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AssigneeBayer Aktiengesellschaft
InventorsHellmut Hoffmann, Fritz Maurer, Uwe Priesnitz, Hans-Jochem Riebel
Estimating the term…
Styryl-cyclopropane derivatives of the formula ##STR1## in which R.sup.9 represents independently of one another when n=2, halogen, cyano, nitro, or an optionally halogen-substituted alkyl, alkoxy, alkylthio or alkylenedioxy radical, n represents zero, 1, 2, 3, 4 or 5, R.sup.10 represents hydrogen or halogen and Y represents acetyl, cyano or carbamoyl, are produced by reacting a benzylphosphonic acid ester of the formula ##STR2## in which R.sup.4 each independently represents alkyl or phenyl or together represent alkylene, with a formylcyclopropane derivative of the formula ##STR3## or by reacting an .alpha.-hydroxyphosphonic acid ester of the formula ##STR4## with an olefinating agent of the formula ##STR5## in which Z' represents a phosphorus-containing radical ##STR6## wherein R.sup.5 and R.sup.6 are identical or different and individually represent alkyl, phenyl, alkoxy or pehnoxy or R.sup.5 and R.sup.6 together represent alkanedioxy, R.sup.7 represents alkyl or phenyl and X represents halogen, in the presence of a base at a temperature between about -70.degree. and +150.degree. C. Other olefins can be similarly prepared. Many intermediates are new and the end products are themselves intermediates for insecticides.
A process for the preparation of an alkene of the formula ##STR57## in which R.sup.2 represents hydrogen or halogen,
Dependencies are inferred from the claim text.
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By condensation reactions: involving a phosphorus compound, e.g. Wittig synthesis
Compounds containing at least one halogen atom bound to a six-membered aromatic ring: halogenated aromatic hydrocarbons with unsaturated side chains
Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds: by hydrogenolysis…
By pyrolysis, rearrangement or decomposition: of compounds containing doubly bound oxygen atoms, e.g. esters
Term ended 16 Apr 2000 (estimated)
USPTO file history isn’t available for this patent, so only indexed dates are shown.
The invention relates to an unobvious process for the preparation of certain alkenes, some of which are known, to certain new styryl cyclopropane derivatives which can be prepared by this process and by other processes, and to intermediate products for the preparation of said alkenes.
It is known that such alkenes as, for example, 3-(2-methyl-2-methoxy-carbonyl-vinyl)-2,2-dimethyl-cyclopropane-1-carboxyl ic acid tert.-butyl ester, which can be used as an intermediate product for insecticidally active pyrethroids, are obtained when aldehydes or ketones, for example 3-formyl-2,2-dimethyl-cyclopropane-2-carboxylic acid tert.-butyl ester, are reacted with phosphorus-ylides (phosphorus-ylenes), for example (1-methoxy-carbonylethylidene)-phosphonic acid diethyl ester (see Organic Reactions, Volume 25 (1977), page 73-253, in particular page 85 and page 121, and the literature quoted there).
It is also known, as a special case of the abovementioned synthesis method, that certain 3-(2-chloro-2-phenyl-vinyl)-2,2-dimethyl-cyclopropane-1-carboxylic acid esters, for example 3-(2-chloro-2-phenyl-vinyl)-2,2-dimethyl-cyclopropane-1-carboxylic acid ethyl ester, are obtained when corresponding benzyl-phosphonic acid esters are treated with a strong base, for example butyl-lithium, and the ylides intermediately formed are reacted with carbon tetrachloride and then with 3-formyl-2,2-dimethyl-cyclopropane-1-carboxylic acid esters (see DE-OS (German Published Specification) No. 2,738,150).
Compounds of the formula (XI) in which Y represents carboxyl or alkoxycarbonyl can be used as intermediate products for the preparation of pyrethroids which have an insecticidal and acaricidal action (see DE-OS (German Published Specification) No. 2,730,515).
22.8 g (0.1 mol) of benzylphosphonic acid diethyl ester were added dropwise to a solution, cooled to 0.degree. to 5.degree. C., of 22.4 g (0.2 mol) of potassium tert.-butylate in 100 ml of tetrahydrofuran (dried over sodium) in the course of 15 minutes. The mixture was stirred for one hour; a solution of 28 g (0.1 mol) of .alpha.-hydroxy-4-chlorobenzylphosphonic acid diethyl ester in 50 ml of tetrahydrofuran was then added to the mixture, while cooling to 0.degree. to 5.degree. C., and the mixture was stirred at room temperature (about 20.degree. C.) for a further 15 hours. It was then poured into 1 liter of ice-water, filtered off and dried. 18 g (84% of theory) of 1-(4-chlorophenyl)-2-phenyl-ethylene were thus obtained in the form of colorless crystals of melting point 130.degree. C.
28 g (0.1 mol) of .alpha.-hydroxy-4-chloro-benzyl-phosphonic acid diethyl ester and 30 g (0.1 mol) of .alpha.-chloro-4-chloro-benzyl-phosphonic acid diethyl ester were dissolved in 50 ml of toluene and this solution was added dropwise to an intensively stirred mixture of 100 ml of toluene, 100 ml of 40% strength sodium hydroxide solution and 2 g of tetrabutyl-ammonium bromide at an internal temperature of 30.degree. to 35.degree. C. in the course of 30 minutes. The mixture was stirred at room temperature (about 20.degree. C.) for a further 15 hours, the organic phase was separated off, washed twice with water, dried and filtered and the solvent was distilled off from the filtrate in vacuo. The residue was obtained as crystals from ligroin: 14 g (49% of theory) of 1-chloro-1-(4-chlorophenyl)-2-(4-chloro-phenyl)-ethylene; melting point: 89.degree. C.