CA1305156C - Preparation of phenoxyalkanoltriazole compounds and intermediates therefor - Google Patents

Preparation of phenoxyalkanoltriazole compounds and intermediates therefor

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CA1305156C
CA1305156C CA000531048A CA531048A CA1305156C CA 1305156 C CA1305156 C CA 1305156C CA 000531048 A CA000531048 A CA 000531048A CA 531048 A CA531048 A CA 531048A CA 1305156 C CA1305156 C CA 1305156C
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substantially pure
formula
alkene
compounds
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Guenter Schulz
Walter Trautmann
Hubert Sauter
Wolfgang Mackenroth
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BASF SE
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Steroid Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

ABSTRACT OF THE DISCLOSURE:

Compounds of the formula where: X is hydrogen, fluorine, chlorine, bromine, C1-C3-alkyl, C1-C3-alkoxy, trifluoromethyl, phenyl or phenoxy; m is 1, 2 or 3, the individual atoms or groups being identical or different when m is greater than 1; and n is 2, 3, 4, 5 or 6, in the form of their substantially pure diastereomers, are prepared by reacting alkene oxides of the formula

Description

5~
O.Z. l~050/383~3 Preparation of phenoxyalkanoltriazc,le compounds and intermediat~s therefor The present invention relates to a process for preparing phenoxyzlkanoltriazole compounds in the form of S their substantially pure diastereomers~ to intermediates therefor and to processes for Preparing the intermediates in the form of their substantially pure isomers.
It is known to use phenoxyalkanoltriazole compounds, for example 8-(Z-fluorophenoxy)-4-~1,2,4-triazol-1-yl)-3-hydroxy-2,2-dimethyloctane, as fungicides (EP 40 350).
These compounds, having two chiral centers in the mole-cule, exist in the form of optical isomers and as di-astereomers. The fungicidal action of the diastereomeric pairs of enantiomers is not always the same, so that there is interest in preparing the more active diastereomer.
It is known that this can be done by selective reduction of the corresponding triazolyl ketones (DE 33 21 023~3).
However, the chemical yields and the isomeric purity of the diastereomers obtained in the reduction is not al~Jays satisfactory.
We have found a process for preparing a compound of the formula I
OH
~CH~ -o ~N
where X is hydrogen~ fluorine, chlorine, bromine, C1-C3-alkyl, C1-C3-alkoxy, trifluoromethyl, phenyl or phenoxy, m is 1, 2 or 3, the individual atoms or groups being identical or different when m is greater than 1, and n is 2, 3, 4, 5 or 6, in the form of its substantially pure diastereomers by reacting an alkene oxide of the formula II

--C--C--C--I CH2 ) --~

:L3~ s~
- 2 - o.Z~ Q050/38303 where X, n and m have the abovementioned meanings, in the form of its substan~ially Pure E- or Z-isomer with tri-a~ole in the presence of an acid amide and of an alkaline compound at 130 - 230C.
S A substantially pure diastereomer contains 95 (by weight) or more of the diastereomer, based on the total diastereomer content.
C1-C3-alkyl is for example methyl, ethyl, propyl or isopropyl. C1-C3-alkoxy is for example methoxy, ethoxy, propoxy ar isopropoxy. The reaction is carried out in the presence of an alkali metal hydroxide, or of an alkaline earth metal hydroxide or of a comparable alkali compound, for example sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, in an acid amide, in particular N-methylpyrrolidone or cdimethylformamide as a diluent, and at from 130 to Z30C. This reaction surpris--ingly preserves the spatial orientation of the various substituents on the chiral centers. The spatial structure of the end product is thus the same as that of the alkene oxide used for the reaction. In this way it is possible to obtain end products of defined spatial structure in a simple reaction. With a high yield based on the chemical conversion, a diastereomer which is not less than 95% pure relative to the isomer content is obtained without problems.
The alkene oxide required for the reaction is ob-tained by oxidizing an alkene of the formula III

+ C~=CH-(CH21 ~0 m where X, n and m have the abovementioned meanings, in the form of its substantially pure E- or Z-isomer with an 3û organic peracid in the presence of an organic liquid at from -10 to ~30C. An organic peracid is for example m-chloroperbenzoic acid or peracetic acid. This oxidation is carried out for example in a chlorinated hydrocarbon, ~3~
- 3 - O.Z. 0050/38303 in particular in methylene chloride if the oxidizing agent is m-chloroperbenzoic acid, or in a protic solvent, in particular in aqueous acetic acid in the case of peracetic acid as the oxidizing agent. If the oxidation is carried S out with peracetic acid, this oxidizing agent can be formed in situ from ~22 ancl acetic acid. The oxidation is car-ried out at from -10 to -i30C, in particular at from ~15 to ~2SC~
The two process steps of oxiclation and reaction with triazole give very high chemical yields with selec-tivities, based on the isomers, of in each ~ase not less than 95%. In this way the E-alkene of the formula III is smoothly converted to the pair of RS/SR enantiomers of the formula I and the Z-alkene of the formula III to the pair of RRtSS-enantiomers of the formula I.
The problem of the diastereoselective synthesis of I has consequently been reduced to the synthesis of a stereochemically uniform ~- or Z-alkene of the formula III.
The alkene of the formula III

+ CH--CH--~CH2~

where X is hydrogen, fluorine, chlorine, bromine, C1-C3-alkyl, C1-C3-alkoxy, trifluoromethyl, phenyl or phenoxy, m is 1, 2 or 3, the individual atoms or groups being identical or different when m is greater than 1, and n is Z, 3, 4, 5 or 6, is obtained in the form of its substantially pure E-iso-mer by heating a compound of the formula IV
OR
f CH-CH2-~cH2) ~~
m ~3~
- 4 - o.Z. 0050/3~303 where X is hydrogen, fluorine, chlorine, bromine, C1-C3-alkyl, C1-C3-alkoxy, trifluoromethyl, phenyl or phenoxy, m is 1, 2 or 3, the individual atoms or groups being S identical or different when m is greater than 1, and n is Z, 3, 4, 5 or 6, and R is -COCH3 or -CSSCH3, to 200 - 400C or 100 - 300C.
In the case of the acetate, the substance is heated as such or in a high-boiling inert diluent to 200 - 400C.
If the reaction is carried out in substance, the range from 250 to 350C is preferred. In the case of the xanthogenate, it is sufficient to heat the compound to 100 - 300C, either in the presence or absence of a high-boiling diluent. If the reaction is carried out in sub-stance, ie. in the absence of a high-boiling diluent, the preferred temperature range extends from 150 to 250C.
The resulting alkene of the formula III is distilled under atmospheric pressure or reduced pressure. The chemical yielcl is between 90 and 100X; the selectivity based on isomer is not less than 95%. The preparation of the acetate or xanthogenate can be effected in a conven-tional manner from the alcohols described in DE 34 00 829.
Another way of preparing the alkene of the formula 2S III in the form of its substantially pure E-isomer com-prises treating an alkene of the formula III which is pre-sent in the form of its Z-isomer with short-~ave light in the presence of diphenyl disulfide and of a hydrocarbon.
A hydrocarbon is for example an alkane or cycloaLkane of 5 to 8 carbon atoms, for examPle pentane, hexane, cyclo-hexane, heptane or octane. Short-wave light is for example light which has the spectral distribution of a mercury vapor high pressure lamp. The treatment can be effected at customary temperatures, for example room temperature 35 (20C), or at any other temperature.
The alkene of the formuLa III in the form of its substantially pure Z-isomer is obtained by reacting ~3~S~
- 5 - O.Z. 0050/33303 pivalaldehyde of the formula (CH3)3C-CHO ~ith a compound of the formula V

(C~H5)3P--CH--lCH2) --X
m where X is hydrogen, fluorine, chlorine, bromine, C1-C3-alkyl, C1-C3-alkoxy, trifluoromethyl, phenyl or phenoxy, m is 1, Z or 3, the individual atoms or groups being identical or different when m is greater than l, and n is 2, 3, 4, 5 or 6.
The reaction is carried out under salt-free con-ditions, ie. in polar aprotic solvents in the absence of dissolved metal cations (cf. HØ House, Modern Synthetic Reactions, 2nd ed. 1972, pp. 7û7).
Suitable solvents for this reaction are linear or cyclic ethers, in particular tetrahydrofuran. The reaction takes place at 20 - 100C, in particular if tetrahydro-furan is used as solvent at 50 - 60C (reflux temperature).
Removal of triphenylphosphine oxide after the reaction has ; ended gives the ~-alkene of the formula III in a high chemical yield with a seleçtivity of not less than 90% in respect of the Z-isomer. The intermediates required for preparing the phosphorus compound are known (EP 40 350).
EXAMPLES
The example of preparing 8-(2-fLuorophenoxy)-4-(1,2,4-triazol-1-yl)hydroxy-2,2-dimethyloctane as a pair of 3R,4S/3S,4R-enantiomers is used to ilLustrate the in-dividual pracess steps. The process described in the examples can be used to synthesize the compounds listed in the tables.
Preparation of acetate acetic anhydride ¦ ¦
-f-C ~o~ ~ - I -c ~o~3 ~ F F

~3~5~
- 6 - O.Z. 00~0,'3830i 58 9 t~.23 mol) of the octanol derivative are refluxed for 2 h in 200 ml of acetic anhydride in the presence of 1 ml of concentrated hydrochloric acid. Distillation gives the acetate after an acetic acid/acetic anhydride cut. 30iling point/0.05 mm Hg: 135C (65 g) H-NMR (CDCl3): 0.9 s 9H, 1.25-1.65 m 6 H, 1.8 m 2 H, 7.05 s 3H, 4.0 t 2 H, 4.75 dd lH, 6.8 - 7.1 m 4H.

CH2--(CH21--o~ 3 m 10 No. Xm n Physical data IV/1 2-F 4 Boiling point 135C/0.05 mm Hg IV/2 2-Cl 4 15 IV/4 4-f 4 IV/7 2,4-Cl2 4 IV/8 2,4,6-Cl3 4 Preparation of xanthogenate OH 1. NaH O--C--S--CH3 -c-c ~ o~3 2. CS2 C-l ~O~>
3 . C H 3 I F

To 53 9 (0.23 mol) of the octanol derivative in a solution in toluene is added in total 1 equivalent of sodium hydride a little at a time. To obtain complete alcoholate formation, the mixture is refluxed for 3 h. The tempera-ture is then reduced to 20C, and CS~ is added dropwise in ~3(~5f~
- 7 - O.Z. 0050/333~3 the form of a solution in 100 ml of diethyl ether. About 1 h after the CS2 has been added, about 1.5 equivalents of methyl iodide are added dropwise, and the mi~ture is refluxed for 2 h. Filtration and evaporation af all the readily volatile constituents under reduced pressure leaves 77 9 of the ~anthogenate as an almost colorless oil.
H-NMR (CDCl3): 0.95 s 9H, 1.3-1.9 m 8H, 2 55 s 3H, 4.3 t 2H, 5.72 dd 1H, 6.8-7.3 m 4H.
IR (coating): 2951, 15û7, 1456, 1Z81, 1223, 1206, 1110, 1051 cm 1.

TA~LE 2 S

--I--C ~I CH2 ) --~
X
m No. X~ n Physical data IV/ 9 2-F 4 NMR/IR see example 15 IU/10 2-Cl 4 IV/13 4-Cl 4 20 IV/15 2,4-Cl2 4 IV/16 2,4,6-Cl3 4 Preparation of alkene from acetate --c--c ~,o~ -- --c--c~o~3 IIIa/l 81 g (0.26 mol) of acetate IV/1 are heated to 350C
in a metal bàth,with f;rst acetic acid and then alkane IIIa/1 distilling off through an attached column. 64 9 are obtained ~3~ 1S6 - 8 - O.Z. ~050/38303 of the alkene of boiling point 295C/760 mm Hg. rhe E-configuration of the double bond can be unmistakably identified through the POsition of carbons 3 and 4 in 13C_NMR (in CDCl3) S C-3 142.1 ppm C-4 124.2 ppm Preparation of alkene from xanthogenate _l_1 ~o~ ~ -I~ ~0~
F H F
IIIi~11 20 9 of xanthogenate IV/9 (0.057 mol) are heated to - 10 about 200C in a slow stream of N2. In the course of 2 h, 10.3 9 of alkene IIIa/1 are driven by the stream of N2 into the receiver. The configuration of the double bond is un-mistakably shown in 13C-NMR as being E:
C-3 142.1 ppm C-4 124.2 ppm Preparation of alkene IIIa/1 by isomerization I short-wave -C-- ~ ~0~ ~ C--C~ ~
H f F diphenyl H F
disulfide II~b/1 IIIa/1 33 9 (0.132 mol) of Z-8-(2-fluorophenoxy)-2,2-dim-ethyloct-3-ene IIIb/1 are dissolved in 4ûO ml of cyclohex-ane. 2.83 9 (0.013 mol) of diphenyl disulfide are added, andthe solution is flushed with nitrogen for 30 min. The solu-tion is subsequently irradiated with a mercury high pres-sure lamp (125 W Philips HPK) through a Duran filter at an internal temperature of 35C. After 3 h of exposure to irradiation, the conversion is 95~. The reaction solution is filtered, and the filtrate is distilled through a col-umn. 25.8 9 of E-8-(2-fluorophenoxy)-2,2-dimethyloct-3-ene IIIa/1 having a boiling point of û.2 mbar/90C

~3Q~516 - 9 - O.Z. 0~53/383~3 are obtained.

rAaLE 3a _I-C ~ ~CH2~ - ~ E-configuration H X
m No. X~ n Physical data . _ _ : 5 IIIa/1 2-f 4 aoiling point 295Ci760 mm ~9 IIIa/2 2-Cl 4 IIIa/3 2-CH3 4 IIIa/4 4-F 4 IIla/5 4-Cl 4 10 IIIa/6 4-CH3 4 IIIa/7 2,4-Cl2 4 IIIa/8 2,4,6-Cl3 4 Preparation of alkene IIIb/1 ~ e I ~ -C- ~~~
( C 6 H5 ~ 3 P--CH I CH~ ~ 4--o~ c--c , ~c F
F H H
I I I b / 1 261.5 9 (0.5 mol) of tr;phenyl-~5-(3-fluorophenoxy)-pentyl]-phosphonium bromide are prepared from equimolar amoun~s of triphenylphosphine and 5-(2-fluorophenoxy)bromo-pentane at 130 - 140C. After cooling down, the solidified melt is comminuted and suspended in 1,000 ml of tetrahydro-furan. 370 ml (O.SS mol) of a 1.5-molar butyl lithium solution in n hexane are added dropwise with cooling. The internal temperature is maintained at 20 - 30C while the mixture is subsequently stirred for 1 h. To the resulting brown solution is then added dropwise, in the course of about 30 min~ a solution of 43 9 (O.S mol) of pivalaldehyde - 10 - O.Z. ~~05~/333~3 in 150 ml of tetrahydrofuran. rhis is followed by stirring at 20C for 20 h and refluxing at 60C for Z4 h until a white, granular precipitate is formed.
The mixture is hydrolyzed with 2 l of water, the organic phase is separated off, and the aqueous ~hase is extracted a further three times with diethyl ether. The combined organic phases are washed t~ice with water, dried over Na2S04 and evaporated. To the residue are added 250 ml of ether to precipitate triphenylphosphine oxide.
After filtration with suction the filtrate is distilled to give 33~5 9 of Z-8-(2-fluorophenoxy)-2,2-dimethyloct-3-ene IIIb/1 as a colorless liquid having a boil ing point of 127C/2 mbar.

TA8L8 3b -C~ (CH2) -0 ~ Z-configuration H H X
III b No. Xm n Physical data . ~
IIIbl1 2-F 4 80iling point 127C/2 mbar IIIb/Z 2-Cl 4 I I Ib/3 2-CH3 4 20 I I Ib/4 4-F 4 IIIb/S 4-Cl 4 IIIb/6 4-CH3 4 IIIbl7 2,4-Cl2 4 IIIb/8 2,4,6-Cl3 4 Preparation of alkene oxicle H F I \C/ \ ~ C ) ~3 IIIa/t IVa/l ~3~5~
- 11 - O.Z. 0050/38303 50 9 (0.2 mol) of E-8-(2-fluoropheno~y)-2,Z-dimethyloct-3-ene lIIa/1 are dissolved in 300 ~l of methylene chloride.
While stirring, a solution of 39.7 g (O.Z3 mol) cf 3-chloro-perbenzoic acid in 550 ml of methylene chloride is added S drop~ise in the course of 20 min and the temperature is maintained at 20C by cooling. Gradually a white pre-cipitate (3-chloroben~oic acid~ is formed. Stirring is continued at Z0C for 2 days. Thereafter all the start^
ing material has been converted (analysis by gas chroma-tography). As workup, this is follo~ed by stirring ~Jith1,000 ml of 10% strength aqueous sodium sulfite solution until peroxide is no longer detectable. The mixture is brought to pH 7 with sodium hydroxide solution, the methylene chloride phase is separated off, and the aqueous phase is extracted once more with methylene chloride~ The combined organic phases are washed twice with sod;um car-bonate solution and twice with distilled water, dried over sodium sulfate and evaporated at 40C in a rotary eva-porator under reduced pressure to give 55.6 9 of a crude product containing (gas chromatography) 90% of 2-~4-(2-fluorophenoxy)butyl]-3-tert.butyloxirane IIa/1. According to H-NMR, the ratio of E~ compound is 99:1.
H-NMR (CDCl3~: 0.9 s 9H, 1.5-1~7 m 4H, 1.8-1.9 ~ 2H, 2.49 m 1H, 2.82 m 1H, 4.05 t 2Hr 6.8-7.1 m 4H.
TAEILE 4a I ,O~ ,H
f I tCH2) - ~ E-configuration ~v a ' 5~5g~
12 O.Z. 0~5~ 333.3 No. Xm n Physical data IIa/1 2-F 4 1H NMR see example IIa/2 2-Cl 4 IIa/3 Z-CH3 4 5 Ila/4 4-F 4 IIa/S 4-Cl 4 IIa/6 4-CH3 4 lIa/7 2,4-Cl2 4 IIa/8 2,4,6-Cl3 4 TALLE 4b H H
(CH2~ - ~ Z-configuration IVb m No. Xm n Phys ical data IIb/1 2-F 4 IIbf2 2-Cl 4 15 IIb/3 3-CH3 4 lIb/4 4-F 4 ; IIb/S 4-Cl 4 Ilb/6 4-CH3 4 IIb/7 Z,4-Cl2 4 ZO IIb/8 2,4,6-Cl3 4 Preparation ûf triazole co~pound H o H OH
-I-C -~IC-(cH2)4-O ~ N~N Na_~ -C-C ~ ~CH2)4 - ~
H F N~N~ F

pair of Ia/1 3R/4S-3S/4R-enantiomers ~ 3C~5~
- 13 - O.Z. OOS0/38303 9.5 9 (0.036 mol) of E-2-(2-fluorophenoxybutyl)-3-t-outyl-oxiran IIa/1 tabout 90% strength according to gas chroma-tography), S0 ml of N-methylpyrrolidone, 1.5 9 (0.036 mol) of sodiu~ hydroxide and 2.5 9 (0.036 mol) of 1,2,4-triazole are added together and stirred at 180C. The reaction is monitored by gas chromatography. After 4 h the conversion is greater than 98~. N-methylpyrrolidone is distilled off in a high vacuum, and the residue is dissolved after cooling down in water/methylene chloride. The aqueous phase is extracted once more ~ith methylene chloride The combined methy~ene chloricle phases are washed with water until acid-free, and dried over sodium sulfate and con-centrated. The remaining brown oil (10.9 9) is dissolved in 150 ml of cyclohexane by heating, and the solution is stirred with 0.5 9 of active carbon for 30 min and filtered off hot. The filtrate gives, on evaporation, 8.6 9 of 8-(2-fluorophenoxy)-4-(1,2,4-triazol-1-yl)-3-hydroxy-2,2-dimethyloctane as a colorless oil which crystallizes on standing. The diastereomeric ratio according to NMR is 0 (RR+SS):~RS+SR) = 1:99. Melting point: 87C.
TAPLE 6a I 1~
--f--C~( CH2 ~ --o~3 N~N~ x l m pair of 3R,4S/3S,4R-enantiomers No. Xm n Physical data 2S la/1 2-F 4 see examPle Ia/2 2-Cl 4 Ia/3 2-CH3 4 Ia/4 4-F 4 Ia/5 4-Cl 4 30 la/6 4-CH3 4 Ia/7 2,4-Clz 4 Ia~8 2,4,6-Cl3 4 ~l3~5~Z~5~
- 14 - O.Z. OOSO/38303 TA8LE 6b OH
c l~ CH2 ) ~0~) N~N~ X
~N m pa i r of 3R,4R/3S,45-endnt iorners No. Xm n Physical data 5 Ib/ 1 2-F
Ib/2 2-Cl 4 Ib/3 2-CH3 4 Ib/4 4-F 4 Ib/5 4-Cl 4 10 Ib/6 4-CH3 4 Ib/7 2,4-Cl2 4 Ib/8 2,4,6-Cl3 4 .

Claims (2)

1. A process for preparing a compound of the formula I

where X is hydrogen, fluorine, chlorine, bromine, C1-C3-alkyl, C1diastereomers,-C3-alkoxy, trifluoromethyl, phenyl or phenoxy, m is 1, 2 or 3, the individual atoms or groups being identical or different when m is greater than 1, and n is 2, 3, 4, 5 or 6, in the form of its substantially pure diastereomers, which comprises reacting an alkene oxide of the formula where X n and m have the abovementioned meanings, in the form of its substantially pure E- or Z-isomer with triazole in the presence of an acid amide and of an alkaline compound at 130 - 230°C.
2. A process for preparing 8-(2-fluorophenoxy)-4-(1,2,4-triazol-1-yl) hydroxy-2,2-dimethyloctane in the form of a pair of 3R,4S/3S,4R-enantiomers, which comprises reacting in the form of its substantially pure E- or Z-isomer, with triazole in the presence of an acid amide and an alkaline compound at 130 - 230°C.
CA000531048A 1986-03-04 1987-03-03 Preparation of phenoxyalkanoltriazole compounds and intermediates therefor Expired - Lifetime CA1305156C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863606947 DE3606947A1 (en) 1986-03-04 1986-03-04 METHOD FOR PRODUCING PHENOXYALCANOLTRIAZOLE COMPOUNDS AND INTERMEDIATE PRODUCTS FOR THIS
DEP3606947.7 1986-03-04

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DE3642632A1 (en) * 1986-12-13 1988-06-23 Basf Ag METHOD FOR PRODUCING PHENOXY-SUBSTITUTED ESTERS AND INTERMEDIATE PRODUCTS HERE
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WO2010029065A1 (en) * 2008-09-10 2010-03-18 Basf Se Imidazole and triazole compounds, use thereof and agents containing said compounds
BRPI0918516A2 (en) * 2008-09-10 2015-08-04 Basf Se Compost, composition of active compound, seed, methods for controlling phytopathogenic fungi, and for preparing an antimycotic, and, medicament
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ES2019313B3 (en) 1991-06-16
DK108387D0 (en) 1987-03-03
CS141287A2 (en) 1989-05-12
ATE59384T1 (en) 1991-01-15
CS268171B2 (en) 1990-03-14
ZA871509B (en) 1988-11-30
EP0236884B1 (en) 1990-12-27
EP0236884A1 (en) 1987-09-16
PL149238B2 (en) 1990-01-31
DK108387A (en) 1987-09-05
GR3001514T3 (en) 1992-11-23
HU199434B (en) 1990-02-28
DE3606947A1 (en) 1987-09-10
IL81677A (en) 1992-02-16
JPS62212376A (en) 1987-09-18
IL81677A0 (en) 1987-09-16
DD254733A5 (en) 1988-03-09
HUT44021A (en) 1988-01-28
DE3766986D1 (en) 1991-02-07

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