DD289045A5 - METHOD FOR PRODUCING DERIVATIVES OF ACRYLIC ACIDS FOR USE AS FUNGICIDES, INSECTICIDES, MITICIDES AND COMPOSITIONS - Google Patents

Abstract

The invention relates to a process for the preparation of derivatives of acrylic acid for use as fungicides, insecticides and miticides and compositions containing these compounds and which can be used to combat fungi, insects and mites. According to the invention, compounds of formula (I) are prepared and stereoisomers thereof. A and R2 have the meaning given in the description and in the claims. Formula (I) {acrylic acid derivatives; fungicides; Insecticides; miticides; Fighting fungi; Insects; mites}

Description

CO-CO-O-CH ₃

with a methoxymethylenating agent; wherein A, R ¹ and R ² are as defined above, L is a leaving group and R ⁵ is a metal atom.

2. Fungicidal, insecticidal or miticidal composition, characterized in that it consists of a compound as defined in claim 1 as an active ingredient and a fungicidal, insecticidal or miticidally acceptable carrier or diluent therefor.

3. Method, characterized in that it is used

(a) for the control of fungi, consisting in the application (to a plant, a plant seed or its location) of a fungicidally active amount of a compound as claimed in claim 1;

b) for the killing or control of insects or mites, consisting in the application to the insect or mite of an insecticidally or miticidally active amount of a compound claimed in claim 1 or to its whereabouts.

Field of application of the invention

The invention relates to a process for the preparation of derivatives of acrylic acid for use as fungicides, insecticides and miticides, compositions containing them and methods of their use for controlling fungi, especially fungal infections of plants, for killing or controlling insects and mites.

Characteristic of the known state of the art There is no information available on compounds which are useful both for the control of fungi and for the control of Insects and mites can be used. There is also no information available about processes for the preparation of derivatives of acrylic acid. Object of the invention The aim of the invention is to provide novel compounds which are applicable as fungicides, insecticides and miticides. Explanation of the essence of the invention

The invention has for its object to find new compounds with the desired properties and processes for their preparation.

According to the invention, compounds of the formula (I) are prepared

H ₃ COOC

and stereoisomers thereof, wherein A is hydrogen, halogen, hydroxy, C ^ alkyl, C ^ alkoxy, C _{(_} "- haloalkyl, C ^ haloalkoxy, C ^ alkylcarbonyl, Ci-4-alkoxycarbonyl, phenoxy, nitro or cyano R ¹ and R ² , which may be the same or different, are hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkylalkyl, optionally substituted aralkyl, optionally substituted heteroarylalkyl, optionally substituted aryloxyalkyl, optionally substituted heteroaryloxyalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted aryloxy, optionally substituted heteroaryloxy, nitro, halo, cyano, -NR ³ R 1 -COOR 1 -CO-NR ³ R ⁴ , -CO-R ³ , -S {O) _n -R ³ , where _{n is} 0, ¹ or ² , - (CH 2) _m ^ ^> O (OR ³ ) 2, wherein m is 0 or ^1, or R ¹ and R ² together form a carbocyc aliphatic or heterocyclic ring system; and R ³ and R ⁴ , which may be the same or different, are hydrogen, optionally substituted alkyl, optionally substituted aralkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl or optionally substituted heteroaryl. The compounds of the invention contain at least one carbon-nitrogen double bond and at least one carbon-carbon double bond and are sometimes obtained in the form of mixtures of geometric isomers. However, these mixtures can be separated into the individual isomers and this invention includes these isomers and mixtures thereof in all proportions.

The individual isomers resulting from the unsymmetrically substituted double bond of the acrylate group and the oxime are identified by the commonly used terms "Ε" and "Ζ". These terms are defined according to the system of Cahn, Ingold and Prelog, which has been fully described in the literature (see, for example, J. March, "Advanced Organic Chemistry", 3rd Edition, Wiley-Interscience, p. 109ff.).

With respect to the carbon-carbon double bond of the propenoate group, it is generally true that one isomer is more fungicidally active than the other, with the more active isomer being that in which the groups -COOCH ₃ and -OCH _{3 are} on opposite sides of the olefin. Bonding of the propenoate group stand (the Ε-isomer). These (E) -isomers form a preferred embodiment of this invention

 Halogens are fluorine, chlorine, bromine and iodine.

Alkyl and the alkyl moieties of alkoxy, aralkyl and aryloxyalkyl can be in the form of straight or branched chains and, unless otherwise indicated, usually contain 1-6 carbon atoms. Examples are methyl, ethyl, isopropyl and tert-butyl. Optional substituents include halo (especially chloro and fluoro), hydroxy, and C, _ ₄ -Allkoxy. Examples of substituted alkyl and substituted alkoxy are trifluoromethyl and trifluoromethoxy.

Cycloalkyl is normally Cs-e-cycloalkyl, for example cyclopropyl and cyclohexyl, and cycloalkylalkyl is normally Cj-e-cycloalkyKCnlalkyl, for example cyclopropylethyl. Alkenyl and alkynyl suitably contain 2-6 carbon atoms, typically 2-4 carbon atoms, in the form of straight or branched chains. Examples are ethenyl, allyl and propargyl. Substituted alkenyl and alkynyl groups optionally include substituted arylalkenyl (especially optionally substituted phenylethenyl) and arylalkynyl groups.

Aryl and the aryl groups of aralkyl, arylalkenyl, arylalkynyl, aryloxy and aryloxyalkyl are phenyl and naphthyl. The carbocyclic or heterocyclic ring system which R ¹ and R ² may form together is suitably an aliphatic, aromatic or mixed aliphatic / aromatic carbocyclic carbon-fuming system, for example cyclopentyl, cyclohexyl, cyclohexadienonyl, or a group comprising a fused benzene ring and / or or substituents such as methyl; or it may be a 5-10 membered heterocyclic ring system, for example, tetrahydropyranyl. The term heteroaryl is used to describe aromatic, heterocyclic groups. Heteroaryl and heterocyclyl and the heteroaryl and heterocyclyl moieties of other groups such as heteroaryloxyalkyl and heterocycloalkyl are typically 5- or 6-membered rings having one or more O, N or S heteroatoms attached to one or more other aromatic, heteroaromatic or heterocyclic rings such as one Benzene ring can be condensed. Examples are thienyl, furyl, pyrrolyl, triazolyl, thiazolyl, pyridyl, pyrimidyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolyl and quinoxaline and N-oxides thereof.

Substituents which may be present in optionally substituted aryl and heteroaryl moieties include one or more of the following: halo, hydroxy, mercapto, (V ₄ alkyl (especially methyl and ethyl), C ₂ -4 alkenyl (especially Ally!) , C ₂ -4 alkynyl (especially propargyl), C, ^ - alkoxy (especially methoxy), C ₂ ^ alkenyloxy (especially allyloxy), C ₂ ^ alkynyloxy (especially propargyloxy), halo C ^ alkyl ( especially trifluoromethyl), halo-C 1-4 alkoxy- (especially trifluoromethoxy), C 1-6 -alkylthio (especially methylthio), hydroxy-C 1-6 -alkyl, C 1-6 -alkoxy-C 1-6 -alkyl, C 1-6 -cycloalkyl, C 1-6 -alkyl CycloalkylC ^ alkyl, optionally substituted aryl (especially optionally substituted phenyl), optionally substituted heteroaryl (especially optionally substituted pyridyl or pyrimidinyl), optionally substituted aryloxy (especially optionally substituted phenoxy), optionally substituted heteroaryloxy (especially optionally substituted pyridyloxy or pyrimidinyloxy ), optionally substituted aryl-C, al kyl (especially optionally substituted benzyl, optionally substituted phenethyl and optionally substituted phenylpropyl) in which the alkyl moiety is optionally substituted by hydroxy, optionally substituted heteroarylC ^ alkyl (especially optionally substituted pyridyl or pyrimidinylC ^ alkyl), optionally substituted aryl -C ₂ _4 alkenyl (optionally substituted special Phenylothenyl), optionally substituted heteroaryl-C ^ alkenyl (especially optionally substituted Pyridyiethenyl or Pyrimidinylethenyl), optionally substituted aryl-C _M alkoxy (especially optionally substituted

Benzyloxy), optionally substituted heteroaryl-C 1-4 -alkoxy (especially optionally substituted pyridyl or pyrimidinyl-C 1-4 -alkoxy), optionally substituted aryloxy-C 1-4 -alkyl (especially phenoxymethyl), optionally substituted heteroaryloxy-C 1-4 alkyl (especially optionally substituted pyridyloxy or pyrimldinyloxy-Ct ^ -alkyl), acyloxy, including C 1-4 alkanoyloxy (especially acetoxy) and benzoyloxy, cyano, thlocyanato, nitro, -NR'R ", -NH-CO-R ', -NH-CO-NR'R ", -CO-NR'R", -COOR ', -O-SOj-R', -SO ₂ -R ', -CO-R', -CR '= NR "or -N = CR ¹ R 'in which R' and R "are independently hydrogen, C ^ alkyl, CI_ ₄ alkoxy, CI_ ₄ alkylthio, Cj-yCycloalkyl, C ^ cycloalkyl-C ^ alkyl, phenyl or Benzyl, wherein the phenyl or benzyl group is optionally substituted by halogen, C ^ alkyl or Ci _ »- alkoxy.

Substituents are present substituents in the aryl or heteroaryl rings one of the foregoing, one or more of the following: halogen, hydroxy, mercapto, d ^ alkyl, C ^ alkenyl, C ₂ _ ₄ alkinyl, C | _4- Alkoxy, Cj ^ -Alkenyloxy, C ₂ -4-Alkrnyloxy, halo-C ^ -alkyl, halo-C ^ -alkoxy, Ci-4-alkylthio, hydroxy-C ^ -alkyl, C ^ -cycloalkyl-C ^ -alkyl , C, ^ - alkoxy-C, ^ -alkyl, C ^ -cycloalkyl. Alkanoyloxy, benzoyloxy, cyano, thiocyanato, nitro, -NR'R ", -NH-CO-R ', -NH-CO-NR'R", - CO-NR'R ", - COOR', - SO ₂ - R ', - O-SO ₂ -R', - CO-R ', - CR' = NR "or -N = CR'R", in which R 'and R "have the meanings given above.

In one aspect, the invention comprises a compound of formula (I) wherein A is hydrogen, halogen, hydroxy, methyl, methoxy, trifluoromethyl, trifluoromethoxy, C ,. _2- alkylcarbonyl, C 1-4 alkoxycarbonyl, phenoxy, nitro or cyano; R 'is C 1-8 -alkyl, halo-C 1-4 -alkyl, C 1-4 -alkoxy, halo-C 1-4 -alkoxy, C 1-4 -alkylcarbonyl, C 1-3 -alkoxycarbonyl, cyano, phenyl-C 1-4 -alkyl, Phenyl, a 5- or 6-membered aromatic heterocycle having one or more O, N or S, optionally fused to a benzene ring, wherein the aromatic or heteroaromatic units are each optionally substituted with one or more halo, hydroxy, C 1-6 -alkyl, halo-C 1-4 -alkyl. alkyl, C 1-4 alkoxy, haloC 1-4 alkoxy, C 1-6 alkylcarbonyl, C 1-4 alkoxycarbonyl, nitro, cyano, phenyl, phenoxy, benzyl or benzyloxy; and R ² is hydrogen, halogen, C 1-6 alkyl, halo-C 1-6 alkyl, C 1-6 alkylcarbonyl, C 1-4 alkoxycarbonyl, cyano or phenyl; or R 'and R ^{2 taken} together form a Cfr-to-carbocyclic ring system.

In a further aspect, the invention comprises a compound of formula (I) wherein A is hydrogen or halogen; R ¹ is Ct-4 alkyl, benzyl, C 1-4 alkylcarbonyl, C 1-4 alkoxycarbonyl, cyano, phenyl, thionyl, triazolyl, thiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl or quinoxalinyl, wherein the aromatic or heteroaromatic Each optionally substituted with one or more halo, C 1-4 alkyl, trifluoromethyl, C 1-4 alkoxy, trifluoromethoxy, nitro, cyano, phenyl or benzyloxy; and R ² is hydrogen, Ct-4 * alkyl, C 1-4 alkylcarbonyl. C _t _4-alkoxycarbonyl, cyano or phenyl; or R ¹ and R ² together form a cyclopentyl or cyclohexyl ring to which a benzene ring is optionally condensed. This invention is illustrated by the compounds listed in Table I below. Throughout Table I, the methyl S-methoxy-acrylate group has (E) configuration.

Table I

CH ₃ O ₂ C

COMPOUND R ¹ R ² A oxime " Olefinic * MELTING ISOMER NO. 2-CH ₃ OC ₆ H ₄ H H 8:50 7.60 POINT ⁰ C RATIO ⁺⁺ 1 3-CH ₃ OC ₈ H ₄ H H 8:05 7.60 Oil 2 4-CH ₃ OC ₆ H ₄ H H Oil 3 2-CH ₃ -C ₈ H ₄ H H 4 3-C Hj-Ce H4 H H 8:05 7:59 (JI 4-CH ₃ -C ₈ H ₄ H H 8:07 7.60 Oil β 2-FC ₈ H ₄ H H Oil 19: 1 7 3-FC ₆ H ₄ H H 8th 4-FC H _{4 8} H H 9 2-Ci-C ₆ H ₄ H H 10 3-CkC ₆ H ₄ H H 8:04 7:59 11 4-CI-C ₆ H ₄ H H Oil 12 2-Br-C ₆ H ₄ H H 13 3-Br-C ₈ H ₄ H H 14 4-Br-C ₆ H ₄ H H 15 2-NO ₂ -C ₆ H ₄ H H 16 3-NO ₂ -C ₆ H ₄ H H 8.14 7.61 17 4-NO ₂ -C ₆ H ₄ H H Oil 18 2-CF ₃ -C ₆ H ₄ H H 19 3-CF ₃ -C ₆ H ₄ H H 8.12 7.60 20 4-CF ₃ -C ₆ H ₄ H H Oil 21 CoH ₅ H H 8.10 7.60 22 63-6

Table I (Contd.]

COMPOUND R ' R ² A oxime " Olefinic * MELTING ISOMER NO. C ₆ H ₅ CH ₃ H 7:59 POINT ⁰ C RATIO ⁺ * 23 C ₈ H ₆ C ₈ H ₆ H Oil 24 2-CeH (P ^- C (Jr ^ H H 25 3-CeHgrCel · ^ H H 26 4-CeH ₆ -C ₆ H ₄ H H 27 2- (CH 2 CHjO) -CeH ₄ H H 28 3- (CeH ₆ CH ₂ O) -CeH ₄ H H 8:06 7.60 29 4- (C ₆ H ₆ CHjOhC ₆ H ₄ H H Oil 30 2-cyano-C ₆ H ₄ H H 31 3-cyano-C ₆ H ₄ H H 8:07 7.60 32 4-cyano-C ₆ H ₄ H H Oil 33 2-CF ₃ O-CeH ₄ H H 34 3-CF ₃ OC ₆ H ₄ H H 35 4-CF ₃ OC ₆ H ₄ H H 36 pyrid-2-yl H H 8.19 7.60 37 pyrid-3-yl H H 8.10 7.60 Oil 38 pyrid-4-yl H H 8:03 7.61 Oil 39 pyrid-2-yl CH ₃ H 7.60 110.5-111.5 40 pyrid-2-yl cyano H 7.63 Oil 41 pyrid-2-yl CO ₂ CjH ₆ H 7:56 144-6 42 pyrid-2-yl CO ₂ CH ₃ H Oil 43 pyrimidin-2-yl H H 44 pyrimidin-4-yl H H 8:07 7.61 45 thien-2-yl H H 96-9 46 thien-2-yl CH ₃ H 7:58 47 5-CI-thien-2-yl H H Oil 16: 1 48 COjC ₂ Hs CO ₂ C ₂ H ₆ H 7:58 49 CO ₂ CH ₃ CO ₂ CH ₃ H Oil 50 COCH ₃ COCH ₃ H 51 cyano cyano H 52 0 0 H 53 0 0 H 54 0 0 H 7:58 55 tert-C ₄ H _a H H Oil 56 C ₆ H ₆ CH ₂ H H 57 2,4-di-CI-C6H ₃ H H 58 2,4-di-FC ₆ H ₃ H H 59 3,5-di-CH ₃ -C _e H ₃ H H 60 3.5 KJt CH ₃ OC ₆ H ₃ H H 61 pyrazin-2-yl CH ₃ H 7.61 62 6-CH ₃ -pyrid-3-yl CH ₃ H 7.60 116-118.5 63 pyrid-2-yl C ₂ H ₆ H 7.60 67-73 64 pyrid-3-yl CH ₃ H 7.60 70-80 65 pyrimidin-5-yl IsO-C ₃ H ₇ H 7.60 Oil 24: 1 66 JSO-C ₃ H ₇ pyrimidin-5-yl H 7:53 Oil 67 pyrid-4-yl CH ₃ H Oil 68 6-Cl-pyrid-2-yl CH ₃ H 69 5-Cl-pyrid-2-yl CH ₃ H 70 4-CI-pyrid-2-yl CH ₃ H 71 3-CPpyrid-2-yl CH ₃ H 72 6-cyano-pyrid-2-yl CH ₃ H 73 5-cy-η-pyrid-2-yl CH ₃ H 74 cyano-pyrid-2-yl CH ₃ H 7.61 75 3-cyano-pyrid-2-yl CH ₃ H 98-99 76 6-Br-pyrid-2-yl CH ₃ H 77 5-Br-pyrid-2-yl CH ₃ H 78 4-Br-pyrid-2-yl CH ₃ H 79 3-Br-pyrid-2-yl CH ₃ H 80 6-CHj-pyrid-2-yl CH ₃ H 81 5-CH3-pyrid-2-yl CH ₃ H 82 4-CH ₃ -pyrid-2-yl CH ₃ H 83 3-CH ₃ -pyrid-2-yl CH ₃ H 84 6-F-pyrid-2-yl CH ₃ H 85 5-F-pyrid-2-yl CH ₃ H 86

Table I (Contd.)

COMPOUND R ¹ R ² A OXIME » Olefinic MELTING ISOMER NO. 4-F-pyrid-2-yl CH ₃ H ⁺ POINTX RATIO ⁺ * 87 3-F-pyrid-2-yl CH ₃ H 88 3-CH ₃ -pyrazine-2-yl CH ₃ H 7.60 89 3-C ₂ Hs-pyrazir> -2-yl CH ₃ H 7:59 106-8 90 3-Cl-pyrazin-2-yl CH ₃ H 74-76.5 91 3-OCHj-pyrazin-2-yl CH ₃ H 7:58 92 5-CO ₂ CHa-pyrazir> -2-yl CH ₃ H 7.60 Oil 93 5-CO2C ₂ Hs-pyrroleir> -2-yl CH ₃ H Oil 4: 1 94 3 - <: yani> -pyrazir> -2-yl CH ₃ H 95 pyrimidin-4-yl CH ₃ H 96 2-Cl-pyrimidin-4-yl CH ₃ H 97 2-OCHA-pyrimidin-4-yl CH ₃ H 98 2-CH3-pyrimidin-4-yl CH ₃ H 99 2-cyano-pyrimidir> -4-yl CH ₃ H 100 thiazol-2-yl CH ₃ H 7.60 101 thien-3-yl CH ₃ H 7.60 107-114 10: 1 102 5-CI-thieiv2-yl CH ₃ H Oil 103 5-CHHhien-2-yl CH ₃ H 104 5-Br-thien-2-yl CH ₃ H 105 5-cyano-thien-2-yl CH ₃ H 106 3-CHj-thien-2-yl CH ₃ H 107 2-OCH ₃ -CeH ₄ CH ₃ H 7:57 108 3-OCH ₃ -C ₆ H ₄ CH ₃ H Oil 109 4-OCHr-C ₆ H ₄ CH ₃ H 7:57 110 2-CH ₃ -C ₈ H ₄ CH ₃ H 7:58 85-7 111 3-CH ₃ -C ₆ H ₄ CH ₃ H 7:58 Oil 112 4-CH ₃ -C ₆ H ₄ CH ₃ H 7:58 Oil 113 2-FC ₆ H ₄ CH ₃ H 7:59 Oil 114 3-FC ₆ H ₄ CH ₃ H 7.60 Oil 115 4-FC ₆ H ₄ CH ₃ H 7:59 Oil 116 2-CI-C ₆ H ₄ CH ₃ H Oil 117 3-CI-C ₆ H ₄ CH ₃ H 7:59 118 4-CI-C ₆ H ₄ CH ₃ H Oil 119 2-Br-C ₆ H ₄ CH ₃ H 120 3-Br-C ₆ H ₄ CH ₃ H 7:59 121 4-Br-C ₆ H ₄ CH ₃ H Oil 122 2-NO ₂ -C ₆ H ₄ CH ₃ H 7:59 123 3-NO ₂ -CeH ₄ CH ₃ H 70-72 124 4-NO ₂ -C ₆ H ₄ CH ₃ H 7.60 125 2-CF ₃ -C ₆ H ₄ CH ₃ H .100-2 126 3-CF ₁ -C ₆ H ₄ CH ₃ H 7.60 127 4-CF ₃ -C ₆ H ₄ CH ₃ H Oil 128 2-cyano-C _e H ₄ CH ₃ H 129 3-CyOnO-C ₆ H ₄ CH ₃ H 7.60 130 4-cyano-C ₆ H ₄ CH ₃ H 7:59 75.5-77 131 3,4,5- (OCH ₃ ) JC ₆ H ₄ CH ₃ H Oil 132 3,5-di-F-pyrid-2-yl CH ₃ H 133 3,4,5,6-F ₄ -pyrid-2-yl CH ₃ H 134 2,6-di-Cl-pyrid-3-yl CH ₃ H 135 pyridazin-3-yl CH ₃ H 136 pyridazin-4-yl CH ₃ H 137 6-CHj-pyridazin-3-yl CH ₃ H 138 4-cyano-quinolin-2-yl CH ₃ H 7.63 139 quinoxaline-2-yl CH ₃ H 7.62 160.5-162 140 C ₆ H ₅ CH ₃ 6-F 179-181 141 C ₆ H ₆ CH ₃ 6-Cl 142 tV CHr-pyrimidine - ^ - yl CH ₃ H 7.60 143 4-CH ₃ -pyrimidin-5-yl CH ₃ H 7:58 Oil 4: 1 144 4-CHj-pyrimidin-2-yl CH ₃ H 7:57 Oil 6: 1 145 4,6-di-CH ₃ -pyrimidin-2-yl CH ₃ H Oil 146 2,6-di-CH ₃ -pyrimidin-4-yl CH ₃ H 147 2,4-di-CH ₃ -pyrimidin-5-yl CH ₃ H 148 6-CI-pyrimidir> -4-yl CH ₃ H 149 e-OCHj-pyrimidirM-yl CH ₃ H 150

Table I (Contd.)

COMPOUND R ¹ R ² A oxime " Olefinic MELTING ISOMER NO. 4,6-di-OCH3-pyrimidin-2-yl CH ₃ H * POINT ⁰ C RATIO ⁺ * 151 0 0 H 7:58 152 0 0 H 7:58 Oil 153 N-oxide-pyrid-2-yl CH ₃ H 7:52 109-110 154 5-C ₂ H ₆ -pyrid-2-yl CH ₃ H Oil 155 CH ₃ CO CH ₃ H 7:59 156 C ₆ H ₆ CO CH ₃ H 7:56 78 157 N-CHj-pyrrol-2-yl CH ₃ H 7:57 55 158 4-CI-quinolin-2-yl CH ₃ H 7.62 Oil 159 2.4 ^ i-CkC ₆ H ₃ 1,2,4-triazol- H 7.61 114-116 160 _1-yl-CH2 Oil 2.4 ^ i-Ch-C ₆ H ₃ pyrid-3-yl-CH ₂ H 161 ^^ i-CHa-thiazol-ö-yl CH ₃ H 7:58 162 furan-2-yl CH ₃ H 7:58 Oil 163 ^ Di-CHj-furan-S-yl CH ₃ H Oil 164 pyrid-2-yl pyrid-2-yl H 7:56 165 6-C ₆ Hs-pyrimidin-4-yl CH ₃ H Oil 166 4-cyano-pyrid-3-yl CH ₃ H 167 1,2,4-triazin-5-yl CH ₃ H 168 3-CHH, 2,4-triazin-5-yl CH ₃ H 169 3-C ₆ H ₅ -1,2,4-triazin-5-yl CH ₃ H 170 3-SCHH, 2,4-triazin-5-yl CH ₃ H 171 3-OCH ₃ -1,2,4-triazine-5- / l CH ₃ H 172 5-CONH ₂ -pyrazine-2-yl CH ₃ H 7.60 173 5-cyano-pyrazin-2-yl CH ₃ H 7.62 146-8 3: 1 174 CH ₃ H 7.60 89-92 175 S, S-di-CHr-pyrazine ^ yl CH ₃ H 7:59 11Λ-6 176 S. E-di-CJVpyrazin ^ yl CH ₃ H 7:59 56-60 7: 3 177 5-CHr-pyrazin-2-yl CH ₃ H Oil 178 6-CH3-pyrazin-2-yl CH ₃ H 179 5-Cl-pyrazin-2-yl CH ₃ H 180 6-Cl-pyrazin-2-yl CH ₃ H 181 5,6-dicyano-pyrazin-2-yl CH ₃ H 182 4-SO ₂ CH ₃ -C ₆ H ₄ CH ₃ H 7:59 183 4-NHz-C ₆ H ₄ CH ₃ H 7:58 Oil 184 2,4-di-CI-C ₆ H ₃ CH ₃ H 7.60 Oil 185 2,4-dkCHr-C ₆ H ₃ CH ₃ H 7:57 79-82 186 4-NHCONH ₂ -C ₆ H ₄ CH ₃ H 66-68.5 187 C ₆ H ₆ cyclopropyl H 7:57 188 C ₆ H ₅ Cl H Oil 8: 1 189 4-C ₂ H ₆ OC ₆ H ₄ CF ₃ H 7:55 190 C ₆ H ₆ SCH ₃ H 7:57 Oil 191 C ₆ H ₆ F H Oil 192 C ₆ H ₆ OC ₂ H ₆ H 193 C (CH ₃ ), CH ₃ H 7:57 194 cyclohexyl CH ₂ CH ₃ H Oil 195 C ₆ H ₆ -CH ₂ CH ₃ H 7:57 196 pyrazine-2-yl-CH ₂ CH ₃ H Oil 197 (E) -C ₆ H ₆ -CH = CH CH ₃ H 7:58 198 C ₆ H ₆ -OCH ₂ CH ₃ H Oil 199 C ₆ H ₆ CH ₂ Cl H 200 benzothiazol-2-yl CH ₃ H 201 benzoxazoJ-2-yl CH ₃ H 202 pyrazin-2-yl C ₂ H ₆ H 203 5-OCH ₃ -pyrazine-2-yl CH ₃ H 204 6-OCH3-pyrazin-2-yl CH ₃ H 205 6-cyano-pyrazin-2-yl CH ₃ H 206 5-cyano-pyrid-3-yl CH ₃ H 207 6-cyano-pyrid-3-yl CH ₃ H 208 3-cyano-pyrid-4-yl CH ₃ H 209 2-cyano-pyrid-4-yl CH ₃ H 210 pyrimidin-5-yl CH ₃ H 211 2-CH3-pyrimidin-5-yl CH ₃ H 212 S-OCHR-isoxazol-e-yl CH ₃ H 213

Table I (Contd.)

COMPOUND R ¹ R ² A oxime " Olefinic * MELTING ISOMER NO. 3-BHsoxazol-5-yl CH ₃ H POINT ⁰ C RATIO ⁺ * 214 5-NOHhiazol-2-yl CH ₃ H 215 5-CHj-triiazol-2-yl CH ₃ H 216 4-CHj-thiazol-5-yl CH ₃ H 217 2-Cl, 4-CH3-thiazo! -5-yl CH ₃ H 218 3,5-dhOCHr-i, 2,4- CH ₃ H 219 triazin-6-yl 3,6-di-CHr-pyridazin-4-yl CH ₃ H 220 2- (CH ₆ OHC ₈ H ₄ CH ₃ H 221 3- (C ₈ H ₆ O) -CeH ₄ CH ₃ H 222 4- (CH ₆ OhC ₆ H ₄ CH ₃ H 223 1,2,4-triazol-yl-CH ₂ CH ₃ H 224 C ₈ H ₆ OCH ₃ H 7:53 225 OCH ₃ C ₆ H ₆ H 7:58 Gum 226 CH ₆ CH ₃ S (O) H 7.60 Gum 227 C ₆ H ₆ CH ₃ S (O) ₂ H 7.60 Gum 228 C ₆ H ₆ N (CHj) ₂ H Gum 229 C ₆ H ₆ O CH ₃ H 230 C ₆ H ₆ br H 231 CH ₆ I H 232 CH ₆ (CH ₃ I ₂ CHS H 233 Pyrimidir> -2-yl CH ₃ O H 234 Pyrazin-2-yl Cl H 235

statement

Chemical shift of the singlet of the olefinic proton of the 3-methoxyacrylate group of the main oxime ether isomer (ppm versus tetramethylsilane) Chemical distribution of the singlet of the proton on the aldoxime, where present Of isomers formed by unsymmetrically substituted oxime double bonds R 'and R ² together form a ring as follows:

Compound 53 is:

• λ /

- ⁰ X

CH.

OCH.

CH ₃ O ₂ C

Compound 54 is:

CH ₃ O ₂ C

Compound SS is:

CH ₃ O ₂ C

Compound 152 is:

CH ₃ O ₂ C

Compound 153 is:

CH

OCH.

Table II: NMR data of selected protons

Table II shows NMR data of selected protons for certain compounds described in Table I. The chemical shifts are measured in ppm with tetramethylsilane as standard, and the solvent used was all but deuterochloroform. The column headed "Frequency" refers to the operating frequency of the NMR spectrometer and the following abbreviations were used:

br = broad s = singlet d = doublet t = triplet q = quartet m = multiplet

COMPOUND NO.

FREQUENCY MHz

2 6

270

400 270

270

3.69 (3H, s), 3.82 (3H, s), 3.83 (3H, s), 5.12 {2H, s), 6.84-6.99 (2H, m), 7.11-7.2 (1H, m), 7.25-7.4 (3H, m), 7.5-7.62 (1H, m), 7.60 (1H, s), 7.74-7.0 (1H, m), 8.50 (1H, s) ppm. 3.70 (3H, s), 3.80 (3H, s), 3.81 (3H, s), 5.13 (2H, s), 6.9-7.54 (8H, m), 7.60 (1H, s »ppm. (Major isomer) 2.36 (3H, s), 3.68 (3H, s), 3.80 (3H, s), 5.10 (2H, s), 7.1-7.5 (8H, m), 7.60 (1H, s), 8.07 (1H, s) ppm.

3.70 (3H, s), 3.81 (3H, s), 5.14 (2H, s), 7.15-7.20 (1H, m), 7.24-7.43 (5H, m), 7.48-7.54 (1H, m), 7.48-7.54 (1H, m), 7.58-7.62 (1Hm), 7.59 (1H, s), 8.04 (1H, s) ppm.

Table II (Contd.l

COMPOUND NO.

FREQUENCY MHz

17 20

23 29

32 37 38 40 42

47 49 55 65 66 67 92 93

102 108 111 112 113

114 115 116 118 121

127 131 143

270 270

270 270

270 270

270 270 270

270 270

270 270 270 270 270 270

270 270

270 270 270

270 270 270 270 270

270 270 270 3.70 (3H, 3), 3.84 (3H S _1), 5.17 {2H, s), 7:16 to 7:22 (1 H, m), 7:32 to 7:39 (2H.m), 7:49 to 7:58 (2H, m ), 7.60 (1 H ₁ S) ₁ 7.88 (1 H, d), 8.14 (1 Hs), 8:17 to 8:23 (1 Hm), 8:42 (1 H, m) ppm.

3.70 (3H, s), 3.83 (3H, s), 5.i6 (2H, s), 7.14-7.20 (1H, m), 7.31-7.38 (2H, m), 7.46-7.55 (2H, m), 7.55-7.64 (1H, m), 7.60 (1H, s), 7.7-7.77 (1H, d), 7.83 (1H, s), 8.12 (1H, s) ppm.

2.25 (3H, s), 3.69 (3H, s), 3.81 (3H, s), 5.16 (2H, s), 7.13-7.20 (1Hm), 7.3-7.4 (5H, m), 7.5-7.55 (1 H, m), 7.59 (1H, s), 7.6-7.66 (2H, m) ppm.

3.68 (3H, s), 3.80 (3H, s), 5.08 (2H, s), 5.13 (2H, s), 6.94-7.07 (1H, m), 7.07-7.56 (12H, m), 7.60 (1 H, s), 8.06 (1H, s) ppm.

3.70 (3H, s), 3.83 (3H, s), 5.14 (2H, s), 7.1-7.9 (8H, m), 7.60 (1H, s), G.07 (1H, s) ppm.

3.69 (3H, s), 3.81 (3H, s), 5.18 (2H, s), 7.16-7.82 (7H, m), 7.60 (1H, s), 8.19 (1H, s), 8.6 (1H , m) ppm.

3.69 (3H, s), 3.82 (3H, s), 5.14 (2H, s), 7.14-7.53 (5H, m), 7.60 (1H, s), 7.90-7.96 (1H, m), 8.10 (1 H, s), 8.55-8.62 (1H, m), 8.72 (1H, m) ppm.

2.34 (3H, s), 3.69 (3H, s), 3.81 (3H, s), 5.19 (2H, s), 7.1-7.7 (6H, m), 7.60 (1H, s), 7.89 (1H, d), 8.59 (1H, d) ppm.

1:32 to 1:40 (3H, t), 3.63 (3H, s), 3.77 (3H ₁ S) ₁ 4:33 to 4:44 (2H, q), 5.25 (2H, s), 7:13 to 7:20 (1H, m), 7.26- 7.42 (4H, m), 7.56 (1H, s), 7.7-7.77 (2H, m), 7.6e-7.71 (1H, m) ppm.

2.24 (3H, s), 3.69 (3H, s), 3.82 (3H, s), 5.11 (2H, s), 6.9-7.55 (7H, m), 7.58 (3H, s) ppm.

1.3 (6H, q), 3.70 (3H, s), 3.83 (3H, s), 4:36 (4H, q), 5.28 (2H, s), 7.1-7.5 (4H, m), 7:58 (1 H ₁ S) ppm.

2.85-3.12 (4H, m), 3.69 (3H, s), 3.82 (3H, s), 5.14 (2H, s), 7.1-7.7 (8H, m), 7:58 (1H, s)

(major isomer) 2.24 (3H, s), 3.68 (3H, s), 3.81 (3H, s), 5.16 (2H, s), 7.1-7.5 (5H, m), 7.60 (1H, s), 7.9 ( 1H, m), 8.57 (1H, m), 8.83 (1H, m) ppm.

1.22 (6H _/ d), 3.57 (1H, m), 3.69 (3H, s7.3.82 (3H _< s) ₍ 5.13 (2H _l s), 7.1-7.5 (4H ₍ m), 7.60 (1H, s) , 8.81 (2H, s), 9.18 (1H, s) ppm.

1.14 (6H, d), 2.83 (1H, m), 3.66 (3H, s), 3.78 (3H, s), 5.00 (2H, s), 7.1-7.4 (4H, m), 7.53 (1Hs) , 8.66 (2H, s), 9.17 (1H, s) ppm.

2.26 (3H, s), 3.68 (3H, s), 3.80 (3H ₁ S) ₁ 4.00 (3H, s), 5.21 (3H, s), 7.1-7.6 (4H, m), 7.58 (1H, s ), 8.08 (1H, d), 8.16 (1H, d) ppm.

(major isomer) 2.30 (3H, s), 3.69 (3H, s), 3.83 (3H, s), 4.03 (3H, s), 5.24 (2H, s), 7.1-7.55 (4H, m), 7.60 ( 1 H, s), 9.20 (1 H, m), 9.23 (1 H, m), (minor isomer) 2.30 (3H, s), 3.64 (3H, s), 3.80 (3H ₁ S), 4:03 (3H , s), 5.12 (2H, s), 7.1-7.55 (4H, m), 7.57 (1H, s), 9.32 (1H, m), 9.37 (1H, m) ppm.

2.22 (3H, s), 3.68 (3H, s), 3.83 (3H, s), 5.12 (2H, s), 7.15-7.55 (7H, m), 7.60 (1H, s) ppm.

2.20 (3H, s), 3.67 (3H S _1), 3.80 (3H, s), 3.83 (3H, s), 5.14 '2 H ₁ S), 6.87-7.60 (8H Oi _{1) 1} 7:57 (1 H ₁ S) ppm.

2.20 (3H, s), 2.30 (3H, s), 3.68 (3H ₁ S) ₁ 3.80 (3H, s), 5.13 (2H ₁ S) ₁ 7.15-7.4 (7H, m), 7.54 (1H, m ), 7.58 (1H, s) ppm.

2.23 (3H, s), 2.37 (3H ₁ S) ₁ 3.68 (3H, s), 3.81 (3H, s), 5.16 (2H, s), 7.1-7.55 (8H, m), 7.58 (1H, s ) ppm.

2.22 (3H ₁ S) ₁ 2.35 (3H, s), 3.68 (3H, s), 3.81 (3H, s), 5.13 (3H, s), 7.1-7.5 (8H, m), 7.58 (1H, s ) ppm.

2.26 (3H, s), 3.68 (3H, s), 3.81 (3H ₁ S) ₁ 5.16 (2H, s), 7.0-7.55 (8H, m), 7.59 (1H, s) ppm.

2.02 (3H, s), 3.68 (3H ₁ S) ₁ 3.82 (3H, s), 5.15 (2H, s), 7.0-7.55 (8H, m), 7.60 (1H, s) ppm.

2.22 (3H, s), 3.68 (3H, s), 3.82 (3H, s), 5.13 (2H, s), 6.99-7.65 (8H, m), 7.59 (1H, s) ppm.

2.21 (3H, s), 3.69 (3H, s), 3.81 (3H, s), 5.16 (2H, s), 7.14-7.66 (8H, m), 7.59 (1H.s) ppm.

2.21 (3H, s), 3.69 (3H, s), 3.82 (3H, s), 5.16 (2H, s), 7.1-7.55 (7H ₁ Oi) ₁ 7.59 (1H, s), 7.81i1H, m) ppm.

2.26 (3H, s), 3.69 (3H, s), 3.83 (3H, s), 5.18 (2H ₁ S) ₁ 7.15-7.92 (8H, m), 7.60 (1H ₁ S) ppm.

2.22 (3H ₁ S) ₁ 3.68 (3H, s), 3.82 (3H, s), 5.18 (2H ₁ S) ₁ 7.1-7.8 (8H, m), 7.59 (1H, s) ppm.

(major isomer) 2.28 (3H, s), 2.53 (3H, s), 3.69 (3H, s), 3.83 (3H, s), 5.22 (2H, s), 7.1-7.5 (4H, m), 7.60 ( 1H, s), 7.72 (1H, s), 9.06 (1H, s) ppm.

(minor isomer) 2.27 (3H, s), 2.48 (3H, s), 3.69 (3H, s), 3.83 (3H, s), 5.21 (2H, s), 7.1-7.5 (4H ₍ m), 7.61 ( 1H, s), 7.77 (1H, s), 9.10 (1H, s) ppm.

Table II (Contd.)

COMPOUND NO.

FREQUENCY MHz

144

145 152 154 158 160 162 163 165 177 183 184 188

190 191 194 196 198 225 22C 227 228

270

270 270 270 270 270 270 270 270 270 270 270 270 270

270 270 270 270 270 270 270 270 270 (major isomer) 2.22 (3H, s), 2.50 (3K, s), 3.67 (3H, s), 3.81 (3H, s), 5.14 (2H, s), 7.1- 7.5 (4H, m), 7.58 (1H, s), 8.53 (1H, s), 9.02 (1Hs) ppm.

(minor isomer) 2.17 (3H, s), 2:40 (3H ₁ S), 3.65 (3H, s), 3.77 (3H, s), 5.00 (2H, s), 7.1-7.5 (4H, m), 7.52 (1H, s), 8.37 (1H, s), 9.05 (1H, s) ppm.

2.39 (3H, 8), 2.57 (3H, s), 3.68 (3H, s), 3.81 (3H, s), 5.33 (2H, s), 7.11 (1H, d), 7.1-7.55 (4H, m ), 7.57 (1H, s), 8.64 (1H, d) ppm.

2.92 (2H, t), 3.68 (3H, s), 3.82 {3H, s), 4.18 (2H, t), 5.14 (2H, s), 6.8-7.0 (2H, m), 7.1-7.5 {5H, m), 7.58 (1H, s), 7.87 (1H, m) ppm.

2.22 (3H, s), 3.61 (3H, s), 3.75 (3H, s), 5.08 (2H, s), 7.0-7.5 (7H, m), 7.52 (1H, s), 8.12 (1H, m ) ppm.

2.08 (3H, s), 3.67 (6H, s), 3.80 (3H, s), 5.06 (2H, s), 6.08 (1H, m), 6.38 (1H, m), 6.06 (1H, m ), 7.1-7.5 (4H, m), 7.57 (1H, s) ppm.

3.69 (3H, s), 3.82 (3H, s), 5.19 (2H, s), 5.42 (2H, s), 7.1-7.5 (7H, m), 7.61 (1H, s), 7.77 (1H, s), 8.05 (1H, s) ppm.

2.21 (3H, s), 2.46 (3H, s), 2.62 (3H, s), 3.68 (3H, s), 3.82 (3H, s), 5.10 (2H, s), 7.1 -7.5 (4H, m) , 7.58 (1H, s) ppm.

2.16 (3H, s), 3.68 (3H, s), 3.81 (3H, s), 5.17 (2H, s), 6.42 (1H, m), 6.61 (1Hm), 7.1-7.55 (6H, m) , 7.58 (1H, s) ppm.

3.63 (3H, 8), 3.7e (3H, s), 5.22 (2H, s), 7.1-7.8 (10H, m>, 7.56 (1H, s), 8.55 (1Hd), 8.70 (1H, d ) ppm.

2.29 (3H, s), 2.51 l3H, s), 2.53 (3H, s), 3.68 (3H, s), 3.81 (3H, s), 5.15 (2H, s), 7.1-7.g (4H, m ), '.59 (1H, s), 8.24 (1H, s) ppm.

2.24 (3H, s), 3.03 (3H, s), 3.68 (3H, s), 3.82 (3H, s), 5.20 (2H, s), 7.1-7.5 (4H, m), 7.59 (1H, s ), 7.8-8.0 (4H, m) ppm.

2.18 (3H, s), 3.67 {3H, s), 3.78 (3H, s), 3.80 (2H, br.s), 5.11 (2H, s), 6.59 (2H, d), 7.1-7.55 (6H, m), 7.58 (1H, s) ppm.

(major isomer) 0.65 (2H, m), 0.90 (2H, m), 2.32 (1H, m), 3.67 (3H, s), 3.80 (3H, s), 5.13 (2H, s), 7.1-7.6 (9H, m), 7.57 (1H, s) ppm.

(minor isomer) 0.65 (2H, m), 2.32 (1H, m), 3.63 (3H, s), 3.76 (3H, s), 4.97 (2H, s), 7.1-7.6 (9H, m), 7.77 (1H, s) ppm.

1.41 (3H, t), 3.64 (3H, s), 3.76 (3H, s), 4.05 (2H, q), 5.18 (2H, s), 6.8-7.55 (8H, m), 7.55 (1H, s ) ppm.

2.04 {3H, s), 3.66 (3H, s), 3.78 (3H, s), 5.19 (2H, s), 7.1-7.4 (8H, m), 7.5-7.6 (1H, m), 7.57 (1 H, s) ppm.

1.10 (9H, s), 1.81 (3H S _1), 3.68 (3H, s), 3.81 (3H, s), 4.99 (2H, s), 7.1-7.5 (4H, m), 7:57 (1H, s) ppm.

1.76 (3H, s), 3.46 (2H, s), 3.67 (3H, s), 3.80 (3H, s), 5.06 (2H, s), 7.1-7.5 (9H, m), 7.57 (1H, s ) ppm.

2.10 (3H, s), 3.69 (3H, s), 3.82 (3H, s), 5.11 (2H, s), 6.85 (2H, s), 7.1-7.5 (9H, m), 7.58 (1H, s) ppm.

3.60 (3H, s), 3.70 (3H, s), 3.78 (3H, s), 4.94 (2H ₁ S) ₁ 7.1-7.5 (7H, m), 7.53 (1H, s), 7.77-7.81 (2H , m) ppm.

3.66 (3H, s), 3.77 (3H, s), 3.98 (3H, s), 5.04 (2H, s), 7.10-7.58 (7H, m), 7.58 (1H, s), 7.60-7.70 (2H , m) ppm.

2.88 (3H, s), 3.67 (3H, s), 3.79 (3H, s), 5.18 (2H, dd), 7.1-7.5 (7H, m), 7.60 (1H, s), 7.6-7.7 {2H , m) ppm.

3.20 (3H, s), 3.67 (3H, s), 3.80 (3H, s), 5.30 (2H, s), 7.1-7.6 (9H, m), 7.60 (1H, s) ppm.

The compounds of formula (I) of this invention can be represented by the step shown in Scheme 1. The terms A, R ¹ and R ² are defined wio above, and X is a leaving group such as halogen (chlorine, 3rom or iodine).

Scheme 1

(II)

Ho.b = C

(III)

- C

(I)

CH ₃ O ₂ C

The compounds of formula (I) can be prepared by reacting oximes of general formula (III) with a suitable base (such as sodium hydride or sodium methylate) in a suitable solvent (such as dimethylformamide or tetrahydrofuran) to form the anion and then adding a compound of Formula (II).

Oximes of the general formula (III) are well known in the chemical literature. The compound of general formula (II) wherein X is bromo and has the alkyl group (E) configuration is described in EP-A-0203606.

Scheme 2

CW CH,

.CH

CH ₃ O ₂ C CH (OCH ₃ J ₂

(V)

CHtC (OCH ₃ ) (OSiR ₃ )

CH ₂ CO ₂ CH ₃

(IV)

(VI)

(III)

• (VII)

XCH ₂ CH ₂ CO ₂ CH ₃

CH ₃ O ₂ C

(X)

(VIII)

Alternatively, compounds of formula (I) of this invention can be represented by the steps shown in Scheme 2. The terms A, R ¹ , R ² and X are as defined above, R ⁶ is hydrogen or a metal (such as sodium or potassium), L is one Leaving group such as halide (chloride, bromide or iodide), a CH ₃ SO ₄ -an (on or a sulfonyl anion

at a suitable temperature and usually, but not always, in a suitable solvent.

The compounds of formula (I) of the invention can be prepared from phenylacetates of formula (VI) or ketoesters

of the formula (X) by the steps shown in Scheme 2.

Thus, the compounds of formula (I) may be prepared by treating the phenyladetates of formula (VI) with a base (such as Sodium hydride or sodium methylate) and methyl formate. If then a connection of the Formula CHjL, wherein L is as defined above, is added to the reaction mixture, compounds of formula (I)

to be obtained. When a proton-containing acid is added to the reaction mixture, compounds of the

Formula (IX), in which R ^{6 is} hydrogen, obtained. Alternatively, members of formula (IX) wherein R ^{5 is} a metal (such as Sodium), in turn, be isolated from the reaction mixture. Compounds of formula (IX) in which R ^{5 is} a metal can be converted into compounds of formula (I) by Treating with a compound CH ₃ L, where L is as defined above. Compounds of the formula (IX) in which R ^{B is} hydrogen,

can be converted to compounds of formula (I) by sequential treatment with a base (such as

Potassium carbonate) and a compound of the general formula CH ₃ L. Alternatively, compounds of formula (I) can be obtained from acetates of formula (IV) by eliminating methanol

under either acidic or basic conditions.

Examples of reagents or reagent mixtures that can be used for these conversions are lithium

diisopropylamide, potassium hydrogen sulfate (see, for example, T. Yamada, H. Hagiwara and H. Uda, J. Chem. Soc. Chemical

Communications, 1980, 838 and references therein) and triethylamine, often in the presence of a Lewis acid such as titanium tetrachloride

(see, for example, K. Nsunda and L. Heresi, J.Chem.Soc.Chemical Communications, 1985, 1000).

Acetals of the formula (IV) can be prepared by treating methylsilyl ketene acetals of the formula (V) in which R

is an alkyl group, with trimethyl orthoformate in the presence of a Lewis acid such as titanium tetrachloride (see for

Example K. Saigo, M.Osaki and T.Mukaiyama, Chemistry Letters, 1976, 769). Methylsilylketenacetale of formula (V) can be represented by phenylacetates of formula (Vl) by treatment with a Base and trialkylsilyl halide of the formula R ₃ SiCl or R ₃ SiBr such as trimethylsilyl chloride or with a base (such as triethylamine)

and a trialkylsilyl triflate of the formula R ₃ Si-O-SO ₂ -CF ₃ (see, for example, C. Ainsworth, F. Chen and Y. Kuo, J. Organometallic Chemistry, 1972, 46, 56).

It is not always necessary to isolate intermediates (IV) and (V); under suitable conditions Compounds of the formula (I) are represented by phenylacetates of the formula (VI) in a one-pot reaction

successive addition of suitable reagents listed above.

Phenylacetates of the formula (VI) can be prepared from phenylacetates of the formula (VII). So if an oxime the

general formula (III) is treated with a suitable base (such as sodium hydride or sodium methylate) and the

Phenylacetate of formula (VII) are added, phenylacetates of the formula (Vl) are obtained. Phenylacetates of the formula (VII) are obtained from isochromanones of the formula (VIII) by treatment with HX, in which X is pin Halogen is (like bromine) in methanol. This conversion can also be done in two stages, if the Isochromanone (VIII) in a non-alcoholic solvent is treated with HX, and the resulting phenylacetic acid

is esterified using standard methods (see, for example, I. Matsumoto and J. Yoshizawa, Jap. Kokai (Tokyo

Koho) 79138536, 07.10.1979, Chem. Abstr., 1980, 92, 180829h; and G.M.F. Lim, Y.G. Perron and R.D. Droghini, Res. Disci., 1979,

Chem. Abstr., 1980, 92, 128526t). Isochromanones of formula (VIII) are well known in the chemical literature.

Alternatively, compounds of formula (I) can be prepared by treating ketoesters of formula (I) with Methoxymethylenierungsmitteln such as methoxymethylene-triphenylphosphorane (see, for example, W.Steglich, G. Schamm, T. Anke and F. Oberwinkler, EP 0044448.4.7.1980). Ketoesters of the formula (XI) can be prepared from keto esters of the formula (X) by treatment with the anion of oximes

of the formula (III) as described above. Ketoesters of the formula (X) are described in EP 0331061.

The compounds of the invention are / are potent fungicides and can be used to control one or more of

following pathogens:

Pyricularia oryzae on rice. Puccinia recondita, Puccinia striiformis and other types of rust on wheat, Puccinia hordei, Puccinia striiformis and others Rust on barley and rust on other host plants, such as coffee, pears, apples, peanuts, vegetables and Ornamentals. Erysiphe graminis (powdery mildew) on barley and wheat and other powdery mildew on various Host plants such as Sphaerotheca macularis on hops, Sphaerotheca fuliginea on squash plants (for example cucumbers), Podosphaera leucotricha on apples and Uncinula necator on wine. Helminthosporium spp., Rhynchosporium spp., Septoria spp., Pyrenophora spp., Pseudocercosporella herpotrichoides and Gaeumannomyces graminis on cereal. Cercospora arachidicola and Cercosporidium personata on peanuts and other Cercospora species on other host plants,

for example, sugar beets, bananas, soybeans and rice.

Botrytis cinerea (gray mold) on tomatoes, gooseberries, vegetables, wine and other host plants. Alternaria spp., On vegetables (for example, cucumbers), oilseed rape, apples, tomatoes and other host plants. Venturia inaequalis (scab) on apples. Plasmopara viticola on wine. Other powdery mildew species such as Bremia lactucae on lettuce, Peronospora spp. on soybeans, tobacco, onions and others Host plants, Pseudoperonospora humuli on hops and Pseudoperonospora cubensis on pumpkins. Phytophthora infestans on potatoes and tomatoes and other Phytophthora spp. on vegetables, stew berries. Avocado, Peppers, ornamental plants, tobacco, cocoa and other host plants. Thanatephorus cucumeris on rice and other Rhizoctonia species

on different host plants such as wheat and barley, vegetables, cotton and turf.

Some compounds show a broad spectrum of action against fungi in vitro. They can also be effective against different Post-harvest diseases of fruits have (for example Penicillium digitatum and italicum and Trichoderma viride on Oranges, Gloeosporium musarum on bananas and Botrytis cinerea on grapes). Further, the compounds may be used as seed dressing against Fusarium spp., Septoria spp., Tilletie spp., (Fire, one with the seed

transmitted disease of wheat), Ustilago spp. and Helminthosporium spp. on cereals, Rhizoctonia solani on cotton and Pyricularia oryzae on rice.

The compounds may have systemic movement in the plants. Moreover, the compounds may be volatile enough

to be effective in the vapor phase against fungi on Pflanzenenn.

The invention therefore provides a method for combating fungus, the application to the plant, on the plant seeds or

to the plant site in a fungicidally effective amount of a compound as defined above or a composition containing it.

Some of the compounds have insecticidal activity and, at suitable rates of application, they can be used Variety of insects and mites to combat. Therefore, another aspect of the invention is the delivery of a method for killing or controlling insects or Mites, as the administration of an insecticidally or miticidally effective amount of a compound or compound as defined above

a composition containing them on the insects or mites or their whereabouts.

The compounds can be used directly for agricultural purposes, but they become compositions

formulated using a vehicle or thinner. The invention thus provides fungicidal, insecticidal and miticidal

Compositions containing a compound described above and a compatible carrier or diluent therefor

includes.

The compounds can be applied in various ways. For example, they can be formulated or

unformulated, applied directly to the leaves of a plant, to the seeds or to the medium in which the plants are to grow or in which they are to be planted, or they may be sprayed, dusted or creamed

Paste formulation can be applied or they can be used as a vapor or slowly releasing granules. The application can be applied to any part of the plant, leaves, stems, twigs or roots, or to which the Roots surrounding soil or the soil in general, in the irrigation water or hydroponic culture systems. The Compounds of the invention may also be injected into the plants or using an electrodynamic Spraying or other methods with a small volume to be sprayed on the plants. The term "plant" as used herein includes seedlings, shrubs and trees Invention preventive, protective, prophylactic and eradicating treatments. The compounds are preferably used for agricultural and horticultural purposes in the form of a composition

used. The type of composition used in a particular case depends on the particular purpose.

The compositions may take the form of dustable powders or granules containing the active ingredient (invention compound) and

a solid diluent or carrier, for example fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate,

Talc, powdered magnesia, filler soil, gypsum, diatomaceous earth and clay. Such granules can preformed granules soin, without

further treatment suitable for use on the ground. These granules can be obtained either by impregnation of

Filler pellets made with the active ingredient or by pelleting a mixture of active ingredient and powdered filler

become. Seed treatment compositions may contain an agent for promoting adhesion to the seed (for example a mineral oil); alternatively, the active ingredient may be formulated for seed treatment purposes using organic solvent (for example N-methyl-pyrrolidone, propylene glycol or dimethylformamide).

The compositions may also take the form of wettable powders or water-dispersible granules! have, the network or Dispersing agent to facilitate dispersion in liquids. The powders and granules can also fillers and Contain suspending agent. Emulsifiable concentrates or emulsions can be prepared by dissolving the active ingredient in an organic Solvent, optionally containing a wetting or emulsifying agent, and then adding the mixture to water, also

may contain a wetting or emulsifying agent. Suitable organic solvents are aromatic solvents such as

Alkylbenzenes and alkylnaphthalenes, ketones such as isophorone, cyclohexanone and methylcyclohexanone, chlorinated Hydrocarbons such as chlorobenzene and trichloroethane, alcohols such as benzyl alcohol, furfuryl alcohol, butanol and glycol ethers. Suspension concentrates of highly insoluble solids can be prepared by milling in a ball mill with a dispersing or Suspending agents are prepared which prevent the settling of the solid. Compositions to be used as a spray may take the form of aerosols, the formulation

in a container under the pressure of a propellant gas, for example fluorotrichloromethane or dichlorodifluoromethane

The compounds of the invention may be mixed in a dry state with a pyrotechnic mixture to form a To form a composition which is suitable for generating a smoke in trapped cavities, the Contains compounds. Alternatively, the compounds may be used in the form of microcapsules. They can also be biodegradable Formulations can be formulated with polymers to achieve a slow, controlled release of the active ingredient. By including appropriate additives, for example additives to improve distribution, adhesion and Rain repellency on treated surfaces, the compositions can better match the different Uses to be adapted. The compounds of the invention may be used in admixture with fertilizers (for example, nitrogen, potassium or potassium)

phosphorus fertilizers). Compositions comprising fertilizer granules with the incorporated compound, for

Example as a coating are preferred. Such granules contain up to 25% by weight of the compound. So the invention also provides

a fertilizer composition consisting of fertilizer and the compound of the general formula (I) or a salt or metal complex thereof.

Meshable powders, emulsifiable concentrates and suspension concentrates normally contain surface-active substances, for example wetting, dispersing, emulsifying or suspending agents. These agents can be cationic, anionic or nonionic agents.

Suitable cationic agents are quaternary ammonium compounds, for example cetyltrimethylammonium bromide. Suitable anionic agents are soaps, salts of allphatic monoesters of sulfuric acid (for example sodium lauryl sulphate) and salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, butyl naphthalene sulphonate and a mixture of sodium diisopropyl- and -triisopropylnaphthalensulfonat).

Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl or cetyl alcohol or with alkylphenols such as octyl or nonylphenol and octylcresol. Other nonionic agents are partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of said partial esters with ethylene oxide and lecithins. Suitable suspending agents are hydrophilic colloids (for example polyvinyl pyrrolidone and sodium carboxymethyl cellulose) and swelling clays such as bentonite or attapulgite. Compositions for use as aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high level of active ingredient and diluted with water prior to use. The concentrates should preferably be capable of storage for extended periods of time, and after such storage should be dilutable with water to form an aqueous preparation that remains homogeneous for a sufficiently long time to be applied by conventional sprayers. The concentrates may conveniently contain up to 95, suitably 10-85, for example 25-60%, by weight of active ingredient. After dilution to form aqueous preparations, they may contain varying amounts of active ingredient, depending on the intended purpose, aqueous preparations of 0.0005 or 0.01-10% by weight of active ingredient may be used.

The compositions of this invention may contain other compounds having biological activity, for example, compounds having similar or complementary fungicidal activity, or those having plant growth regulating, herbicidal or insecticidal activity.

A fungicidal compound which may be present in the composition of the invention may be those used for combating cereal diseases (for example in wheat) such as Septoria, Gibberella and Helminthosporium species, seed and soil born diseases and softer and more powdery Mildew on grapefruit, powdery mildew and scab on apples, etc. is suitable. By including another fungicide, the composition can have a broader spectrum of activity than the compound of general formula (I) alone. Further, the other fungicides may have a synergistic effect on the fungicidal activity of the compound of general formula (I). Examples of fungicidal compounds which may be included in the composition of the invention are (±) -2- (2,4-dichloro-phenyl) -3- (1H-1,2,4-triazol-1-yl) -propyl- 1,1,2,2-tetrafluoroethyl ether, (RSI-1-Amino-propylphosphonic acid, (RS) -4- (4-chloro-phenyl) -2-phenyl-2- (1H-1,2,4- triazol-1-ylmethyl) butyronitrile, (RS) -4-chloro-N- (cyano (ethoxy) methyl) benzamide, (Z) -N-but-2-enyloxymethyl-2-chloro-2 ', 6'-diethyl acetanilide, 1- (2-cyano-2-methoxyimino-acetyl) -3-ethyl-urea, 1 - [(2RS, 4RS) -4-bromo-2- (2,4-dichlorophenyl) tetrahydrofurfuryl-iH-i -triazol.ai ^ -dichloro-phenyD ^ -ie-i. ^ - triazol-i-yD-SH-quinazolin ^ -on.a-ChloM-H-methyl ^ -ie-i ^^ - triazol-i-ylmethyD -ia-dioxolan ^ -ylJ-phenyM-chloro-phenyl ^ bromo ^ -cyano-NN-dimethyl-etrifluormethyl-benzimidazol-1-sulphonamide, 4-chloro-benzyl-N- (2,4-dichloro-phenyl) - 2- (iH-1,2,4-triazol-1-yl) thioacetamidate, S-ethyl-Se-dihydro-e-oxoII.sl-dioxoloKS-glinoline-y-carboxylic acid. Α-IN-O-Chloro ^. xylyl-methoxy-acetamidol-Y-butyrolactone, anilazine, BAS 454, benalaxyl, benomyl, Biloxazole, binapacryl, bitertanol, blasticidin S, bupirimat, buthobate, captafol, carbendazim, carboxin, chlorobenzothiazon, chloroneb, chlorothalonil, chlorozolinate, copper-containing compounds such as copper oxychloride, copper sulphate and Bordeaux mixture, cycloheximide, cymoxanil, cyproconazole, cyprofuram, bis (pyridine) 2-yl) disulfide 1,1'-dioxide, dichlofluanid, dichlone, diclobutrazole, diclomethine, diclorane, dimethamorph, dimethirimol, diniconazole, dinocap, ditalimfos, dithianone, dodemorph, dodin, edifenphos, etaconazole, ethirimol, (Z) -N Benzyl N- (methyl (methylthioethylidene-aminoxycarbonylaminothiol-.beta.-alanine ethyl ester, etridazole, fenapanil, fenarimol, fenfuram, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, flutolanil, flutriafol, flucilazole, folpet, fosetyl) aluminum, Fuberidazole, Furalaxyl, Furconazole-cis, Guazatin, Hexaconazole, Hydroxyisoxazole, Imazalil, Iprobenfos, Iprodione, Isoprothiolane, Kasugamycin, Mancozeb, Maneb, Mepronil, Metalaxyl, Methfuroxam, Metsulfovax, My clobutanil, neoasocin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, organo-mercury compounds, oxadixyl, oxycarboxin, penconazole, pencycuron, N-furfuryl-N-limidazol-1-ylcarbonyO-DL-homoalanine-fpenM-enyl ester), phenazine oxide, phthalide , Polyoxin D, polyram, probenazole, prochloraz, procyidone, propamocarb, propiconazole, propyneb, prothiocarb, pyrazophos, pyrifenox, pyroquilon, pyroxyfur, pyrrolnitrin, quinomethionate, quintozene, streptomycin, sulfur, techlofthalam, tecnazene, tebuconazole, thiabendazole, thiophanate-methyl, Thiram, tolclofos-methyl, 'U' -mino-bis-octamethylene-di-guanidine triacetate, triadimefon, triadimenol, triazobutyl, tricyclazole, tridemorph, triforin, validamycin A, vinclozolin and zineb. The compounds of general formula (I) may be mixed with soil, peat or other rooting material to protect the plants against seed, soil or leaf-induced fungal diseases.

Suitable insecticides which can be incorporated into the composition are buprofezin, carbaryl, carbofuran, carbosulfan, chlorpyrifos, cycloprothrin, demeton-s-methyl, diazinone, dimethoate, ethofonprox, fenitrothion, fenobucarb, fenthione, formothione, isoprocarb, isoathione, monocrotophos, Phenthioate, Pirimicarb, Propaphos and XMC. Plant growth regulating compounds are those which control weeds or selectively control the growth of less desirable plants (for example grasses).

Examples of suitable plant growth regulating compounds for use with the compounds of the invention are 3,6-dichloro-picric acid, 1- (4-chloro-phenyl) -4,6-dimethyl-2-oxo-1,2-dihydropyridine-3 carboxylic acid, methyl 3,6-dichloranisside, abscissic acid, asulam, benzoylprop-ethyl, carbetamide, daminozide, difenzoquat, dikegulac, ethephon, fenpentezene, fluoridamide, glyphosate, glyphosine, hydroxybenzonitriles (for example bromoxynil), inabenfid, isopyrimole, long chain fatty alcohols and acids Maleic hydrazide, mefluidide, morphactines (for example chlorofluoroecole), paclobutrazole, phonoxyacetic acids (for example 2,4-D or MCPA), substituted benzoic acid (for example triiodobenzoic acid), substituted quaternary ammonium and phosphonium compounds (for example chloroquat,

Chlorophonium or mepiquat chloride), tecnazene, the auxines (for example indoleacetic acid, indolebutyric acid, naphthylacetic acid or naphthyloxyacetic acid), the cytokines (for example benzimidazole, benzyladenine, benzylaminopurine, diphenylurea or kinetin), the glbberellins (for example GAi, GA ₄ or GA ₇ ) and tri-penthenol.

embodiment

The following examples illustrate the invention. In all examples, the term "ether" means diethyl ether, magnesium sulfate was used to dry the solutions, and the solutions were concentrated under reduced pressure The reactions with air-borne water-sensitive intermediates were carried out under a nitrogen atmosphere and the solvents were analyzed before use, Unless otherwise indicated, chromatography was carried out on a column of silica gel as the stationary phase and, where shown, the infrared and NMR data are selective and no attempt was made to list all absorbances in all cases. Unless otherwise indicated, N-NMR separators were recorded using CDCl ₃ solutions and the following abbreviations were used throughout:

THF = tetrahydrofuran s - singlet DMF = dimethylformamide d = doublet NMR = nuclear magnetic resonance t - triplet IR = infrared m = multiple «

m. p. - melting point br = wide

HPLC = high performance liquid chromatography. example 1 This example illustrates the preparation of (E, E) -3-methoxy-2- [2- (3-methyl)

Benzylidenaminooxymethyl) phenyl] acrylic acid methyl ester (Compound No. 5 in Table I).

A solution of (E) -3-methylbenzaldehyde oxime (0.23g) in DMF (5ml) was added dropwise and with stirring to a suspension

of sodium hydride (0.051 g) in DMF (5 ml) at room temperature. After 0.5 hours, a solution of (E) -2- (bromomethyl) -phenyl-3-methoxy-acrylic acid methyl ester (0.5 g, prepared as in EP-A-0203606) in DMF (5 ml) was added to the

The reaction mixture was then stirred for 4 hours at room temperature. The mixture was in water

poured and extracted (2x) with ether. The combined extracts were washed with water, dried, concentrated and washed with water

Ether chromatographed as eluent, whereby the title compound (0.132 g, 23% yield) was obtained as a pale yellow oil. IR maxima (film): 1709.1631 cm " ¹ .

¹ H-NMR (270 MHz) δ: 2.35 (3H, s); 3.69 (3H, s); 3.80 (3H, s); 5,12 (2H, s); 7.1-7.55 (8H, m); 7.59 (1H, s); 8.05 (1H, s) ppm.

Example 2 This example illustrates the preparation of a (E ₁ E) and (Z, E) mixture of 2- [2- (1- [3,5-dimethylpyrazine-1]

ylethylideneaminooxymethyl) phenyl] -3-methoxy-acrylic acid methyl ester (Compound No. 176 in Table I).

To a mixture of 2,6-dimethylpyrazine (3.24g), sulfuric acid (15ml of a 3.4m solution) and acetaldehyde (10ml), at ⁰ ° C

stirred simultaneously, a solution of iron (II) sulfate (50.1 g in 150 ml of water) and tert-butyl hydroperoxide (16.2 ml of a 70% aqueous solution) were added simultaneously. The temperature was kept below 3 ^° C. during the addition. After the addition, the reaction mixture was stirred at 0 ° C for 1 hour. Sodium metabisulfate was added until the mixture gave a negative iodine-starch reaction. The reaction mixture was extracted with dichloromethane, the combined extracts were washed with water, then dried, concentrated and chromatographed using a mixture of ether and petroleum ether (60-80 ° C, 4: 1) as eluent to give 2-acetyl-3, 5-dimethylpyrazine (2.65 g, 59% yield) was obtained as a pale yellow oil.

IR maxima (film): 1694,1551,1262,1175cm "'.

¹ H-NMR (270MHz) δ: 2.62 (3H, s); 2.70 (3H, s); 2.80 (3H, s); 8.36 (1H, s) ppm.

2-Acetyl-3,5-dimethylpyrazine (2.65g), hydroxylamine hydrochloride (2.5g) and sodium acetate trihydrate (3.5g) were refluxed in methanol (50ml) for 1 hour. The reaction mixture was concentrated, diluted with water (75 ml) and washed with

Extracted ethyl acetate. The combined extracts were dried and concentrated to give an oil which was added Treat with ether and petroleum ether (60-SO ⁰ C) 3,5-dimethyl-2- (1-hydroxy-imino-ethylpyrazine) (2.54 g, 87% yield) as a white Solid (mp 85-89 ⁰ C) and as a 1: 1 mixture of the (E / Z) isomers. IR maxima (film): 2925,1465,1376,1086,930cm " ¹ .

¹ H NMR (270MHz) δ: 2.23 (3H, s); 2.33 (3H, s); 2.53 (3H, s); 2.56 (3H, s); 2.58 (3H, s); 2.68 (3H, s); 8.32 (1H, s); 8.35 (1H, s); 9.45 (1H, br, s); 9.85 (1H, br, s) ppm.

A 1: 1 mixture of (E / Z) -3,5-dimethyl-2- (1-hydroxyimino-ethyl) -pyrazine (0.87 g) was added in portions with stirring Suspension of sodium hydride (0.25g) in DMF (20ml) at about 5 ° C. After 1 hour, the reaction mixture became O ⁰ C with a solution of (E) -2- (2-bromomethyl-phenyl) -3-methoxy-acrylic acid methyl ester. After 1.5 hours, that became Mixture poured into water and extracted (2x) with ether. The combined extracts were washed with brine,

dried, concentrated and purified using EthenHexan (1: 1) as eluent to give the title compound as an oxime isomers (7: 3) as a pink solid (0.57 g, 30% yield, mp 56-60 ⁰ C) was obtained ,

IR maxima (film): 1707,1624,1132cm ' ¹ .

¹ H NMR (270 MHz) major isomer δ: 2.39 (3H, s); 2.54 (3H, s); 2.57 (3H, s); 3.67 (3H, s); 3.82 (3H, s); 5.15 (2H, s); 7.1-7.9 (4H, m); 7.59 (1H, s); 8.27 (1H, s) ppm. Minor isomer - δ: 2.22 (3H, s); 2.51 (3H, s); 2.57 (3H, s); 3.67 (3H, s); 3.82 (3H, s); 5.27 (2H, s); 7.1-7.9 (4H, m); 7.76 (1H, s); 8.33 (1H, s) ppm.

Example 3 This example illustrates the preparation of (E, E) -3-methoxy-2- [2- (1-phenyl)

EthylldenaminooxymethyUphenyllacrylsäuremethylester (Compound No. 23 of Table I).

A solution of acetophenone oxime (1.23g) in DMF (5ml) was added dropwise with stirring to a suspension of Add sodium hydride (0.367 g) in DMF (26 ml). After 1 hour, a solution of (E) -2- [2- (bromomethyl) phenyl] -3-

methoxy-acrylic acid methyl ester (2.0 g) in DMF (15 ml) was added to the reaction mixture, which then be 16 hours be!

Room temperature was stirred. The mixture was poured into water and extracted (2x) with ether. The combined extracts

were washed with water, dried, concentrated and concentrated using ether: petroleum ether (40-60 ° C)

Chromatography to give an oil. HPLC using ether: petroleum ether (40-6O ⁰ C, 1: 1) gave the Title compound (0.55 g, 23% yield) as a pale yellow oil. IR maxima (film): 1708.1631 cm " ¹ .

¹ H NMR is in Table !! specified.

Example 4 This example illustrates the preparation and separation of the (E ₁ E) and (Z, E) isomers of 3-methoxy-2- (2- (1- (pyrimidin-5-yl) -2-

Methyl-propylidenaminooxymethyl) phenyl) acrylic acid methyl ester (compounds Nos. 66 and 67 of Table I).

A solution of isopropyl (pyrimidin-5-yl) ketone oxime (0.29 g of a 5: 2 mixture of (E) and (Z) isomers) in DMF (5 mL)

added with stirring to a suspension of sodium hydride (0.09g) in DMF (10ml). After 2 hours, the mixture was allowed to rise

O ⁰ C cooled and with a solution of (E) -2- (2-bromomethyl-phenyl) -3-methoxy-acrylic acid methyl ester (0.5 g) in DMF (5 ml)

was added, then stirred for 3 hours. The mixture was poured into water and extracted with ether. The United

Extracts were washed with water, dried and concentrated to give an oil, the crude mixture of

(E, E) · and (Z, E) -isomers. HPLC using ether as the eluent was used to separate these isomers:

1. The faster eluted fraction-the (Z) oxime ether (E) -acrylate. (0.115g, 18% yield). Clear oil (Compound No. 67 of Table I).

2. The slower eluted fraction-the (E) oxime ether (E) -acrylate. (0.098g, 15% yield). Clear oil (Compound No.66 of Table I).

¹ H-NMR is given in Table II.

Example 5 This example illustrates the preparation of a stereoisomer of 2- (2- (phenyl (methylthio) methylaminooxymethyl) phenyl) -3-

methoxy-acrylic acid methyl ester (Compound No. 191 of Table I).

A solution of chlorine (1.5g) in carbon tetrachloride (4kml) was added portionwise with stirring a partial solution of Benzaldehoxoxime (2.5 g; ¹ H NMR: δ 8.18 (1H, s); 9.40 (1H, br, s) ppm) in carbon tetrachloride (20 mL) at room temperature

added. Following the addition, the reaction mixture was stirred for 3 hours at room temperature and then poured into water. The organic layer was separated, dried and concentrated to give almost pure benzhydroximic acid chloride (3.2 g) as a yellow liquid. A solution of sodium methanethiolate (0.68 g) in methanol (15 ml) was added dropwise to an ice-cooled and stirred solution of a portion of this benzhydroximyl chloride (1.5 g) in methanol (15 ml). Following the

Addition, the Reairtionsgemisch was stirred for 2 hours with cooling with ice-water. The methanol was underwent

reduced pressure and the residue was chromatographed using dichloromethane as eluent to give a single steroisomer of α-methylthio-benzaldehyde oxime (0.670g, 42% yield) as white crystals, m.p.

76-78 ⁰ C was obtained. ¹ H-NMR: δ 2.08 (3H, s); 9.12 (1H, s) ppm.

A solution of α-methylthio-benzaldehyde oxime (0.575g) in DMF (10ml) was added at room temperature with stirring Suspension of sodium hydride (85 mg) in DMF (15 ml) was added dropwise. One hour later, a solution of (E) -2- (2- Bromomethyl-phenyl) -3-methoxy-acrylic acid methyl ester (0.990 g) was added dropwise in DMF, after a further 3 hours was Mixture poured into water and extracted with ethyl acetate. The organic extracts were washed with water,

dried, concentrated and using increasing proportions of ethyl acetate in hexane as eluent chromatographies, wherein

the title compound (1.05 g, 83%) was obtained as a colorless oil.

IR: 1706cm " ¹ .

¹ H-NMR is given in Table II.

Example 6 This example illustrates the preparation of individual stereoisomers of 2- (2- [phenyl (methylsulfinyl) methyleneaminooxymethyl]

phenyl) -3-methoxy-acrylic acid methyl ester and 2- (2- [phenyl (methylsulfonyl) methyleneaminooxymethyl] phenyl) -3-methoxyacryic acid methyl ester (Compound Nos. 227 and 228 of Table I).

M-chloro-perbenzoic acid (0.250g, with 45% m-chloro-benzoic acid) became a stirring within 30 minutes with stirring

Solution of 2- (2- (phenylmethylthio | methyleneaminooxymethyl) phenyl) -3-methoxyacrylate (0.300 g, prepared

as described in Example 5) in dichloromethane (20 ml) with cooling in ice-water. After a further 15 minutes, the reaction mixture was washed successively with aqueous sodium bicarbonate solution and water, dried, concentrated, and chromatographed using a 1: 1 mixture of ethyl acetate and hexane / eluent

Title compound was obtained: (i) the sulfone, eluted first, as a gum (0.090 g, 28% yield); (ii) the sulfoxide, also as Gum (0.150g, 48% yield).

¹ H-NMR is given in Table II.

Example 7 This example illustrates the representation of the two stereoisomers of

2- [2- (Phenyl [methoxymethyleneaminooxymethyl) phenyl] -3-methoxyacrylic acid methyl ester (Compound Nos. 225 and 226 of the

Table I). A mixture of the stereoisomers of a-methoxy-benzaldehydoxim was in two stages of methyl benzoate

successive treatment with Lawesson's reagent and hydroxylamine (see for example EP 0299382). The

Stereoisomers were separated by chromatography using dichloromethane as eluent.

(i) Isomer A, eluted first, a pale yellow solid, mp 55-57 ⁰ C, ¹ H-NMR: δ 3.83 (3H, s); 7.72 (1H, s) ppm; (il) Iscmer B, colorless gum, ¹ H-NMR: δ 3.96 (3H, s); 8.84 (1H, s) ppm.

These two stereoisomeric oximes were individually synthesized into the title compounds using the procedure described in Example 5 Method, that is, by successive treatment with sodium hydride and (E) -2- (2-bromomethyl-

phenyl) -3-methoxy-acrylic acid methyl easter. Isomer A gives the title compound No. 225 of Table I as a gum; Isomer B gives the title compound # 226 of Table I, also as a gum.

¹ H-NMR is given in Table II.

The following are examples of compositions suitable for agri-cultural and horticultural purposes,

which may be formulated from the compounds of the invention. Such compositions form a further aspect of the invention. The percentages are by weight.

Example 8 An emulsifiable concentrate was prepared by mixing and stirring the ingredients until all were dissolved. Compound No.45 of Table I 10% Benzyl alcohol 30% Caclium dodecyl benzene sulphonate 5% Nonylphenol ethoxylate (13 moles of ethylene oxide) 10% Alkylbenzene 45% Example 9 The active ingredient is dissolved in methylene chloride, and the resulting liquid was applied to the granules of attapulgite clay

sprayed. The solvent is then evaporated off to give a granulated composition.

Compound No. 45 of Table I 5% Attapulgite granules 95% Example 10 A composition suitable for use as a seed dressing is obtained by grinding and mixing the three ingredients

shown.

Compound No. 45 of Table I 50%

Mineral oil 2%

Kaolin 48%

Example 11 A dusting powder is prepared by milling and mixing the active ingredient with talc. Compound No. 45 dor Table I 5%

Talc 95%

Example 12 A suspension concentrate is prepared by milling the ingredients in a ball mill to form an aqueous Suspension of the gemahlenon mixture with water. Compound No. 4B of Table I 40% Sodium lignosulfonate 10% Bentonite clay 1%

Water 49%

This formulation can be used as a spray by dilution in water or applied directly to the seeds

become.

Example 13 By mixing together and grinding the ingredients to complete mixing is a wettable powder formulation

shown. '

Compound No. 45 of Table I 25% Sodium lauryl sulfate 2% Sodium lignosulphonate 5% Silica 25%

Kaolin 43%

Example 14 The compounds were tested against a variety of fungal strains of the leaves of plants. The technique used

was the following:

The plants were grown in John Innes Potting Compost (# 1 or 2) in 4cm diameter pots. The Test compounds were formulated either by milling in a ball mill in aqueous dispenser oil T or as a solution

in acetone or acetone / ethanol, diluted to the required concentration immediately before use. For the

Leaf diseases, the formulations (100 ppm active ingredient) were sprayed on the leaf and on the plant roots in the soil

applied. The sprays were applied to maximum retention and the root stalks to a final concentration of about 40 ppm a. i. in dry soil. Tween 20 was added to a final concentration of 0.05% when the

Sprays were applied to cereals. For most tests, the compounds on the soil (roots) and on the leaves (by spraying) were one or two Days before the plant was inoculated with the disease. An exception was the test on Erysiphe graminis, in which

the plants were treated 24 hours before inoculation. The leaf pathogens were as spore suspension through

Spray applied to the leaves of the plants. After inoculation, the plants were placed in their environment, the one Progression of the infection and incubation allowed until the disease was ready for treatment. The period between Inoculation and treatment varied from four to fourteen days depending on disease and circumvention. The course of the disease was described by the following graduation:

4 = no illness

3 = Traces - 5% disease on untreated plants 2 = 2-26% Disease on untreated plants 1 = 26-59% Disease on untreated plants 0 = 60-100% Disease on untreated plants

The results are shown in Table III. Example 15 The insecticidal properties of the compound of formula (I) were demonstrated as follows:

Table III

COMPOUND TABLE PUCCINIA ERYSIPHE VENTURIA PYRICULARIA CERCOSPORA PLASMOPARA PHYTOPHTHORA NO. NO. RECONDITA GRAMINISINAEQUALIS ORYZAE ARACHIDICOLA VITICOLA INFESTANS

(WHEAT) HORDEI (APPLE) (RICE) (PEANUT) (VINE) (TOMATO)

Wheat (BARLEY) apple rice peanut wine tomato

barley

1 _ 3 4 4 4 4 4 2 4 4 4 4 4 4 3 5 4 4 4 - 4 4 3 O - 4 4 3 4 4 4 11 4 4 4 - 4 4 3 17 4 4 4 - 4 4 3 20 4 4 4 - 4 4 3 22 3 4 4 4 4 4 23 4 4 4 - 4 4 4 29 4 1 4 _ 4 4 1 32 3 4 4 4 4 4 3 37 4 4 4 - 4 4 4 38 4 4 4 - 4 4 0 39 I 3 0 0 - 2 0 0 40 4 4 4 - 4 4 4 41 I 3 4 2 0 _ 4 4 42 1 0 4 - 3 4 3 45 3 4 4 0 - 2 2 47 4 4 4 4 4 4 4 49 0 0 4 _ 2 4 0 55 I 4a 4a 4a 3a 4a 4a 4a 62 4 4 4 4 - 4 4 63 4 4 4 4 4 4 4 64 4 4 4 3 4 4 0 65 4 4 4 3 4 4 0 66 _ 4 4 0 2 4 4 67 - 3 0 0 3 4 2 89 4 4 4 4 4 4 4 90 4a 4a 4a Oa 4a 4a Oa 92 4 4 4 - - 4 4 93 3 2 3 _ - 4 3 101 4 4 4 3 4 4 3 110 4 4 4 _ _ 4 2 112 4 4 3 3 - 0 0 113 4 4 4 4 - 4 4 116 4 4 4 - - 4 4 121 4 4 0 3 - 0 0 125 4 4 4 3 4 4 3 127 4 4 4 _ _ 4 4 130 4 4 4 _ - 4 2 139 4 3 4 0 4 4 0 140 3 3 4 3 - 4 3 143 4 4 4 4 4 4 0 144 i 3 4 4 3 - 4 4 152 4 4 4 4 2 4 3 153 2 0 2 0 2 0 0 154 4 4 4 4 - 4 3

Table III (Contd.)

COMPOUND TABLE PUCCINIA ERYSIPHE VENTURIA PYRICULARIA CERCOSPORA PLASMOPARA PHYTOPHTHORA NO. NO. RECONDITA GRAMINIS INAEQUALIS ORYZAE ARACHIDICOLA VITICOLA INFESTANS

(WHEAT) HORDEI (APPLE) (RICE) (PEANUT) (VINE) (TOMATO)

Wheat (BARLEY) apple rice peanut wine tomato

barley

156 157 158 159 162 165 173 174 175 176 177 183 184 185 186 188

3a

4a

4 4 3 4 4 O 4

3a

4a

3a

4a

O 2 2 2 4

Oa

3 3 3 3 4 1 4 4 4 4

4a 4

4a

4a

3a

Oa

(-) No result, (a) 10ppm (PPM) foliar spray only TU TU MP NC NC MD MD BG BG HV HV SP SP DB ml Table IV 1000 EO NG MC NC NG AK AC NK NC LR LG LR LG LR JC 25 TU 0 0 0 0 0 9 9 0 0 0 0 5 5 0 COMPOUND RATE 1000 AC 0 NO 25 9 0 0 0 5 9 0 0 0 0 0 0 0 0 0 20 0 0 22

1000 25

0 0

500 25

0 0

0 Ö

0 0

0 0

37 1000 0 0 0 0 0 9 0 0 0 0 0 0 0 0 9 0 25 38 1000 5 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 25 40 1000 0 0 0 9 9 9 9 0 0 0 9 0 0 5 0 25 0 0 42 1000 9 0 5 0 0 0 0 0 0 0 0 0 0 0 25 0 0 47 500 0 5 9 0 0 0 0 0 0 0 0 0 49 1000 0 0 0 0 9 0 0 0 0 0 0 0 0 25 0 0 62 500 0 0 0 0 5 0 0 0 0 0 63 500 0 0 0 5 0 9 9 9 0 0 0 0 0 0 5 0 12.5 64 500 5 0 0 5 0 0 9 9 0 0 0 0 0 0 5 0 12.5 89 500 0 0 0 0 5 9 5 9 0 0 0 0 9 0 12.5 93 500 0 0 0 0 0 0 0 9 0 101 500 0 0 0 0 5 0 0 0 5 0 0 12.5 112 500 9 5 5 0 0 0 0 0 0 9 C 12.5

COMPOUND NO RATE (PPM) TU AC TU EO TU MP NG MC NC NC NC NG MD AK MD AC BG NK BG NC HV LR HV LG SP LR SP LG DB LR Ml JC 125 500 12.5 0 0 0 5 9 0 0 0 0 0 0 140 500 9 0 0 0 0 0 0 0 0 0 144 500 0 0 0 0 0 0 0 0 9 0 0 9 152 500 12.5 0 0 0 0 5 0 0 0 0 0 0 0 0 0 0 0 153 500 12.5 0 9 0 0 0 0 9 0 0 157 500 5 0 9 0 0 0 0 0 0 0 0 9 158 500 0 0 5 0 0 0 0 0 9 0 0 0 159 500 9 9 0 0 0 0 0 5 5 5 9 160 500 12.5 5 0 0 9 0 0 0 0 0 0 0 174 500 12.5 0 0 0 9 9 0 5 0 9 9 0 175 500 12.5 0 0 0 0 5 0 0 0 0 5 0 176 500 12.5 0 0 0 9 9 0 0 0 0 0 0 177 500 12.5 0 0 0 5 0 0 0 0 0 5 0

Example 15 Dio insecticidal properties of the compound of formula (I) were demonstrated as follows: The activity of the compound was determined using a variety of insects, mites and nematodes. Except the case of knockdown activity against Musca domestica, where the test procedure will be described later

uses the compound in the form of liquid formulations containing 12.5-1000 parts per million (ppm) weight of the compound. The preparations were prepared by dissolving the compound in acetone and diluting the solutions with

Water containing 0.1% by weight of a wetting agent sold under the trade name "Synperonic" NX until the liquid ones Preparations containing the required product concentration. "Synperonic" is a registered trade name. The test procedure used with respect to each pest was basically the same and was the delivery

a number of pests on a medium, which is usually a host plant or nutrient on which the

Eating pests, and treating the pests and / or the medium with the preparations. The mortality of Pests were estimated to be in periods varying between one and seven days. The test results are given in Table IV for each of the compounds listed in the first column and in the second Column indicated concentration shown in ppm. There is one degree of mortality, called 9.5 or 0, where 9 is a Mortality of 80-100% (70-100% root canal reduction compared to untreated plants for Meloidogyne

5 indicates 50-79% mortality (50-69% root canal reduction for Meloidogyne incognita semi-in vitro test) and 0 indicates less than * 50% mortality.

In Table IV, the pest used is designated by a letter code. The meaning of the code, that Carrier medium or nutrient and the type and duration of the test is given in Table V. The knockdown efficacy against Musca domestica was demonstrated as follows. A sample of the compound was diluted to 0.1% in a 50:50 mixture of ethanol / acetone and 0.1% aqueous Synperonic-NX solution brought to a solution of 1000 ppm. The solution (1 ml) was then applied directly to ten house flies

sprayed in a drinking vessel with a piece of sugar which was also sprayed.

Immediately after spraying, the dig cup was inverted and allowed to dry. An assessment of the knockdown was made

when the vessels were reestablished 15 minutes later. The flies were then wet

Supplied with cotton swabs and then in a room for 48 hours, conditioned to 25 ° C and 65% relative humidity,

held before a mortality estimate was made.

Table V

codebook Test species Trägerme Type of test duration bushes dium / feed (Days) TUAC Tetranychus urticae green beans Contact 3 (Spider mite, ad.) (Sheet) TÜO Tetranychus urticae green beans Contact 3 (Spider mite, egg) (Sheet) TUNG Tetranychus urticae green beans Contact 6 (Spider mite, doll) (Sheet) (Dev.) MPMC Myzus persicae Chinese cabbage Contact 3 (Aphid) sheet NCNC Nephotettixcincti- rice plant Contact 2 cepe (grasshopper, Doll) NCNG Nephotettixcincti- rice plant Contact 6 ceps (grasshopper, (Dev.) Doll) MDAK Muscadomestica plastic pot Contact 15 (House fly, ad.) (knock min down) MDAC Muscadomestica plastic pot Contact 3 (House fly, ad.) BGNK Blattella germanica plastic pot Contact 15 (Cockroach, doll) (knock min down) BGNC Blattella germanica plastic pot Contact 2 (Cockroach, doll) HVLR Heliothisvirescens Cotton, return 2 (Tobacco Knospenste sheet was standing cher, larva) SPLR Spodoptera exigua Cotton, return 2 (small cotton moth, sheet was standing Larva) SPLG Spodoptera exigua 'Cotton, return 2 (small cotton moth, sheet was standing Doll) DBLR Diabroticabalteata Filter paper, return 2 (Gui kenkäfor, doll) corn seeds was standing MIJC Meloidogyn9 incognita in vitro Contact 1 (Root knot nematode, Doll)

"Contact" test means that both pests and medium were treated, residue indicates that the medium was treated with the pests prior to occupation.

Claims (1)

g (I) and stereoisomers thereof, wherein A is hydrogen, halogen, hydroxy, C 1-4 alkyl, C ₁ C 1-4 haloalkyl, C 1-4 haloalkoxy, C 1-4 alkylcarbonyl, C 1-4 alkoxycarbonyl, phenoxy, nitro or cyano; R ¹ and R ² , which may be the same or different, are hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted cycloalkylalkyl, optionally substituted aralkyl, optionally substituted heteroarylalkyl, optionally substituted aryloxyalkyl, optionally substituted heteroaryloxyalkyl, optionally substituted Alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted aryloxy, optionally substituted heteroaryloxy, nitro, halo, cyano, -NR ³ R ⁴ .- COOR ³ , -CO-NR ³ R ⁴ , -CO-R ³ , -S (O) _n -R ³ , where _{n is} 0.1 or 2, ~ (CH ₂ ) _m -PO (OR ³ ) ₂ , wherein m is 0 or 1, or R ¹ and R ² together form one carbocyclic or heterocyclic ring system; and R ³ and R ⁴ , which may be the same or different, are hydrogen, optionally substituted alkyl, optionally substituted aralkyl, optionally substituted alkenyl, optionally substituted alkynyl> optionally substituted aryl or optionally substituted heteroaryl, characterized in that the following reactions are carried out : (a) Composition of a compound of formula (II): (II) CH ₃ -O-CO wherein A has the abovementioned meaning and X is a leaving group, with the salt of an oxime of the formula (III), R ² wherein R ¹ and R ^{2 have} the abovementioned meaning, under basic conditions; or (b) treatment of a compound of formula (IX) SH ₂ -ON = CR ¹ j (IX, I o / ^ ₅ ^R CH ₃ -O-CO CH-O-R ^D with a compound of formula CH ₃ -L; or (c) Elimination of the elements of the methanol from a compound of the formula (IV) CH
• (CH ₃ O) ₂ CH '^ CO-O-CH ₃ under acidic or basic conditions; or
(d) Treatment of a ketoester of the formula (XI) R ²
H ₂ -ON = CR ^{1 (XI)}