DD260491A5 - PROCESS FOR PREPARING COMPOUNDS - Google Patents

Abstract

The present invention relates to a process for the preparation of acrylic acid derivatives of the general formula (I). The inventive method is characterized by the fact that z. B. a compound of general formula (VIII) with an appropriate acidic or basic reagent. The compounds prepared according to the invention can be used as fungicides. Formulas (I) and (VIII)

Description

χι

  ^ χ (ID

in which R ¹ , X, Y and Z have the abovementioned meaning, but R ^{1 is} not a hydrogen atom, with a compound of the general formula (V):

Ph ₃ P-CHOR ² (V)

in which R ^{2 has} the abovementioned meaning but is not a hydrogen atom, is reacted,

b) a compound of general formula (VII):

CH ₂ CO ₀ R ¹ .

(VII)

wherein X, Y and Z and R ^{1 have} the abovementioned meaning, but R ^{1 is} not a hydrogen atom, is reacted with a base and a compound of the general formula HCO ² R ¹ , in which R ^{1 has} the abovementioned meaning, but is not a hydrogen atom, and then in the same reaction vessel, or in a separate step with a base present, the resulting species with a compound of the general formula R ² OJ n of R ^{2 has} the abovementioned meaning and O is an outgoing group, such as a halogen atom, for reaction is brought

c) a compound of the general formula (VIII):

(VIII)

CH (OR ² )

U,

wherein R ¹ , R ² , X, Y and Z have the abovementioned meaning, with an appropriate acidic or basic reagent.

Field of application of the invention

The invention relates to a process for the preparation of acrylic acid derivatives of the following general formula (I). The compounds according to the invention can be used as fungicides both in agriculture and in industry.

Characteristic of the known technical solutions

The compounds of the general formula (I) according to the invention

CO ₂ H ¹

(D

R ¹ and R ^{2 are} not hydrogen atoms, which may be the same or different, are alkyl, cycloalkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted aralkyl, or cycloalkyl groups, and metal complexes thereof, X, Y, Z may be the same or different, hydrogen or halogen atoms or optionally substituted alkyl, optionally substituted aryl, optionally substituted alkynyl, haloalkyl, alkoxy, haloalkoxy, optionally substituted aryloxy, optionally substituted arylalkoxy, optionally substituted acyloxy , optionally substituted amines, optionally substituted arylaze, acylamino, nitro, nitrile, -CO ₂ R ³ -, -CONR ⁴ R ⁵ -, -COR ⁶ -, -CR ⁷ = NR ⁸ -or-N = CR ⁹ R ¹⁰ groups, or the groups X and Y, when in adjacent positions on the phenyiring, can combine to form a fused ring which is either aromatic or aliphatic and optionally contains one or more heterostoms Senior Citizen:

and R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ , which may be the same or different, are hydrogen or alkyl, cycloalkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted aralkyl or cycloalkyl groups and metal complexes thereof may be prepared by treatment of keto esters of the general formula (II)

(II)

for example ..

in which R ¹ , X, Y, Z have the previous meaning, with phosphoranes of the general formula (V)

PH ₃ P CHOOR ² (V)

wherein R ^{2 has} the previous meaning, in a suitable solvent, for. B. Diethyl ether, are prepared (see, for example: W. Steglich, G. Schamm, T. Anke and F. Oberwinkler, EP 0044448, 4,7, 80).

Object of the invention

The invention provides as fungicides useful derivatives of acrylic acid and processes for their preparation. The compounds may be acropetally permeated into the plant tissue and may be so volatile as to be effective in the vapor phase against fungi found on the plants.

They can also be used as industrial (as opposed to agricultural) fungicides. Some of the compounds exhibit herbicidal activity and some also show plant growth regulating activity.

Explanation of the essence of the invention

The object of the invention is to provide compounds which are useful as fungicides and their production processes which are very versatile.

The invention relates to a compound of general formula (I):

,1

and stereoisomers thereof, wherein X, Y and Z, which may be the same or different, are hydrogen or halogen atoms or optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, optionally substituted alkynyl, haloalkyl, alkoxy , Haloalkoxy, optionally substituted aryloxy, optionally substituted arylalkoxy, optionally substituted acyloxy, optionally substituted amono, optionally substituted arylazo, acylamino, nitro, optionally substituted arylazo, acylamino, nitro, nitrile, CO ₂ R ³ -, -CONR ⁴ R ⁵ -, -COR ⁶ -, -CR ⁷ = NR ⁸ - or -N = CR ⁹ R ¹⁰ groups, or the groups X and Y, if they are in adjacent Positions on the phenyl ring may combine to form a fused ring which is either aromatic or aliphatic and optionally contains one or more heteroatoms; and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ , which may be the same or different, are hydrogen or alkyl, cycloalkyl, alkonyl, alkynyl -, optionally substituted aryl, optionally substituted aralkyl, or cycloalkyl groups and metal complexes thereof.

The compounds of the invention contain at least one carbon-carbon double bond and are sometimes obtained in the form of mixtures of geometric isomers. However, these mixtures can be decomposed into individual isomers and the invention includes such isomers.

Alkyl groups may be in the form of straight or branched chains and preferably contain from 1 to 6 carbon atoms; Examples are methyl, ethyl, propyl, (n-undiso-propyl) and butyl (η-, sec-, iso-or-tert-butyl). The methyl group is the preferred alkyl group for R ¹ and R ² . In a further aspect, the invention relates to compounds of the general formula (I):

GO ₉ R ¹

^c 2

OR ' ¹

and stereoisomers thereof, wherein X, Y and Z, which may be the same or different, are hydrogen or halogen atoms or optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, optionally substituted alkynyl, haloalkyl, alkoxy, haloalkoxy -, optionally substituted aryloxy, optionally substituted arylalkoxy, amino, acylamino, nitro, nitrile, -CO ₂ R ³ , -CONR ⁴ R ⁵ or -COR ⁶ groups; and R ¹ , R ² , R ³ , R ⁴ , R ^s and R ⁶ , which may be the same or different, are hydrogen or alkyl, cycloalkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted aralkyl, or cycloalkylalkyl groups, and metal complexes thereof. In a further aspect, the invention relates to compounds of the formula (I):

(I)

and stereoisomers thereof, wherein X, Y and Z, which may be the same or different, are hydrogen or halogen atoms or optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, optionally substituted alkynyl, haloalkyl, alkoxy, optionally substituted aryloxy, optionally substituted arylalkoxy, optionally substituted amino, -CO ₂ R ³ -, -COR ⁶ - groups, or the groups X and Y, when they are in adjacent positions on the phenyl ring, to form a fused can combine aromatic ring; and R ¹ , R ² , R ³ and R ⁶ , which may be the same or different, are alkyl, optionally substituted phenyl or optionally substituted aralkyl groups. In yet another aspect, the invention relates to compounds of general formula (I):

CO ₂ E

(D

CH

oor

and stereoisomers thereof, wherein X, Y and Z, which may be the same or different. Hydrogen, fluorine, chlorine or bromine atoms or C 1 -C 4 -alkyl, C ₂ -S-alkenyl, C ₂ -5-alkynyl, phenyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, Phenoxy, benzyloxy, or mono or dialkylamino groups, or the groups X and Y, when in adjacent positions on the phenyl ring, combine to form a fused aromatic ring, the aliphatic moieties of each of the above groups being optionally substituted with one or more C 1 - Alkoxy groups, fluorine, chlorine or bromine atoms, phenyl rings, which in turn are optionally substituted, heterocyclic rings which are either aromatic or non-aromatic and are themselves optionally substituted, nitro, amino, nitrile, hydroxyl or carboxyl groups; and wherein the phenyl moieties of each of the above groups are optionally substituted with one or more fluorine, chlorine or bromine atom phenyl rings, C 1-4 alkyl, C 1-4 alkoxy, nitro, amino, nitrile, hydroxyl or carboxyl groups ; and R ¹ and R ² , which may be the same or different, are C ₁ -alkyl, phenyl or benzyl groups, each of which is optionally substituted with halogen atoms. , ,

In yet another aspect, the invention relates to compounds of the general formula (XI):

CO ₂ CH ₃

(XI)

wherein R represents an optionally substituted phenyl or an optionally substituted benzyl group and Y is a hydrogen or halogen atom (fluoro, chloro or bromo) or a methyl, methoxyl, nitro, nitrile, carboxyl or methoxycarbonyl group

 In another aspect, the invention relates to compounds of general formula (XII):

CO ₀ CH-ι 2 3

CH OCH

(XIL)

and stereoisomers thereof, wherein X is an alkyl, alkenyl, alkynyl, aryloxy or arylalkoxy group, each of which is optionally substituted.

In yet another aspect, the invention relates to compounds of the general formula (XIII):

(XlIl)

OCH

and stereoisomers thereof, wherein X is an optionally substituted alkyl, optionally substituted alkenyl or optionally substituted alkynyl group.

The invention more particularly relates to compounds in which the optional substituents in the preceding section are phenyl, which in turn optionally contains one or more of the following groups: fluoro, chloro, bromo, Ci-4-alkyl (especially methyl), C ^ -Alkoxy (especially methoxy) or nitro is substituted.

In yet another aspect, the invention relates to compounds of the general formula (XIV):

CO ₂ CH ₃

(XIV)

and stereoisomers thereof, wherein X represents an optionally substituted aryloxy group or an optionally substituted arylalkoxy group.

In the preceding section, X may be phenoxy or benzyloxy, each of which is optionally substituted with one or more halogen atoms (fluoro, chloro or bromo) or a methyl, methoxyl, ethyl, ethoxyl, nitro, nitrile, carboxyl or Methoxycarbonylgruppe is substituted.

In yet another aspect, the invention relates to compounds of the general formula (XV):

Co ₂ CH ₃

and stereoimers thereof, wherein X, Y and Z, which may be the same or different, are fluorine, chlorine, bromine or hydrogen atoms or methyl, methoxyl or nitro groups. The invention relates to the compounds:

Ci)

CH ₃ O ₂ C

(Compound No. 9 of the following Table I) (ii)

CH ₃ O ₂ C

(Compound No. 13 of the following Table I) (iii) '

OCH.

CH ₃ O ₂ G

OCH.

(Compound No. 19 of the following Table I)

(Iv)

CH ₃ O ₂ C

OCH

(Compound No. 1 of the following Table I

(IIA)

CH ₂ CH ₂

OCH

(Compound No. 1 of the following Table IV) Table I

(D

OR '

Connection no.

R ¹

Melting point ( ⁰ C)

olefinically *

Isomer ⁺

1. CH ₃ CH ₃ H H H 37-38 7.55 e 2 CH ₃ CH ₃ H H H Oil 1) 6.65 Z 3 CH ₃ CH ₂ CH ₃ H H H OEMs) 7.53 e 4 CH ₃ CH ₃ CH ₂ H H H 011) 7.62 e 5 CH3CH2 CH3CH2 H H H OEMs) 7.62 e 6 C6H5CH2 CH ₃ H H H Oil 1) 7.56 e 7 CH ₃ C6H5CH2 H H H 37-38 7.67 e 8th (CH ₃ J ₃ C CH ₃ H H H 011) 7.44 e 9 CH ₃ CH ₃ 2- (EC ₆ H ₅ CHiCH) H H 107-108 7.63 e 10 ν CH ₃ CH ₃ 2- (EC ₆ H ₅ CHiCH) H H Oil 1) 6.57 Z 11 CH ₃ CH ₃ 3- (EC ₆ H ₅ CHiCH) H H 104-105 7.58 e 12 CH ₃ CH ₃ 4- (EC ₆ H ₅ CHiCH) H H 75-76 7.56 e 13 CH ₃ CH ₃ 2- (ZC ₆ H ₅ CHiCH) H H 011) 7.50 e 14 CH ₃ CH ₃ 2- (ZC ₆ H ₅ CHiCH) H H 93-94 6.34 'Z 15 (CH _{3) 3} C CH ₃ 2- (ZC ₆ H ₅ CHiCH) H H Oil 1) 7.37 e 16 CH ₃ (CH ₃ J ₃ C 2- (ZC ₆ H ₅ CHiCH) H H OEMs) 7.87 e 17 CH ₃ CH ₃ 2-C ₆ H ₅ CH ₂ CH (CH ₃ ) H H e

Continuation Table I

Connection no.

R ²

Melting point ( ⁰ C)

olefinically *

Isomer ⁺

18 CH ₃ CH ₃ 2-C ₆ H ₅ CH ₂ C (CH ₃ ) ₂ H H 96-87 7.58 e 19 CH ₃ CH ₃ .2-C ₆ H ₅ C: C H H Oil 1) 7.57 e 20 CH ₃ CH ₃ 2-CH ₂ : CH H ' H 65-66 7.60 e 21 CH ₃ CH ₃ 2-CI H H 61-62 7.56 e 22 CH ₃ CH ₃ 4-CI H H 68-69 7.56 e 23 CH ₃ CH ₃ 2-CI 4-CI H 141-142 7.61 e 24 CH ₃ CH ₃ 2-CI 6-Cl H 126-127 7.58 e 25 CH ₃ CH ₃ 3-CI 5-CI H OM) 6.70 e 26 CH ₃ ' CH ₃ 3-CI 5-CI H 79-80 7.62 Z 27 CH ₃ CH ₃ 2-CI 6-F H 011) 7.55 e 28 CH ₃ CH ₃ 2-CH ₃ H H 62-63 6.52 e 29 CH ₃ CH ₃ 2-CH ₃ H H Oil 1) 7.52 Z 30 "CH ₃ CH ₃ 2- (CO ₂ CH ₃ ) H H 65-66 7.56 e 31 CH ₃ CH ₃ 2-CF ₃ H H 106-107 7.34 e 32 CH ₃ CH ₃ 2-C ₆ H ₅ H H , e 33 CH ₃ CH ₃ 2-C ₆ H ₅ N (CH ₃ ) CO H H 34 CH ₃ CH ₃ 2-C ₆ H ₅ CON (CH ₃ ) H H 82-85 7.30 35 CH ₃ CH ₃ 2-C ₆ H ₅ CO H H e 36 CH ₃ CH ₃ 2-C ₆ H ₅ CO ₂ H H e 37 CH ₃ CH ₃ 2-C ₆ H ₅ O ₂ C H H e 38 CH ₃ CH ₃ 2- (CH ₃ ) ₃ CO ₂ C H H e 39 CH ₃ CH ₃ 2- (cyclohexyl) 0 ₂ C H H Oil 1) 7.48 e 40 CH ₃ CH ₃ 2-C ₆ H ₅ CH ₂ H H e 41 CH ₃ CH ₃ 2- (4-Cl-C ₆ H ₄₎ CH ₂ H - H Oil 1) 7.50 e 42 CH ₃ CH ₃ 2- (4-CH ₃ OC ₆ H ₄ ) CH ₂ H H e 43 CH ₃ CH ₃ 2-C ₆ H ₅ (CHa) ₂ C H H e 44 CH ₃ CH ₃ 2-C ₆ H ₆ CH (OH) H H Oil 1) under2) e 45 CH ₃ CH ₃ 2-NO ₂ H H aromatics e 46 CH ₃ CH ₃ 2-NH ₂ H H e 47 CH ₃ CH ₃ 2-C ₆ H ₅ N = N H H e 48 CH ₃ CH ₃ 2- (4- (CH ₃ ) ₂ NC ₆ H ₄ N: N) H H e 49 CH ₃ CH ₃ 2- (4-CH ₃ OC ₆ H ₄ N: N H H e 50 CH ₃ CH ₃ 2-CH ₃ O ₂ CCH ₂ CH ₂ H H e 51 CH ₃ CH ₃ 3- (CH ₃ J ₂ CH H H Oil 1) 7.51 e 52 CH ₃ CH ₃ 2-C ₆ H ₅ S H H Oil 1) under2) e 53 CH ₃ CH ₃ 2-C ₆ H ₅ S (O) H H aromatics e 147-148 under2) 54 CH ₃ CH ₃ 2-C ₆ H ₅ S (O) ₂ H H _ decomp.3) aromatics e

CH ₃

CH ₃

CH ₃

CH ₃

2- (S ^ ₀ JL CH: CH) 2- H (E-O * CH: CH) h

57 58 59 CH ₃ CH ₃ CH ₃ CO CO CO XXX O O U 3-C ₆ H ₅ O 4-C ₆ H ₅ O 4-C ₆ H ₅ O 60 CH ₃ , CH ₃ 61 CH ₃ CH ₃ 62 CH ₃ CH ₃ 63 CH ₃ CH ₃ 64 CH ₃ CH ₃   4 ·.

H H H

H H

OEMs)

107.5 to 110

Oil 1)

97-98 Ö11)

124-125 83-84

122-123

7.63

6.56

7.54 7.54 6.64

7.47 7.63

7.73

E E Z

E E

E E

 φ substituents are fused rings. Thus, compound 60 is:

Compound 62 is:

CH ₃ O ₂ C

Connection 64 is:

Continuation Table I

Compound 61 is: Compound 63:

CH ₃ O ₃ C

GH

CH ₃ O ₂ C CH

Connection no.

R ¹ melting point ( ⁰ C)

olefinic * isomer *

65 CH ₃ CH ₃ 2- (C ₆ H ₅ (CH ₃ )) H H 011) under2) e aromatics 66 CH ₃ CH ₃ 2- (4-CH ₃ OC ₆ H ₄ CO) H H 011) 7.32 e 67 CH ₃ CH ₃ 2-C ₆ H ₆ OCH ₅ H H e 68 CH ₃ CH ₃ 2-C ₆ H ₆ CH (CH ₃ ) CH ₂ H H e 69 CH ₃ CH ₃ 2-C ₆ H ₅ C (CH ₃ ) ₂ CH ₂ H H e

CH ₃

CH-,

CH,

CH ₃

CH ₃

! (Ο

CH)

71 CH ₃ CH ₃ 2- (E-4-CI-C ₆ H ₄ CH: CH) H H 72 CH ₃ CH ₃ 2- (E-4-FC _e H ₄ CH: CH) H H 73 CH ₃ CH ₃ 2- (E-2,6-di-CI-C ₆ H ₃ CH: CH) H H 74 CH ₃ CH ₃ 2- (EC ₆ H ₅ C (CH ₃ ): C (CH ₃ )) H H 75 CH ₃ CH ₃ 2- (EC ₆ H ₆ C (CH ₃ ) ME) H H 76 CH ₃ CH ₃ 2- (EC ₆ H ₆ CH: C (CH ₃ )) H H

CH ₃

CH ₃

Μ ,. Ο

CH: CH)

79 CH ₃ CH ₃ 2-C ₆ H ₅ OCH ₂ H H 80 CH ₃ - CH ₃ 2-C ₆ H ₆ OCH (CH ₃ ) H H 81 CH ₃ CH ₃ 2-C ₆ H ₅ OC (CH ₃ ) ₂ H H 82 CH ₃ CH ₃ 2-C ₆ H ₆ C (CH ₃ ) ₂ C (CH ₃ ) ₂ H H

CH ₃

2- (E-

, CH: CH) "

EE E E

E E

Continuation Table I

Compound No. R ¹

Melting point ( ⁰ C)

olefinically *

isomer

CH ₃ CH ₃

CH: CH)

CH: CH)

CH ₃ CH ₃ 2- (E-J. ¹

H H

H H

CH ₃

CH ₃

2 (C ₆ H ₅ ) ₂ C: CH

H H

CH ₃

CH ₃

CH ₃

(2-

CH)

88 CH ₃ CH ₃ 2-C ₆ H ₅ CONH H H 89 CH ₃ CH ₃ 2-C ₆ H ₅ NHCO H H

CH ₃

99-100

under2) aromatics

E E

* Chemical rearrangement of the singlet from the olefinic proton to the B-methoxyacrylate group (ppm of tetramethylsilane). Solvent:

COCI ₃

+ Geometry of B-methoxyacrylate group 1) oil, 2) aromatics, 3) decomposition

Table II

RO

CO ₂ CH-

OCH.

Connection no.

Melting point ( ⁰ C) olefinic *

Isomer ⁺

1 C ₆ H ₅ 2 2-FC ₆ H ₄ 3 3-FC ₆ H ₄ 4 4-FC ₆ H ₄ 5 2-CI-C ₆ H ₄ 6 3-CI-C ₆ H ₄ 7 4-CI-C ₆ H ₄ 8th. 2-Br-C ₆ H ₄ 9 3-Br-C ₆ H ₄ 10 4-Br-C ₆ H ₄ 11 2-1-C ₆ H ₄ 12 3-1-C ₆ H ₄ 13 - 4-1-C ₆ H ₄ 14 2-CH3 G5H4 15 3-CH3-C6H4 16 4-CH ₃ -C ₆ H ₄ 17 2-CH ₃ CH ₂ -C ₆ H ₄ 18 3-CH ₃ CH ₂ -C ₆ H ₄ 19 4-CH ₃ CH ₂ -C ₆ H ₄ 20 2- (CH ₂ ) ₂ CH-C ₆ H ₄ 21 3- (CH ₂ ) ₂ CH-C ₆ H ₄

OM)

7.7-78 oil 1)

Oil 1)

Oil 1)

80-81

7.50 7.46 7.45 '7.48

E N G E R E S E R E S E R E S

Continuation Table II

Connection no.

Melting point R

olefinically *

Isomer ⁺

22 4- (CH ₃ J ₂ CH-C ₆ H ₄ Oil 1) 7,51 23 2- (CH ₃ J ₃ CC ₆ H ₄ 24 3- (CH ₃ J ₃ CC ₆ H ₄ 25 4- (CHa) ₃ CC ₆ H ₄ 26 2-CH ₃ OC ₆ H ₄ 27 3-CH ₃ OC ₆ H ₄ 28 4-CH ₃ OC ₆ H ₄ 29 2-CF ₃ OC ₆ H ₄ 30 3-CF ₃ OC ₆ H ₄ 31 4-CF ₃ OC ₆ H ₄ 32 2-C ₆ H ₅ OC ₆ H ₄ 33 3-C ₆ H ₅ OC ₆ H ₄ 34 4-C ₆ H ₅ OC ₆ H ₄ 35 2-NO ₂ -C ₆ H ₄ 36 3-NO ₂ -C ₆ H ₄ 37 4-NO ₂ -C ₆ H ₄ 38 2-NH ₂ -C ₆ H ₄ 39 3-NH ₂ -C ₆ H ₄ 40 4-NH ₂ -C ₆ H ₄ 41 2-C6H5-C6H4 42 3-C6H5-C6H4 43 4-C ₆ H ₆ -C ₆ H ₄ 44 2-HO ₂ CC ₆ H ₄ 45 3-HO ₂ CC ₆ H ₄ 46 4-HO ₂ CC ₆ H ₄ 47 2-CH ₃ O ₂ CC ₆ H ₄ 48 3-CH ₃ O ₂ CC ₆ H ₄ 49 4-CH ₃ O ₂ CC ₆ H ₄ 50 2- (CN) -C ₆ H ₄ 51 3- (CN) -C ₆ H ₄ 52 4- (CN) -C ₆ H ₄ 53 2-HO-C ₆ H ₄ 54 3-HO-C ₆ H ₄ 55 4-HO-C ₆ H ₄ 56 2-CH ₃ C (O) NH-C ₆ H ₄ 57 3-CH ₃ C (O) NH-C ₆ H ₄ 58 4-CH ₃ C (O) NH-C ₆ H ₄ 59 2,3-di-FC ₆ H ₃ 60 2,4-di-FC ₆ H ₃ Oil 1) 7,48 61 2,5-di-FC ₆ H ₃ 62 2,6-di-FC ₆ H ₃ 132-133 7.62 63 3,4-di-FC ₆ H ₃ 64 3,5-di-FC ₆ H ₃ 65 2,3-di-CI-C ₆ H ₃ 66 2,4-di-CI-C ₆ H ₃ 67 2,5-di-CI-C ₆ H ₃ 68 2,6-di-CI-C ₆ H ₃ 69 3,4-di-CI-C ₆ H ₃ 70 3,5-di-CI-C ₆ H ₃ 71 2,3-di-CH ₃ -C ₆ H ₃ 72 2,4-di-CH ₃ -C ₆ H ₃ 73 2,5-di-CH ₃ -C ₆ H ₃ 74 2,6-di-CH ₃ -C ₆ H ₃ 75 3,4-di-CH ₃ -C ₆ H ₃ 76 3,5-di-CH ₃ -C ₆ H ₃ 77 2,3-di-CH ₃ OC ₆ H ₃ 78 2,4-di-CH ₃ OC ₆ H ₃ 79 2,5-di-CH ₃ OC ₆ H ₃ 80 2,6-di-CH ₃ OC ₆ H ₃ 81 '3,4-di-CH ₃ OC ₆ H ₃ 82 3,5-di-CH ₃ OC ₆ H ₃ 83 2-F, 3-Cl-C ₆ H ₃ 84 2-F, 4-CI-C ₆ H ₃ 85 2-F, 5-CI-C ₆ H ₃ 86 2-F, 6-Cl-C ₆ H ₃ 87 3-F, 4-CI-C ₆ H ₃

E N G E E R E S E R E S E S E S E S E S E S E S E S E S E S E S E S E S E S E R E S E S E R E S E S E S E S E R E S E S E S E S E S E S E S E S

Continuation Table II

connection R No. 3-F, 5-CI-C ₆ H ₃ 88 2-CI-3-FC ₆ H ₃ 89 2-0 !, 4-FC ₆ H ₃ 90 2-Cl, 5-FC ₆ H ₃ 91 3-Cl, 4-FC ₆ H ₃ 92 2-F, 3-CH ₃ -C ₆ H ₃ 93 2-FACH ₃ -C ₆ H ₃ 94 2-F, 5-CH ₃ -C ₆ H ₃ 95 2-F, 6-CH ₃ -C ₆ H ₃ 96 3-FACH ₃ -C ₆ H ₃ 97 3-F, 5-CH ₃ -C ₆ H ₃ 98 2-CH ₃ , 3-FC ₆ H ₃ 99 2-CH ₃ AF-C ₆ H ₃ 100 2-CH _3, 5-FC ₆ H ₃ 101 3-CH ₃ AF-C ₆ H ₃ 102 2-F, 3-CH ₃ OC ₆ H ₃ 103 2-FACH ₃ OC ₆ H ₃ 104 2-F, 5-CH ₃ OC ₆ H ₃ 105 2-F, 6-CH ₃ OC _e H ₃ 106 3-FACH ₃ OC ₆ H ₃ 107 3-F, 5-CH ₃ OC ₆ H ₃ 108 2-CH ₃ O, 3-FC ₆ H ₃ 109 2-CH ₃ OAF-C ₆ H ₃ 110 2-CH ₃ O, 5-FC ₆ H ₃ 111 3-CH ₃ OAF-C ₆ H ₃ 112 2-01, ₃ -CH ₃ -C ₆ H ₃ 113 2-Cl, 4-CH ₃ -C ₆ h ₃ 114 2-01.5-CH ₃ -C ₆ H ₃ 115 2-01, 6-CH ₃ -C ₆ H ₃ 116 3-CIACH ₃ -C ₆ H ₃ 117 3-01.5-CH ₃ -C ₆ H ₃ 118 2-CH ₃ , 3-CI-C ₆ H ₃ 119 2-CH ₃ ACI-C ₆ H ₃ 120 2-CH ₃ , 5-CI-C ₆ H ₃ 121 3-CH ₃ ACI-C ₆ H ₃ 122 2-01, ₃ -CH ₃ OC ₆ H ₃ 123 2-Ciach ₃ OC ₆ H ₃ 124 2-0!, 5-CH ₃ OC ₆ H ₃ 125 2-01, 6-CH ₃ OC ₆ H ₃ 126 3-Ciach ₃ OC ₆ H ₃ 127 3-0!, 5-CH ₃ OC ₆ H ₃ 128 2-CH ₃ O, 3-CI-C ₆ H ₃ 129 2-CH ₃ OACl-C ₆ H ₃ 130 2-CH ₃ 0.5-CI-C ₆ H ₃ 131 3-CH ₃ OACl-C ₆ H ₃ 132 2-CH ₃ , 3-CH ₃ OC ₆ H ₃ 133 2-CH ₃ ACH ₃ OC ₆ H ₃ 134 2-CH ₃ , 5-CH ₃ OC ₆ H ₃ 135 2-CH _3/ 6-CH ₃ OC ₆ H ₃ 136 3-CH ₃ ACH ₃ OC ₆ H ₃ 137 3-CH ₃ , 5-CH ₃ OC ₆ H ₃ 138 2-CH ₃ O, 3-CH 5 C ₆ H ₃ 139 2-CH ₃ OACH ₃ -C ₆ H ₃ 140 2-CH ₃ O, 5-CH ₃ -C ₆ H ₃ 141 3-CH ₃ OACH ₃ -C ₆ H ₃ 142 2,4,6-tri-FC ₆ H ₂ 143 2,4,6-tri-CI-C ₆ H ₂ 144 2,4,6-tri-CH ₃ -C ₆ H ₂ 145 2,6-di-F, 4-CI-C ₆ H ₂ 146 2,6-di-Me, 4-FC ₆ H ₂ 147 2,6-di-Cl, 4-FC ₆ H ₂ 148 2,3,5,6-tetra-CI-C ₆ H 149 pentafluorophenyl 150 pentachlorophenyl 151 H 152 CH ₃ 153

melting point

( ⁰ C) olefinic *

Isomer*

7.52

E N G E E R E S E R E S E S E S E S E S E S E S E S E S E S E S E S E S E S E R E S E S E R E S E S E S E S E R E S E S E S E S E S E S E S E S

Continuation Table II

Compound melting point

No. R ( ⁰ C) olefinic * isomer " ¹ "

E N G E R E S E R E S E S

• E N G L I S H E Z

* -Chemical rearrangement of the singlet from the olefinic proton at the B-methoxyacrylate group (ppm of tetramethylsilane).

Solvent: CDCI ₃

+ Geometry of the B-methoxyacrylate group 1) oil *.

The following Table III contains compounds of the general formula:

154 CH ₃ CH ₂ Oil 1) 7.38 • 6.55 155 CH3CH2CH2 Oil 1) 7.46 6.60 156 (CH ₃ I ₂ CH Oil 1) 7.46 157 CH3CH2CH2CH2 158 (CH ₃ I ₃ C 159 cyclohexyl 160 CH ₂ : CHCH ₂ Oil 1) 7.43 161 EC ₆ H ₅ CH: CHCH ₂ 162 CH ₂ : C (CH ₃ ) CH ₂ 163 E-CH ₃ CH: CHCH ₂ 164 2-tetrahydropyranyl 165 2-pyridyl 166 3-pyridyl 167 4-pyridyl 168 2- (5'-CF ₃ -pyridyl) 169 2-pyrimidyl 170 4-pyrimidyl 171 5-pyrimidyl 172 3,4-methylene 76-77 7.49 173 1-naphthyl 174 2-naphthyl 175 CH ₃ SCH ₂ 74-75 176 CgHsSCr ^ oil 177 C ₆ H ₅ CH ₂ 178 C ₆ H ₅ C (CH ₃ I ₂ 179th 4-CI-C ₆ H ₄ C (CH ₃ J ₂ 180 CH ₃ 181 C ₆ H ₅

wherein the group R comprises all of the groups R listed in Table II for each of the following substitution models on the phenyl ring shown above. The acrylate group may in either case have either the E or Z geometry.

Table III

Y Z

3-F H

4-F H

5-F H

6-F H

3-CI H

4-CI H

5-CI. , H

6-CI H

3-CH3H

4-CH ₃ H

5-CH ₃ H

6-CH ₃ H

3-NO ₂ . H

4-NO ₂ H

5-NO ₂ H

Continued Tab. Ill Z Y H 6-NO ₂ H 5-CF ₃ 5-CI 3-NO ₂ 5-NO ₂ 3-NO ₂ H 3-SCH ₃ 5-CH ₃ O 4-CH ₃ O H 4- (CH ₃ I ₂ N 4,5-methylenedioxy

Specific examples of the compounds of the type listed in Table III are the following:

Verbin R Y Z enamel olefinically * Isomer " ¹ " dung C ₆ H ₅ 3-CI H Point e No. C ₆ Hs 4-NO ₂ H C ⁵ C) e 1 C ₆ H ₅ 5-CI H 7.47 e 2 C ₆ H ₅ 6-NO ₂ H e 3 C ₆ H ₅ 5-NO ₂ H Oil 7.60 e 4 5 Oil

* Chemical rearrangement of the singlet from the olefinic proton to the B-methoxyacrylate group (ppm of tetramethylsilane).

Solvent: CDCl ₃ + geometry of B-methoxyacrylate group.

Table IV

RGH ₂ CH ₂

CO ₂ CH ₃

Connection no.

melting point

olefinically *

Isomer ⁺

1 C ₆ H ₆ 2 2-FC ₆ H ₄ 3 3-FC ₆ H ₄ 4 4-FC ₆ H ₄ Oil 2-CI-C ₆ H ₄ 6 3-CI-C ₆ H ₄ 7 4-CI-C ₆ H ₄ 8th 2-Br-C ₆ H ₄ 9 3-Br-C ₆ H ₄ 10 4-Br-C ₆ H ₄ 11 2-1-C ₆ H ₄ 12 3-1-C ₆ H ₄ 13 4-1-C ₆ H ₄ 14 2-n3 "C6n4 15 3-CH3-C6H4 16 4-CH ₃ -C ₆ H ₄ 17 2-CH ₃ CH ₂ -C ₆ H ₄ 18 3-CH ₃ CH ₂ -C ₆ H ₄ 19 4-CH ₃ CH ₂ -C ₆ H ₄ 20 2- (CH ₃ J ₂ CH-C ₆ H ₄ 21 3- (CH ₃ J ₂ CH-C ₆ H ₄ 22 4- (CH ₃ J ₂ CH-C ₆ H ₄ 23 2- (CH ₃ J ₃ CC ₆ H ₄ 24 3- (CH ₃ J ₃ CC ₆ H ₄ 25 4- (CH ₃ J ₃ CC ₆ H ₄ 26 2-CH ₃ OC ₆ H ₄

Oil

7.59

E E E

E N G E E R E S E R E S E T E R E S

Continuation Table IV

Connection no.

Melting point ( ⁰ C)

olefinically *

Isomer ⁺

27 3-CH ₃ OC ₆ H ₄ 28 4-CH ₃ OC ₆ H ₄ 29 2-CF ₃ OC ₆ H ₄ 30 3-CF ₃ OC ₆ H ₄ 31 4-CF ₃ OC ₆ H ₄ 32 2-C ₆ H ₆ OC ₆ H ₄ 33 3-C ₆ H ₅ OC ₆ H ₄ 34 4-C ₆ H ₅ OC ₆ H ₄ 35 2-NO ₂ -C ₆ H ₄ 36 3-NO ₂ -C ₆ H ₄ 37 4-NO ₂ -C ₆ H ₄ 38 2-NH ₂ -C ₆ H ₄ 39 3-NH ₂ -C ₆ H ₄ 40 4-NH ₂ -C ₆ H ₄ 41 2-C ₆ H ₅ -C ₆ H ₄ 42 3-C ₆ H ₅ -C ₆ H ₄ 43 4-C ₆ H ₅ -C ₆ H ₄ 44 2-HO ₂ CC ₆ H ₄ 45 3-HO ₂ CC ₆ H ₄ 46 4-HO ₂ CC ₆ H ₄ 47 2-CH ₃ O ₂ CC ₆ H ₄ 48 3-CH ₃ O ₂ CC ₆ H ₄ 49 4-CH ₃ O ₂ CC ₆ H ₄ 50 2- (CN) -C ₆ H ₄ 51 3- (CN) -C ₆ H ₄ 52 4- (CN) -C ₆ H ₄ 53 3-HO-C ₆ H ₄ 54 3-HO-C ₆ H ₄ 55 4-HO-C ₆ H ₄ 56 2-CH ₃ C (O) NH-C ₆ H ₄ 57 3-CH ₃ C (O) NH-C ₆ H ₄ 58 4-CH ₃ C (O) NH-C ₆ H ₄ 59 2,3-di-FC ₆ H ₃ 60 2,4-di-FC ₆ H ₃ 61 2,5-di-FC ₆ H ₃ 62 2,6-di-FC ₆ H ₃ 63 3,4-di-FC ₆ H ₃ 64 3,5-di-FC ₆ H ₃ 65 2,3-di-CI-C ₆ H ₃ 66 2,4-di-CI-C ₆ H ₃ 67 2,5-di-CI-C ₆ H ₃ 68 2,6-di-CI-C ₆ H ₃ 69 3,4-di-CI-C ₆ H ₃ 70 3.5 ^ i-CI-C ₆ H ₃ 71 2,3-di-CH ₃ -C ₆ H ₃ 72 2,4-di-CH ₃ -C ₆ H ₃ 73 2,5-di-CH ₃ -C ₆ H ₃ 74 2,6-di-CH ₃ -C ₆ H ₃ 75 3,4-di-CH ₃ -C ₆ H ₃ 76 3,5-di-CH ₃ -C ₆ H ₃ 77 2,3-di-CH ₃ OC ₆ H ₃ 78 2,4-di-CH ₃ OC ₆ H ₃ 79 2,5-di-CH ₃ OC ₆ H ₃ 80 2,6-di-CH ₃ OC ₆ H ₃ 81 3,4-di-CH ₃ OC ₆ H ₃ 82 3,5-di-CH ₃ OC ₆ H ₃ 83 2-F, 3-Cl-C ₆ H ₃ 84 2-F, 4-CI-C ₆ H ₃ 85 2-F, 5-CI-C ₆ H ₃ 86 2-F, 6-Cl-C ₆ H ₃ 87 3-F, 4-CI-C ₆ H ₃ 88 3-F, 5-CI-C ₆ H ₃ 89 2-CI-3-FC ₆ H ₃ 90 2-CI, 4-FC ₆ H ₃ 91 2-Cl, 5-FC ₆ H ₃ 92 3-Cl, 4-FC ₆ H ₃

E N G E E R E S E R E S E S E S E S E S E S E S E S E S E S E S E S E R E S E S E R E S E S E R E S E S E R E S E S E S E S E S E S E S E S E S E S

Continuation Table IV

Connection no.

Melting point ( ⁰ C)

olefinically *

Isomer ⁺

93 2-F, 3-CH ₃ -C ₆ H ₃ 94 2-F, 4-CH ₃ -C ₆ H ₃ 95 2-F, 5-CH ₃ -C ₆ H ₃ 96 2-F, 6-CH ₃ -C ₆ H ₃ 97 3-F, 4-CH ₃ -C ₆ H ₃ 98 3-F 1 -CH ₃ -C ₆ H ₃ 99 2-CH ₃ , 3-FC ₆ H ₃ 100 2-CH ₃ AF-C ₆ H ₃ 101 2-CH _3, 5-FC ₆ H ₃ 102 3-CH ₃ , 4-FC ₆ H ₃ 103 2-F, 3-CH ₃ OC ₆ H ₃ 104 2-F, 4-CH ₃ OC ₆ H ₃ 105 2-F, 5-CH ₃ OC ₆ H ₃ 106 2-F, 6-CH ₃ OC ₆ H ₃ 107 3-F, 4-CH ₃ OC ₆ H ₃ 108 3-F, 5-CH ₃ OC ₆ H ₃ 109 2-CH ₃ O, 3-FC ₆ H ₃ 110 2-CH ₃ O, 4-FC ₆ H ₃ 111 2-CH ₃ O, 5-FC ₆ H ₃ 112 3-CH ₃ OAF-C ₆ H ₃ 113 2-01, ₃ -CH ₃ -C ₆ H ₃ 114 2-01, 4-CH ₃ -C ₆ H ₃ 115 2-01.5-CH ₃ -C ₆ H ₃ 116 2-01, 6-CH ₃ -C ₆ H ₃ 117 3-01, 4-CH ₃ -C ₆ H ₃ 118 3-01.5-CH ₃ -C ₆ H ₃ 119 2-CH ₃ , 3-CI-C ₆ H ₃ 120 2-CH ₃ , 4-CI-C _e H ₃ 121 2-CH ₃ , 5-CI-C ₆ H ₃ 122 3-CH ₃ , 4-CI-C ₆ H ₃ 123 2-01, ₃ -CH ₃ OC ₆ H ₃ 124 2-CI, 4-CH ₃ OC ₆ H ₃ 125 2-01.5-CH ₃ OC ₆ H ₃ 126 2-01, 6-CH ₃ OC ₆ H ₃ 127 3-01, 4-CH ₃ OC ₆ H ₃ 128 3-01.5-CH ₃ OC ₆ H ₃ 129 2-CH ₃ O, 3-CI-C ₆ H ₃ 130 2-CH ₃ OACl-C ₆ H ₃ 131 2-CH ₃ O, 5-CI-C ₆ H ₃ 132 3-CH ₃ OACl-C ₆ H ₃ 133 2-CH ₃ ^ -CH ₃ OC ₆ H ₃ 134 2-CH ₃ , 4-CH ₃ OC ₆ H ₃ 135 2-CH ₃ , 5-CH ₃ OC ₆ H ₃ 136 2-CH ₃ , 6-CH ₃ OC ₆ H ₃ 137 3-CH ₃ ACH ₃ OC ₆ H ₃ 138 3-CH ₃ , 5-CH ₃ OC ₆ H ₃ 139 2-CH ₃ O, 3-CH ₃ -C ₆ H ₃ 140 2-CH ₃ OACH ₃ -C ₆ H ₃ 141 2-CH ₃ O, 5-CH ₃ -C ₆ H ₃ 142 3-CH ₃ OACH ₃ -C ₆ H ₃ 143 2,4,6-tri-FC ₆ H ₂ 144 2,4,6-tri-CI-C ₆ H ₂ 145 2,4,6-tri-CH ₃ -C ₆ H ₂ 146 2,6-di-FACI-C ₆ H ₂ 147 2,6-di-Me, 4-FC ₆ H ₂ 148 2,6- (Ji-CIAF-C ₆ H ₂ 149 2,3,5,6-tetra-CI-C ₆ H 150 pentafluorophenyl 151 pentachlorophenyl 152 · · H 153 CH ₃ 154 CH ₃ CH ₂ 155 CH3CH2CH2 156 (CH ₃ ) ₂ CH 157 CH3CH2CH2CH2 158 (CH ₃ J ₃ C

E E

E N G E E R E S E R E S E S E S E S E S E S E S E S E S E S E S E S E

Continuation Table IV

connection

melting point

( ⁰ C)

olefinically *

Isomer*

159 cyclohexyl 160 CH ₂ : CHCH ₂ 161 EC ₆ H ₅ CH: CHCH ₂ 162 CH ₂ : C (CH ₃ ) CH ₂ 163 E-CH ₃ CHiCHCH ₂ 164 2-tetrahydropyranyl 165 2-pyridyl 166 3-pyridyl 167 4-pyridyl 168 2- (5'-CF ₃ -pyridyl) 169 2-pyrimidyl 170 4-pyrimidyl 171 5-pyrimidyl 172 3,4-methylene 173 1-naphthyl 174 2-naphthyl 175 CH ₃ SCH ₂ 176 C ₆ H ₆ SCH ₂ 177 C ₆ H ₅ 178 2-furyl 179 3-furyl 180 2-thiophenyl 181 3-thiophenyl 182 2-pyrrolyl 183 3-pyrrolyl 184 ~ C ₆ H ₅ CH ₂ 185 C ₆ H ₅ CH (CH ₃ ) 186 C ₆ H ₅ C (CH ₃ I ₂

Oil

6.24

E N G E E N G L I S E R E S E T E R E S E S E

* Chemical rearrangement of the singlet from the olefinic proton to the B-methoxyacrylate group (ppm of tetramethylsilane).

Solvent: CDCl ₃ + geometry of B-methoxyacrylate group.

Table V

Table V contains compounds of the general formula:

RCH ₂ GH ₂

CO ₂ GH ₃

OCH

wherein the group R contains all the groups R listed in Table IV for each of the following substitution models on the phenyl ring shown above. The acrylate group may in either case have either E or Z geometry.

3-F

4-F

5-F

6-F

3-CI

4-CI

5-CI

6-Cl

3-CH ₃

4-CH ₃

5-CH ₃

6-CH ₃

3-NO ₂

4-NO ₂

H H H H H H H H H H H H

Continuation Table V Z Y H 5-NO ₂ H 6-NO ₂ H 5-CF ₃ 5-Cl 3-NO ₂ 5-NO ₂ 3-NO ₂ H 5-SCH ₃ 5-CH ₃ O 4-CH ₃ O H 4- (CH ₃ J ₂ N 4,5-methylenedioxy

Table Vl: Selected Proton NMR Data Table Vl shows selected proton NMR data for certain compounds described in Tables I to V characterized as oils therein. The chemical changes are measured in ppm of tetramethylsilane and deuterochloroform was consistently used as the solvent. The following abbreviations are used:

br = broad t = triplet

s = singlet q = quartet

d = doublet m multiple «

Connection no.

Table no.

III

1.27 (3H, t J 7Hz), 3.83 (3H, s), 4.21 (2H, qJ 7Hz), 7.32 (5H, br s), 7.53 (1H, s ).

1.30 (3H, t J 7 Hz), 3.72 (3H, s), 4.06 (2H, q J 7Hz), 7.31 (5H, br s), 7.62 (1H, s ). '.'

1.27 and 1.31 (2 triplet "J7 Hz, je3H"), 4.08 and 4.22 (2 quartet J7 Hz, je2H), 7.33 (5H, brs),

7.62 (1H, s).

3.81 (3H, s), 5.21 (2H, s), 7.34 (10H, brs), 7.56 (1H, s). 1.49 (9H, s), 3.82 (3H, s), 7.31 (5H, brs), 7.44 (1H, s). 1.42 (9H, s), 3.70 (3H, s), 6.50 (2H, s), 7.37 (1H, s).

., 28 (9H, s), 3.83 (3H, s), 6.46 (2H, s), 7.87 (1H, s).

3.67 (3H, s), 3.79 (3H, s), 5.18 (1H, dJ and 1Hz), 5 _r 65 (1H, dd, J18 and 1Hz), 6.68 (1H, dd, J18 and 11Hz) , 7.57 (1 H, s).

3.78 (3H, s), 3.95 (3H, s), 6.70 (1H, s).

2.18 (3H, s), 3.68 (3H, s), 3.82 (3H, s), 7.55 (1H, s).

3.68 (3H, s), 3.83 (6H, s), 7.25-7.6 (3H, m), 7.52 (1H, s), 7.9-8.1 (1H, m). 3.60 (3H, s), 3.66 (3H, s), 3.87 (2H, s), 7.48 (1H, s).

3.60 (3H, s), 3.70 (3H, s), 3.75 (3H, s), 3.80 (2H, s), 7.50 (1H, s).

3.6 (3H, s), 3.75 (3H, s), 7.0-8.15 (5H, m). '

3.66 (3H, s), 3.76 (3H, s), 7.51 (1H, s).

3.56 (3H, s), 3.73 (3H, s), 7.1-7.7 (9H, m), 7.9-8.1 (1H, m).

3.73 (3H, s), 3.85 (3H, s), 7.54 (1H, s).

3.77 (3H, s), 3.91 (3H, s), 6.64 (1H, s).

3.05 (3H, s), 3.43 (3H, s), 3.61 (3H, s).

3.53 (3H, s), 3.67 (3H, s), 3.85 (3H, s), 7.32 (1H, s).

3.63 (3H, s), 3.78 (3H, s), 6.80-7.40 (8H, m), 7.46 (1H, s).

3.60 (3H, s), 3.76 (3H, s), 6.8-7.0 (4H, m), 7.14-7.32 (4H, m), 7.45 (1H , s).

3.62 (3H, s), 3.77 (3H, s), 7.48 (1H, s).

3.66 (3H, s), 3.80 (3H, s), 3.82 (3H, s), 6.8-7.3 (8H, m), 7.51 (1H, s).

3.65 (3H, s), 3.79 (3H, s), 7.48 (1H, s).

3.70 (3H, s), 3.79 (3H, s), 3.82 (3H, s), 7.53 (1H, s).

1.1-2.1 (10H, m), 3.65 (3H, s), 3.76 (3H, s), 4.20 (1H, br s), 7.38 (1H, s) ,

3.63 (3H, s), 3.80 (3H, s), 4.51 (2H, d), 5.05-6.39 (3H, m), 6.70-7.35 (4H, m) , 7.46 (1H, s).

3.60 (3H, s), 3.74 (3H, s), 4.66 (2H, d), 6.00-7.40 (11H, m), 7.46 (1H, s).

3.54 '3H, s), 3.88 (3H, s), 6.60 (1H, s).

3.55 (3H, s), 3.74 (3H, s), 6.80 (1H, d), 6.95 (1H, m), 7.15-7.40 (4H, m), 7 , 43 (1H, s), 7.65 (1H, m), 8.19 (1H, m).

3.61 (3H, s), 3.78 (3H, s), 6.8-7.3 (8H, m), 7.47 (1H, s).

3.69 (3H, s), 3.88 (3H, s), 6.84 (1H, d), 7.60 (1H, s), 8.10 (1H, dd), 8.20 (1H, d ).

The compounds of the general formula (I) according to the invention can be prepared from substituted benzene of the general formula (IV) according to the steps explained in Scheme I. Throughout Scheme I, the terms R ¹ , R ² , X, Y and Z are as defined above, L is a halogen atom (iodine, bromine or chlorine) or a hydrogen atom and M is a metal atom (eg a lithium atom) or a metal atom plus an associated halogen atom (eg MgI, MgBr or MgCl). Thus, compounds of general formula (1) wherein R ¹ and R ^{2 are} not hydrogen atoms may be treated by treating ketoesters of general formula (II) wherein R ^{1 is} not hydrogen) with phosphoranes of general formula (V wherein R ^{2 is} not Hydrogen atom) in a suitable solvent, e.g. B. Diethyl ether, are prepared (see, for example: W. Steglich, G. Schramm, T. Anke and F. Oberwinkler, EP 0044448.4.7.80).

Ketoesters of the general formula (II, wherein R ^{1 is} not a hydrogen atom) can be prepared by treating meta lated species (III) with an oxaate (V ¹ , wherein R ^{1 is} not a hydrogen atom) in a suitable solvent, eg, diethyl ester or tetrahydrofuran. The preferred method often requires the slow addition of a solution of the metalated species (III) to a stirred solution of an excess of oxaiate (VI) (see, for example, LM Weinstock, RB Currie and AV Lovell, Synthetic Communications, 1981, 11, 943 and literature therein). , The metailed species (III), in which M = MgI, MgBr or MgCl (Grignard reagents), can be prepared by standard methods from the corresponding aromatic halides (IV) in which L = I ₁ Br or Cl, getting produced. With certain substituents X, Y and Z, the metailed species (III) in which M = Li can be prepared by direct lithiation of compounds (IV) in which L = H using a strong lithium base, e.g. For example, n-butyllithium or lithium diisopropylamide (see, for example, HW Gschwend and HR Rodriguez, Organic Reactions, 1979, 26, 1).

Compounds of general formula (IV) can be prepared by standard methods described in the chemical literature.

.Schema I

PH ₃ P. CHOR ² (V)

(II)

R ¹ O ₂ CCO ₂ R ¹ (VI)

(III)

(IV)

Alternative methods of preparing ketoesters of the general formula (II wherein R ^{1 is} not hydrogen) are described in the chemical literature (see, for example, DC Atkinson, KE Godfrey, B. Meek, JF Saville and MR Stillings, J. Med. Chem. , 1983, 26, 1335, D.Home, J. Gaudino and WJ Thompson, Tetrahedron Lett., 1984, 25, 3529, and GP Axiotis, Tetrahedron Lett., 1981, 22, 1509).

Alternative possibilities for compounds of the general formula (I) according to the invention are shown in Scheme II. Throughout Scheme II, the terms R ¹ , R ² , X, Y and Z are as defined above.

Scheme II

1. HCO ₀ R '

2 w * SX VA.

CH (OR ^),

(VIII)

(VII)

Compounds of general formula (I) wherein R ^{1 is} not hydrogen can be prepared by treating phenyl acetates of general formula (VII where R ^{1 is} not hydrogen) with a base and a formic ester, ζ. For example, methyl formate or HCO ₂ R ¹ , wherein R ^{1 has} the meaning described above, but is not a hydrogen atom, are prepared in a suitable solvent. When the reaction with a species of the general formula R ² Q, wherein R ^{2 is} as defined above, but is not a hydrogen atom and Q is an outgoing group, for. As a halogen atom is quenched, compounds of general formula (I) wherein R ^{2 is} not a hydrogen atom can be recovered. In contrast, when the reaction is quenched with water, compounds of general formula (I) wherein R ² = H are obtained. Compounds of general formula (I) in which R ² = H may be prepared in compounds (I) wherein R ^{2 is} not hydrogen by successive treatment with a base (eg potassium carbonate or sodium hydroxide) and a species of general formula R ² Q, wherein R ² and Q are as defined above, are converted into a suitable solvent.

In addition, compounds of general formula (I) wherein neither R ¹ nor R ^{2 are} hydrogen, may be prepared from acetals of general formula (VIII) wherein neither R ¹ nor R ^{2 are} hydrogen atoms under either basic or acidic conditions in suitable solvents and at suitable temperatures getting produced. An example of a suitable base is lithium diisopropylamide, and potassium bisulfate is an example of a suitable acidic reagent (see T. Yamada, H. Hagiwara and H. Uda, Journal of the Chem. Soc, Chem. Cammun., 1980, 838, and Acetals of the general formula (VIII) wherein neither R ¹ nor R ^{2 are} hydrogen may be prepared from phenylacetic esters of the general formula (VII wherein R ^{1 is} not hydrogen) by treatment with alkylsilyl ketene acetal derivatives of the species (VII) with trialkyl orthoformates Presence of a Lewis acid in a suitable solvent and at a suitable temperature (see for example K. Saigo, M. Osaki and T. Mukaiyama, Chem. Letts., 1976, 769) Alternative routes to the compounds of the general formula according to the invention (I) are shown in Scheme III. Throughout Scheme III, the terms R ¹ , R ² , X, Y and Z are as defined above.

Scheme III

0O ₂ R

CHOIR*

(12)

Thus, compounds of general formula (I) wherein R ^{1 is} not hydrogen and R ² = H may be prepared by partial reduction of malonate derivatives (IX wherein R ^{1 is} not hydrogen) using a reducing agent, e.g. B.

Lithium aluminum hydride, in a suitable solvent, for. For example, diethyl ether (see, for example

M. Barczai-Beks, G. Dornyei, G. Thoth, J. Tamas and Cs. Szantay, Tetrahedron, 1976, 32, 1153 and contained therein

Published data).

In addition, compounds of general formula (I) may be prepared from acrylic acid derivatives of general formula (X) by sequential treatment with bromine, a reagent of general formula R ² OM in which R ² and M are as defined above, and sodium hydrogensulfate or a related chemical See, for example, G. Shew and RN Warrener, Journal of the Chemical Society, 1958, 153 and incorporated herein

Published data).

Compounds of the general formulas (VIIj, (IX) and (X) can be synthesized by means of those described in the chemical literature

Standard procedures are produced.

All of the above methods, either in whole or in part (step), or in portions (steps) thereof, in any combination thereof, are to be considered as inventive methods. The compounds of the invention and metal complexes are effective fungicides, especially in the following diseases:

Pyricularia oryzae in rice

Puccinia recondita, Puccinia striiformis and other rust diseases in wheat, Puccinia hordei, Puccinia striiformis and other rust diseases in barley and rust diseases on other host plants, e.g. Coffee, pears, apples, peanuts, vegetables and

Ornamentals.

Erysiphegraminis (powdery mildew) in barley and wheat and other types of powdery mildew in various host plants

like Sphaerotheca macularis in hops.

Sphaerothecafuliginea in cucurbits (e.g., cucumbers), Podosphaera leucotricha in apples, and Uncinula necator

Vines.

Helminthosporium spp., Rhynchosporium spp., Septoria spp., Pseudocercosporella herpotrichoides and Gauomannomyces graminis in cereals. Cercespera arachidicola and Cercosporidium personata in peanuts and other Cercospora species in other host plants, for example sugar beets, bananas, soybeans and rice.

Botrytis cinera (gray mold) on tomatoes, strawberries, vegetables, vines and other host plants.

Alternaria species in vegetables (cucumbers), oilseeds, oilseed rape, apples, tomatoes and other host plants. Venturia inaequalis (scab) on apples, Plasmopara viticola on vines. Other types of frosted mildew such as Bremis lactucas in lettuce, Peronospera spp. in soybeans, tobacco, onions and other host plants and Pseudoperonospora humili in hops and Pseudoperonospera cubensis in pumpkin plants. Phytophthora infestans in potatoes and tomatoes and other Phytophthora spp. vegetables, strawberries, avocados, peppers, ornamental plants, tobacco, cocoa and other host plants. Thanatephorus cucumeris in rice and other Rhizoctonia species in various host plants, e.g. Wheat and barley, vegetables,

Cotton and grass.

Some of the compounds have also demonstrated a broad potency against fungi in vitro. They are effective against various post-harvest diseases of fruits (eg Penicillium digitatum and italicum and Trichoderma viride in oranges and Gloesporium musarum in bananas).

Further, some of the compounds are effective seed dressings against Fusarium spp., Tilletia spp., Septoria spp., (Wheat brandy, a seed-derived disease in wheat), Ustilago spp., Helminthosporium spp. in cereals, Hhizoctonia solani in cotton and Pyricularia oryzae in rice.

The compounds can penetrate acropetally into the plant tissue. In addition, the compounds may be so volatile that they are effective in the vapor phase against fungi found on the plants.

The compounds can also be used as industrial (as opposed to agricultural) fungicides, e.g. B. to prevent fungal infestation of wood, hides, leather and especially paints.

Some of the compounds exhibit herbicidal activity and can be used in the correspondingly larger application amount for controlling weeds.

In addition, some of the compounds also show plant growth regulating activity and can be reused in appropriate amounts for that purpose. The invention therefore includes the above-described uses of the compounds (and the compositions containing them) in addition to their principal

Use as fungicides.

The compounds can be used as such for fungicidal purposes, but mostly become compositions

formulated for such use.

embodiments

In the following examples, the invention will be explained. In all of these examples, the term "ether" refers to diethyl ether, magnesium sulfate was used to dry solutions, and reactions yielding water-sensitive intermediates were made under a nitrogen atmosphere, and unless otherwise stated, chromatography using silica gel became stationary If indicated, infrared and NMR data are selective and no attempt has been made to record each absorbance, the following abbreviations are always used:

THF = tetrahydrofuran S = singlet

DMF = Ν, Ν-dimethylformamide d = doublet

GC = gas chromatography t = triplet

MS = mass spectrum m = multiple «

example 1

This example illustrates the preparation of 2E, 1 "Z-methyl-3-methoxy-2- [2 '- (2" -phenylethenyl) phenyl] propenoate (Compound Number 13 of Table I).

Potassium tert-butoxide (5.30g) was added in one portion to a vigorously stirred suspension of benzyltriphenylphosphonium chloride (21.02g) in dry ether (250ml). After 25 minutes the resulting orange mixture was treated with a solution of 2-bromobenzaldehyde (5.00 g) in dry ether (50 ml) and the mixture showed a lighter color. After an additional hour, the mixture was poured into water and extracted with ether. The extracts were washed with water, dried, concentrated under reduced pressure and chromatographed using dichloromethane as eluent to give 1-phenyl-2- (2-bromophenyl) ethylene (5.95 g, 85% yield). An almost colorless oil formed as a 6: 1 mixture of Z: E isomers (by GC / MS).

A solution of the Grignard reagent prepared from a portion of the mixture of the above described isomers of 1-phenyl-2- (2-bromophenoxyethylene (5.58 g) and magnesium (0.63 g) in dry THF (20 mL) was added dropwise over 30 minutes to a stirred solution of dimethyloxalate (5.06 g) in dry THF (40 ml) cooled to -15 ° C. The resulting mixture was stirred at about -15 ° C. for 30 minutes. then poured into dilute hydrochloric acid for one hour and extracted with ether, the extracts were washed with water, dried, concentrated under reduced pressure and then twice [(i) 30% ether in benzone; (ii) 20% hexane in Dichloromethane] to give isometrically pure Z-methyl-2- (2'-phenylethenyl) phenylglyoxalate (1.76 g, 31% yield) as a yellow oil, 1 H NMR (CDCl ₃ ): delta 3.87 (3H, s), 6.78 (center of 2 doublets, each 1 H ₁ J 12Hz) ppm.

Potassium tert-butoxide (2.00g) was added as a single portion to a stirred suspension of (methoxymethyl) -triphenylphosphonium chloride 6.78g) in dry ether (80ml). After 25 minutes, the resulting red suspension was treated with a solution of Z-methyl-2- (2'-phenylathenyl) -phenylglyoxalate (1.76g) in dry ether (20ml) to leave the color. After IV2 hours, the reaction mixture was poured into water and extracted with ether. The extracts were washed with water, dried, passed through a short column of silica gel with dichloromethane, then carefully chromatographed using 30% ether in gasoline as eluent to give the title compound (0.46g, yield 24%) as a Infrared (film): 1715.1 635 cm ^-1 ; ¹ H NMR (CDCl ₃ ): delta 3.62 (3 H, S), 3.73 (3 H, S), 6.48 (2 H, s), 7.50 (1H, s) ppm.

Example 2

In this example, the preparation of E- and Z-methyl-3-methoxy-2-phenylpropenoate (compounds Nos. 1 and 2 of Table I) is illustrated.

Potassium tert -butoxide (9.52g) was added as a single portion to a stirred suspension of (methoxymethyl) triphenylphosphonium chloride (34.3g) in dry ether (300ml). After 45 minutes, the resulting red suspension was treated with a solution of methyl benzoylformate (8.20 g) in dry ether (100 ml) (color left, exothermic). After 3 hours, the mixture was diluted with water, treated with magnesium sulfate and charcoal, then concentrated under reduced pressure to give the crude product (36.39 g) as a yellow oil which partially crystallized on standing. It was passed through silica gel using dichloromethane, then carefully using dichloromethane: petrol (2: 1 (chromatographed to give E-methyl-3-methoxy-2-phenylpropenoate (4.83 g, 50% yield) as a pale yellow, first alumina oil, infrared (film): 1710.1630 cm ^-1 , 1 H NMR (CDCl ₃ ): delta 7.55 (s, olefinic proton) and Z-methyl-3-methoxy-2-phenylpropenoate (3, 43 g, yield 36%) which eluted second, as a light yellow oil, infrared (film): 1715.1 630CnTVH NMR (CDCl ₃ ): delta 3.76 (3H, s), 3.90 (3H, s), 6.65 (1H, s), 7.28 (5H, s) ppm.

A sample of E-methyl-3-methoxy-2-phenylpropenoate prepared from methyl phenylacetate by the method described in Examples 4 and 7, that is by reaction with sodium hydride and methyl formate and treating the resulting enol with potassium carbonate and dimethyl sulfate on standing and had a melting point of 37-38 ° C.

Example 3

In this example, the preparation of 2E, 1 "E and 2Z, 1" E-methyl-3-methoxy-2- [2 '- (2 "-phenylethenyl) phenyl] propenoate (compounds Nos. 9 and 10 of Table I) explained.

A solution of 2-bromobenzaldehyde (18.50 g) in dry ether (20 ml) was added dropwise to a stirred solution of benzylmagnesium chloride [prepared from benzyl chloride (12.64 g) and magnesium (2.68 g)] in dry ether (120 ml ) so that a thick precipitate formed during the addition. The mixture was stirred for 1 hour at room temperature, then poured into water, acidified with 2N hydrochloric acid and extracted with ether. The extracts were washed with water, dried, concentrated and chromatographed using dichloromethane and benzene (1: 1) as eluent to give 1- (2-bromophenyl) -2-phenylethan-1-ol (10.95g, yield 40%). ) was recovered in the form of a white solid having a melting point of 84 to 85 ⁰ C.

A stirred mixture of 1- (2-bromophenyl) -2-phenylethane-1-ol (15,50g) of orthophosphoric acid (150ml) was maintained for 1 hour at 17O ⁰ C and then poured into iced water and extracted with ether. The extracts were washed with water, dried and concentrated to give the crude product as an orange oil (14.29g). Evaporation distillation (0.3 Torr, oven temperature 14O ⁰ C) gave E-1-phenyl-2- (2-bromophenyl) ethylene (12.53 g, 86% yield) as a light yellow oil of 97% purity GC.

A solution of the Orignard reagent prepared from E-1-phenyl-2- (2-bromophenyl) ethylene (8.56 g) and magnesium (0.96 g) in dry tetrahydrofuran (20 mL) became dropwise over 30 minutes stirred solution of dimethyloxalate (7.76g) in dry tetrahydrofuran (70ml) which had been cooled to -15 ° C. The resulting mixture was stirred for 30 minutes at about -15 ⁰ C, then extracted at room temperature, then poured into dilute hydrochloric acid and sä with ether for 1 hour. The extracts were washed with water, dried and concentrated to give the crude product as a yellow oil (17.22g). Purification by column chromatography using dichloromethane and benzene (1: 1) as the eluent followed by evaporation distillation (0.07 torr, oven temperature 17O ⁰ C) gave E-methyl-2- (2'-phenylethenyl) phenylglyoxalate ( 2.01 g, yield 23%) in the form of a yellow oil, pure by GC, ¹ HNMR (CDCl ₃ ): delta 3.78 (3H, s), 6.88 (center of 2 doublets, each 1H, J16Hz) ppm.

Potassium tert -butoxide (2.19 g) was added in a single portion to a stirred suspension of (methoxymethyl) triphenylphosphonium chloride (7.41 g) in dry ether (100 ml). After 25 minutes, the resulting red suspension was treated with a solution of E-methyl 2- (2'-phenylglyoxalate (1.92 g) in dry ether (20 ml), which faded to color After 15 minutes, the mixture was dissolved in water The extracts were washed with water, dried and chromatographed using 30% ether in gasoline as the eluent to obtain (i) the first eluted 2E, 1 "E isomer of the title compound as a light yellow oil (1 , 06g, yield 50%), which crystallized on standing and gave a white solid with a melting point of 103-104 ° C.

An analytical sample recrystallized from an ether-petrol mixture had a melting point 107-108 ⁰ C, infrared (nujol mull): 1700.1 630CM ^{"1; 1} H NMR (CDCI _3): delta 3.68 (3H, s ), 3.80 (3H, s), 7.06 (2H, s), 7.63 (1H, s) ppm, and (ii) the 2Z, 1 "Is isomer of the titer compound which was eluted second in the form of a viscous oil (0.260g, yield 12%), infrared (film): 1710.1 625cm ^-1 ; ¹ H NMR (CDCl ₃ ): delta 3.65 (3H, s), 3.92 (3H, s), 6.57 (1H, s), 6.99 and 7.24 (each 1H, dJ 16Hz) ppm.

Example 4

In this example, the preparation of E-methyl-2- (2-chloro-6-fluorophenyl) -3-methoxypropenoate (Compound No. 27 of Table I) is illustrated.

A mixture of methyl (2-chloro-6-fluorophenyl) acetate (5.20 g) and methyl formate (31.4 ml) in dry DMF (40 ml) was added dropwise to a stirred suspension of sodium hydride (1.23 g) in dry DMF (40 ml) at a temperature between 0 and 5 ° C temperature. There was strong gas evolution. The reaction mixture was stirred for 3½ hours at room temperature, then poured into a mixture of ice and aqueous sodium carbonate and washed with ether. The resulting aqueous mixture was acidified with concentrated hydrochloric acid and extracted with ether. The extracts were washed with water, dried and concentrated to give methyl 2- (2-chloro-6-fluorophenyl) -3-hydroxypropenoate (3.44g) as a white solid.

A stirred solution of this crude product in dry DMF (30 ml) was treated sequentially with potassium carbonate (4.11 g) and dimethyl sulfate (1.34 ml). The resulting mixture was stirred for 1 hour at room temperature and then poured into water and extracted with ether. The extracts were washed with water, dried and concentrated to afford the title compound (2.91 g) as a white solid having a melting point of 77-78 ° C. Crystallization from 60 to 80 ° C gasoline, colorless crystals [2.61 g, yield 42% of methyl (2-chloro-6-fluorophenyl) acetate], having a melting point of 79 to 80 ° C, ¹ NMR ( CDCl ₃ ): Delta 3.69 (3H, s), 3.84 (3H, s), 7.62 (1H, s) ppm.

Example 5

In this example, the preparation of E-methyl-2- (2-phenoxy) -phenyl-3-methoxyacrylate (Compound No. 1 of Table II) is illustrated.

Potassium tert-butoxide (5.6 g) was dissolved in dry ether (150 ml) (12.3 g) at -70 ⁰ C to a stirred solution of diphenyl ether. The resulting mixture was stirred for 15 minutes at this temperature, then m-butyllithium (30.5 ml) of 1.62 M solution in hexane) was added to give a red-brown suspension which was allowed to warm to room temperature. This mixture (250 ml) at -1O ⁰ C given in the course of 20 minutes to a stirred suspension of dimethyl oxalate (11.8 g) in ether, then allowed to warm to room temperature. After 30 minutes, the mixture was poured into water and extracted with ether. The combined extracts were washed with water, dried, then concentrated to give a red oil (14.21 g). Chromatography using 20% ether in gasoline as eluant afforded methyl 2-phenoxybenzoylformate (2.23g) as a yellow oil.

Potassium tert -butoxide (2.64g) was added to a vigorously stirred suspension of (methoxymethyl) triphenylphosphonium chloride (8.93g) in dry ether (100ml). After 20 minutes, the resulting red suspension was treated with a solution of methyl 2-phenoxybenzoylformate (2.23g) in dry ether (20ml), the color fading.

After 15 minutes, the mixture was poured into water and extracted with ether. The combined extracts were washed with water, dried and concentrated to give a yellow oil (7.30g).

Chromatography using dichloromethane as the eluant afforded the title compound (0.61g) as a colorless oil, infrared (film): 1 710.1 635 CiTT ¹ , ¹ H NMR (CDCl ₃ ): Delta: 3.60 (3H , s), 3.75 (3H, s), 7.47 (1H, s) ppm.

Example 6

In this example, an alternative process for the preparation of E-methyl-2- (2-phenoxy) phenyl-3-methoxy-propenoate (Compound Number 1 of Table II) is described.

A 1 M solution of borane-tetrahydrofuran complex (30ml) was added dropwise to a stirred solution of 2-phenoxybenzoic acid (5.35 g) in dry, chilled to 0 ⁰ C THF (50 ml) (effervescence). Following this addition, the mixture was stirred for 15 minutes at 0 ⁰ C, then IV2 hours at room temperature. It was poured into water and extracted with ether. The extracts were washed successively with water, aqueous sodium bicarbonate, aqueous sodium carbonate, then dried and concentrated under reduced pressure to obtain 2-phenoxybenzyl alcohol (4.83 g, yield 97%) as a colorless oil.

Thionyl chloride (1.92 ml) was added in one portion to a solution of 2-phenoxybenzyl alcohol (4.80 g) in dry dichloromethane (50 ml). The resulting mixture was stirred for 2 hours at room temperature, then washed with water (2x), aqueous sodium bicarbonate (2x) and aqueous sodium chloride, dried and concentrated under reduced pressure to give 2-phenoxybenzyl chloride (4.87 g, 93% yield) as colorless oil was obtained.

Carbon dioxide was dissolved in a solution of 2-Phenoxybenzylmagnesiumchlorid [2-phenoxybenzyl chloride (4.80 g) and magnesium turnings (0.64 g)] in dry ether (15 ml) which was cooled to 0 ⁰ C blown. Dry THF was added to aid solubility. When the exothermic reaction was completed, no further carbon dioxide was bubbled through the mixture and this was left to warm to room temperature. The mixture was poured into water, washed with ether, then treated with hydrochloric acid and extracted with ether. The extracts were washed with water, dried and concentrated reduced pressure to give 2-phenoxyphenylacetic acid (61% 3,06g, yield) was obtained as a solid having a melting point of 82-85 ⁰ C. An analytical sample recrystallized from ether / gasoline had a melting point of 85 to 86 ^° C.

A solution of 2-phenoxyphenylacetic acid (2.75 g) in dry methanol (30 ml) containing concentrated sulfuric acid (0.3 ml) was refluxed for 2 hours, then allowed to cool, poured into water and extracted with ether. The extracts were washed with water, dried and concentrated under reduced pressure to give methyl 2-phenoxyphenylacetate (2.65 g, 91% yield) as a pale yellow oil.

This ester was converted in 2 steps to the title compound by the procedure described in Example 4, that is, by reaction with sodium hydride and methyl formate and by treating the resulting enol with potassium carbonate and dimethyl sulfate (total yield = 65%).

Example 7

This example describes the preparation of E-methyl-2- (2-benzyloxy) phenyl-3-methoxyacrylate (Compound Number 177 of Table II).

A mixture of methyl formate (24.4 ml) and methyl o- (benzyloxy) -phenylacetate (5.10 g) in dry DMF (30 ml) was added dropwise to a stirred suspension of sodium hydride (0.95 g) in dry DMF (30 ml ) at between 0 to 5 ° C. There was a violent evolution of gas. The reaction mixture was stirred for 372 hours at room temperature, then poured into a mixture of ice and aqueous sodium carbonate. The resulting aqueous solution was washed with ether (3x), then acidified with concentrated hydrochloric acid and extracted with ether. The extracts were washed with water, dried and concentrated to give methyl 2- (2-benzyloxy) phenyl-3-hydroxyacrylate (4.38g) as a yellow oil.

Potassium carbonate (4.26g) and dimethyl sulfate (1.38ml) were added sequentially to a stirred solution of methyl 2- (2-benzyloxy) phenyl-3-hydroxyacrylate (4.38g) in dry DMF (40ml). After one hour at room temperature, the reaction mixture was poured into water and extracted with ether. The extracts were washed with water, dried, concentrated and triturated with petrol to give the title compound (3.38 g, 57% yield from methyl o- (benzyloxy) phenylacetate) as a white solid having a melting point of 74-75 ⁰ C. to win. Crystallization of the entire sample from methanol gave colorless crystals (2.35 g) with a melting point of 76-77 ° C, ¹ H NMR (CDCl ₃ ) delta 3.63 (3H, s), 3.76 (3H, s), 5.05 (2H, s), 7.49 (1H, s) ppm.

Examples

In this example, the preparation of E-methyl-2- (4-chlorophenyl) -3-methoxypropenoate (Compound Number 22 of Table I) is described. A solution of methyl 4-chlorophenylacetate (3.51 g) in dry THF (25 ml) was added dropwise to a stirred solution of lithium diisopropylamide [of diisopropylamine (2.88 g) and n-butyllithium (16.4 ml of 1.62M solution (of η-hexane)] in dry THF 25ml) at -7O ⁰ C. After IV2 hours at the same temperature, a solution of trimethylsilyl chloride (5.16g) in dry THF (5ml) was added and after 10 minutes, the solution was allowed to warm to room temperature. Volatile components of the resulting mixture were removed under reduced pressure, and the ethereal fraction of the residue was collected by repeated trituration with dry ether, filtration and concentration of the filtrate under reduced pressure. This gave the crude methyl silyl enol ether (5.18 g) as an orange oil whose infrared spectrum showed almost no carbonyl absorption and a maximum of 164 OCm ^-1 .

A solution of titanium tetrachloride (3,60g) in dry dichloromethane (5 ml) was added dropwise to a stirred solution of trimethyl orthoformate (1.92 g) in dry dichloromethane (30ml) at -70 ⁰ C. After 15 minutes at the same temperature a solution of the crude Methyleilylenolethers (5,18g) described above was dissolved in dry dichloromethane (20 mL) still at -70 ⁰ C. After V2 hours, aqueous potassium carbonate was added to the still -70 ° C reaction mixture, and this was extracted with ether. The extracts were washed with water, dried, concentrated under reduced pressure and chromatographed using ether: gasoline (1: 1) as eluent to give methyl 2- (4-chlorophenyl) -3,3-dimethoxypropanoate (2.26 g , Yield 46% of methyl 4-chlorophenyl acetate) in the form of a white solid having a melting point of 61 to 62 ° C was recovered.

A solution of methyl 2- (4-chlorophenyl) -3,3-dimethoxy-propanoate (1.65 g) in dry THF (20ml) was added at -70 ⁰ C was added dropwise to a stirred solution of lithium diisopropylamide [from diisopropylamine (0, 84g) in n-butyl lithium (4.7 ml of 1.62 M solution in η-hexane] in dry THF (20 ml). After V2 hour at -70 ⁰ C the reaction mixture was poured into water and extracted with ether. The extracts were washed with water, dried, concentrated under reduced pressure and chromatographed using 40% ether in gasoline as eluent to give the title compound (0.31 g, Yield 21%) as a light yellow solid, mp 61-62 ° C, infrared (Nujol) 1 685, 1615cm- ¹ , ¹ HNMR (CDCl ₃ ) delta 3.74 and 3.88 (3H, s each), 7.56 (1H, s) ppm.

Example 9

This example describes the preparation of E-methyl-2- (2- (4-methylphenoxy) phenyl-3-methoxylpropenoate (Compound Number 16 of Table II).

4-Methylphenol (8.40g) was added to a stirred methanolic solution of sodium methoxide [of sodium (1.78g) in dry methanol (50ml)]. After 2h, the methanol was removed under reduced pressure and the residue was mixed with 4-methylphenol (4.20g), 2-chloroacetophenone (6.00g) and a catalytic amount of copper bronze. The resulting mixture was maintained at 135 ⁰ C IV2 hours, then allowed to cool, diluted with water and extracted with ether. The extracts were washed successively with aqueous sodium hydroxide and aqueous sodium chloride, then dried and concentrated under reduced pressure to yield a dark oil (8.20 g). This crude product was purified by evaporation distillation (130-135 ° C at 0.02 Torr) to give 2- (4-methylphenoxy) acetophenone (7.29 g, 83% yield) as a colorless liquid. Infrared (Film) 1670cm " ¹ .

A solution of boron trifluoride etherate (18.06g) and 2- (4-methylphenoxy) acetophenone (7.29g) in dry methanol (8.3ml) was added to a stirred ice-cold suspension of lead tetraacetate (14.97g) in dry ether (70ml). given. The resulting mixture was stirred at room temperature for 18 hours, then poured into water and extracted with ether. The extracts were washed successively with water and aqueous sodium bicarbonate, dried and concentrated under reduced pressure to give a red oil (7.53 g), the methyl 2- (4-methylphenoxy) phenylacetate and the starting acetophenone ( 4: 1 by GC). The mixture was treated with aqueous potassium hydroxide and the resulting substituted phenylacetic acid was purified by acid-base extractions and reesterified in acidic methanol to give methyl 2- (4-methylphenoxy) -phenylacetate (5.00 g) as a thick oil , Infrared (film) 1730 cm "" ¹ . This ester was converted to the title compound in two steps by the method described in Examples 4 and 7, that is, by reaction with sodium hydride and methyl formate and treatment of the resulting enol with potassium carbonate and dimethyl sulfate (total yield = 32%).

The product had after recrystallization from methanol has a melting point of 80-81 ⁰ C, infrared (nujol) 1 690.1 620 cm ^{"1, 1} H NMR (CDCI ₃₎ delta 2.30 (3H, s), 3.62 (3H, s), 3.77 (3H, s), 7.50 (1H, s), ppm.

Example 10

This example describes the preparation of E- and Z-methyl-3-methoxy-2- (2-phenylethyl) phenylpropenoate (Compounds Nos. 1 and 177 of Table IV).

Trifluoroacetic acid (46 ml) was added in one portion to a stirred mixture of 1- (2-bromophenyl) -2-phenylethan-1-ol (16.51 g, prepared as described in Example 3) and triethylsilane (13.80 g). The resulting mixture was stirred at room temperature for about 22 hours, after which excess trifluoroacetic acid was removed under reduced pressure. The residue was dissolved in ether and washed successively with water, aqueous sodium bicarbonate (3x) and water (2x), then dried, concentrated under reduced pressure and chromatographed using 10% dichloromethane in gasoline as eluent to give 1- (2- Bromophenyl) -2-phenylethane (8.02g, 52% yield) was recovered as a colorless oil.

This sample of 1- (2-bromophenyl) -2-phenylethane was converted to the title compounds in two steps by the method described in Examples 1 and 3, that is by reaction of the magnesium derivative with dimethyl oxalate and treatment of the resulting ketoester with methoxymethylenetriphenylphosphorane , The Ε isomer, which eluted first in 30% ether in gasoline, was an oil, infrared (film) 1 705 and 1 630 cm ^-1 , ¹ H NMR (CDCl ₃ ) delta 2.79 (4H, s), 3, 69 (3H, s), 3.79 (3H, s), 7.59 (1H, s) ppm. The second Z-isomer was also an oil, infrared (film) 1715, 1695 and 1630 cm ^-1 , ¹ H NMR (CDCl ₃ ) delta 2.84 (4H, s), 3.68 (3H, s), 3.84 (3H, s), 6.24 (1H, s) ppm.

Example 11

In this example, the preparation of 2E, 1E "- and 2Z, 1" E-methyl-2- [2 '- [2 "-2"' - furyl ethenyl) phenyl] -3-methoxy-propenoate (compounds number 55 and 56 of Table I).

A mixture of 2-bromobenzyl bromide (12.10g) and trimethyl phosphite (8.56ml) was stirred in a flask connected via a distillation head to a condenser. This reaction mixture was maintained at 110 ⁰ C for 1 hour (then additional trimethyl phosphite [5 mm] was added) and then kept at 13O ⁰ C for 2V2 hours, the temperature at the distillation head always being below 4O ⁰ C. The mixture was allowed to cool and the volatile fraction was removed under reduced pressure leaving a near colorless liquid (21.65 g). By evaporative distillation of part of this liquid (18,35g) was dimethyl-2-brombenzylphosphanat (8, Ö2g, yield 55%) as a colorless liquid, collected at 175 to 180 ⁰ C (0.15 mbar), with a Purity of 78% obtained by GC. An analytical sample purified by chromatography using ethyl acetate: 60-80 ° C gasoline (2: 1) as eluent had ¹ H NMR (CDCl ₃ ) delta 3.43 (2H, d J 23Hz), 3.72 ( DJ 11 Hz) ppm.

A solution of dimethyl 2-bromobenzylphosphonate (10.35g) in dry DMF (50ml) was added dropwise at room temperature to a stirred suspension of sodium hydride (0.979g) in dry DMF (100mL) (effervescence). After 20 minutes, a solution of furfural (3.56 g) in dry DMF (50 ml) was added (exothermic) and the resulting mixture was stirred for 4 hours at room temperature, then diluted with water, extracted with ether. The extracts were washed with water, treated with magnesium sulfate and charcoal, filtered, concentrated under reduced pressure and chromatographed using 40-60 ° C gasoline as the eluent to give egg- (2-furyl) -2- (2-bromophenyl ) ethylene (3.755g), a light yellow liquid (containing about 6% of the corresponding Z isomer according to GC).

This ethylene was converted to the title compounds in two steps by the method described in Examples 1 and 3, that is, by the reaction of the magnesium derivative with dimethyl oxalate and treatment of the resulting ketoester with methoxymethylenetriphenylphosphorane. The Ε, Ε isomer, which eluted first in 30% ether in petrol, was an oil, infrared (film) 1715 and 1 637 cm ^-1 , ¹ H NMR (CDCl ₃ ) delta 3.68 (3H, s), 3 , 81 (3H, s), 6.31 (1H, dJ 3.5Hz), 6.40 (1H, ddJ 3.5 and 2Hz), 6.83 and 6.98 (1H each, d J 16 Hz), 7.63 (1 H, s) ppm: the Ζ, Ε-isomer was a solid having a melting point 101.5 to 110 ⁰ C, infrared (nujol) 1 717 and 1 625cm- ^{1, 1} N NMR (CDCI ₃₎ delta 3.65 (3H, s), 3.93 (3H, s), 6.33 (1 H, d J 3.5Hz), 6.40 (1 H, dd J 3 , 5 and 2Hz), 6.56 (1 H, s) 6.82 and 7.10 (1 H, d J 16Hz each) ppm.

Claims (1)

1. Process for the preparation of compounds of general formula (I) and stereoisomers thereof, wherein X, Y and Z, which may be the same or different, are hydrogen or halogen atoms or optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, optionally substituted alkynyl, haloalkyl, alkoxy, haloalkoxy -, optionally substituted aryloxy, optionally substituted arylalkoxy, optionally substituted acyloxy, optionally substituted amino, optionally substituted arylazo, acylamino, nitro, nitrile, - CO ₂ R ³ -, - CONR ⁴ R ⁵ -, -COR ⁶ -, - CR ⁷ = NR ⁸ -or-N = CR ⁹ R ¹⁰ groups; or the groups X and Y, when in adjacent positions on the phenyl ring, can combine to form a fused ring which is either aromatic or aliphatic and optionally contains one or more heteroatoms; and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ , which may be the same or different, are hydrogen or alkyl, cycloalkyl, alkenyl, alkynyl -, optionally substituted aryl, optionally substituted aralkyl or cycloalkylalkyl groups, and metal complexes thereof, characterized in that a) a compound of general formula (II):