GB2168053A

GB2168053A - Phenexy-phenyl oxirane compounds

Info

Publication number: GB2168053A
Application number: GB08530463A
Authority: GB
Inventors: Elmar Sturm; Walter Kunz
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1982-11-23
Filing date: 1985-12-11
Publication date: 1986-06-11
Also published as: EP0117378A1; PL141026B1; JPS59106467A; ZA838695B; DE3377986D1; CA1210404A; AU584000B2; PL244693A1; DK534083D0; IL70288A0; TR21666A; ES527438A0; ZA838696B; PH19709A; AU2158283A; IL70284A0; CA1215374A; SU1331427A3; AU570653B2; PT77700A

Abstract

Oxirane derivatives of the formula II <IMAGE> wherein R1 and R2 are each independently hydrogen, halogen, C1-C4alkyl or CF3, and Rn denotes one to three alkyl, alkoxy, haloalkoxy, haloalkyl, halogen and/or cyano groups, R4 is hydrogen, C1-C10alkyl, C3-C6cycloalkyl or unsubstituted or substituted phenyl; and A is the radical <IMAGE> wherein R6 and R7 are each independently C1-C12alkyl, unsubstituted or substituted phenyl, or both together form a C2-C4-alkylene bridge which is unsubstituted or substituted by one or more identical or different members selected from the group consisting of C1-C4alkyl, C2-C4alkenyloxymethyl or C1-C3alkoxymethyl, are useful for preparing microbicidal 1-phenoxyphenyl-2-azolylethanol compounds.

Description

1

GB 2 168 053 A 1

SPECIFICATION

Oxirane compounds

5 The present invention relates to novel oxirane compounds, their preparation and use. g

Accordingly, the invention relates to compounds of the general formula II

Yx*2 o

" x : n A

10 • - 0 -4- -H c—CH (II) 10

X / \ ' I

Rn.=. \/ A

R4

15 15

wherein

Rt and R2 are each independently hydrogen, halogen CrC4 alkyl or CF3, and Rn denotes one to three alkyl,

alkoxy, haloalkoxy, haloalkyl, halogen and/or cyano groups,

R4 is hydrogen, CrC10alkyl, C3-C6cycloalkyl or unsubstituted or substituted phenyl, and 20 A is the radical 20

I

-C-OR7

I /

25 0Re' 25

wherein

30 Reand R7 are each independently CrC12alkyl, unsubstituted or substituted phenyl, or both together form a 30 C2-C4alkylene bridge which is unsubstituted or substituted by one or more identical or different members selected from the group consisting of Ci-C4alkyl, C2-C4alkenyloxymethyl or Ci-C3alkoxymethyl.

Depending on the indicated number of carbon atoms, alkyl by itself or as moiety of another substituent comprises e.g. the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl 35 etc., and their isomers, e.g. isopropyl, isobutyl, tert-butyl, isopentyl etc. 35

Throughout this specification, halogen denotes fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. Alkenyl is is e.g. propen-l-yl, allyl, buten-1-yl, buten-2-yl or buten-3-yl. Depending on the number of carbon atoms, cycloalkyl denotes e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,

cycloheptyl, cyclooctyl etc. Possible substituents of unsubstituted or substituted phenyl, phenoxy or benzyl, 40 regardless of the position of the phenyl, phenoxy or benzyl in the molecule, are C-|-C4alkyl, C-|-C4alkoxy, 40

CrCahaloalkyl, halogen and/or cyano. Haloalkyl denotes here a mono-to perhalogenated alkyl substituent, e.g. CHCI2, CHF2, CH2CI, CCI3, CH2F, CH2CH2CI, CHBr2 and preferably CF3.

Where R6and R7 in the molecular fragment

45

-C-OR7

| 1

OR£'

45

50 50

together form a C2-C4alkylene bridge, said fragment, depending on the number of carbon atoms, is an unsubstituted or substituted 1,3-dioxolan, 1,3-dioxan or 1,3-dioxepane ring.

The oxirane compounds of the present invention are useful for preparing microbicidal 1-phenoxyphenyl-2-55 azolylethanol compounds as described and claimed in copending application No. 8330970 (Serial No. 55

2130584). On account of the pronounced microbicidal action of the corresponding 1-phenoxyphenyl-2-azolylethanol compounds, preferred compounds of the formula II in increasing order of preference, are those compounds which contain the following substituents or combinations thereof:

For Rt and R2, each independently of the other:

60 a) hydrogen, halogen, CrC3alkyl, CF3; 60

b)H,F,CI,Br,CH3,C2H5,CF3.

c) R1: H, 2-CI, 2-Br, 2-F, 2-CF3,3-F, 3-CI, 3-Br, 3-CF3,4-CI, 4-Br, 4-F, 4-CF3, 5-CI, 5-Br, 5-F, 5-CF3.

R2: H.

d) R-i: 2-H, 2-F, 2-CI, 2-Br, 2-CH3.

65 R2: H. 65

2

GB 2 168 053 A

2

For Rn:

a) Cn-C4alkyl, CrC4alkoxy, CrC4haloalkoxy, Ci-C3haloalkyl, halogen and/or cyano;

b) chlorine, dichloro, fluorine, bromine, methyl, difluoro, CF3, OCF3;

c) 4-chloro, 2,4-dichloro, 4-fluoro, 2,4-difluoro, 4-bromo, 4-methyl, 4-CF3,4-OCF3;

5 d) All meanings as under c), except that for the p-phenoxyphenyl group: 5

I I

For A: a) -C-0(CrC4alkyl), -C-0(CrC4alkyl),

I I

10 0(CrC4alkyl) Ofunsubstituted or substituted phenyl) 10

-c- -c- -c-

/\ /\ /\ 0 0 0 0 0 0

15 11 1 I II 15

1b •—• > *—alkyl, C^-C^alkyl-*—•-Cj-C^.alkyl,

-C- -C- -o

/\ A A

0 0 0 0 0 0

,n 1 I I I' II 20

• •—CH^OCH^ , • •-CH20CH2CH=CH2 , . • ,

-c- -C- -c-

/\ A A

oc 0 0 0 0 0 0 oc

25 I I II II 25

• • I • • • •

\/\ \/ ■ /\/\ '

• Cj-C^alkyl Cj-C^-alkyl • C^-alkyl

30 ^"^alkyl Cj-C^alkyl 3Q

-C- -C-

/\ . /\

0 0 0 0

1 i ii

35 • •-C,-C. alkyl • • 35

\/ 1 4 \/

• •

/\ \

Cj^-C^alkyl C,-Chalky1 C^-C^alkyl ,

40 | [ 40

b) -C-OCH3 -C-OC2,H5 ^C- -C-

0CH3 0C2Hs

0 0 0 0

•—• , •—•-C.-C,alkyl ,

45 13-' 45

-c- -c- -c- • -c-

/\ /\ /\ /\

00 00 0000

II II I I I I

• —CH.0CH, , CH,—• »-CH,

50 2 3 3 \/ \/\ 50

• • CHj

-C- -C- -C-

/\ /\ /\

0 0 0 0 0 0

55 I I I I I I 55

• « . •• • * «

/\/\ \/ \/

CH3 • CH„

/\

CH, CH_ CH.

60 3 3 3 60

For R4:

a) hydrogen, CrC6alkyl, C3-C6cycloalkyl, phenyl, or phenyl substituted by C1-C4alkyl, CrC4alkoxy, CrC4haloalkyl, halogen or cyano;

b) hydrogen, CrC4alkyl, C3-C6cycloalkyl, phenyl or phenyl substituted by methyl, methoxy, CF3, F, CI, Br or

65 CN; 65

3

gb 2 168 053 a

3

c) hydrogen, methyl, phenyl, 2,4-dichlorophenyl;

d) hydrogen.

• Accordingly, the following groups of compounds for example are preferred in increasing order of preference:

5 a) compounds of the formula II, wherein R-i and R2 are each independently hydrogen, halogen, C-i-Csalkyl 5 or CF3; Rn is CrC4alkyl, C-|-C4alkoxy, CVC^haloalkoxy, CrC3haloalkyl, halogen and/or cyano; A is one of the molecular fragments

10 -C-0(Ci-C4alkyI)( -C-0(C1-C4alkyl), 10

I I

0(Cn-C4alkyl) Ofunsubstituted or substituted phenyl)

15 A A A 15

0000 oo-

1 I II. II

• —• , •—•-C^-C^alkyl, Cj-C^alkyl-"—•-C^-C^alkyX,

20 A A A 20

0 0 0 0 ' 0 0

> •-CH2OCH3 , • •-CH^CH, CH=CH2

\/

25 * 25

-c- -c- - -c-

/\ /\ A

0 0 0 0 0 0

II II II

30 \ /\ ' \ / ' A A . 30

• C^-C^alkyl • Cj-C^-alkyl • C^-C^-alkyl

C^-C^alkyl C^-C^alkyl

-C- -C-

35 / \ A 35

0 0 0 0

II II

• •-C.-C.alkyl Or • •

\/ 1 4 \/

• •

40 A \ 40

C^-C^alkyl C^C^alkyl Cj-^alkyl , ;and

R4 is hydrogen, CrCealkyl, C3-C6cycloalkyl, phenyl or phenyl substitued by CrC4aikyl, CrC4alkoxy,

CrC3haloaikyl, halogen or cyano.

45 b) compounds of the formula a II, wherein each of Rn and R2are independently hydrogen, fluorine, 45

chlorine, bromine, methyl, ethyl or CF3; Rn is hydrogen, chlorine, dichloro, fluorine, bromine, methyl,

difluoro, CF3 or OCF3; A is one of the molecular fragments j | -c- -c-

-c-och3 -c-oc2h5 A A

I I oooo och3 oc2h5

•— -Cj-Cjalkyl ,

-c-

/\ 0 0

-c-

/\ 0 0"

-c-

A

0 0

-c-

/\ 0 0

-•-CH20CH3

CH3-»—*-CH3

\/

\/\

CH-

4 GB 2 168 053 A

4

-c- -c-

/\ /\

0 0 0 0

II II

• • or • • ;and

5 \/ \/ 5

• •

I /\

ch3 chj ch3

10 R4 is hydrogen, CrC4alkyl, C3-C6cycloalkyl, phenyl or phenyl substituted by methyl, methoxy, CF3, F, CI, Br or 10 CN.

c) compounds of the formula II, wherein R1 is hydrogen, 2-CI, 2-Br, 2-F, 2-CF3,3-F, 3-CI, 3-Br, 3-CF3,2-CH3, 4-CI, 4-Br, 4-F, 4-CF3,5-CI, 5-Br, 5-F or 5-CF3; R2 is hydrogen; Rn is 4-chloro, 2,4-dichloro, 4-fluro, 2,4-difluoro, 4-bromo, 4-methyl, 4-CF3 or 4-OCF3; A is one of the molecular fragments 15 15

[ | -g- -c-

-c-och3 -c-oc2h5 / \ / \

1 I oooo

I ' 1 'II II

och3 oc2h5 l_i . i_i_c c lkyl ,

20 1 3 20

-c- -c- -c- -c-

/\ /\ /\ /\ 00 00 oooo

II II I I I I

25 * CH2OCH3 1 CH3-° CH3 ' \/ ' \/\ ' 25

• • ch.

30 _c_ -c- -c- 30

/\ /\ /\

00 00 00

11 11 11

. • • • or • • ; and

35 /X/X X/ X/ ' 35

1,5 ch3 • ch3 • • d5>

ch3 ch3 ch3

40 R4 is hydrogen, methyl, phenyl or 2,4-dichlorophenyl. 40

d) compounds of the formula II, wherein R-i is 2-H, 2-F, 2-CI, 2-Br or 2-CH3; R2is hydrogen; Rn in a para-positioned phenyl group is 4-chloro, 2,4-dichloro, 4-fluoro, 2,4-difluoro, 4-bromo, 4-methyl, 4-CF3 or 4-OCF3; A is one of the molecular fragments

1 1 ?C\ "A

-C-OCHg -C-OC2H5 . / \ / \

I I 00 00

och3

oc2h5

• —

• •

—*"Cl~C3alkyl

-c-

/\

0 0

1 |

-c-

/\

0 0

1 1

-c-

/\

0 0

1 1

-c-

/\

0 0

1 1

1 i

• —CUyOCK^

, ch3-

1 1 -.——ch3

l l

' \/ •

1 1 • •

\/\ • ch3

-c-

/\

0 0

1 1

-c-

/\

0 0

1 i

-g-

/\

0 0

1 |

i 1 • •

/\/\ a3 • cil3

1 1

• \/ •

1

ch3

or i 1 • •

\/

•

/\

ch3 ch3

. ; and

5

GB 2 168 053 A 5

R4is hydrogen.

The oxiranes of formula II are novel and constitute specially developed intermediates for the preparation of the valuable 1-phenoxyphenyl-2-azolylethanol compounds described in copending application No.

8330970. Their structural nature makes it possible for them to be converted in simple manner into those 5 compounds. 5

Further, some of the compounds of formula II arefungicidally active against harmful fungi of thefamilies Ascomycetes, Basidiomycetes or Fungi imperfecti.

The oxiranes of the formula II can be prepared in a manner known perse by epoxidation of the corresponding styrene derivatives of the formula VI

10 — Yx*2 10

// w x /"°1; i—r* ,w'

is V f

R4

wherein Rt to R4are as defined for formula II, for example by oxidation with peracids such as peracetic acid, tert-butylhydroperoxide, m-chloroperbenzoic acid, H202 and the like, and optionally in the presence of a 20 base such as NaOH, KOH, NaHC03, in conventional inert solvents. Mo(CO)6 can be used as catalyst in this 20 reaction.

The styrene derivatives of the formula VI can be prepared as described in Org. Synth. 60,6, from the known styrenes of the formula VIII

25 Y/2 25

// \

• - 0 -+ -H CH=CH, (VIII),

v=* \/

30 30

wheren Rt to R3 are as defined for formula I, by reaction with dichlorocarbene (CHCI3/NaOH) and subsequent alcoholysis with alcohols of the formula R6OH, R7OH and/or HO-R6R7-OH.

Epoxides of the formula II, wherein the molecular fragment A is the group

35 | 35

-C-OR7

I '

OR£'

40 40

can be prepared in a manner known perse from ketones of the formula IX

R, • R„ R

45

'm

40R

7, 45

^ * • / (,X)

• • - o -4- -P c—c ' llX)

X / • / II \ ■

r •=• \ / 0 OR,

n # 6

50 by reaction with dimethylsulfonium methyl imide or dimethyloxo-sulfonium methyl imide (Corey and 50

Chaykovsky, J ACS, 1962,84,3782).

The ketones of formula IX are obtainable by different methods which are known from the literature, e.g.

where R4 is hydrogen, e.g. by reacting known substituted acetophenones with the corresponding known alcohols R6-OH or R7-OH, in the presence of nitrosyl chloride, or with the alkyl nitrites ReO-NO or R70-N0 55 (q-v. DE-OS 2 730 462 and DE-OS 2 432 563). 55

Further, substituted phenylglyoxals can also be converted selectively into the acetals of the formula IX.

Acetals or ketones of the formula IX, wherein e.g. R4 is hydrogen and R6and R7 are alkyl, can also be prepared from a-halo-a-acetoxyacetophenone by reaction with alcohols [W. Madelung and M.E. Oberweg-ner, Chem. Ber. 65,931 (1932)].

60 Unless otherwise expressly specified, one or more inert solvents or diluents may be present in the 60

preparation of all starting materials, intermediates and final products mentioned herein. Examples of suitable inert solvents or diluents are: aliphatic and aromatic hydrocarbons such as benzene, toluene,

xylenes, petroleum ether; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ethers and ethereal compounds such as 65 dialkyl ethers (diethyl ether, diisopropyl ether, tert-butylmethyl ether etc.), anisole, dioxane, tetrahydrofur- 65

6

GB 2168053 A

6

ane; nitriles such as acetonitrile, propionitrile; N,N-dialkylated amides such as dimethyl formamide; dimethylsulfoxide; ketones such as acetone, diethyl ketone, methyl ethyl ketone; and mixtures of such solvents with each other. It can often be convenient to carry out the reaction, or partial steps of a reaction,

under an inert gas atmosphere and/or in absolute solvents. Suitable inert gases are nitrogen, helium, argon 5 or, in certain cases, also carbon dioxide. 5

The above described preparatory process, including all partial steps, constitutes an important object of the present invention.

The invention is illustrated in more detail by the following Examples, without implying any restriction to what is described therein. Parts and percentages are by weight.

10 10

Preparatory examples Example PI:

a) Preparation of the intermediate

OCH-

15 / \ / \ / 3 15

Cl-« •-0-* •-C-CH.

\ / \ / I! \

•=• •=• 0 0CH3

20 4-(4-Chlorophenoxy)phenylglyoxal dimethyl acetal 20

158g of a-acetoxy-a-bromo-4-(4-chlorophenoxy)acetophenone in 800 ml of absolute methanol are heated to 60°Cfor 1 hour. After half of the methanol has been distilled off, the solution is poured into water and extracted with diethyl ether. The combined extracts are dried over sodium sulfate, filtered, and concentrated in vacuo. The residue is recrystallised from diisopropyl ether. Yield: 61 g of yellowish crystals with a melting

25 point of 63°-64°C. 25

b) Preparation of the final product

30

OCH,

!/ \ H \ / 3

Cl-« •-()-• •—C CH

\ \

0GH3

\ / \ /

30

o

2-[4-(4-Ch/orophenoxyphenylJ-2-dimethoxymethy/oxirane 35 To a dispersion of 80% sodium hydride in 400 ml of absolute dimethyl sulfoxide are added 47.9 g of 35

trimethyloxosulfonium iodide in portions under nitrogen. After the exothermic reaction has subsided, the mixture is stirred for 90 minutes and then a solution of 55 g of 4-)4-chlorophenoxy)phenylglyoxal dimethyl acetal in 150 ml of tetrahydrofuran is added dropwise at normal temperature. The mixture is heated to 60°c and stirred for 1 hour. Then the reaction mixture is poured into ice/water and extracted repeatedly with 40 diethyl ether. The combined extracts are washed with brine and water, dried over sodium sulfate, filtered, 40 and concentrated in vacuo, affording 59 g of a brown oil which can be either purified by column chromatography or further processed as crude product.

The following final products can be prepared in corresponding manner;

7

GB 2 168 053 A 7

10

obtained as viscous oils or resins.

Compound

R1

R2

R

A

R4

4.1

H

4"0C,H.C1(4) 6 4

-C-

CH30/ X0CH3

H

4.2

H

4-OC.H,Cl(4) 6 4

H

4.3

H

4-OC6H4F(4)

H5C2O' nOC2H5

H

4.4

CI (2)

H

4-OC,H.Cl(4) 6 4

;c\

H^CO OCH3

H

4.5

H

4-OCgH4Cl(4)

? ? —LC2H5

H

4.6

H

4-OC6H4Br(4)

CH30 OCH3

H

4.7

H

4-OCgH4Br(4)

-c-

??

C2H5

H

4.8

CH3(2)

H

4-0C,H.Cl(4)

b 4

-c-

ch3ooch3

H

TABLE 4 Compounds of the formula

I1

X / \ 2

B. t"

R2 t

*4

10

8 GB 2 168 053 A

8

TABLE 4 (continuation)

Compound

R1

R2

r a

R4

4.9

CH3(2)

H

4-0C,H,CI(4)

b *+

A

H

4.10

CH3(2)

H

4-0C,H Br(4)

0 4

-C-

CH30X N0CH3

H

4.11

CH3(2)

H

4-OC6H4Cl(4)

-c-

H5C2Q/ 0C2H5

h

4.12

H

h

4-OC6H4Cl(4)

-c-CH30X 0CH3

ch3

4.13

h

H

4-OCgH4Br(4)

7c\

H5C2O/ nOC2H5

ch3

4.14

CH3(2)

H

4-0C6H4ClC4)

-c-

H5C2O/ nOC2H5

ch3

4.15

CH3(2)

H

4-OC H.Cl(4) 6 4

-c-

< ?

c2h5

4.16

CH3(2)

H

4-0C,H.Br(4) 6 4

-c-

CH30/ 0CH3

c2Hs

GB 2 168 053 A 9

TABLE 4 (continuation)

Compound

R1

R2

R

A

4.17

CH3(2)

H

4-OC.H,F(4)

6 4

?A?

2 5

C3H7-n

4.18

CH3(2)

H

4-OC6H4Cl(4)

n-H

^C30 OC3H7~U

C(CH3)3

4. 19

CH3(2)

H

4-OCgH^Br(4)

7C\ ch3o noch3

C3H7-i

4.20

CH3(2)

H

4-OC5H4Cl(4)

O—•

i/ \

•v./

ch3

4.21

Cl(2)

H

4-OC5H4Cl(4)

CH3(/C~0CH3

H

4.22

H

4-OC,H.Cl(4) 6 4

—C—

H5C20/ 0C2H5

H

4.23

H

4-OC H CI(4) 6 4

h5c2o oc2h5

H

4.24

H

4-OC6H3Cl2(2,

4)

A

1—l-c2s5

H

10 GB 2 168 053 A

TABLE 4 (continuation)

Compound

*1

*2

R

A

R4

4.25

H

4-OC6H4Cl(4)

?A?

• l-ch2och3

H

4.26

CH3(2)

H

4-0C H.C1(4) 6 4

/s

• l-ch20ch3

H

4.27

CH3(2)

H

4-OCgH^CX(4)

.3C-A-CH,

H

4.28

CI (2)

H

4-OC HCI(4) 6 4

"3C"—---C".

H

4.29

H

4-OCgH^Cl(4)

A

H

\ /T

CH3

4.30

CH3(2)

H

4-OC6H4Cl(4)

A

H

x-/ nch3

4.3 1

CI (2)

h

4-OC6H4Cl(4)

nAn ? ?

V\H3

H

GB 2 168 053 A 11

TABLE 4 (continuation)

Cora-

R1

r2

r

A

R4

pound

1

4.32

Cl(2)

H

4-OC H CI (2,4) 6 J *•

?/C\

—i-C2H5

H

4.33

CH3(2)

H

4-0CgH4Cl(4)

/S

~C2H5

H

4.34

CH3(2)

H

4-0C,H.Cl(4)

o 4

?A?

3 7*11

H

4.35

CH3(2)

H

4-OC6H4Cl(4)

?A?

! LC2H5

H

4. 36

CH3(2)

H

4-OCgH4Cl(4)

?A?

CH3

v\*3

4. 37

CI (2)

H

4-OC.H Cl(4) b 4

i—J-ch2och3

CH3

4. 38

CH3(2)

H

3-OC,H,Cl(4) o 4

-c-

cn^ nOCH3

H

4. 39

CH3(4)

H

3-OC6H4Cl(4)

;c"

CH30 0CH3

H

4.4°

CI (2)

h

3-OC6H4Cl(4)

A « *

H

12

GB 2 168 053 A

12

TABLE 4 (continuation)

5

Compound

R1

R2

R

A

R4

5

10

4.4 1

CH3(2)

H

3-0C,H.CH,(4)

/S

i c2h5

H

10

4.42

CH3(2)

H

3-OC,H,Cl(4) 6 4

~-CA

H

15

20

25

4.43

CI (2)

H

3-0C H,CI(4) 6 4

A

V\H3

H

25

30

4.44

CH3(2)

H

3-OC6H4Cl(4)

A • •

\ / \ IT

CH3

H

30

4.45

CH (2) 3

H

3-OC H.CI(4) 6 b-

?/G>

• i-CH20CH3

H

35

4.46

CI (2)

H

3-OC,H,Cl(4) 6 4

?A?

• 1-CH20CH3

H

40

Claims

45 CLAIMS

1. A compound of the formula II

50

Yx*2 o

• • - 0 —|- 4 G —CH-

x ' \r 1

R •=• \ / A

55

\

(ID

wherein

Rt and R2 are each independently hydrogen, halogen CT^alkyl or CF2, and Rn denotes one to three alkyl, alkoxy, haloalkoxy, haloalkyl, halogen and/or cyano groups,

R4 is hydrogen, C1-C10alkyl, C3-C6cycloalkyl or unsubstituted or substituted phenyl, and 60 A is the radical

45

50

55

60

-C-OR7

a*;

13

GB 2 168 053 A

13

wherein

R6 and R7 are each independently CrC12alkyl, unsubstituted or substituted phenyl, or both together form a C2-C4alkylene bridge which is unsubstituted or substituted by one or more identical or different members selected from the group consisting of CrC4alkyl, C2-C4alkenyloxymethyl or CrCsalkoxymethyl. 5 2. a compound ofthe formula II according to claim 1, wherein Rt and R2 are each independently 5

hydrogen, halogen, Ci-C3alkyl or CF3; Rn is CrC4alkyl, Ci-C4alkoxy, CrC4haloalkoxy, Cn-C3haloalkyl, halogen and/or cyano; A is one of the molecularfragments

10 -C-0(CrC4alkyl), -C-0(CrC4alkyl), 10

I I

0(CrC4alkyl) Ofunsubstituted or substituted phenyl)

-c- -c- -c-

15 /\ /\ /\

0000 00

1 I I I II

• —• . , • — •-C^-C^alkyl, Cj-C^alkyl-* — •-C^-C^alkyl,

-C- -C- -C-

20 / \ / \ / \

0 0 0 0 0 0

• •-CH20CH3 , • •-CH20CH2CH=CH2

\/

0 0 0 0

och3 oc2h5

, •—•-C^-C^alkyl ,

-C- -c- -C- -C-

/\ /\ /\ /\ 00 00 oooo

-CH2OCH3 , CH3~«—«-CH3

\/ \/\ • • CH,

15

20

25 A A A 25

00 0 0 0 0

II II II

• • I • • I • •

\/\ \/ /\/\ 30 • Cj-C^alkyl • C^C^alkyl • C^C^-alkyl 30

C^-C^alkyl C^-C^alkyl

-c- -C-

35 / \ . / \ 35

00 00

II II

* -C, alkyl or • •

\/ \/

• .

40 r r ,, {\ 0 ,, , \ 40

CrC4alkyl C1-C4alkyl C1-C4alkyl ; and

R4 is hydrogen, Cn-C6alkyl, C3-C6cycloalkyl, phenyl or phenyl substitued by CrC4alkyl, CrC4alkoxy,

CrCshaloalkyl, halogen or cyano.

45 3. Acompound of the formula II according to claim 1 wherein each of the R-i and R2 independently 45

hydrogen, fluorine, chlorine, bromine, methyl, ethyl or CF3; Rn is chlorine, dichloro, fluorine, bromine,

methyl, difluoro, CF3 or OCF3; A is one of the molecularfragments

II -c- -c-

-C-0CH3 -C-OC2H5 / \ A

14 GB 2 168 053 A

14

-c-

/\

-c-

/\

0 0

1 1

0 0

1 1

1 1 • •

1

or , .

\/

\/

I

A

gh3

ch3 ch.

10 R4 is hydrogen, Ci-C4alkyl, C3-C6cycloalkyl, phenyl or phenyl substituted by methyl, methoxy, CF3, F, CI, Br or 10 CN.

4. A compound of the formula II according to claim 3, wherein R-i is hydrogen, 2-CI, 2-Br, 2-F, 2-CF3,3-F, 3-CI, 3-Br, 3-CF3,2-CH3,4-CI, 4-Br, 4-F, 4-CF3,5-CI, 5-Br, 5-F or 5-CF3; R2 is hydrogen; Rn is 4-chloro,

2,4-dichloro, 4-fluoro, 2,4-difluoro, 4-bromo, 4-methyl, 4-CF3 or4-OCF3; A is one of the molecularfragments 15 15

"A A

-C-OCH3 -C-OC2H5

I I oooo

' ' ' 'II II

OCH3 OC2H5 l_l i_i_c c alkyl ,

20 1 3 20

-c- -c- -c- -c-

A /\ /\ /\

00 00 oooo

II II I I I I

25 CH2OCH3 ■ CH3 • \/ • \/\ ■ 25

e • .CH3

-C- -C- -C-

/\ /\ /\

30 00 0 0 0 0 30

II II II

A/\ ' \/ or \/ ;and ch3 • ch,

/\

35 ch3 ch3 ch3 35

R4 is hydrogen, methyl, phenyl or 2,4-dichlorophenyl.

5. A compound of the formula II according to claim 4, wherein R1 is 2-H, 2-F, 2-CI, 2-Br or2-CH3; R2is hydrogen; Rn in a parapositioned phenyl group is 4-chloro, 2,4-dichloro, 4-fluoro, 2,4-difluoro, 4-bromo, 40 4-methyl, 4-CF3or4-OCF3; A is one of the molecularfragments 40

I 1 "A ?c\

—C—OCHs —C—OC2H5 / \ / \

I ' 1 'II II

45 OCH3 OC2H5 •—• , •—•-Cj-C3alkyl , 45

-c- -c- -c- -c-

/\ /\ /\ /\ 00 00 oooo

II I I I I I I

50 •—•-ch.och, , ch,-«—•-ch- , 50

2 3 3 3 \/ \/\

• • ch3

-c-

/X 55

55 0 0 0 0 0 0 55

-c-

/\

-c-

/\

0 0

1 1

0 0

1 I

1 1 • •

1 1 or • •

\/

\/

I

A

ch3

ch3 ch.

A/\ ■ • •

>3 • C

60 ch- ch ch-

R4 is hydrogen.

15

GB 2 168 053 A

15

6. A process for the preparation of a compound of the formula II as defined in claim 1, which comprises epoxidation of the corresponding styrene derivative of formula VI

5 YX*2 5

M ^ ii (VI), • • - o-4- -H c=ch,

x ' \; 1

rn.=. \/ a

10 R4 10

wherein R1( R2, Rn, R4 and A are as defined in claim 1.

7. A process for the preparation of a compound of the formula II as defined in claim 1 wherein the molecular fragment A is the group

15 15

-C-OR7

| /

ORe

20 20

which comprises reacting a ketone of the formula IX

25

// \ • •

x /

r •=•

n r, • r„

>yx2

or

\/

/ c

\

7,

(IX)

25

or,

30 wherein R! , R2, Rn, R4- ^6 and R7 are as defined in claim 1, with dimethylsulphonium methyl imide or dimethyloxosulfonium methyl imide.

8. An oxirane compound of the formula II defined in claim 1 substantially as hereinbefore described with reference to any one of the foregoing Examples.

30

Printed in the UK for HMSO, D8818935, 4/86, 7102.

Published by The Patent Office, 25 Southampton Buildings, London, WC2A 1AY, from which copies may be obtained.