CS241500B2 - New oxirans production method - Google Patents

Description

The present invention relates to a process for the preparation of the novel oxiranes of the following general formula II which are used as starting materials in the preparation of the novel 1-hydroxyethylazole derivatives of the general formula I

OH fV-Y-C-R

and m is 0, 1, 2 or -3, as well as their addition salts with hydrochloric acid and naphthalene-1,5-disulfonic acid.

The compounds of the formula I and their acid addition salts are used as active ingredients of plant growth regulating agents and fungicidal agents.

Oxirans of formula II

-m

Y-C-R

Z \ o — ch ₂ (m in which

R is tert-butyl, cyclopropyl or optionally substituted phenyl,

Y denotes -0CH ₂ -, -CH ₂ -, -CH ₂ - or -CH = CH-, (n

In which

R is tert-butyl, cyclopropyl or optionally substituted phenyl,

X is a-th nitrogen or —CH—,

Y is -OCH ₉ , -CH ₂ CH ₂ - or -CH = CH-,

Z represents a fluorine atom, a chlorine atom, a methyl group, a tert-butyl group, a methoxy group, a methylthio group, a trifluoro-fluorine-substituted trifluoride group; Uihlqru; a methyl group, a tert-butyl group, a methoxy group, a methylthio group, a trifluoromethoxy group, and / or an optionally substituted phenyl group and a methyl group; ;

m is 0, 1, 2 or 3 are new compounds.

According to the capsule of the invention, oxiranes of the formula II are produced by the formation of ketones of the formula IV

γ-C-R

O (IV) wherein

R, Y, Z and m are as defined above, with a compound of the formula wherein n is 0 or 1 in the presence of a solvent.

Preferably, the ketones of formula IV are reacted cey with dimethyloxosulfonium methylide of formula V

S ⁺ S ~ _{(CH) 2} SOC ₂ (V) in the presence of diluents and / or 3) trimethylsulfoniummethylsulfátem VI '·.' =! 'in.' . t, ·

oxosulfonium iodide with sodium hydride or sodium amide in the presence of a diluent.

. The trimethylsulfonium methylsulfate of the formula VI required for the production according to variant (3) is also a known substance [cf. Heterocycles 8, 397 (1977)]. In the above reaction, it is also used in the freshly prepared state by being prepared by reacting dimethylsulfide with dimethylsulfate in situ. · /;>

In a variant of the process for preparing the oxanes of the formula II, dimethylsulphoxide is preferably used as the diluent. '- /

The reaction temperatures can also be varied within a wide range in the process variant described above.

In general, temperatures between 20 ° C and 80 ° C are used.

The procedure for the preparation of oxiranes of the formula II according to variant 1) and the reaction mixture resulting from this synthesis are carried out according to the usual methods [cf.

J. Amer. Chem., Soc. 87, 1363-1364 (1965 ^ ;;

In the variant β] of the process for the preparation of the biphenyls ^{5 of the} formula II, acetonitrile is preferably used as the inert organic solvent

The bases used in the present invention may be strong antir-A or organic bases. Sodium nietboxide is preferably used. The reaction temperatures may vary within a certain range in the above-described process variant (3). In general, the reaction is carried out at temperatures between 0 ° C and 60 ° C, preferably at room temperature.

In carrying out the process for the preparation of oxiranes of the formula II according to variant β) and in working up the reaction product resulting from the synthesis, the process is M according to the procedure described in the invention. pbvyklýeh. me-, · / tod | cf. Heterocycles' 8, μ897 (1977)

For further use · jakp starting materials for the .. '· preparation of compounds of formula, I, _{J; The} SEI may oxiranes of formula II optionally without isolation, be directly in the next reaction.

The following examples illustrate the process of the invention, but do not limit the scope of the invention in any way. (VI) Example 1 in the presence of an inert organic solvent as well as in the presence of a base.

The ketones of formula IV which are used as starting materials in the preparation of oxiranes of the formula II are known [cf. German Patent Specification No. 2 201 063, DOS 2 705 678, DOS 2 737 489, Tetrahedron 31, 3 (1975) and Chemical Abstracts 84, 73 906 n], or can be prepared by methods known in principle.

The dimethyloxosulfonium methylide of formula (V), which is required as a starting material in the production according to variant (a), is also a known substance [cf. J. Amer. Cheim Soc. 87, 1363-1364 (1965)]. In the above reaction, it is processed in a freshly prepared state by being prepared in situ by the reaction of trimethylCl

CH * ³³

To a solution of 189 ml (20 mol) of dimethylsulphate in 1200 ml of absolute acetonitrile at room temperature was added a solution of 162 ml (2.2 mol) of dimethylsulfixd in 400 ml of absolute acetonitrile. The reaction mixture was allowed to stir overnight at room temperature. Then 118.8 g (2.2 mol) of sodium methoxide are added. The reaction mixture was allowed to stir for 30 minutes and then a solution of 272 g (1.2 mol) of 1- (4-chlorophenoxy) -3,3-dimethylbutan-2-one in 600 ml of absolute acetonitrile was added dropwise over 30 minutes. The reaction mixture was allowed to stir overnight. Then the reaction mixture is concentrated, the residue is partitioned between water and ethyl acetate, the organic phase is separated, washed twice with water and once with saturated sodium chloride solution, dried over sodium sulphate, concentrated and the residue is distilled under vacuum. 242.4 g (84% of theory) of 2- (4-chlorophenoxymethyl) -2-tert-butyloxirane, b.p. 115 DEG-122 DEG C./0.4 mbar and m.p. 50 DEG-52 DEG C., are obtained.

The following compounds of the general formula II shown in Table 1 are also obtained in an analogous manner to that described in Example 1:

y-C ~ R

Zrrx O-CH ₂ (Π)

Table 1

example number Z _m Y R boiling point (° C) / / pressure (Paj II— 2 2,4-Cl ₂ —O — ch ₂ - -C (CH ₃ ) ₃ 125–127 / 40 II— 3 4-CH 3, —O — ch ₂ - -C (CH ₃ ) ₃ 85 / 9.3 II— 4 _2-CH3 —O — ch ₂ - -C (CH ₃ ) ₃ 89 / 9.3 II— 5 4-C1, _2-CH3 —O — ch ₂ - -C (CH ₃ ) ₃ 114—117 / 40 II— 6 4-C1 —Ch ₂ —ch ₂ - ~ -C (CH ₃ ) ₃ 99—103 / 0.7 II— 7 2,4-Cl ₂ —CH ₂ —CH ·, - -C (CH ₃ ) ₃ 79 / 0.5 II— 8 4-F -CH ₂ -CH ₂ - -C (CH ₃ ) ₃ 79-89 / 0.4 II— 9 4-CH3 —Ch ₂ —ch ₂ - -C (CH ₃ ) ₃ 74—78 / 0.4 II — 10 _2-CH3 —Ch ₂ —ch ₂ - -C (CH ₃ ) ₃ 95 / 0.7 II — 11 4-C1 —CH = CH— -C (CH ₃ ) ₃ t.t 61-62.5 11—12 2,4-Cl ₂ —CH ^ CH— -C (CH ₃ ) ₃ product not insulated 11—13 _4-CH3 —CH = CH— -C (CH ₃ ) ₃ product not insulated 11—14 4-F —CH — CH— -C (CH ₃ ) ₃ 75 / 0.7 11—15 _2-CH3 —CH = CH— -C (CH ₃ ) ₃ 71—74 / 1,3 11—16 2,6-Cl ₂ —CH — CH— -C (CH ₃ ) ₃ product not insulated the subject of the invention

Y — C — R

Claims (3)

Y — C — R II O (IV) A process for the preparation of novel oxiranes of the general formula II wherein: R is tert-butyl, cyclopropyl or optionally substituted phenyl, Y denotes -OCH ₂ -, -CH ₂ -, -CH ₂ - or -CH = CH-, Z represents a fluorine atom, a chlorine atom, a methyl group, a tert-butyl group, a methoxy group, a methylthio group, a trifluoromethoxy group and / or an optionally substituted phenyl group and m is a number 0, 1, 2 or 3; IV in which R, Y, Z and _m are as defined above, with a compound of formula (CH ₃ ) ₂ S (O) _n CH ₂ in which n is 0 or 1, in the presence of a solvent. 2. Method of claim 1, wherein the TM that the ketones of general formula IV with dimethyloxosulfoniummethylidem δ'ό formula V _{'(CH3) 2} SOC ₂ (V) in the presence of a diluent. 3. Process according to claim 1, characterized in that the ketone of Formula IV with trimethylsulfoniummethylsulfátem VI _{[(CH3) 3]} CH 3, SO 4 in the presence of an inert organic duction and in the presence of a base. (VI)