FI76329C - OXIRANDERIVAT OCH FOERFARANDE FOER DERAS FRAMSTAELLNING. - Google Patents

Description

76329

Oxirane derivatives and method for their preparation

Divided by application 811472 5

The invention relates to novel oxirane derivatives and to a process for their preparation. These oxirane derivatives have the formula (II) in which R is a tert-butyl radical or a phenyl radical which is optionally mono- or di-substituted by fluorine, chlorine and / or or methyl, Y is a group -OCH2- or -CH2-CH2-, Z is a fluorine, chlorine or bromine atom, a methyl tert-butyl, methoxy, methylthio or trifluoromethoxy radical or a phenyl radical which is optionally mono- - or di-substituted by fluorine, chlorine and / or methyl, and m is 0, 1, 2 or 3.

The oxirane derivatives of formula (II) can be used as intermediates in the preparation of new 1-hydroxyethylazole derivatives of formula (I) useful as plant growth regulators and fungicides.

OH

Λ0 / - Y- c —R

7 X'- 'CH0 30 Zm I 2 (I)

I, XX

wherein R, Y, Z and m are as defined above and X is a nitrogen-3 atom or -CH group. The properties of the compounds of formula (I) and their preparation from oxirane derivatives of formula (II) are described in more detail in patent application 811472.

The invention also relates to a process for the preparation of oxirane derivatives of formula (II). They are obtained by reacting ketones of formula (IV), wherein R, Y, Z and m are as defined above, reacting either (15) dimethyloxosulfonium methylide of formula (V), (CH n) With S 0 CH 2 (V) ol in the presence of a diluent, or 20 R 2) trimethylsulfonium methyl sulfate of formula (VI), (+) (-) (CHq). (VI)

25 o O —Λ OH

in the presence of an inert organic solvent and a base.

The ketones of the formula (IV) required as starting materials for the preparation of the oxiranes of the formula (II) are known (cf. DE-PS 2201063, DE-OS 2705678, DE-OS 2737489, Tetrahedron 31 (1975) 3, Chemical Abstracts 84.73906η), or they can in principle be prepared by known methods.

The dimethyloxosulfonylmethylide of formula (V) required in Preparation (oC) is also known 3 7 6 3 2 9 (cf. J. Amer. Chem. Soc. 87 (1965) 1363-1364). It is used in the above reaction freshly prepared; reacting trimethyloxosulfonium iodide with sodium hydride or sodium amide in the presence of a diluent.

The trimethylsulfonium methyl sulfate of formula (VI) required in Preparation (I) is also known (cf. Heterocycles 8 (1977) 397).

It is also used in the above-mentioned reaction by the reaction of freshly prepared n-methylsulfine with dimethyl sulfate.

In the preparation of oxiranes of the formula (II) («A), e.g. dimethyl sulfoxide can be used as diluent.

The reaction temperatures can vary over a fairly wide range in the above-mentioned damping option.

For Y1, temperatures of 20-8 ° C are used.

The preparation of the oxiranes of formula (II) by method (X), as well as the isolation of the synthesis product from the obtained reaction mixtures, are carried out by conventional methods (J. / Amer. Chem. Soc., 37 (1965) 1363-13 64). .

In the preparation of oxiranes of formula (II) by the method {β), e.g. acetonitrile can be used as the inert organic solvent.

In the preparation alternative), strong inorganic and organic bases can be used as the base. For example, sodium methylate can be used.

In the above-mentioned ready -30 option (/ 3), the reaction temperatures may vary within certain limits. In general, temperatures of 0 to 60 ° C, preferably room temperature, are used.

The preparation of the oxiranes of formula (II) by the method {β), as well as the isolation of the synthesis products 85 are carried out by conventional methods (cf. Heterocycles 8 (1977) 397).

4 76329

The oxiranes of formula (IX) can be used directly, without isolation, in the preparation of the compounds of formula (I).

The following examples further illustrate the invention.

5 Example 1 ci-ToV 0-CH2 -cc (ch3) 3 (II-1) \ r / / \ o - ch2 ISO in 1 (2.0 mol) dimethyl 11 and acetonitrile (abs. 1200 ml) is dissolved and stirred at room temperature in abs. dimethyl sulfide (162 mL, 2.2 mol) dissolved in acetonitrile (400 mL). The reaction mixture is stirred at room temperature overnight. 113.8 g (2.2 mol) of sodium methylate are then added. After stirring for 30 minutes, 272 g (1.2 mol) of 1- (4-chlorophenoxy) -3,3-dimethylbutan-2-one are added dropwise over 30 minutes. dissolved in acetonitrile (600 ml). The reaction mixture is stirred overnight. The mixture is then evaporated, the residue is extracted with a mixture of water and ethyl acetate, the organic phase is collected, washed twice with water and once with saturated sodium chloride solution, dried over sodium sulfate, evaporated and the residue is distilled under reduced pressure. 242.4 g (34 g of theory) of 2- (4-chlorophenoxymethyl) -2-tert-butyloxirane are thus obtained, b.p. 115-22 ° C / 0.03 mmHg and m.p. 50-52 ° C.

According to Example 1, the compounds of formula (II) shown in the following table are obtained.

30 5 7632 9

Table (py Y-c-r 7 ^ - / / \ (II) m 0 - CH2

Eg Z Y R Boiling point (° C) / no. ra mm Hg II- 2 2,4-Cl2 -O-CH2- -C (CH3) 3 125-27 / 0.3 II- 3 4-CH3 -O-CH2- "85 / 0.07 II- 4 2 -CH3 -O-CH2- "89 / 0.07 II- 5 4-C1,2-CH3 -O-CH2-" 114-17 / 0.33 II- 6 4-C1 -CH2-CH2- "99- 103 / 0.005 II-7 2,4-cy, -CH2-CH2- "79 / 0.004 II-8 4-F -CH2-CH2-" 79-89 / 0.003 II-9 4-CH3 -CH2-CH2- 74-78 / 0.003 11-10 2-CH 2 -ch 2 -ch 2 - "95 / 0.005

Claims (2)

1. Oxirane derivatives of formula (II) 5 / ζΓ \ -Y-C-R. V 1111 m 1 where R is a tert-butyl radical or a phenyl radical optionally nt <> u> - or disubstituted by fluorine, chlorine and / or methyl, Y is the group -OCH2 ~ or -CH2-CH2 ~, Z is a fluorine, chlorine or bromine atom, a methyl, tert-butyl, methoxy, methylthio or trifluoromethoxy radical or a phenyl radical optionally mono- or disubstituted with fluorine, chlorine and / or methyl, and m is 0, 1, 2 or 3. A process for the preparation of oxirane derivatives of formula (II) wherein R is a tert-butyl radical or a phenyl radical optionally mono- or disubstituted with fluorine, chlorine and / or or methyl, Y is the group -OCH 2 - or -CH 2 -CH 2 -, Z is a fluorine, chlorine or bromine atom, a methyl, tert-butyl, methoxy, methylthio or trifluoromethoxy radical or a phenyl radical as optionally is mono- or di-substituted with fluorine, chlorine and / or methyl, and m is 0, 1, 2 or 3, characterized in that ketones of formula (IV) (O) -YCR (IV) 35. cm