GB2166729A - Fluorine containing oxirane compounds - Google Patents

Fluorine containing oxirane compounds Download PDF

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GB2166729A
GB2166729A GB08522010A GB8522010A GB2166729A GB 2166729 A GB2166729 A GB 2166729A GB 08522010 A GB08522010 A GB 08522010A GB 8522010 A GB8522010 A GB 8522010A GB 2166729 A GB2166729 A GB 2166729A
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formula
fluorine
alkyl
oxirane
hydrogen
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GB8522010D0 (en
GB2166729B (en
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Elmar Sturm
Alfred Meyer
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Novartis AG
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Ciba Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
    • C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals

Abstract

The compounds having the formula I: <IMAGE> wherein Ar is an unsubstituted or substituted aromatic radical from the series comprising phenyl, biphenyl, phenoxyphenyl and naphthyl; R2 is hydrogen, fluorine or C1-C6 alkyl; and R3 is hydrogen, fluorine, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-alkylthio, phenyl, phenoxy, phenylthio or C3-C7-cycloalkyl; and each aromatic substituent or aromatic moiety of a substituent is unsubstituted or mono- or poly-substituted, by halogen, C1-C4-alkyl, C1-C4-alkoxy, c1-C4-haloalkyl, nitro and/or cyano; with the proviso that R2 and R3 cannot each simultaneously be fluorine, are new. The compounds of formula 1 are particularly useful as intermediates for 1-azolyl-2-aryl-3-fluoroalkan-2-ols which have microbicidal activity, and also themselves show some fungicidal properties.

Description

1 GB 2 166 729 A 1
SPECIFICATION
Oxirane compounds The present invention relates to oxirane compounds.
In our copending British Patent Application No. 83 32617 (Serial No. 2132195), there are described and claimed compounds having the formula 1:
OR, R2 1 1 A,-CH2-C-C-F 1 1 Ar R3 1 in which A, is 1 H-1,2,4-triazole, 4H-1,2,4-triazole or 1 H-imidazole; Ar is an unsubstituted or substituted 15 aromatic radical from the series comprising phenyl, biphenyl, phenoxyphenyl and naphthyl; R, is hydrogen, Cl-C4-alkyl, C3-C5-alkenyl or benzyl; R2 is hydrogen, fluorine or Cl-C6- alkyl and R3 is hydrogen, fluorine, Cl-C6-alkyl, Cl-C6-haloalkyl, Cl-C6-alkoxy, Cl-C6-alky[thio, phenyl, phenoxy, phenylthio or C3-C7-CYCloalkyl, and each aromatic substituent or aromatic moiety of a substituent is unsubstituted or monoor poly-substituted by halogen, Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4-haloalkyl, nitro and/or cyano; including the acid 20 addition salts, quaternary azolium salts and metal complexes; with the proviso that R2 and R3 cannot each simultaneously be fluorine.
In this divisional Application, there are provided oxirane compounds having the formula IL 0 Ar--\CH2 1 M2-(-;_K3 1 h wherein Ar is an unsubstituted or substituted aromatic radical from the series comprising phenyl, bipheny], phenoxyphenyl and naphthyl; R2 is hydrogen, fluorine or Cl-C6 alkyl; and R3 is hydrogen, fluorine, Cl-C6-alkyl, Cl-C6-haloalkyl, Cl-C6-alkoxy, Cl-C6-alkylthio, phenyl, phenoxy, phenyl-thio or CYC7-CYCloalkyl; 35 and each aromatic substituent or aromatic moiety of a substituent is unsubstituted, or mono- or poly-substituted, by halogen, Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4- haloalky], nitro and or cyano; with the proviso that R2 and R3 cannot each simultaneously be fluorine.
The term alkyl by itself or as a constituent of another substituent is to be understood as meaning, for example, one of the following groups, depending on the number of carbon atoms stated; methyl, ethyl, propyl, butyl, pentyl, hexyl and the like and their isomers, for example isopropyl, isobutyl, tert.-butyl, isopentyl and the like. Haloalkyl is a monohalogenated to perhalogenated alkyl substituent, for example CHC12, CHF2, CH2C1, CC13, CH2F, CH2CH2C1, CH2Br and the like, in particular CF3. Here and in the following text, halogen is to be understood as meaning fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. Naphthyl is a- or 0- naphthyl.
Oxirane compounds of formula 11 can be prepared from ketones of the formula Ill:
R2 1 Ar-C-C-1- 11 1 0 R, Ill 50 in a manner which is known per se by reaction with dimethyl-sulfonium methylide or dimethyloxosulfonium 55 methylide (Corey and Chaykovsky, JACS, 1962, 84,3782.
The ketones of the formula Ill are accessible by methods which are known per se from the literature (cf. J Leroy, J Org. Chem. 46,206 (1981) or Houben-Weyl, volume V13, page 211), from the corresponding known et-bromoketones by conventional replacement of the bromine by fluorine, orthey can also be prepared by acylation of the aromatic on which they are based with fluorinated carboxylic acid derivatives, for example ffi) by a Friedel-Crafts reaction.
In principle, unless expressly specified in a particular case, one or more solvents or diluents which are inert in the reaction can be present in the preparation of all the starting substances, intermediates and end products mentioned here. Examples of suitable solvents or diluents are aliphatic and aromatic hydrocarbons, such as benzene, toluene, the xylenes and petroleum ether; halogenated hydrocarbons, such as 65 chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride and tetrachlor- 2 GB 2 166 729 A 2 oethylene; ethers and ether-like compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tertAutyl methyl ether and the like), anisole, dioxane and tetrahydrofuran; nitriles, such as acetonitrile and propionitrile; N,N-dialkylated amides, such as dimethylformamide; dimethylsulfoxide; ketones, such as acetone, diethyl ketone and methyl ethyl ketone, and mixtures of these solvents with one another. In some cases, it may also be advantageous to carry out the reaction or part steps of a reaction under a protective gas atmosphere andfor in absolute solvents. Suitable protective gases are inert gases, such as nitrogen, helium, argon or, in certain cases, also carbon dioxide.
The oxiranes of the formula 11 are novel and are intermediates which have been developed particularlyfor the preparation of the useful active substances of the formula 1. Moreover, some of the compounds of the formula 11 have a fungicidal activity towards harmful fungi from the families of Ascomycetes, Basidiomy- 10 cetes or Fungi imperfecti.
The Examples which follow serve to illustratethe invention in more detail without restricting it. Temperatures are in degrees centigrade. Percentages and parts are by weight. In addition, the following symbols are used: h = hour; d = day; min. = minute; RT = room temperature; N = normality; abs = absolute, anhydrous;DMSO = dimethyisuifoxide; and DMF -dimethylformamide. Pressures are given in 15 millibar mb or bar b.
Example 1 a) Preparation of the intermediate:
cl Cl-i- -CHF-C2H5 0 1-(2,4-Dichlorophenyl)-2-fluorobutanone 31g of dry potassium fluoride were addedto a mixture of 77g of 1-(2,4dichlorophenyi)-2-bromobuta none and 50Orng of 18-crown-6 in 750mI of absolute acetonitrile and the mixturewas slowly heated to 100'Cto 1 10'C, while stirring. After about 48 hours, the reaction had ended (checked by gas chromatography or by 30 NMR). The reaction solution was then poured onto 2 litres of ice-water and extracted several times with diethyl ether. The combined extracts were washed with water, dried over sodium sulfate and evaporated.
Yield: 57g of the oily product. (H-F coupling constant 50Hz) Boiling point: 77-78'10.008 mbar.
b) Preparation of the oxirane compound of the invention:
)Cl cl -.F \7-----CHF-C2He; 0 CH2 2-(2,4-Dichlorophenyl)-2-(1-fluoropropyl)-oxirane 8g of 80% sodium hydride were suspended in 300mi of absolute DMSO. 689 of trimethyloxosulfonium iodide were introduced into this suspension in portions under a nitrogen atmosphere, while stirring. When the evolution of hydrogen had ended and the exothermic reaction had subsided, the mixture was stirred at RTfor a further 2 hours. A solution of 57g of 1-(2,4-dichlorophenyi)-2fluorobuta none in 100mi of tetrahydrofuran was then added dropwise in the course of 30 minutes, and then the resulting mixture was stirred for 3 hours and then diluted to five times its volume with ive-water and extracted several times with diethyl ether. The combined extracts were washed with water, dried over sodium sulfate and freed from the solvent in vacuo. Yield: 55g in the form of brown oil.
c) Preparation of a compound of formula 1.
A mixture of 559 of 2-(2,4-dichlorophenyl)-2-(1-fluoropropyi)-oxirane, 30g of 1,2,4-triazole and 3.5 g of potassium tertAutylate in 50OmI of DMF was stirred at 80'C for 20 hours. The reaction solution was then cooled to RT, poured onto 2 litres of ice-water and extracted several times with diethyl ether. The combined extracts were washed with water, dried over sodium sulfate and concentrated. Yield of 1-0 H-1,2,4-triazol-lyl)-2-(2,4-dichlorophenyi)-3- fluoropentan-2-ol: 269 in the form of colourless crystals. Melting point: 204-2060C.
Example2 a) Preparation of the intermediate:
cl F C1C 1 L-Lti 11 1 0 Br 65 3 GB 2 166 729 A 3 1-(2,4-Dichlorophenyl)-2-bromo-2-fluoroethanone A solution of 169 of bromine in 100m I of carbon tetrachloride was added to a solution of 20.7g of -fluoro-2,4-dichloroacetophenone in 100m I of carbon tetrachloride at 400 to 450C. After about 1 hour, the brown solution had decolourised. Stirring was continued for another hour and the mixture was then extracted by shaking with aqueous sodium bicarbonate solution and evaporated in vacuo. The oily residue was then distilled under a high vacuum. Yield: 17g. Boiling point: 89-92'C/0.02 mbar.
b) Preparation of another intermediate:
cl Cl -CHF-0j/ \\---Cl - 11 \---i 0 1-(2,4-Dichlorophenyl)-2-(4-chlorophenoxy)-2-fluoroethanone 12.8g of chlorophenol and 13.8 g of potassium carbonate were stirred in 200mi of acetone for 1 hour. 28g 15 of 1-(2,4-dichlorophenyi)-2-bromo-2-fluoroethanone in 50mI of acetone were added dropwise to this suspension and the mixture was refluxed for 3 hours. After cooling to RT, the colourless salt precipitate was filtered off, the acetone was removed in vacuo and diethyl ether was added. The ether solution was washed with water, dried over sodium sulfate and filtered and the filtrate was concentrated. The oily crude product crystallises after digestion with n-hexane. Yield: 21.5g in the form of yellowish crystals. Melting point: 85-87'C. c) Preparation of an oxirane compound of the invention:
Cl-f 25 CH2 2-(2,4-Dichlorophenyl)-2-(4-chlorophenoxyfluoromethyl)-oxirane lg of 80% sodium hydride was stirred in 80mi of DIVISO under a nitrogen atmosphere and 10.3g of trimethyloxosulfonium iodide were added in portions. After the exothermic reaction had subsided, the mixture was stirred at RT for a further hour, a solution of 2-(2,4-dichlorophenyi)-2(4-chlorophenoxy)-2- fluoroethanone in 30mi of tetrahydrofuran was then added dropwise and the resulting mixture was stirred at 35 2Wto WC for a further 5 hours and then poured onto 1 litre of water. The product was extracted with diethyl ether, the extracts were washed with water, dried over sodium sulfate and filtered and the filtrate was concentrated. Yield: 159 as a yellowish oil. d) Preparation of a compound of formula 1: 40 A solution of 13g of 2-(2,4-dichlorophenyi)-2-(4chlorophenoxyfluoromethyi)-oxirane, 4g of 1,2,4-triazole 40 and 0.5 of potassium tert.-butylate in 100mi of DIVIF was stirred at 80'to 1OWC for 15 hours. After cooling to RT, the reaction solution was poured into 500m] of water, whereupon the crude product separated out as an oil. The mixture was extracted with diethyl ether, the combined extracts were washed with water, dried over sodium sulfate and filtered and the filtrate was concentrated. Yield: 11 g of an oily crude product, which crystallised on digestion with n-hexane. Yield of the purified product: 7g.
Melting point: 155-157'C.

Claims (1)

1. A compound having the formula It:
0 Ar-C-CH2 1 R2-U-K3 1 I- 11 55 wherein Ar is an unsubstituted or substituted aromatic radical from the series comprising phenyl, biphenyl, 60 phenoxyphenyl and naphthyl; R2 is hydrogen, fluorine or Cl-C6 alkyl; and R3 is hydrogen, fluorine, Cl-C6-alkyl, Cl-C6-haloalkyl, Cl-C6-alkoxy, Cl-C6-alkylthio, phenyl, phenoxy, phenylthio or C3-C7-CYCloalkyl; and each aromatic substituent or aromatic moiety of a substituent is unsubstituted or mono or poly-substituted, by halogen, Cl-C4-alky], Cl-C4-halokyl, nitro and/or cyano; with the proviso that R2 and R3 cannot each simultaneously be fluorine.
4 GB 2 166 729 A 4 2. 2-(2,4-Dichlorophenyi)-2-(1-fluoropropyi)-oxirane. 3. 2-(2,4- Dichlorophenyi)-2-(4-chlorophenoxyfluoromethyl)-oxirane. 4. Compound of formula 11 substantially as described with reference to Example ll(b) or2(c). 5. Process for producing an oxirane compound of formula 11 comprising reacting a ketone of formula Ill:
R2 1 AR-C-C-F 11 1 0 R, Ill wherein, Ar, R2 and R3 are as defined in claim 1, with dimethylsulfonium methylide or dimethyisuifonium methylide or dimethyloxosulfonium methylide.
6. Process according to claim 5 substantially as described with reference to Example 1 (b) or 2(c).
7. Compound of formula 11 when produced bya process claimed in claim 5 or6.
Printed in the UK for HMSO, D8818935, 3186, 7102. Published by The Patent Office, 25 Southampton Buildings, London, WC2A lAY, from which copies may be obtained.
GB08522010A 1982-12-14 1985-09-04 Fluorine containing oxirane compounds Expired GB2166729B (en)

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GB08522010A Expired GB2166729B (en) 1982-12-14 1985-09-04 Fluorine containing oxirane compounds

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