DE2929636A1 - Alkene prodn. from alpha-hydroxy phosphonate - and phosphonate or phosphonium salts, useful as intermediates for pyrethroid insecticides - Google Patents

Abstract

(A) The following process is new: base right arrow opt. catalyst opt. diluent -70 to +150 degrees C (R1 is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aralkyl, aralkenyl, aryl or heterocyclyl, all opt. substd; R2 is H or halogen; R3 is halogen, CN or an opt. substd. alkyl, alkenyl, alkynyl, cycloalkyl, aralkenyl, aryl, alkanoyl, aroyl, alkoxycarbonyl, carbamoyl or heterocyclyl gp.; R4 is alkyl or phenyl, or the two R4 gps. together are alkylene; Z1 is P(O)R5R6 or P(R7)3 + X-; R5 and R6 are each alkyl, phenyl, alkoxy or phenoxy, or together are alkylenedioxy; R7 is alkyl or phenyl; X is halogen). (I), esp. 3-(2-chloro-2-phenyl-vinyl)-2,2-dimethyl-cyclopr opane 1-carboxylic acid esters, and (XI) are intermediates for pyrethroid insecticides and acaricides. (I) can be prepd. in high yield and purity, in a reaction at (or near) room temp., in presence of cheap bases (e.g. alkali metal hydroxides or alcoholates) and water-contg. solvents (c.f. usual Wittig conditions), without using difficult-to-obtain aldehyde intermediates.

Description

Process for the production of alkenes, new alkenes,

Their use and intermediates for their preparation The invention relates to a new process for the preparation of known and new alkenes, new Styrylcyclopropane derivatives which are produced by this and other processes can, intermediate products for their manufacture and their use.

It is known that alkenes such as the intermediate for insecticidally active pyrethroids, 3- (2-methyl-2-methoxy-carbonyl-vinyl) -2,2-dimethyl-cyclopropane-1-carboxylic acid tert-butyl ester, obtained when aldehydes or ketones, such as 3-formyl-2, 2-dimethyl-cyclopropane-1 -carboxylic acid tert-butyl ester, with phosphorus ylides (phosphorus ylenes), such as (1 -Methoxy-carbonyl-ethylidene) -phosphonic acid diethyl ester, converts (compare Organic Reactions, Vol. 25 (1977), pp. 73-253, in particular special p. 85 and P. 121 - and literature cited there).

Next is - as a special case of the synthesis method given above - Known that certain 3- (2-chloro-2-phenyl-vinyl) -2, 2-dimethyl-cyclopropane-1 -carboxylic acid esters, such as 3- (2-chloro-2-phenylvinyl) -2, 2-dimethyl-cyclopropane-1 Ethyl carboxylic acid ester is obtained if the corresponding benzyl phosphonic acid ester is used treated with a strong base, such as butyllithium, and the intermediates formed Ylides with carbon tetrachloride and then with 3-formyl-2, 2-dimethyl-cyclopropane-1 -carboxylic acid ester converts (compare DE-OS 2 738 150).

Has the carbonyl olefination reaction generally illustrated above Although it has a very wide range of applications, it is then for example for industrial Matters no longer interesting if the aldehydes to be used as starting materials (or ketones) can only be produced with a great deal of effort. So you get according to the prior art, the 3-formyl-2 which can be used as pyrethroid intermediates, 2-dimethylcyclopropane-1-carboxylic acid ester by ozonolysis of 3-alkenyl-2,2-dimethyl-cyclopropane-1-carboxylic acid esters, E.g. chrysanthemum acid ethyl ester, which in turn consists of naturally occurring Pyrethroids are to be produced (see US Pat. No. 3,679,667). One technically simple feasible manufacturing method for 3-formyl- 2,2-dimethylcyclopropane-1 -carboxylic acid ester is not known.

The technical implementation of the above-mentioned, known method for the synthesis of 3- (2-chloro-2-phenyl-vinyl) -2, 2-dimethyl-cyclopropane-1 -carboxylic acid esters require: those for ylid formation from benzylphosphonic acid esters The strong bases required, such as butyllithium, are sensitive to moisture and air; therefore, the reaction is carried out in an inert gas atmosphere, for example under nitrogen or argon and using an inert, carefully dried diluent carried out. Since the reaction takes place at a low temperature, around -70 ° C has, the reaction mixture must also be intensively cooled. The work-up for Isolation of the desired products, which are obtained as isomer mixtures also expensive; it involves several extractions and solvent distillations and a chromatographic separation process. For these reasons, the well-known Synthesis method for a preparation of 3- (2-chloro-2-phenylvinyl) -2, 2-dimethyl-cyclopropane-1 carbonic acid esters are not very suitable on an industrial scale.

The present invention relates to (1) a process for the preparation of alkenes of the formula (I) in which R1 represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aralkyl, aralkenyl or aryl radical or an optionally substituted heterocyclic radical, R2 represents hydrogen or halogen and R3 represents Halogen, cyano, for an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aralkenyl, aryl, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl. or aminocarbonyl radical or an optionally substituted heterocyclic radical, characterized in that one ~ ffi-hydroxy-phosphonic acid ester of the formula II in which R¹ has the meaning given above and R4 stands for alkyl or phenyl or the two radicals R4 together stand for straight-chain or branched alkanediyl (alkylene), with phosphorus-containing olefinating agents of the formula III in which R2 and R3 have the meanings given above and Z¹ is a phosphorus-containing radical where R5 and R6 are identical or different and individually represent alkyl, phenyl, alkoxy or phenoxy or together represent alkanedioxy, R7 represents alkyl or phenyl and x represents halogen, in the presence of bases, optionally in the presence of catalysts and if necessary using diluents at temperatures between -70 and + 150 ° C.

(2) new α-hydroxy-phosphonic acid esters of the formula II a in which R4 represents alkyl or phenyl or the two radicals R4 together represent straight-chain or branched alkanediyl (alkylene) and represent cyano, carbamoyl, acetyl or C1-C4-alkoxycarbonyl; (3) a process for the preparation of α-hydroxyphosphonic acid ester of the formula II a (above), characterized in that α-oxo-phosphonic acid ester of the formula IV in which R4 and z2 have the meanings given under (2), with hydride complexes of the formula VM (M'H4) in which M stands for lithium, sodium or potassium and M 'stands for boron or aluminum, optionally in the presence of a buffering agent and optionally Reacts using a diluent at temperatures between -20 and + 50 ° C; (4) new i-oxophosphonic acid esters of the formula IV in which R4 stands for alkyl or phenyl or the two radicals R4 together stand for straight-chain or branched alkanediyl (alkylene) and z2 stands for cyano, carbamoyl, acetyl or C1-C4-alsoxycarbonyl; (5) a process for the production of $ -oxo-pnosphonic acid esters of the formula IV (above), characterized in that carboxylic acid chlorides of the formula VI in which Z² has the meaning given under (4), with phosphorous acid esters of the formula VII R8O-P (OR4) 2 (VII) in which R4 has the meaning given under (4) and R8 stands for methyl or ethyl, at temperatures between - Converts 20 and + 15o0C; (6) new carboxylic acid chlorides of the formula VI in which z2 represents cyano, carbamoyl, acetyl or C1-C4-alkoxycarbonyl; (7) a process for the preparation of carboxylic acid chlorides of the formula VI (above), characterized in that carboxylic acids of the formula VII in which z2 has the meaning given under (6), with a chlorinating agent at temperatures between 20 and 80 ° C.

The present invention also relates to (8) new styryl-cyclopropane derivatives of the formula XI R represents halogen or optionally halogen-substituted radicals alkyl, alkoxy, alkylthio or alkylenedioxy and cyano or nitro, n represents zero to 5, R10 represents hydrogen, halogen or optionally halogen-substituted alkyl, and represents acetyl, cyano or carbamoyl , (9) a process for the preparation of styryl-cyclopropane derivatives of the formula XI (above), characterized in that benzylphosphonic acid esters of the formula XII in which R9, n and R10 have the meanings given above, and the radicals R4 individually represent alkyl or phenyl or together represent alkanediyl (alkylene), with formyl-cyclopropane derivatives of the formula XIII in which Y has the meaning given above, reacts in the presence of bases and, if appropriate, using diluents at temperatures between -70 and + 1500C; (10) new formyl-cyclopropane derivatives of the formula XIII in which Y is acetyl or carbamoyl; (11) a process for the preparation of the formyl-cyclopropane derivative of the formula XIII (above), in which Y stands for acetyl, characterized in that 2-acetyl-3,3-dimethylcyclopropane-1-carboxylic acid chloride of the formula XIV with lithium tri-tert. -butoxy-hydrido-aluminate, optionally using a diluent, is reacted at temperatures between -100 and + 1000C; (12) a process for the preparation of formyl-cyclopropane derivatives of the formula XIII (above), in which Y stands for acetyl, cyano or carbamoyl, characterized in that mano (-hydroxy-cyclopropylmethyl-phosphonic acid ester of the formula XV in which R4 stands for alkyl or phenyl or both radicals R4 together stand for alkanediyl (alkylene), and Y stands for acetyl, cyano or carbamoyl, with aqueous alkali solutions, optionally in the presence of a water-immiscible organic solvent such as methylene chloride at temperatures between 0 and 1000C implements.

Surprisingly, according to the new method 1 (above), which is easy and inexpensive to carry out and for which without great effort starting compounds to be prepared are to be used, alkenes of the formula (I) in good quality Yields and can be obtained in high purity.

The advantages of the new process also lie, for example, in the Possibility of the implementation at room temperature or at least at not far from it Carry out different temperatures, cheap bases such as alkali hydroxides or to use alcoholates and to use water-based solvents.

A particular advantage of the method according to the invention is that that the production of aldehydes, which are generally used as reaction components in the production of alkenes by reacting carbonyl compounds with phosphorus-containing compounds Olefinizing agents are used n can be avoided.

If, for example, d- (3-methoxycarbonyl-2,2-dimethyl-cycloprop-1-yl) <C-hydroxymethane-phosphonic acid dimethyl ester and <-chlorobenzylphosphonic acid diethyl ester are used as starting materials, the reaction according to the invention of these compounds can be carried out by the following equation to be sketched: The t-hydroxyphosphonic acid esters to be used as starting materials are defined by formula (II).

R4 therein are preferably C1-C4-alkyl or phenyl, or both radicals R- together represent 2,2-dimethyl-propane-1,3-diyl and R1 optionally represents halogen-substituted C1-C4-alkyl, for optionally by halogen, cyano, carbamoyl, C1-C4-alkyl, C1-C4-alkyl-carbonyi, C1-C4-alkoxycarbonyl and / or phenoxybenzyloxycarbonyl (which is optionally substituted by fluorine, cyano and / or ethynyl) substituted C3-C6-cycloalkyl, for benzyl or phenylethyl optionally substituted by chlorine, or for optionally substituted by halogen, C2-C4-alkyl and / or C1-C4-alkoxy Phenyl.

In a particularly preferred group of (new) starting compounds of the formula (II), R¹ in this formula represents the remainder where z2 is cyano, carbamoyl, acetyl or C1-C4-alkoxycarbonyl and R4 is methyl or ethyl. Examples are: α-hydroxy-3-methyl-benzyl-, α-hydroxy-4-methyl-benzyl-, α-hydroxy -3,4-dimethyl-benzyl-, -hydroxy-4-fluoro-benzyl-, -hydroxy-3-chlorobenzyl-, -hydroxy-4-chlorobenzyl-, α-hydroxy-3,4-dichloro benzyl-, i-hydroxy-3-bromo-benzyl-, α-hydroxy-4-bromo-benzyl-, -hydroxy-4-methoxy-benzyl- and α-hydroxy-3,4-dimethoxy-benzyl - phosphonic acid dimethyl ester and di ethyl ester; α-Hydroxy-α- (3-methoxycarbonyl-2,2-dimethyl-cycloprop-1-yl) -methanephosphonic acid dimethyl ester and diethyl ester, α-hydroxy-α- (3-ethoxycarbonyl-2,2-dimethyl-cycloprop- l-yl) methanephosphonic acid dimethyl ester and diethyl ester, α-hydroxy-α- (3-acetyl-2,2-dimethyl-cycloprop-l-yl) methanephosphonic acid dimethyl ester and diethyl ester and α-hydroxy- α- (3-cyano-2,2-dimethyl-cycloprop-1-yl) -methanephosphonic acid dimethyl ester and diethyl ester.

Some of the starting compounds of the formula (II) are not yet described in the literature, but can be prepared by processes that are known in principle will.

This is how the new α-hydroxy-methane-phosphonic acid esters are obtained of the formula (II a) by adding the corresponding oxo compounds of the formula IV (above) with a reducing agent of formula V (above) such as sodium tetrahydridoborate (Sodium boronate), optionally using a diluent such as e.g. water or aqueous methanol, at temperatures between -20 and + 50C, preferably between -lo and + 3o0C, converted and by adding a buffering agent such as e.g.

Sodium hydrogen phosphate keeps the pH value between 5 and 8 (compare Chem. Ber. 103: 2984-2986 (1970)).

To work up and isolate the products, extraction is carried out with a ... a water-immiscible solvent such as methylene chloride, dries the organic phase, filtered and the solvent is distilled under reduced pressure Pressure off.

The substituted-oxo-methanephosphonic acid esters of the formula (IV) are not described in the literature.

These compounds are obtained by reacting carboxylic acid chlorides of the formula VI (above) with phosphorous acid esters of the formula VII (above) at temperatures between -20 and + 15? 0C, preferably between 0 and 1200C (compare J. Am. Chem. Soc. 86 (1964), 3862-3866 and methods of organic chemistry (Houben-Weyl-MUller), 4th ed. Volume 12/1, p. 453, Georg-Thieme Verlag, Stuttgart 1963).

To isolate and purify the products, if necessary, under reduced pressure, distilled An alternative way of making part of the Compounds of the formula (II) - see formula (VIII) - is described below.

The not yet known cyclopropanecarboxylic acid chlorides of the formula (VI) is obtained from known cyclopropane carboxylic acid esters according to the reaction scheme below (See J. Am. Chem. Soc. 89 (1967), 3912-3914; J. Org. Chem. 32 (1967), 3351-3355; Tetra.

hedron Lett. 1978, 1847-1850; Bull. Soc.Chim.Belg. 87 (1978), 721-732) by methods known per se, by first preparing the corresponding cyclopropanecarboxylic acids by hydrolysis, for example by reaction with aqueous-alcoholic potassium hydroxide solution at temperatures between 20 and 100 ° C and subsequent acidification, and these with halogenating agents such as thionyl chloride , at temperatures between 20 and 80 ° C. Z2 CO -OAlkyl - Z2 CO- OH z2 COC1 C CH H20 X SOC12 1 3CH3H3CH3 (VII) (VI) The phosphorus-containing olefinating agents to be used further as starting materials are defined by formula (III). Preferably R2 is hydrogen, chlorine or bromine, R3 is phenyl, which is optionally substituted by halogen, C1 -C4 -alkyl, C1 -C2-haloalkyl, C1 -C4-alkoxy, C1-C2-haloalkoxy, C1-C2- (halo ) Alkylenedioxy, C1 -C4-alkylthio and / or C1 C2-haloalkylthio is substituted, and z1 preferably represents the remainder where R5 and R6 are identical or different and individually represent C1-C4-alkoxy, phenoxy or together represent 2,2-dimethyl-propane-1,3-dioxy.

Examples include: dimethyl benzylphosphonate and -di ethyl ester, α-chlorobenzylphosphonic acid dimethyl ester and diethyl ester, α-Bromo-benzylphosphonic acid dimethyl ester and diethyl ester, 4-fluorine, 3-chlorine, 4-chloro, 3,4-dichloro, 3-bromo, 4-bromo, 3-methyl-, 4-methyl-, 3,4-dimethyl-, 4-methoxy- and 3,4-dimethoxy-benzyiphosphonic acid dimethyl ester and diethyl ester; 4-fluorine, 4-chloro, 3-chloro, 3,4-dichloro, 3-bromine, 4-bromine, 3-methyl, 4-methyl, 3,4-dimethyl, 4-methoxy and 3, 4-dimethoxy - d -chlorobenzylphosphonic acid dimethyl ester and diethyl ester; 4-fluorine, 3-chloro, 4-chloro, 3,4-dichloro. 3-bromo, 4-bromo, 5-methyl, 4-methyl, 5,4-dimethyl, 4-methoxy- and 3, 4-dimethoxy- - α-bromobenzylphosphonic acid dimethyl ester and diethyl ester.

The phosphorus-containing olefinating agents of the formula (III) are for Part not yet described in the literature, but can be known in principle Process are produced.

Benzylphosphonic acid esters which fall under formula (III) and are unsubstituted in the t-position obtained by reacting benzyl halides with esters of phosphorous acid (Compare methods of organic chemistry (Houben-Weyl-Müller), 4th edition, volume 12/1, pp. 433-453, Georg-Thieme-Verlag, Stuttgart 1963).

Α-chloro- and 9-bromo-benzylphosphonic acid esters falling under formula (III) are obtained by reacting α-hydroxy-benzylphosphonic acid esters of the formula VIII in which R4 has the meaning given above, R³ stands for optionally substituted phenyl with a chlorinating agent such as thionyl chloride, or with a bromination agent such as dibromotriphenylphosphorane, optionally in the presence of an acid acceptor such as pyridine, and optionally using one Diluents, we e.g.

Methylene chloride or ethylene chloride, at temperatures between lo and 100 ° C or between -50 and -30 ° C (compare J. Am. Chem. Soc. 87 (1965), 2777-2778; Chimia 28: 656-657 (1974)).

Some of the α-hydroxy-benzylphosphonic acid esters of the formula (VIII) are not yet known. They are obtained by the route indicated above for the preparation of compounds of the formula (II) or by reacting benzaldehydes of the formula IX R3-CHO (IX) in which R3 has the meaning given above with phosphorous acid esters of the formula X. in which has the meaning given above, optionally in the presence of a catalyst, such as triethylamine, at temperatures between 0 and 150 ° C., preferably between 20 and 100 ° C. (compare methods of organic chemistry (Houben-Weyl-Müller), 4th edition. Volume 12 / 1, pp. 475-48D, Georg-Thieme-Verlag, Stuttgart 1963).

The aldehydes of the formula IX and the phosphorous acid esters of the formula (X) are widely known.

The process according to the invention for the preparation of alkenes of the formula (I) is preferably carried out using suitable solvents or diluents carried out. In addition to water, practically all inert organic materials come as such Solvents in question. These include in particular aliphatic and aromatic, if appropriate chlorinated hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, toluene, Xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and dichlorobenzenes, ethers such as diethyl and dibutyl ethers, tetrahydrofuran and dioxane, Alcohols such as methanol, ethanol, n- and iso-propanol, n-, iso-, sec- and tert-butanol and aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide.

When working in the two-phase medium, caustic soda in addition to the above or potassium hydroxide organic solvents such as pentane, hexane, heptane, Benzene or toluene used, which are immiscible with water.

As catalysts - when carrying out the invention Process in multiphase reaction media - compounds used usually in reactions in multiphase systems as an aid to phase transfer of reactants to serve. In particular, such phase transfer catalysts are tetraalkyl and Trialkyl-benzyl-ammonium salts, e.g.

Tetrabutylammonium bromide and trimethylbenzylammonium chloride, called.

Can be used as bases when carrying out the process according to the invention the bases customary in carbonyl olefinations are used. Alkali hydroxides are mentioned such as. Potassium and sodium hydroxide, alkali alcoholates such as potassium and sodium methoxide, -ethylate, -n- and -iso-propylate, -n-, -iso-, -sec.- and -tert-butylate, alkali hydrides such as sodium hydride and alkyl lithium compounds such as butyl lithium. Preferably the alkali metal hydroxides and / or alcoholates mentioned are used.

The process is in general carried out at normal pressure. the Reaction temperatures are between -70 and + 150 ° C., preferably between -20 and + 50 ° C.

The starting compounds are used to carry out the process according to the invention of the formulas (II) and (III) are usually used in equimolar amounts. When working is generally used in single-phase systems two base equivalents, when using 5c% alkaline solutions as the second phase, generally the 5 to 15 times the stoichiometrically required amount.

The base and optionally the catalyst are placed in a suitable one Reaction medium before and are added simultaneously or in succession - if necessary dissolved in one of the specified solvents - the starting materials of the formulas (II) and (III). The mixture is stirred for several hours to complete the reaction.

Working up can be carried out by customary methods.

For the isolation of distillable products one can for example Distill off the solvent, the residue in a water immiscible Take up solvents such as ligroin, wash the solution with water, dry it, filter and distill.

The reaction mixture can optionally be used to isolate crystalline products Pour into (ice) water and suck off the crystalline product, or you can Reaction mixture - if the solvent is not miscible with water - with water wash, dry, filter and evaporate. According to the last-mentioned work-up method Oily, difficult-to-distill products can also be obtained relatively pure.

The products are characterized by their melting or Boiling points.

Compounds to be prepared by the process according to the invention Formula (I) can be used as intermediates in the manufacture of insecticides (see DE-OS 2 738 150).

As already mentioned, according to the new method 1 (above) can also the new alkenes of the formula XI are produced. These new connections can but can also be produced by method 9 (above).

If the starting materials used in process 9 (above) are, for example, ~ -chlorobenzylphosphonic acid dimethyl ester and 2-formyl-3,3-dimethyl-cyclopropane-1-carboxamide and sodium hydroxide as the base, the reaction of these compounds can be carried out by the following Formula scheme to be sketched: The new styryl-cyclopropane derivatives of the formula XI are preferably obtained in which R represents fluorine, chlorine, bromine, C1-C4-alkyl, trifluoromethyl, C1-C4-alkoxy, C1-C2-fluoroalkoxy, C1-C2-chlorofluoroalkoxy, C1-C4-alkylthio, C1-C2-fluoroalkylthio, C1-C2-chlorofluoroalkylthio, C1-C2-alkylenedioxy, C1-C2-fluoroalkylenedioxy, cyano or nitro, n is zero to 5, R10 is hydrogen, chlorine, bromine, C1-C4-alkyl or C1-C2-fluoroalkyl, and Y stands for acetyl, cyano or carbamoyl.

The method described under 9 (above) is preferably used under Use of diluents carried out.

Polar organic solvents are particularly suitable as such Consideration. These include carboxamides, such as dimethylformamide and N-methylpyrolidone, Sulfoxides and sulfones, such as dimethyl sulfoxide and tetramethylene sulfone, phosphoric acid amides, such as hexamethylphosphoric acid triamide, ethers such as glycol dimethyl ether, diglycol dimethyl ether, Tetrahydrofuran and dioxane, nitriles such as acetonitrile and propionitrile, as well as Alcohols such as methanol, ethanol, n- and iso-propanol, n-iso-, sec- and tert-butanol.

In process (9), those customary in carbonyl olefinations can be used Bases are used. Alkali hydroxides such as sodium and potassium hydroxide are mentioned, Alkali alcoholates such as sodium and potassium methylate, ethylate, n- and iso-propylate, -n-, -iso-, -sec.- and tert-butoxide, alkali hydrides such as sodium hydride and Alkyllithium compounds such as butyllithium.

Alcoholates are particularly preferred as bases.

The reaction temperatures are generally between -70 and + 1500C, preferably between -20 and + 500C.

The process is in general carried out at normal pressure.

The starting compounds of the formula (XII) and (XIII) are in general used in equimolar amounts.

In a preferred embodiment of process (9) the base is presented in one of the above-mentioned diluents and successively with one Benzylphosphonic acid ester of the formula (XII) and a formylcyclopropane derivative of Formula (XIII) added dropwise. The reaction mixture is stirred for several hours and worked up by one of the usual methods; one dilutes with water and extracted with a water-immiscible solvent such as methylene chloride or toluene, dry the extract, filter and distill off the solvent. The remaining crude product can be purified by vacuum distillation The boiling point and / or the refractive index are used for characterization.

The benzyl phosphonic acid esters to be used as starting materials in process (9) are defined by formula (XII). Preferably, R9 and R10 therein represent those Radicals which are preferred in the definition of the radicals R9 and R10 in formula (XI) were mentioned, n stands for zero to 5 and R4 preferably stands for C1-C4-alkyl, Phenyl or both radicals R4 together represent 2,2-dimethyl-propane-1,3-diyl.

The following are three examples: dimethyl benzylphosphonate and -diethyl ester, α-chlorobenzylphosphonic acid dimethyl ester and diethyl ester, α-Bromo-benzylphosphonic acid dimethyl ester and diethyl ester, 4-fluorine, 3-chlorine, 4-chloro, 3,4-dichloro, 3-bromo, 4-bromo, 3-methyl-, 4-methyl-, 3,4-dimethyl-, 4-methoxy- and 3,4-dimethoxybenzylphosphonic acid dimethyl ester and diethyl ester; 4-fluorine, 4-chloro, 3-chloro, 3,4-dichloro, 3-chloro, 4-bromo, 3-methyl, 4-methyl, 3,4-dimethyl, 4-methoxy- and 3,4-dimethoxy- - α-chlorobenzylphosphonic acid dimethyl ester and diethyl ester; 4-fluorine, 3-chlorine, 4-chlorine, 3,4-dichloro, 3-bromine, 4-bromine, 3-methyl, 4-methyl-, 3,4-dimethyl-, 4-methoxy- and 3, 4-dimethoxy- - α-bromobenzylphosphonic acid dimethyl esters and diethyl esters.

The benzyl phosphonic acid esters of the formula (XII) are not yet in described in the literature, but can be prepared by processes that are known in principle will.

Benzylphosphonic ester according to formula (XII), in which R10 is hydrogen or optionally substituted alkyl is obtained by reacting the appropriate Benzyl halides with esters of phosphorous acid (cf. methods of organic Chemie (Houben-Weyl-Müller), 4th edition, Volume 12/1, pp. 433-453, Georg-Thieme-Verlag, Stuttgart 1963).

Benzyl-phosphonic acid esters according to formula (XII), in which R10 stands for chlorine or bromine, are obtained by reacting α-hydroxy-benzyl-phosphonic acid esters of the formula XVI in which R9, n and R4 have the meanings given above, with a chlorinating agent, such as .3. Thionyl chloride, or with a bromine agent, such as, for example. Dibromotriphenylphosphorane, optionally in the presence of an acid acceptor such as pyridine, and optionally using a diluent such as methylene or ethylene chloride, at temperatures between -50 and + 500C (see J. Am. Chem. Soc. 87 (1965), 2777-2778; Chima 28: 656-657 (1974)).

Hydroxy-benzyl-phosphonic acid esters of the formula (XVI) are obtained by reacting benzaldehydes of the formula XVII in which R9 and n have the meanings given above, with phosphorous acid esters of the formula XVIII in which R has the meaning given above, optionally in the presence of a catalyst, such as triethylamine, at temperatures between 10 and 1000C (see Methods of organic chemistry (Houben-Weyl-Müller), 4th edition, Volume 12/1, Pp. 475-483; Georg-Tieme-Verlag, Stuttgart 1963).

Aldehydes of the formula (XVII) and phosphoric acid esters of the formula (XVIII) are known.

As examples of those used as further starting compounds in processes (9) Formyl-cyclopropane derivatives of the formula (XIII) to be used are: 2-acetyl-3,3-dimethyl-cyclopropane-1-carbaldehyde, 2-cyano-3,3-dimethyl-cyclopropane-1-carbaldehyde and 2-carbamoyl-3,3-dimethyl-cyclopropane-1-carbaldehyde.

For example, 2-acetyl-3,3-dimethyl-cyclopropane-1-carbaldehyde is obtained according to the process given under (11) by reacting 2-acetyl-3,3-dimethylcyclopropane-1 -carboxylic acid chloride (XIV) with lithium tritert.-butoxy-hydrido-aluminate, which one optionally in situ from lithium tetrahydrido-aluminate (lithium alanate) and has produced tert-butanol, optionally in the presence of a diluent, such as tetrahydrofuran, at temperatures between -100 and + 1000C, preferably between -80 and + 500C. Working up can be carried out by customary methods, for example by pouring the reaction mixture into a mixture of hydrochloric acid and ice water, with a water-immiscible solvent, e.g.

Diethyl ether, extracted, the extracts dried, filtered and concentrated. To purify the remaining crude product, distillation is optionally carried out.

In general, formyl-cyclopropane derivatives of the formula (XIII) are obtained according to the process set out under (12) by reacting 4-hydroxycyclopropylmethyl-phosphonic acid esters of the formula XV (above) with aqueous alkali solutions, such as with aqueous sodium hydroxide solution, optionally in the presence of a water-immiscible solvent, such as e.g. methylene chloride, at temperatures between 0 and 100 ° C, preferably between 10 and 500C (see Chem. Ber. 103 (1979), 2984-2986).

For work-up, the organic phase is separated off, dried, filtered, concentrated and the crude product remaining as residue, if appropriate purified by distillation.

dc-Hydroxy-phosphonic acid esters of the formula (XV) are obtained, for example, according to the scheme below, starting from known ones. Cyclopropane carboxylic acid esters of the formula (XIX), by saponifying them to give the corresponding acids of the formula (XVIII), producing the acid chlorides of the formula (XVII) therefrom, producing the cyclopropanoyl phosphonic acid esters of the formula (XVI) by reaction with alkyl phosphites and these with Sodium tetrahydridoborate reduced (R10 stands for C1-C4-alkyl): By hydrolysis of known cyclopropanecarboxylic acid esters of the formula (XIX) (compare J.Org.Chem. 32, (1967), 3351-3355; Bull. Soc.Chim.Belg.87 (1978), 721-732; Tetrahedron Lett. 1978 , 1847-1850), for example by reaction with aqueous-alcoholic potassium hydroxide solution at temperatures between 20 and 100 ° C. and subsequent acidification, the carboxylic acids of the formula (XVIII) are obtained. These can be converted into the acid chlorides of the formula (XVII) by reaction with halogenating agents such as, for example, thionyl chloride, at temperatures between 20 and 1000C.

By reacting the acid chlorides (XVII) with alkyl phosphites at temperatures between -20 and + 150 ° C., preferably between 0 and 100 ° C., the cyclopropanoylphosphonic acid esters are obtained of the formula (XVI) (cf.

J.Am.Chem.Soc. 1964, 86: 3862-3866; Methods of organic chemistry (Houben-Weyl-Müller), 4th edition, Volume 12/1, p. 453, Georg-Thieme-Verlag, Stuttgart 1963).

To isolate and purify the products, if necessary, under distilled under reduced pressure.

The OC-hydroxy-phosphonic acid esters of the formula (XV) are obtained by Reduction of the oxo compounds of the formula (XVI) with sodium tetrahydridoborate, if appropriate using a diluent such as e.g.

Water or aqueous methanol and optionally in the presence of one Solvent immiscible with water, e.g. methylene chloride, at temperatures between -20 and + 50 ° C (see Chem. Ber. 103, (1970), 2984-2986). For work-up is extracted with a water-immiscible solvent, such as methylene chloride, dry the extracts, filter and distill the solvent under reduced pressure Pressure off.

Since the formylcyclopropane derivatives used as starting compounds of the formula (XIII) as well as the styryl-cyclopropane derivatives of the formula (XI) in each case have asymmetric carbon atoms, the compounds of the formulas (XI) and (XIII) occur in a corresponding number of stereoisomeric forms. the Processes according to the invention relate to the preparation of compounds of Formula (XI), either in the form of the individual stereoisomers or as mixtures of stereoisomers.

From the styryl-cyclopropane derivatives of the formula (XI), in which Y stands for cyano or carbamoyl, the corresponding carboxylic acid esters are obtained Formula (XI) in which Y is alkoxycarbonyl in a known manner, for example by reaction with alcohols, e.g.

Methanol or ethanol, in the presence of a mineral acid such as sulfuric acid, at temperatures between 80 and 200 ° C. (cf. DE-OS 2 831 555).

The compounds of the formula (XI) in which Y stands for acetyl can in a known manner, for example by reaction with aqueous sodium hypobromite solution, which has optionally been generated in situ from bromine and sodium hydroxide solution, optionally in the presence of an organic solvent such as dioxane at temperatures between -20 and + 500C, in the corresponding carboxylic acids of the formula (XI) in which then Y stands for carboxy (cf. DE-OS 2 621 833).

Compounds of the formula (XI) in which Y is carboxy or alkoxycarbonyl can be used as intermediates for the production of insecticidal and acaricidal products Pyrethroids are used (cf. DE-OS 2 730 515).

1. Examples of method (1) Example 1 22.8 g (0.1 mol) of benzylphosphonic acid diethyl ester are added to a solution, cooled to 0 to 50 ° C., of 22.4 g (0.2 mol) of potassium tert-butoxide in loo ml of tetrahydrofuran (dried over sodium) within Given dropwise for 15 minutes. The mixture is stirred for one hour; a solution of 28 g (0.1 mol) of diethyl α-hydroxy-4-chlorobenzylphosphonic acid in 50 ml of tetrahydrofuran is then added, while cooling to 0 to 5 ° C., and the mixture is stirred for a further 15 hours at room temperature (approx ). It is then poured into 1 l of ice water, filtered off with suction and dried. This gives 18 g (84% of theory) 1- (4-chlorophenyl) -2-phenylethylene in the form of colorless crystals with a melting point of 130.degree.

Example 2 28 g (0.1 mol) of α-hydroxy-4-chlorobenzylphosphonic acid diethyl ester and 30 g (0.1 mol) of α-chloro-4-chlorobenzylphosphonic acid diethyl ester are dissolved in 50 ml of toluene and this solution is within of 30 minutes to a vigorously stirred mixture of 100 ml of toluene, 100 ml of 40% sodium hydroxide solution and 2 g of tetrabutylammonium bromide at an internal temperature of 30 to 35 ° C. added dropwise. The mixture is stirred for a further 15 hours at room temperature (approx. 20 ° C.), the organic phase is separated off, washed twice with water, dried, filtered and the solvent is distilled off in vacuo. The residue is obtained in crystalline form from ligroin: 14 g (49% of theory) of 1-chloro-1- (4-chloro-phenyl) -2- (4-chloro-phenyl) -ethylene; Melting point 89 ° C.

Example 3 30 g (0.1 mol) of diethyl α-chloro-4-chlorobenzylphosphonate are added dropwise to a solution, cooled to 0 ° to 10 ° C., of 8.8 g (0.2 mol) of sodium methylate in 200 ml of tetrahydrofuran. The mixture is stirred at OOC for one hour; then a solution of i-hydroxy- (3-methoxycarbonyl-2,2-dimethyl-cycloprop-1-yl) -methanephosphonic acid dimethyl ester in 50 ml of tetrahydrofuran is added at 0 to 10 ° C., and the reaction mixture is stirred for 15 hours at room temperature (approx.

20 ° C), the solvent is distilled off and the residue is taken up in ligroin on, the solution was washed with ice water, dried, filtered and distilled.

18 g (6% of theory) of 3- (2-chloro-2- (4-chlorophenyl) vinyl) -2,2-dimethyl-cyclopropane-1-carboxylic acid methyl ester are obtained from the boiling point of loo ° C / o, ol mbar.

Example 4 30 g (0.1 mol) of α-chloro-4-chloro-benzyl-phosphonic acid diethyl ester, dissolved in 50 ml of tetrahydrofuran, are added to a solution of 8.8 g (0.2 mol) of sodium methylate in cooled to 0 to 10 ° C. 200 ml of tetrahydrofuran added dropwise. The mixture is stirred for one hour; a solution of 25 g (0.1 mol) of α-hydroxy (3-acetyl-2,2-dimethyl-cycloprop-l-yl) -methanephosphonic acid dimethyl ester in 100 ml of tetrahydrofuran is then added at 0 to 5 ° C. , the reaction mixture is stirred for 15 hours at 15 ° to 250 ° C., the solvent is distilled off, the residue is taken up in toluene, washed three times with water, dried, filtered and distilled.

18 g (64% of theory) (3- (2-chloro-2- (4-chlorophenyl) vinyl) -2,2-dimethyl-cycloprop-1-yl) methyl ketone are obtained with a boiling point of 9o0C / o, ol mbar.

Example 5 is obtained analogously Boiling point 94 ° C / 0.01 mbar i-Hydroxy-phosphonic acid esters of the formula (II) to be used as starting materials can be prepared, for example, as follows: 2. Examples of process (3) A solution of 50 g (0.2 mol) of α-oxo- $ - (3-acetyl-2,2-dimethyl-cycloprop-l-yl) -methanephosphonic acid dimethyl ester in 50 ml of methylene chloride is converted into a mixture cooled to 0 to 50 ° C 2.5 g of sodium tetrahydridoborate, 100 ml of water and 100 ml of methylene chloride are added dropwise and the reaction mixture is stirred at 0 to 5 ° C. for two hours. The aqueous phase is then separated off from the organic phase and extracted twice more with methylene chloride. The combined organic phases are dried, filtered and evaporated. After recrystallization of the remaining sugar from 200 ml of ethyl acetate / ligroin (2: 8), 31 g (62% of theory) «-Hydroxy- i- (3-acetyl-2,2-dimethyl-cycloprop-1-yl) - methanephosphonic acid dimethyl ester with a melting point of 104 ° C.

Analogously to the above example, one obtains Melting point 690C 3.Examples of procedure (5) 6.5 g (0.05 mol) of trimethyl phosphite are added to a solution, heated to 35 to 40 ° C., of 9 g (0.05 mol) of 3-acetyl-2,2-dimethyl-cyclopropane-1-carboxylic acid chloride in 20 ml Methylene chloride is added dropwise and the reaction mixture is stirred at 15 to 25 ° C. for 15 hours. After the solvent has been distilled off in vacuo, 9 g (72% of theory) -oxo- (3-acetyl-2,2-dimethylcycloprop-1-yl) -methyn-phosphonic acid dimethyl ester are obtained.

Analogously to the above example, one obtains 4.Examples of procedure (7) A mixture of i72 g (1 mol) of 3-methoxycarbonyl-2,2-dimethyl-cyclopropane-1-carboxylic acid, 130 g of thionyl chloride, 2 ml of dimethylformamide and 200 ml of methylene chloride is refluxed for four hours. After distillation in vacuo, 135 g (71% of theory) of 3-methoxycarbonyl-2,2-dimethyl-cyclopropane-carboxylic acid chloride with a boiling point of 860 ° C./15 mbar are obtained.

Analogously one obtains Boiling point 95-980C / 10 mbar 5.Examples of process 9 Example 17 To a solution of 8.9 g (0.042 mol) of sodium methylate in methanol and 80 ml of tetrahydrofuran is added dropwise at 0-100C a solution of 11.8 g (0.04 mol) of X-chloro (4-chlorobenzyl) phosphonic acid diethyl ester in 20 ml of tetrahydrofuran are added and the mixture is stirred at 0-100 ° C. for 1 hour.

5 g (0.04 mol) of 3,3-dimethyl-2-cyano-cyclopropanecarbaldehyde are then added at 10.degree to, the reaction mixture is stirred for 1 hour without further cooling and it is poured then to 300 ml of water. The aqueous solution is three times with 100 ml of methylene chloride extracted, the combined organic phases are dried over sodium sulfate and evaporated in vacuo. 9.4 g (89% of theory) of 3,3-dimethyl-2- (2-chloro-2- (4-chlorophenyl) vinyl) cyclopropanecarboxonitrile remain 22 as yellow bl with the refractive index nD: 1.5611.

Example 18 To a solution of 17.8 g (0.084 mol) of sodium methylate in methanol and 160 ml of tetrahydrofuran is added dropwise at O-100C a solution of 23.7 g (0.08 mol) of diethyl cc-chloro (4-chlorobenzyl) phosphonic acid in 40 ml of tetrahydrofuran are added and the mixture is stirred at 0-100 ° C. for 1 hour.

11.2 g (0.08 mol) of trans 3,3-dimethyl-2-acetyl-cyclopropanecarbaldehyde are then added at 100.degree to, the reaction mixture is stirred for 2 hours without further cooling and it is poured then to 800 ml of water. The aqueous solution is three times with 200 ml of methylene chloride extracted, the combined organic phases are dried over sodium sulfate and evaporated in vacuo.

19.7 g (87% of theory) of trans 3,3-dimethyl-2- (2-chloro-2- (4-chlorophenyl-vinyl) -1-acetylcyclopropane are obtained in this way as a yellow oil with a boiling point of 120-1280C / 0.1 mm.

Example 19 To a solution of 4.9 g (0.09 mol) of sodium methylate in a mixture of 20 ml of methanol and 200 ml of tetrahydrofuran are added at 0 ° C 244.1 g (0.09 mol) of α-chloro (4-chloro) benzyl) phosphonic acid dimethyl ester was added dropwise. Then 12.6 g (0.09 ol) 5,3-dimethyl-2-acetyl-cyclopropanecarbaldehyde in 50 ml of tetrahydrofuran are added at 200 ° C. and the reaction mixture is stirred for a further 5 hours.

After working up as in Example 1, 16 g (62% of theory) are obtained 3,3-Dimethyl-2- (2-chloro-2- (4-chlorophenyl) vinyl) -1-acetyl-cyclopropane in the form of a Oil with the refractive index nD20: 1.5698.

Example 20 13.8 g of bromine are added dropwise to a solution of 11.5 g of sodium hydroxide in 60 ml of water at 5-10 ° C. and then a solution of 8.1 g (0.029 mol) of trans-3,3-dimethyl-2 at 0-50 ° C. - (2-chloro-2- (4-chlorophenyl) vinyl) -1-acetylcyclopropane in 30 ml of dioxane.

The mixture is stirred for 3 hours without cooling, to 250 ml of water poured and extracted twice with 50 ml of ether each time. The aqueous phase is in vacuo freed from adhering ether and then adjusted to pH by adding aqueous hydrochloric acid 2 brought. After crystallization, the product is filtered off with suction and washed with water. 6.2 g (77% of theory) are obtained in this way.

Theory) trans -3, 3-dimethyl-2 (2-chloro-2- (4-chlorophenyl) vinyl) cyclopropanecarboxylic acid in the form of pale yellow crystals with a melting point of 103-1060C.

6. Examples of method 11 Example 21 36.6 g (0.495 mol) of tert-butanol are added dropwise at 20-30 ° C. to a mixture of 6.3 g (0.165 mol) of lithium alanate and 100 ml of tetrahydrofuran.

The mixture is stirred for 2 hours at room temperature and then added dropwise it then at -50 to -600C to a solution of 26.1 g (0.15 mol) of trans-3,3-dimethyl-2-acetyl-cyclopropane-carboxylic acid chloride in 75 ml of tetrahydrofuran. After the addition is complete, the mixture is stirred for 1 hour without cooling, Poured onto a mixture of 30 ml of concentrated sodium chloride and 300 g of ice and extracted twice with 400 ml of ether each time. The organic phases are only with 50 ml of saturated sodium hydrogen carbonate solution and then washed with 100 ml of water, dried over sodium sulfate and evaporated in vacuo. By distilling the The residue in vacuo gives 12.7 g (62 of theory) of trans-3,3-dimethyl-2-acetyl-cyclopropane-carb aldehyde in the form of a colorless oil with a boiling point of 80-860C / 10 mbar.

7. Examples relating to process 12 Example 22 A mixture of 50 g -hydroxy-Oc- (3-acetyl-2,2-dimethyl-cycloprop-1 -yl) -methane-phosphonic acid dimethyl ester, 8 g sodium hydroxide, 60 ml water and 200 ml of methylene chloride is stirred for 90 minutes at room temperature. The organic Phase is separated off, dried and distilled twice. 20 g (71% of theory) 3,3-dimethyl-2-acetyl-cyclopropanecarb aldehyde in the form of a colorless oil with a boiling point of 780C / 8 mbar.

Analogously to example 22 one obtains Boiling point 770C / 3 mbar The cyclopropanecarboxylic acids of the formula (VII) to be used as starting materials in process (7) can be prepared, for example, as follows: Example 24 A suspension of 3-D, 4 g (0.2 mol) of 2-cyano-3,3-dimethyl-cyclopropane-carboxylic acid ethyl ester and 16.8 g (0.3 mol) of potassium hydroxide in 200 ml of water and 100 ml of ethanol is used for 15 hours Stirred at 20-25 ° C. The alcohol is then drawn off, the aqueous solution is acidified with dilute hydrochloric acid and extracted twice with 100 ml of ether (or methylene chloride) each time. The combined organic extracts are dried over Na2SO4, concentrated and distilled. 21.2 g (76% of theory) of 2-cyano-3,3-dimethyl-cyclopropane-carboxylic acid are obtained in the form of an oil with a boiling point of 110-1200 ° C. which crystallizes on cooling (melting point 101-1060 ° C.).

The benzylphosphonic acid esters of the formula (XII) to be used as starting materials in process (9) can be prepared, for example, as follows: Example 25 To a mixture of 20.2 g (0.0725 mol) of 4-chloro-t-hydroxybenzylphosphonic acid diethyl ester, 65 g of dichloromethane and 5.8 g (0.0725 mol) of pyridine are added at 20-400C with slight water cooling within about Added 9.2 g (0.0768 mol) of thionyl chloride for 1 hour. The reaction mixture is then refluxed for 3 hours and stirred for 12 hours without further exposure to heat. The mixture is poured onto about 100 g of ice water, and the organic phase is separated off and dried.

After the solvent has been distilled off, the residue is concentrated at 6 Torr and 45 ° C. 21 g (97.7% of theory) of 4-chloro-chloro-benzyl-phosphonic acid diethyl ester are obtained as a yellow, viscous oil with a purity of 98.6% (gas chromatogram) and a refractive index of nD: 1.5250 Refractive index: nD23: 1.5117 90 g of bromine dissolved in 250 ml of methylene chloride are added dropwise to a solution of 131 g (0.5 mol) of triphenylphosphine in 500 ml of methylene chloride with exclusion of moisture at 30-350 ° C. The mixture is stirred for 1 hour at room temperature, then a solution of 122 g (0.5 mol) of-hydroxybenzylphosphonic acid diethyl ester in 250 ml of methylene chloride is added dropwise at -20 ° within 1 hour, and the mixture is stirred at -20 ° C. for 1 hour 40 g of pyridine, dissolved in 250 ml of methylene chloride, are then added dropwise over the course of 1 hour at -200C. The mixture is allowed to stir for 20 hours, the temperature rising slowly to + 200C.

The reaction mixture is transferred to a pear flask and the Solvent distilled off in a water jet vacuum. The residue is with a Liter of ether and sucked off the undissolved triphenylphosphine oxide. (Triphenylphosphine oxide 120g = 86% of theory). Concentrate the mother liquor in vacuo and distill the residue in a high vacuum.

112 g (72% of theory) of oc-bromobenzylphosphonic acid diethyl ester are obtained as a light yellow oil with a boiling point of 1100C / o, ol Torr and a purity of 95.9% (GC).

28 is obtained analogously Boiling point: 1250C / o, ol Torr. Α-Hydroxy-benzylphosphonic acid esters to be used as starting materials in Examples 25-28 can be prepared, for example, as follows: Example 29 In a mixture of 20.7 g (0.15 mol) of diethyl phosphite and 1.09 g (0.0109 mol) of triethylamine, 21 g (0.150 mol) of chlorobenzaldehyde are passed under water cooling at 50-700C. The reaction mixture is stirred at 70 ° C. for 1 hour. After cooling, the batch is taken up in 40 g of toluene and washed several times with dilute hydrochloric acid and cold water. The organic layer is separated and the solvent is removed in vacuo. The solid residue melts at 70-720C. The yield is 37 g (88.5% of theory) of 4-chloro-M-hydroxy-benzylphosphonic acid diethyl ester.

Claims (12)

Claims 1./Method for the preparation of alkenes of the formula (I) in which R1 represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aralkyl, aralkenyl or aryl radical or an optionally substituted heterocyclic radical, R² represents hydrogen or halogen and R³ represents Halogen, cyano, represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aralkenyl, aryl, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl or aminocarbonyl radical or an optionally substituted heterocyclic radical, characterized in that that one α-hydroxy-phosphonic acid ester of the formula II in which R¹ has the meaning given above and R4 stands for alkyl or phenyl or the two radicals R4 together stand for straight-chain or branched alkanediyl (alkylene), with phosphorus-containing olefinating agents of the formula III in which R2 and R3 have the meanings given above and zl is a phosphorus-containing radical where R5 and R6 are identical or different and individually represent alkyl, phenyl, alkoxy or phenoxy or together represent alkanedioxy, R7 represents alkyl or phenyl and X represents halogen, in the presence of bases, optionally in the presence of catalysts, and if necessary using diluents at temperatures between -70 and + 1500C. 2. iC-hydroxy-phosphonic acid ester of the formula IIa in which R stands for alkyl or phenyl or the two radicals 4 R4 together stand for straight-chain or branched alkanediyl (alkylene) and S2 stands for cyano, carbamoyl, acetyl or C1-C4-alkoxycarbonyl. 3. A process for the preparation of vond (hydroxyphosphonic acid esters of the formula IIa (above), characterized in that α-oxo-phosphonic acid esters of the formula IV in which R4 and z2 have the meanings given under (2), with hydride complexes of the formula VM (M'H4) (V) in which M stands for lithium, sodium or potassium and M 'stands for boron or aluminum, optionally in the presence of one Buffering agent and optionally using a diluent at temperatures between -20 and + 50 ° C 4.QC-oxophosphonic acid ester of the formula IV in which R4 stands for alkyl or phenyl or the two radicals R4 together stand for straight-chain or branched alkanediyl (alkylene) and Z stands for cyano, carbamoyl, acetyl or C1-C4-alkoxycarbonyl. 5. A process for the preparation ofdC-oxophosphonic acid esters of the formula IV (above), characterized in that carboxylic acid chlorides of the formula VI in which z2 has the meaning given under (4), with phosphorous acid esters of the formula VII R8C-P (OR4) 2 (VII) in which R4 has the meaning given under (4) and R8 stands for methyl or ethyl, at temperatures between - 20 and + 150 ° C. 6. Carboxylic acid chlorides of the formula VI in which Z² is cyano, carbamoyl, acetyl or C1-C4-alkoxycarbonyl. 7. Process for the preparation of carboxylic acid chlorides of the formula VI (above), characterized in that carboxylic acids of the formula VII in which z2 has the meaning given under (6), reacts with a chlorinating agent at temperatures between 20 and 80.degree. 8. Styryl-cyclopropane derivatives of the formula XI in which R9 represents halogen or optionally halogen-substituted radicals alkyl, alkoxy, alkylthio or alkylenedioxy and also cyano or nitro, n represents zero to 5, R10 represents hydrogen, halogen or optionally halogen-substituted alkyl, and Y represents acetyl, cyano or carbamoyl stands. 9. Process for the preparation of styryl-cyclopropane derivatives of the formula XI (above), characterized in that benzylphosphonic acid esters of the formula XII in which R, n and R10 have the meanings given above, and the radicals R4 individually represent alkyl or phenyl or together represent alkanediyl (alkylene), with formylcyclopropane derivatives of the formula XIII in which Y has the meaning given above, in the presence of bases and optionally with the use of diluents at temperatures between -70 and + 1500C. 10.Formyl-cyclopropane derivatives of the formula XIII in which Y stands for acetyl or carbamoyl. 11. A process for the preparation of the formyl-cyclopropane derivative of the formula XIII (above) in which Y stands for acetyl, characterized in that 2-acetyl-3,3-dimethylcyclopropane-1-carboxylic acid chloride of the formula with lithium tri-tert.-butoxyhydrido-aluminate, optionally using a diluent, at temperatures between -100 and + 1000C. 12. Process for the preparation of formyl-cyclopropane derivatives of the formula XIII (above), in which Y stands for acetyl, cyano or carbamoyl, characterized in that mandC-hydroxy-cyclopropylmethyl-phosphonic acid ester of the formula in which R4 stands for alkyl or phenyl or both radicals R4 together stand for alkanediyl (alkylene), and Y stands for acetyl, cyano or carbamoyl, with aqueous alkali solutions, optionally in the presence of a water-immiscible organic solvent such as methylene chloride at temperatures between 0 and 1000C implements.