hours the solvent (excess ethanol and diethyl ether) is removed by vacuum distillation; the crude product is obtained in a yield of 285 g with a 95.7 % purity, which corresponds to a theoretical yield of 90.9 %.

The XH-NMR spectrum and the CHP analysis are in agreement with the corresponding data of a comparison sample, synthesized by an independent route.

EXAMPLE 7: Methyl 3- (dimethoxyphosphinyl )propionate 86 g of methylacrylate and 100 g of isobutanol are mixed under nitrogen at room temperature and heated to 80 "C. 124 g of trimethylphosphite are added dropwise to the reaction solution in the course of 1 hour. The reaction mixture is stirred for 5 hours at reflux temperature and the solvent (remainder of isobutanol and isobutyl methyl ether) is removed by vacuum distillation. The crude product is obtained in a yield of 173 g with a 94.1 % purity, which corresponds to a theoretical yield of 83.0 %. The boiling point is 104 - 106°C at 0.93 mbar.

EXAMPLE 8: 3-(Dimethylphosphinyl)propionitrile 135 g of isobutyl dimethylphosphinate are slowly added under nitrogen at 20"C to a mixture of 53 g of acrylo-nitrile and 32 g of methanol, the temperature rising slowly to about 60*C. The reaction mixture is heated for about 3 hours and the solvent (remainder of methanol and isobutyl methyl ether) is removed by distillation. The crude product is obtained in a yield of 125 g with a 95.3 % purity, which corresponds to a theoretical yield of 90.9 %. The boiling point of a distilled sample is 98 -100eC at 0.013 mbar.

EXAMPLE 9: Methyl 3- (dimethylphosphinyl ) -3-methoxycarbonyl ) -propionate 135 g of isobutyl dimethylphosphinate and 144 g of dimethyl maleate are added under nitrogen simultaneously dropwise from two separate dropping funnels at about 70°C to a solution of 67 g of ethylene glycol. After a further hour the reaction mixture is distilled under reduced pressure, i.e. volatile constituents are carefully removed by vacuum distillation. The crude product is obtained in a yield of 215 g with a 95.2 % purity, which corresponds to a theoretical yield of 91.8 %.

The H-NMR spectrum and the CHP analysis correspond to a comparison sample synthesized by an independent route. The boiling point of the product is 128 - 130 eC at 0.013 mbar.

EXAMPLE 10: 138 g of dimethyl phenylphosphonate are slowly added at 20"C under nitrogen to a solution of 120.5 g of methyl 2- chloroacrylate and 94 g of phenol. After a reaction time of 3 hours at 70°C phenetole is removed by vacuum distillation. The residue represents 267 g of crude product with a 93.0 % purity, which corresponds to a theoretical yield of 90.1 %.

The ^- MR spectrum and the CHP analysis of the product correspond to those of a comparison sample, synthesized by an independent route.

COMPARISON EXAMPLE I: (without protic organic substance) 86 g of methyl acrylate are added to 108 g of dimethyl methanephosphonate at 70 "C and the reaction mixture is heated at 70"C for a further 4 hours. The reaction mixture is worked up by vacuum distillation, yielding 194 g of a highly viscous oil which according to the ¾-NMR and 31P-NMR spectra does not contain the desired methyl 3- (dimethylphosphinyl)propionate. If the reaction mixture is worked up by distillation, no distillable product is obtained, which points to polymerization occurring in the experiment.

COMPARISON EXAMPLE II: in accordance with examples from the literature (Houben-Weyl, Methoden der org. Chemie, volume 12/1, pp. 259-260 and literature cited therein) 108 g of dimethyl methanephosphonate are added dropwise at 70 °C to a solution of 86 g of methacrylic acid and 32 g of methanol in the course of 30 minutes. After a reaction time of 3 hours the reaction mixture is worked up by vacuum distillation. 59 g of 3-(dimethylphosphinyl)-2-methylpropionic acid are obtained with a 91.1 % purity, which corresponds to a theoretical yield of 29.5 %.

COMPARISON EXAMPLE III: (in the presence of water as protic substance) 108 g of dimethyl methanephosphonate are added dropwise at an initial temperature of 25"C to a solution of 86 g of methylacrylate and 20 g of water in the course of 30 minutes. The temperature rises to 65"C during the addi-tion. The reaction mixture is then heated for 3 hours at 70"C.

After working up of the reaction mixture by vacuum distillation, no methyl 3- (dimethylphosphinyl)propionate is obtained. On the other hand the hydrolysis product methyl methanephosphonate, which could be isolated in an amount of 91 g by distillation, is obtained in a yield of 91.4 % with a 94.4 % purity. The boiling point of the distilled sample is 55 - 58"C at 10 - 15 torr. The ¾-NMR spectrum and the CHP analysis correspond to the compound obtained from a comparison sample, synthesized by an independent route.

COMPARISON EXAMPLE IV: (in the presence of formic acid as protic polar substance) 108 g of dimethyl methanephosphonate are added dropwise at 70°C to a solution of 86 g of methylacrylate and 50 g of formic acid in the course of 2 hours and the reaction mixture is heated at 70*C for 2 hours. After working up the reaction mixture by vacuum distillation, 123 g of a crude product are obtained which from its H-NMR and 31P-NMR spectra and gas chromatographic analysis contains none of the desired product. The reaction mixture is composed of several substances, the bulk of them being acid compounds of phosphorus in the oxidation stage V.

Claims (8)

HOE 89/F 100 Patent claims

1. A process for the preparation of compounds of the formula ( I ) in which R1 and R2 independently of one another are alkyl, alkoxy, h Z_!1 "^substituted or~ substitutes 'phenyl , ~ ~"~ ~ " ~ _ underlined-r3 anc* r5 independently of one another are hydrogen, 21.3.90 alkyl, unsubstituted phenyl or phenyl mono- or multisubstituted by halogen or mono- or disub- stituted by alkoxy; or are alkoxycarbonyl, alkoxycarbonylalkoxy, halogen, cyano, alkoxy, alkoxyalkoxy, alkylcarbonyl, alkoxycarbonyl- alkyl, carbamoyl, alkylaminocarbonyl or dialkylaminocarbonyl, R* and R6 independently of one another are hydrogen, alkyl, unsubstituted phenyl or phenyl mono- or multisubstituted by halogen or mono- or disub- stituted by alkoxy; or are halogen, alkoxycarbonyl, alkoxycarbonylalkoxy, cyano, alkoxy, alkoxyalkoxy, alkylcarbonyl, alkoxycarbonyl- alkyl, carbamoyl, alkylaminocarbonyl or dialkylaminocarbonyl; or jointly are a divalent radical of the formula - CO - R7 - CO in which R7 is oxygen, a radical of the formula NR*, in which R* represents hydrogen, Cj-Ce-alkyl, unsubstituted phenyl or phenyl mono- or multi- substituted by halogen; or is sulfur, 93838/2 which ~cornorisesj~~reacting__a_c nipou ¾"_or~"¾he~ "formula (II ) in which have the meanings defined above and is alkyl or optionally substituted phenyl, with a compound of the formula (III) in which R3, R*r R3, R8 and R7 have the meanings defined above, and with at least an equimolar amount of a protic organic substance selected from: alcohols, mercaptans, amines, phenols, thiophenols or anilines or mixtures of these substances.

2. The process as claimed in claim 1, wherein R1 and Rz independently of one another are Cx-C8-alkyl, phenyl or Cx-Ce-alko y, R3 and R5 independently of one another are hydrogen, Cj-Ce-alkyl , unsubstituted phenyl or phenyl mono- or multisubstituted by halogen; or are C2-C6-alkoxycarbonyl , C2-C6-alkylcarbonyl , (C1-C^-alkyl ) carbonyl-Ci-Cm-alkyl , halogen, cyano, Ci-Ce-alkoxy, carbamoyl, N-(C1-C4-alkyl)aminocarbonyl, N,N- di (C1-C4-alkyl ) aminocarbonyl , 1- (Cx-C^-alkoxy) - 1-hydroxymethyl or 1, l-bisfCi-CV-alkoxyJmethyl, R* and R6 independently of one another are hydrogen, C1-Ce-alkyl, unsubstituted phenyl or phenyl - 16 - 93838/2 mono- or multisubstituted by halogen; or are C2-C6-alkoxycarbonyl, C2-C6-alkylcarbonyl , (Cx-C4-alkyl)carbonyl-Ci-Cio-alkyl, haloge , cyano Cx-Ce-alkoxy, (Cx-C4-alkoxy)-Cx-C4-alkoxy, carbamoyl, N-(C1-C4-alkyl)amlnocarbonyl N,N- di(Cx-C4-alkyl)aminocarbonyl, 1-(Cx-C4-alkoxy)- 1-hydroxymethyl or or jointly are a divalent radical of the formula - CO - R7 - CO -, in which R7 is oxygen, a radical of the formula NR*, in which R* represents hydrogen, (C1-C6)-alkyl, unsubstituted phenyl or phenyl mono- to trisub- stituted by halogen; or is sulfur.

3. . The process as claimed in claim 1 or 2, wherein R1 and R2 independently of one another are methyl, ethyl, methoxy, ethoxy or phenyl, R3 is hydrogen, R* is hydrogen or (Cx-C4-alkoxy)carbonyl, R5 is hydrogen and R6 is hydrogen, halogen, cyano, (Cx-C*-alkoxy)- carbonyl or carbamoyl.

4. The process as claimed in one or more of Claims 1 to 3, wherein the temperature for the reaction of the compounds (II) and (III) is between -20°C and 150°C.

5. The process as claimed in Claim 4, wherein the temperature for the reaction of the components (II) and (III) is between 0°C and 100°C. ~ A/ ~ 93838/2

6. The process as claimed in one or more of claims 1 to 5, wherein the process is carried out in the customary organic solvents or mixtures thereof.

7. The process as claimed in claim 6 , wherein excess protic organic substance is used as organic solvent.

8. The process as claimed in one or more of claims 1 to 7, wherein the reaction is performed in an inert gas atmosphere . Tel-Aviv