KR950004003B1 - Fungicides - Google Patents

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Description

disinfectant

The present invention relates to acrylic acid derivatives useful in agriculture (particularly useful as fungicides as well as insecticide plant growth regulators), cultivating compositions containing them (particularly bactericidal) and methods of controlling fungi, pesticidal and plant growth in plants.

This invention provides the compound of following General formula (1), and its stereoisomer and metal complex.

Wherein W is R ¹ O ₂ CC═CH—ZR ² (R ¹ and R ² are the same or different from each other and are an alkyl or fluoroalkyl group, Z is an oxygen or sulfur atom): A is an oxygen or sulfur atom, -NR ³ -or CR ⁴ R ⁵ : X, Y6 and Z ¹ are (identical or different) hydrogen or halogen atoms, or hydroxy, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkylalkyl, Optionally substituted aralkyl, optionally substituted heteroarylalkyl, optionally substituted aryloxyalkyl, optionally substituted heteroaryloxyalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl , Optionally substituted alkoxy, optionally substituted arylalkoxy, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted acyloxy, optionally substituted amino, optionally substituted acyl amino, optionally substituted arylazo, nitro, cyano, -CO ₂ R ⁶ , -CONR ⁷ R ⁸ , -COR ⁹ , -CR = NR ^l0 , -CR = NO When R ¹⁰ or -N = CR ^ll R ¹² groups, or groups X and Y, are in an adjacent position in the ring, they are optionally bonded to form a fused ring and become aromatic or aliphatic and optionally contain one or more hetero atoms , R, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ^lo , R ^l1 and R ¹² are the same or different from each other, hydrogen atoms (where R ⁴ and R ⁵ Is not hydrogen) or optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkylalkyl, optionally substituted aralkyl, optionally substituted heteroarylalkyl, optionally substituted aryloxyalkyl, optionally substituted heteroaryloxyalkyl, optionally substituted alkenyl , Optionally substituted alkynyl, optionally substituted aryl or optionally substituted hetero aryl group.

The compounds of the present invention have at least one carbon-carbon double bond and are sometimes obtained in the form of mixtures of geometric isomers. However, such mixtures are separable into their respective isomers, and the present invention encompasses such mixtures in all proportions, including those composed of such isomers and those consisting mostly of ( Z ) -isomers and those consisting largely of ( E ) -isomers.

Each isomer resulting from the asymmetric substituted double bond of substituent W is usually named " E " and " Z ". This term is defined according to the Cahn-IngoId-Rrelog system, which is fully described in the literature (e.g., J March, "Advaced Organic Chemistry", 3rd edition Wiley-Interscience, p. 109). That is, for example, compound 3 of Table 1 is the ( Z ) -isomer.

Compound 36 in Table 1 is an ( E ) -isomer.

In contrast, compound 3 of Table 3 (furan analog of the trivalent compound thiophene of Po 1) is the ( E ) -isomer.

Usually one isomer is more active gatneunde sterilization, more active isomers W substituent _{^{(R l O 2 CC = CH}} -ZR 2) -ZR 2 group is numbered 5, where the double bond represented by the general formula (1) on over the others It is on the same side as. These isomers are all ( E ) -isomers except for the thiophene compound in which the group W is in the 2-position of the ring (the isomer in this case is the ( Z ) -isomer). Such isomers are preferred embodiments of the present invention.

In the compound of formula (1), the alkyl moiety of the alkyl group and the alkoxy group may be in straight or branched chain form and preferably contains 1-6 carbon atoms, more preferably C _1-4 . Such as methyl, ethyl, propyl, a (butyl n -, sec -, iso - - , and tert), (n - -, and isopropyl), and butyl. Optional substituents of alkyl include hydroxy, halogen (particularly chlorine and fluorine) and alkoxycarbonyl. Trifluoromethyl is the most preferred optionally substituted alkyl group.

R ¹ and R ² (alkyl or fluoroalkyl group) are preferably both methyl. The fluoroalkyl group is preferably fluoromethyl containing one, two or three fluorine atoms.

Cycloalkyl (preferably C _3-6 cycloalkyl) comprises cyclohexyl and cycloalkylalkyl (preferably C _3-6 cycloalkyl (C _1-4 ) alkyl comprising cyclopropylethyl). Any substituent is halogen (Particularly fluorine or chlorine), hydroxy and C _1-4 alkoxy.

Aralkyl is especially phenylalkyl (especially benzyl, phenylethyl, phenylpropyl, phenylbutyl or phenylhexyl), where the double alkyl moiety may have other substituents such as hydroxy and the aryl moiety is for example one or more different. May be substituted with; Halogen, hydroxy, C _1-4 alkyl (methyl and ethyl), C _1-4 alkoxy (methoxy), halo (C _1-4 ) alkyl (especially trifluoromethyl), halo (C _1-4 ) alkoxy (especially trifluoromethoxy), C _l-4 alkylthio (especially methylthio), C _1-4 alkoxy (C _1-4) alkyl, C _3-6 cycloalkyl, C _3-6 cycloalkyl (C _{1 -4} ) alkyl, aryl (especially phenyl), aryloxy (especially phenyloxy), aryl (C _1-4 ), alkyl (especially benzyl, phenylethyl and phenyl n -propyl), aryl (C _1-4 ) alkoxy ( Especially benzyloxy), aryloxy (Ci _-4 ) alkyl (especially phenyloxyketyl), acyloxy (especially acetyloxy and benzoyloxy), cyano, thiocyanato, nitoro, -NR'R ", NHCOR ' , -NHCONR'R ",-CONR'R",-COOR ",-SOS ₂ R ',-SO ₂ R',-COR ',-CR' = NR" or -N = CR'R (where R ' And R ″ are each hydrogen), C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkylthio, C _3-6 cycloalkyl, C _3-6 cycloalkyl (C _1-4 ) alkylphenyl, or Benzyl and the phenyl and benzyl groups are optionally halogen, C It may be substituted with _1-4 alkyl or C _1-4 alkoxy.

Allyloxyalkyl especially includes phenoxyalkyl (especially wasteoxymethyl or phenoxyethyl) wherein the alkyl moiety may have other substituents such as hydroxy and the aryl moiety can be substituted in the same way as the aryl moiety in the aralkyl. Do.

Heteroarylalkyl and heteroaryloxyalkyl are alkyl (preferably C ₁ ) having heteroaromatic substituents (connected by oxygen atoms in the case of heteroaryl oxyalkyl), including pyridinyl, pyriminyl, thienyl, furyl and pyrrolyl _-4 alkyl, in particular ethyl for heteroarylalkyl and methyl for heteroaryloxyalkyl). Heteroaromatic portion is optionally substituted in the same way as the aryl moiety in said aralkyl, especially, trifluoromethyl, halogen (especially fluorine, chlorine or bromine), nitro, C _1-4 alkyl, C _l-4 alkoxy , Trifluoromethoxy and amino.

Alkenyl and alkynyl groups contain C _2-6 , preferably C _2-4 in straight or branched chain form. Examples of alkenyl groups are ethenyl, propenyl and butenyl. Optional substituents of alkenyl (particularly ethyl) include aromatic and heteroaromatic groups (such as phenyl, furyl, thienyl or pyridyl), which are the same substituents as in the aryl moiety in the aralkyl, in particular halogen (particularly chlorine, or Fluorine). Especially preferred are optionally substituted phenylethenyl and pyridinylethenyl. The terminal carbon atom of the alkenyl group may also form part of a 5- or 6-membered cycloalkyl group. Alkynyl includes ethynyl and is optionally substituted, for example, with aryl (substitutable on its own as in the aryl moiety in the aralkyl). Especially preferred is phenylethynyl.

Aryl is preferably phenyl: heteroaryl is for example pyridinyl, pyrimidinyl, triazinyl, 1,2,4,5-tetrazinyl, thienyl, quinolinyl, isoquinolinyl, quinoxalinyl and benzothio Heteroaromatic groups such as phenyl; ethers may be substituted in the same manner as in the aryl moiety in the aralkyl.

Alkoxy is preferably C _1-4 alkoxy and is optionally substituted with, for example, hydroxy halogen (especially chlorine or fluorine) and C _1-4 alkoxy. Arylalkoxy includes phenyl (C _1-4 ) alkoxy (especially benzyloxy). Aryloxy includes phenyloxy and heteroaryloxy includes pyridinyl- and pyridinyl-oxy.

Aryloxy includes acetyloxy and benzoyloxy.

Optionally substituted amino and acylamino include the groups -NR'R "and -NHCOR ', wherein R' and R" are as defined above. It includes an optionally substituted benzoylamino and furo ylamino a - (especially methyl N) - acylamino, for example N (C _1-4) alkyl.

Group -COR ⁹ includes in particular formyl, acetyl and optionally substituted benzoyl and group -CR = NOR ^l0 comprises oxime ether -CH = N.OCH ₃ .

Arylazo is for example phenylazo, wherein the aryl moiety is optionally substituted in the same manner as in the aryl moiety in the aralkyl and in particular substituted with alkynyl, alkoxy (particularly methoxy) or dialkylamino (particularly dimethylamino).

Whenever referring to an optionally substituted aryl or hetero aryl moiety, or an optionally substituted fused ring, optional substituents include those that may be present in the aryl moiety in the aralkyl as described above.

Especially interesting compounds of formula (1), which is X, Y and Z is selected from the group consisting of the following: hydrogen, halogen, C _1-4 alkyl (especially methyl), aryl (C _l-4) alkyl (especially benzyl, Phenylethyl and phenyl n -propyl-where the phenyl ring is optionally substituted, for example with halogen or nitro), acyl (especially formyl and benzoyl optionally substituted with halogen), heteroaryl (Ci _-4 ) -alkyl, heteroaryloxy ( C _1-4 ) Alkyl and heteroaryloxy (where the heteroaryl groups are for example pyridinyl, pyrimidinyl, pyridazinyl, pyrrolyl, furyl and especially thienyl such as thienylethyl, thienyloxymethyl and pyridinyloxy Aryloxy- (Ci _-4 ) alkyl (such as phenoxymethyl, for example, the phenyl ring is optionally substituted with halogen, methyl, methoxy or ethoxy), Cl _-4 alkoxy (especially methoxy), aryl (C _1-4) alkoxy (especially benzyloxy pyenil ring as for example halogen, methyl again A-methoxy-a is optionally substituted), aryloxy (especially phenoxy) aryl (C _2-4) alkenyl and heteroaryl (C _2-4) alkenyl (especially phenylethenyl, pyridinyl and thienyl-ethenyl It may be ( E ) -isomer or ( Z ) -isomer as tenyl and aromatic or heteroaromatic rings are optionally substituted, for example with halogen methyl or methoxy), aryl (C _2-4 ) alkynyl (especially phenylethynyl), heteroaryl (C _2-4 ) alkynyl, cyano, C _1-4 alkoxycarbonyl and aryloxycycarbonyl (such as n -propoxycarbonyl and phenylosiocarbonyl, wherein the phenyl ring is optionally substituted with halogen, for example) , Such compounds include those in which X, Y and Z ¹ are hydrogen. However, it is preferred if the hydrogen is not on the heterocycle adjacent to the substituent W. When A is -NR ^3- , this group may be R ³ . When X and Y are in adjacent positions in the heterocycle ring, they may combine to form a fused ring such as a fused benzene ring.

It is preferred that at least one of R ¹ and R ² is methyl, more preferably R ² is methyl, most preferably both methyl.

It is preferred that A is sulfur or -NR ^3- .

It is preferable that Z (in substituent W) is oxygen.

In a particular embodiment of the present invention, the following compound (1a) is included.

Preferably in the acrylic acid salt is the 2-position (Z) - for isomers X in the acid salt of the adjacent location is halogen, C _1-4 alkyl, halo (C _l-4) alkyl (especially halomethyl), aryl (C _l-4 ) alkyl (especially benzyl, phenylethyl and phenyl n -propyl), aryloxy (C _1-4 ) alkyl (especially pentyloxyalkyl), aryl- (C _2-4 ) alkenyl (especially phenylethenyl) It is preferred if aryloxy (particularly phenyloxy), acyl (particularly proyl and benzoyl) and Y and Z ¹ are as described above and both are hydrogen.

In another embodiment are included compounds of Formula (1b).

Wherein R ³ is hydrogen, C _1-4 alkyl (particularly methyl or ethyl) or aryl (C _1-4 ) alkyl (particularly benzyl, pentylethyl and phenyl- n -propyl): X is hydrogen, C _1-4 alkyl (Especially methyl), aryl (C _1-4 ) alkyl (especially benzyl, phenylethyl and phenyl n-propyl), aryl (C _2-4 ) alkenyl (especially phenylethenyl) or acyl (especially poromyl); And Y and Z ¹ are as described above and both are hydrogen; Or when X is hydrogen, Y and Z ¹ together form a fused benzene ring.

The compounds of the present invention are shown by way of example in Pos 1-6.

TABLE 1

+ Geometry of beta-methoxyacrylate or beta- (methylthio) acrylate groups

* Single-line chemical shift (ppm from tetramethylsilane) solvent from olefinic on beta-methoxyacrylate or beta- (methylthio) acrylate group Solvent: CDC1 ₃

≠ C ₄ H ₃ is thienyl

XC ₅ H ₄ N is pyridinyl

TABLE 2

연결하여 융합된 방향족 환을 형성하는 치환체

Substituents that connect to form fused aromatic rings

Compound 56 is

Compound 57

+ Geometry of beta-methoxyacrylate or beta-8methylthio) acrylate

* Single-line chemical shift (ppm from tetramethylsilane) from olefinic protons on beta-methoxyacrylate or beta- (methylthio) acrylate groups Solvent: CDCl ₃

≠ C ₄ H ₃ is thienyl

XC ₅ H ₄ N is pyridinyl

α Single isomer, no geometry.

TABLE 3

+ Geometry of beta-methoxyacrylate or beta- (methylthio) acrylate groups

* Chemical shift of singlet from olefinic both on beta-methoxyacrylate or beta- (methylthio) acrylate group (ppm from tetramethylsilane) Solvent: CDCl ₃

≠ C ₄ H ₃ is thienyl

XC ₅ H ₄ N is pyridinyl

TABLE 4

연결하여 융합 방향족 환을 형성하는 치환체

Substituents that link together to form a fused aromatic ring

Compound 56 is

Compound 57:

Compound 58:

+ Geometry of beta-methoxyacrylate or beta- (methylthio) acrylate groups

* Chemical shift of single line from both olefinic on beta-methoxyacrylate or beta- (methylthio) acrylate group (ppm from tetramethylsilane) Solvent: CDCl ₃

≠ C ₄ H ₃ is thienyl

XC ₅ H ₄ N is pyridinyl

TABLE 5

+ Geometry of beta-methoxyacrylate or beta- (methylthio) acrylate groups

* Chemical shift (ppm from tetramethylsilane) to a single line from orefinic protons on beta-methoxyacrylate or beta- (methylthio) acrylate groups Solvent: CDCl ₃

≠ C ₄ H ₃ is thienyl

XC ₅ H ₄ N is pyridinyl

TABLE 6

+ Geometry of beta-methoxyacrylate or beta- (methylthio) acrylate groups

* Chemical shift of singlet from olefinic both on beta-methoxyacrylate or beta- (methylthio) acrylate group (ppm from tetramethylsilane) Solvent: CDCl ₃

≠ C ₄ H ₃ S is thienyl

XC ₅ H ₄ N is pyridinyl

연결하여 융합벤젠 환을 형성하는 치환체

Substituents that connect to form a fused benzene ring

Compound 57:

Compound 58:

TABLE 7

Table 7: NMR data of select quantum

Table 7 shows select quantum nmr data for the compound compounds described in Tables 1-6. Chemical shifts are measured in ppm from tetra methylsilane. The solvent is second chloroform. Both of the following are used:

br = wide t = triple

s = single line g = quartet

d = double line m = multiple line

Compounds of the invention of formula (1) may be prepared by the steps shown in Schemes 1-4. In this scheme, R ¹ , R ² , X, Y, Z, Z ¹ , W and A are as described above, L is halogen (iodine, bromine or chlorine), M is metal (such as lithium) or halogen-bonded metal (Eg MgI, MgBr or MgC1), R ¹³ is hydrogen or metal (eg sodium) R ¹⁴ is alkyl and R ¹⁴ is alkyl or optionally substituted aryl.

Each transition shown in Schemes 1-4 is done in a suitable temperature and a suitable solvent.

The compound of formula (1) may exist as a mixture of geometric isomers, which may be separated by chromatography, type or fractional crystallization. The following general formula is:

As follows, it means a separable mixture that is geometric isomers for acrylate double bonds.

및

And

Scheme 1

In Scheme 1, the compound of formula (1) can be prepared by treating the ketoester of formula (2) with phosphorane of formula (6) in a solvent such as, for example, diethyl ether. EP-A-0044448 and EP-A-0178826) The compounds of the general formula (1) wherein Z is sulfur furthermore, the ketoester of the general formula (2) is substituted with a lithio of the general formula (CH ₃ ) ₃ SiCH (Li) SR ² -By treating with species (see DJ Peterson. J. Org Chem ., 1968, 33 , 780 and FA Carey and AS Court, J. Org. Chem., 1972, 37, 939).

Ketoesters of formula (2) can be prepared by treating metal-substituted species (3) in oxalate (7) and diethyl ether or tetrahydrofuran. Preferred methods include the slow addition of a metal-substituted species (3) solution to the excess oxalate (7) stirred solution (see LM `Veinstock, RB Cuttie and AV Love 11 , Synthetic Communtcations , 1981, 11 , 943 and references therein).

Metal substituted species (3) (M is MgI, MgBr, MgCl (Grignard reagent)) can be prepared by standard methods from the corresponding halide 4 (L is I, Br or C1, respectively). Metal substituted species (3) (M is lithium) can be prepared by standard methods by treating the corresponding halide (4) with an organolithium reagent such as n -butyl-lithium. Metal substituted species (3) (A is oxygen, sulfur or NR ³ and M is a lithium atom in the 2- or 5-position) uses a strong lithium base such as n-butyl-lithium or lithium diisopropylamide It is also prepared by direct oxidization of compound (5) (see HW Gachwend and HR Rodriguez, Organic Reactions 1979, 26 , 1).

The ketoester of formula (2) is also treated by treating the compound of formula (5) with the acid chloride of formula (8) in the presence of a suitable solvent (such as chloroform) in the presence of Lewis acid (such as aluminum chloride or boron trifluoride). Can be obtained.

In another approach, the ketoester of the general chamber (2) is treated with oxali chloride of the compound of the general formula (5), optionally in the presence of Lewis acid, and the acid chloride obtained is generalized in the presence of a base such as triethylamine. It can be prepared by treating with the formula R ¹ OH (R ¹ is as described above). The intermediate acid chloride is removable.

The acylation described above, ie, acylating thiopan, philol or furan with alkyl oxalyl chloride or oxalyl chloride is generally reggioselective. Regio-selective approaches are described in the chemical literature on acylating these ring systems with various acid chlorides (see Comprehensive Heterocyclie Chemistry, AR Katritzky and CW Rees, Editors, Vol. 4, Pergamon Press, 1984). , Acylation median position or position and substituent form, if any, depending on the thiophene, pyrrole or furan ring.

While acylation generally occurs at the 2- or 5-position (when either or both of these positions are unsubstituted), certain substituents on the nitrogen of the pyrrole, such as many substituents at the 3-position of the benzenesulfonyl- or furan ring Are preferentially acylated more preferentially at the 2-position (opposite to the 5-position), examples of such substituents include (E) -styryl, phenoxymethyl- and CH ₂ O ₂ CC = CH-OCH ₃ groups There is this.

Other methods for the preparation of ketoesters of formula (2) are described in the chemical literature (see DC Atkinson, KE Godfrey, B Meek, J fs Saville and MR Stillings, J. Med. Chem ., 1983 26). , 1353: D Horne, J Gaudino and WJ Thompson, Tetrahedron Lett ., 1984, 25, 3529: and GP Axiotis.Tetrahedron Lett ., 1981, 22. 1509).

The compound of formula (4) (5) is prepared by standard methods described in the chemical literature.

Another approach to the compound of the invention (Z) is an oxygen atom of general formula (1) is shown in Scheme 2. R ¹³ is hydrogen or a metal (preferably an alkali metal such as sodium or potassium) and R ¹⁴ is an alkyl group.

Scheme 2

Compounds of formula (1) (Z is oxygen) are formulated as bases (such as sodium hydrate or sodium alkoxides of formula R ¹ ONa (R ¹ is as described above) and formic acid esters). (General formula HCO ₂ R ¹ (R ¹ is as described above)). If the general formula R ² Q (Q is a leaving group such as halide (chloride, bromide or iodide), R ² SO ₄ -anion, sulfonyloxy-anion (R ² is as described above)) When added to, a compound of formula (1) (Z is oxygen) is obtained. If protic acid is added to the reaction mixture, a compound of formula (13) (R ¹³ is hydrogen) is obtained. In addition, the compound of formula (13) (R ¹³ silver metal) is self-separable from the reaction mixture.

The compound of formula (13) (R ¹³ is a metal) can be converted to a compound of formula (1) (Z is oxygen) by treatment with formula R ² Q (R ² and Q are as described above). . Compounds of formula (13) (R ¹³ is hydrogen) can be converted to compounds of formula (1) (Z is oxygen) by successive treatment with a base (such as potassium carbonate) and a formula R ² Q compound.

In addition, compounds of formula (1) (Z is oxygen) can be prepared from acetals of formula (10) by releasing alcohol R ² OH (R ² is as described above) under acidic or basic conditions. Examples of reagents or mixtures of reagents that can be used for this transition include lithium di-isopropylamide: potassium hydrogen sulfate (T Yamada, H Hagiwara and H Uda, J. Chem, Soc., Chemical Communications , 1980, 838). And double references), and triethylamine, sometimes in the presence of Lewis acids such as titanium tetrachloride. (See K Nsunda and L Heresi, J. Chem. Soc., Chemical Communications , 1985, 1000).

Acetal of formula (10) is treated with trialkyl orthophotomate in formula (R ² O) ₃ CH with alkyl silyl ketan of formula (14) (R ¹⁴ is an alkyl group) in the presence of a Lewis acid such as titanium tetrachloride. (K Saigo, M OsaKi and T Mukaiy-ama, Chemistry Letters , 1976, 769).

Alkyl silyl ketene acetals of formula (14) may be treated with terminus and trialkylsilyl halides (such as trimethylsilyl fluoride) such as formula R ¹⁴ ₃ SiC1 or R ^l4 ₃ SiBr or with bases (such as triethylamine) and general formula It can be prepared from the compound of formula (9) by treatment with trialkylsilyl triflate of R ¹⁴ ₃ Si-OSO ₂ CF _3. (C Ainsworth, F Chen and Y Kuo, J. Organometallic Chemistry , 1972, 46 , 59).

It is not always necessary to separate the intermediates 14 and 10; Under suitable conditions, the compound of formula (1) can be prepared from the compound of formula (9) at once by successively adding the appropriate reagents noted above.

Compounds of formula (9) can be prepared by standard methods described in the chemical literature.

Another approach for compounds of the invention of general formula (1) (Z is oxygen) is shown in Scheme 3.

Scheme 3

Partial reduction of the malonate derivative of formula (11) with a reducing agent (such as lithium aluminum hydrate) in a suitable solvent such as diethyl ether, followed by acidic or aqueous operation to give formula (13) (R ^l3 is hydrogen). Compounds can be prepared and converted to compounds of formula (1) (Z is oxygen) by the method shown in the step of Scheme 2 (see M Barczai-Beke, G Dornyei, G Toth, J Tamar and Cs Szantay, Tetrahedron , 1976, 32 , 1153 and double references).

In addition, the compound of formula (1) may be prepared by continuously treating with bromine, a reagent of formula R ² OM (R ² and M are as described above), sodium hydrogen sulfate, or related chemicals. It can be made from acrylic acid derivatives (G Shaw and RN Warrener, Journal of the ChemicaI Society , 1958, 153 and related literature).

Compounds (11) and (12) can be prepared by standard methods described in the chemical literature.

Scheme 4

Compounds of formula (1) (Z is sulfur) can be prepared from compounds of formula (13) (R ¹³ is hydrogen) according to the steps shown in Scheme 4:

(i) from enols of formula (13) (R ¹³ is hydrogen: such compounds are reacted with thiols of the general formula R ² SH (R ² is as described above) under acidic conditions, sometimes in the presence of a dehydrating body. Is in equilibrium with the mutant formyl acetate).

(ii) from the beta-chloroacrylate of formula (15) by treatment with thiolate of formula R ² SM (R ² and M are as described above), for example, chlorinated hydrocarbons; In a suitable solvent such as can be prepared from the enol of formula (13) (R ¹³ is hydrogen) using a chlorinating agent such as phosphorus pentachloride.

(iii) beta-sulfonyloxyacrylate (16) from beta-sulfonyloxyacrylate of formula (16) by treatment with thiolate of formula R ² SM (R ² and M are as described above) From the enol of formula (13) (R ³ is hydrogen) using sulfonyl chloride of the general formula R ¹⁵ SO ₂ Cl (R ^l5 is as described above) in the presence of a base such as pyridine or triethylamine. Can be.

(iv) from the dithioacetal of formula (17) by releasing thiol R ² SH under acidic or basic conditions, for example, the dithioacetal (17) is a compound of formula (1) (Z is oxygen) under acidic conditions. It can be prepared by several methods described in the literature, such as by treatment with excess thiol R ² SH.

Another aspect of the invention provides a process for preparing the compounds of the invention and intermediate chemicals of formulas (2) and (9)-(17).

Compounds and metal complexes of the present invention are active fungicides and may be used to inhibit one or more pathogens:

Pyricularia oryzae of rice

Puccinia recondita Puccinia striifonnis and of wheat

Other greenery, Puccinia hordei, Puccinia striiformis and of barley

Other green nuts, and other hosts such as coffee, pears, apples, peanuts, vegetables and ornamental plants.

Barley and wheat Erysiphe graminis (powder fungus) and other powdery fungi on various hosts such as

Hop Sphaerotheca macularis

Sphaerotheca fuliginea of calabash (such as cucumber)

Podosphaera leucotricha of apples and Uncinula necator of grapes

Grain of Helminthosporium spp. , Rhynchosporium spp., Septoria spp., Pseudocercosporella herpotrichoides Gaeumannomyces graminis

Cercospora arachidicola and Cercosporidium personata of peanuts, and other Cercospora species of other hosts, such as sugar beets, bananas, beans and rice

Botrytis cinerea (gray fungus) on tomatoes, strawberries, vegetables, grapes and other hosts

Alternaria on vegetables (such as cucumbers), rapeseed oil, apples, tomatoes, and other hosts

Venturia inaequalis on apple

Plasmopara viticola on the stamen

Gray mold, such as Bremia lactucae on lettuce

Peronospora spp., On beans, tomatoes, onions and other hosts

Pseudoperonospora humuli of hops and Pseudoperonospora cubensis of calabash

Phytophthora infestans on potatoes and tomatoes and Phytophthora spp. On vegetables, strawberries, avocados , peppers, ornamentals, tobacco, cocoa and other hosts.

Thanatephorus cucumeris of rice

Rhizoctonia on several hosts, such as wheat and barley, vegetables, cotton, and grass

Several compounds have shown widespread activity against fungi in vitro.

They are also active against post-harvest diseases of fruits (eg Orange Penicillium digitatum and italicum and Trchoderma viride and Banana Gloesporium musarum)

Some compounds are also active as seed dressings against Fusarium spp., Septoria spp., And Tilletia spp. (Mycosis of wheat, disease called seeds).

Cereals Ustilago spp., Helminthosporium spp.

Rhizoctonia solani of cotton

Pyricularia oryzae of rice

The compound can move spherically in plant tissues. Moreover, the compound is volatile enough to be active in the vapor phase against plant fungi.

The compounds are also useful as industrial fungicides (as opposed to agricultural use) to prevent fungi on wood, animal hides, leather and especially paint films.

Some compounds of the invention in particular formula (1) (A is —NR ³ , X, Y and Z ¹ are hydrogen and W is R ^l O ₂ CC═CHZR ² , Z is oxygen, R ¹ and R ² are alkyl) Shows pesticidal activity. It was developed that compound 38 of Table 5 is active against Diabrotica balteata (root worm larva).

Similarly, some compounds show plant growth inhibitory activity, which can be developed when utilized at an appropriate rate.

The present invention therefore encompasses the use of the aforementioned compounds (and compositions containing them) in addition to the main purpose as fungicides.

The compounds may be used directly for sterilization purposes, but may be more conveniently formulated into compositions using carriers or diluents. Therefore, a bactericidal composition containing the compound of formula (1) of the present invention and a carrier or diluent acceptable for sterilization is provided.

The present invention also provides a method for combating fungus by administering the compound, or compound containing composition, to a plant, plant seed, plant or place of seed.

The compound is administered in several ways. For example, it may be administered directly to a medium that is formulated, unformulated, or in which the leaves, seeds or plant of the plant grow or are planted. It may be sprayed, sprinkled, applied in the form of a cream or paste, or administered in the form of a vapor or slow relief. Administration may be any part of the plant, including leaves, stems, branches or roots, and may be administered to the soil around the roots or to seeds before drinking or generally to soil, paddy or water cultivation systems. The compounds of the present invention can be injected into lumps or sprayed onto plants using electromechanical spraying techniques or other small volume methods.

The term "plant" includes seedlings, bushes and trees. Moreover, the sterilization methods of the present invention include prophylactic, protective and modulating treatments.

The composition comprises an active ingredient (compound of the invention) and solid diluents or carriers such as kaolin, bentonite, diatomaceous earth, dolomite, gypsum, talc, powder magnesia, fill earth, calcium carbonate, diatomaceous earth and clay May be in the form of a powder or granules. Such granules may be preformed granules suitable for application to the soil without further treatment. Such granules can be prepared by impregnating the filler eggs in the active ingredient or pillifying the active ingredient and powder filler. The dressing seed composition may comprise a reagent (eg mineral oil) to aid in the attachment of the composition to the seed, and the active ingredient may also be prepared using an organic solvent (eg N-methylpyrrolidone, propylene glycol or dimethyl formamide) It may be formulated for seed dressing. The composition may also be in the form of a wettable powder or water dispersible granule comprising a wetting agent or a dispersing agent to facilitate dispersion in a liquid. Powders and granules may also contain fillers and suspending agents.

Emulsifying concentrates or emulsions can be prepared by dissolving the active ingredient in an organic solvent containing a wetting or emulsifying agent and adding the mixture to water, which also contains 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 trchlorethane and alcohols such as furfuryl alcohol, butanol and Glycol ethers.

Suspension concentrates of photoinsoluble solids can be prepared by adding a suspending agent to stop solid precipitation after ball milling or bead milling with a dispersant.

The composition used for spraying may be in the form of an aerosol, in which the formulation is contained in a container under pressure in the presence of a spray drug such as, for example, fluorotrichloromethane or dichlorodifluoromethane.

The compounds of the present invention can be mixed dry in a mixture of chemical techniques to form a composition suitable for producing smoke containing the compound in an enclosed space.

The compounds can also be used in microencapsulated form. They can also be formulated in biodegradable polymerization formulations to obtain slow and controlled relaxation of the actives.

By adding suitable additives such as additives for improving distribution, additives for improving adhesion, additives for improving the resistance to rain on the treated surface, the different compositions are more suitable for various applications.

The compounds of the present invention can be used in admixture with fertilizers (nitrogen-, calcium-, phosphorus-containing fertilizers). Preferred are compositions containing compound coated fertilizer granules. Such granules contain 25% by weight of the compound. The present invention therefore provides a fertilizer composition comprising a compound or salt of formula (1) or a metal complex thereof and a fertilizer thereof.

Wettable powders, emulsifiable concentrates and suspension concentrates usually contain surfactants such as wetting agents, dispersants, emulsifiers or suspending agents. Such reagents may be anionic, cationic or nonionic.

Suitable cationic reagents are quaternary ammonium compounds such as cetyltrimethylammonium bromide. Suitable anionic reagents are soaps, aliphatic monoester salts of sulfuric acid (such as sodium lauryl) and salts of sulfonated aromatic compounds (such as sodium dodecylbenzenesulfonate, sodium, calcium or ammonium lignosulfonate, butylnaphthalene sulfonate and Sodium diisopropyl- and triisopropyl-naphthalene sulfonate).

Suitable nonionic reagents are condensation products of ethylene oxide with fatty alcohols such as oleyl or cetyl alcohol or alkyl phenols such as octyl- or nonyl-phenyl and octylcresol. Other nonionic reagents are partial esters derived from long chain fatty acids and hexitol anhydrides, condensation products of these partial esters with ethylene oxide and lecithin. Suitable suspending agents are hydrophilic clades (such as polyvinylpyrrolidone and sodium carboxymethylcellulose), expanded clays such as bentonite or attafilzite.

The composition used as an aqueous dispersion or emulsion is supplied in the form of a concentrate containing a high proportion of active ingredient and the concentrate is diluted with water before use. Such concentrates should preferably be able to withstand long-term storage and should remain homogeneous for a period of time sufficient to be sprayed after dilution with water to form an aqueous formulation after long-term storage. The concentrate contains up to 95%, suitably 10-85%, such as 25-60% by weight of the active ingredient. After being thinned into aqueous formulations, these formulations may contain various amounts of active ingredient, depending on the purpose, but usually contain 0.001% -10% by weight of active ingredient.

The composition of the present invention may contain other compounds having biological activity, such as compounds having similar or supplemental bactericidal activity, compounds having plant growth regulation, herbicidal or pesticidal activity.

Bactericidal compounds in the compositions of the present invention include, for example, Septoria Gibberella and Helminthosporium spp. And it is possible to combat the powdery mold and scabies of apples. By including other fungicides, the composition can have a broader activity than the compound of formula (1) only. Moreover, other fungicides may have a synergistic effect on the bactericidal activity of the compound of formula (1). Examples of bactericidal compounds that may be included in the compositions of the present invention include the following:

Carbendazim, Benomyl, Thiophaneito-Methyl, Thiabendazole, Fuberidazole, Etridazole, Diclofluanide, Simoxanyl, Oxadixyl, PMRace, Metalaccil, Furlaxyl, 4-Chloro- N- (1-cyano-1-ethoxymethyl) benzamide, benaracyl, pocetyl-aluminum, phenarimol, iprodione, prothiocarb, procmidone, vinclozoline, fenconazole, michaelrobuta Neil, propamocarb, diconazole, pyrazophos, etirimole, ditalipfoss, tridemolph, tripolin, noarimol, triazbutyl, giazatin, 1,1-iminodi (octamethylene) digi Triacetate salt of anidine, butiobate, propionazole, prochloraz flutriapol, hexaconazole, (2 RS , 3 RS ) -2- (4-chlorophenyl) -3-cyclopropyl-1- (lH-1,2-4-triazol-1-yl) butan-2-ol, ( RS ) -1- (4-chlorophenyl) -4,4-dimethyl-3- (lH-1,2, 4-triazol-1-ylmethyl) pentan-3-ol, flusilazole, pyridenox, tri Liadimefon, triadimenol, diclobutrazole, fenpropiform, phenpropidine, chlorozolinate, imajaryl, fenfuram, carboxycin, oxycarboxycin, metfuroxam, dodemol, BAS 454, blasti Cidine S, Kasugamycin, Edifenforce, Kitazine P, Cycloheximide, Phthalide, Provenazole, Isoprothiolane, Tricyclazole, Pycloquilon, Chlorbenzthiazone, Neoasazine, Poly Auxin D, validamycin A, mepronyl, flutolanyl, fensaicuron, diclomezin, phenazine oxide, nickel dimethyldithiocarbamate, declophthalam, bitteranol, burimate, etagonazole, Hydroxyisoxazole, streptomycin, cyprophram, biloxazole, quinomethionate, dimethymolol, 1- (2-cyano-2-methoxyimino-acetyl) -3-ethyl urea, phenanyl, tol Clofos-Methyl, Pyroxypur, Polyram, Maneb, Mancozeb, Captapol, Chlorotal Roninil anilazine, thiram, captan, polpet, geneb, propineb, sulfur, dinocap, diclone, chloroneb, vinapacryl, nitrotal, isopropyl, dodine, dithianon, pentine hydroxide, Pentine acetate, technazen, kintogen, dichloran, such as copper oxychloride, copper-containing compounds such as copper sulfate and Bordeux mixtures, and mercury compounds.

The compound of formula (1) can be mixed with soil, peat or other root medium to combat seed burning, soil burning or fungal diseases of leaves.

Suitable pesticides that may be included in the present compositions include pyrimicab, dimethate demethone-S-methyl, formodione, carbaryl, isoprogab, XMC, BPMC, carbofuran, carbosulfan, diazinon pention, Phenythrothione, pentoate, chlorpyriphos, isoxation, thropaphos, monocrotopas, buprofezin, ethoxyproxyfen and cycloprothrin.

Plant growth regulator compounds are compounds that inhibit the formation of weeds or seedheads and selectively inhibit the growth of less desirable plants (such as blades of grass).

Examples of suitable plant control compounds for use with the compounds of the present invention include the following. Gibberellins (e.g. GA ₃ , GA ₄ or GA ₇ ), auxins (e.g. indole acetic acid, indole butyric acid, naphthoxyacetic acid, naphthyl acetic acid), cytokinins (e.g. kinetin, diphenylurea, benzimidazole, benzyl) Aneneine or benzylaminopurine), phenoxyacetic acid (such as 2, 4-D or MCPA), substituted benzoic acid (triadobenzoic acid), fulcthin (such as chlorfluoroethanol), maleic hydrazide, glyphosate , Glyphosine, aliphatic alcohols and acids, dikegilac, paclobutrazole, fluroprimidol, fluoridamide, mefluidide, substituted quaternary ammonium and phosphonium compounds such as chloromefab chlorphonium or mepifab chloride), Etepon, carbetamid, methyl-3, 6-dichloroanisate daminozide, asulam, absinic acid, isopymolole, 1- (4-chlorophenyl) -4, 6-dimethyl-2-oxo- 1,2-dihydropyridine-3-carboxylic acid, hydroxy Crude nitrile (e. G. Bromine oxy carbonyl), dipentene crude kweteu, prop-benzoyl-3-acetate, 6-dichloro-picolinic acid, penpen tejol, and Ben sulfide, tri Appenzell tenol and Tech najen

The following examples illustrate the invention. In the examples, "ether" refers to diethyl ether, where magnesium sulfate is used as a dry solution, and the reactants comprising water sensitive intermediates are run in nitrogen and in a dry solvent. Unless otherwise stated, chromatography is carried out using silica gel as the stationary phase. Infrared and nmr data are generated selectively and not recorded for all absorptions. nmr data is recorded in second chloroform. The following abbreviations are used:

DMSO: dimethyl sulfoxide, delta = chemical shift, THF = tetrahydrofuran, CDC1 ₃ : second chloroform, DMF = N , N -dimethylformamide, s = single line, GC = gas chromatography, d = double line, MS = Mass spectrum, nmr = nuclear magnetic resonance, HPLC = high performance liquid chromatography, mp = melting point, IR = infrared, mmo1 = millimolar, t = triplet, mmHg: millimeter water temperature pressure, m = polyline, J = coupling constant , mg = milligrams, Hz = hertz, g = grams, br: wide.

(Example)

This example is a method for preparing the ( E )-and ( Z ) -isomers of methyl-2- (3-benzyl-2-thienyl) -3-methoxypropenoate. Compound 3).

A solution containing P ₂ I ₄ (3.42 g, 6 mmol) and 3- (1-hydroxybenzyl) thiophene (1.90 g, 10 mmol) in sodium-anhydrous toluene is heated under nitrogen for one hour. The reaction mixture is cooled and then quenched with 10% aqueous sodium sulfite. After the mixture is extracted with ether, the combined organic phases are washed with water, brine and dried. Filtration and evaporation gave a yellow oil, which was bulb-to-bulb (l10 at 0.05 mm Hg) to give a pale pink oil. Chromatography with dichloromedan gave 3-benzylthiophene in the form of an oil (1.02 g, 53% yield): ^l H nmr: Delta 3.84 (2H, s), 7.0-7.2 (8H, m) ppm

A solution of 3-benzylthiophene (1.0 g, 5.75 mmol) and methyl oxalyl chloride in dry dichloromethane (50 ml) was added to the aluminum chloride (1.35 g) stirring suspension in dry dichloromethane (50 ml) over 40 minutes with ice cooling. do. After stirring for 2 hours at room temperature, the reaction mixture is poured onto ice and acidified with dilute, hydrochloric acid. The aqueous layer is separated, extracted with dichloromethane and the combined organic layers are washed with water and brine and dried. Filtration and evaporation under reduced pressure gave a yellow oil (1.63 g) which was chromatographed (30% ether eluent in petrol) to give methyl 2- (3-benzyl-2-thienyl) -2-oxoacetate (240 mg): ^l H nmr: delta 3.90 (3H, s), 4.40 (2H, s), 6.90 (1H, d, J = 4.2Hz), 7.2-7.4 (5H, m), 7.6 (lH, d, J = 4.2Hz ) ppm: and methyl 2- (4-benzyl-2-thienyl) -2-oxoacetate (50 mg), ^l H nmr: delta 3.90 (3H, s), 3.99 (2H, s), 7.0-7.3 (6H) m), 7.95 (1H, d, J = 1.3 Hz) ppm.

Methyl 2- (3-benzyl-2-thienyl) -2 in dry THF (5 ml) in a suspension of (methoxymethyl) triphenylphosphonium chloride and sodamide in dry THF (0.4 g of 1: 1 molar ratio mixture) Add oxoacetate (220 mg, 0.8 mmol) solution. The reaction mixture is stirred for 30 minutes at room temperature. (Methoxymethyl) triphenylphosphonium chloride and sodamide (0.2 g, 1.2 molar mixture) are added and stirred for 1 hour. The reaction mixture is poured into water and extracted with ether. The combined ether layers are washed with water, brine and dried. Filtration through a pad of silica gel to remove trifenyl phosphine oxide, followed by HPLC (eluent dichloromethane) to afford ( Z ) -methyl-2- (3-benzyl-2-thienyl) -3-methoxypropenoate, oil Steamed in the form (100 mg), ^l H nmr: Delta 3.64 (3H, s), 3.78 (6H, s), 6.75 (lH, d), 7.0-7.4 (6H, m), 7.60 (lH, s) ppm: and ( E ) -Methyl 2- (3-benzyl-2-thienyl) -3-methoxypropenoate, oily form (30 mg), ^l H nmr: delta 3.64 (3H, s), 3.80 (3H, s), 3.82 (3H, s), 6.56 (lH, s), 6.75 (lH, d), 7.0-7.3 (6H, m) ppm.

(Example 2)

In this example, ( E ) -methyl 3-methoxy-2- (3-thienyl) propionate (Compound No. 1 in Table 2) was prepared.

Methyl 3-thienyl acetate is prepared by heating 3-thienyl acetic acid in acidic methanol. Oil form ^l H nmr: Delta 3.71 (2H, s), 3.76 (3H, s) ppm.

A solution of methyl 3-thienyl acetate (23.8 g) in methyl formate (94 ml) and DMF (30 ml) is added dropwise at 0-10 ° C. (boiling) temperature in a stirred suspension of sodium anhydride (7.30 g) in DMF (250 ml). After addition, the reaction mixture is stirred for 30 minutes at room temperature. After pouring into water, the resulting mixture is acidified with dilute hydrochloric acid and extracted with ether. The extract is washed with water, dried and concentrated to give an orange oil (38.80 g). Potassium carbonate (42.0 g), and after 15 minutes dimethyl sulfate (13.62 ml) is added continuously to an orange oil stirred solution in DMF (250 ml). After 2 h at rt, the mixture is diluted with water and extracted with ether. The extract was washed with water, dried and concentrated to give an orange oil (22.50 g) which was distilled (short channel distillation apparatus) to give the title compound as a colorless liquid (20.60 g, 68% yield from methyl 3-thienyl-acetate). . ^l H nmr: Table 7

(Example 3)

In this example, ( E ) -methyl 2- (2-formyl-3-thienyl) -3-methoxypropenoate (Compound No. 37 in Table 2) was prepared.

Phosphorus oxychloride (4.70 ml) is added at once in vigorously stirred DMF (4.30 ml) and cooled in an ice bath. The resulting mixture is turbid, diluted with dichloromethane (10 ml) and stirred at room temperature for 30 minutes. A solution of ( E -methyl 3-methoxy-2- (3-thienylpropenoate (10.0 g, prepared as described in Example 2)) in dichloromethane (25 ml) was added dropwise at room temperature for 5 minutes. The resulting mixture is stirred at room temperature for 5 hours, then poured into saturated aqueous sodium acetate (250 ml) and heated in a steam bath until the white solid is separated and further heated for 10 minutes The total mixture is extracted with eta acetate. Was washed with water, dried and concentrated to give an oily solid, which was triturated with ether, filtered and dried to give the title compound as a solid (9.20 g, 81% yield), mp144 -145 ° C.

Recrystallized from ethyl acetate to have mp 147-148 ° C.

¹ H nmr: Delta 3.76 (3H, s), 3.89 (3H, s), 7.06 (lH, d J 5Hz), 7.66 (lH, d J 5Hz), 7.72 (lH, s), 9.72 (1H, s) ppm.

(Example 4)

In this example, ( E ) -methyl 2- (2-benzoyl-3-thienyl) -3-methoxypropenoate (Compound No. 24 in Table 2) was obtained.

Powdered aluminum chloride (1.34 g) was diluted with ( E ) -methyl 3-methoxy-2- (3-thienyl) propenoate (1.00 g, prepared in Example 2) and benzoyl chloride in dichloromethane (10 ml). (0.78 g) Add to stirring solution and cool in ice bath. After addition, the mixture is stirred for 4 hours at room temperature and extracted with ether. The extract was washed with dilute hydrochloric acid (X1), washed with water (X3) and concentrated to dryness to give a black orange oil (0.82 g), which was chromatographed (1: mixture of eluent ethyl acetate and petrol) to give:

(i) ( E ) -methyl 2- (2-benzoyl-4-thienyl) -3-methoxypropenoenite (100 mg, 7% yield) in oil form, ^l Hnmr. Delta 3.76 (3H, s), 3.92 (3H, s) ppm, and (ii) methyl tautomeric equilibrium] (220 mg, 15% yield) gum state, ^l Hnmr: delta 3.61 (3H, s), 7.01 (lH) , d J 5 Hz), 7.57 (lH, d J 5 Hz), 11.76 (lH, d J 13 Hz) ppm.

After 15 minutes of potassium carbonate (114 mg), dimethyl sulfate (0.046 ml) is added to a stirred solution of methyl 2- (2-benzoyl-3-thienyl-3-hydroxypropenoate in DMF (3 ml). After time, the mixture is diluted with water and extracted with ether The extract is washed with water, dried and concentrated to give the title compound (120 mg, 81% yield), tan solid, mp 95-96 ° C. ethyl acedate Mp 96-97 ° C. ^l H nmr delta3.63 (3H, s), 3.73 (3H, s), 7.12 (lH, d J 5Hz), 7.16 (lH, s), 7.56 (lH, d J 5 Hz) ppm.

(Example 5)

( Z )-and ( E ) -isomers of compounds 3-methyl-2- (3-phenoxymethyl-2-thienyl) propenoate (compounds 9 and 10 in Table 1).

Methanesulfonyl chloride (20.3 ml) solution in dichloromethane (20 ml) was added to a stirred solution of 3- (hydroxymethyl) thiophene (20.0 g) and triethylamine (42.8 ml) in dichloromethane (150 ml) over 15 minutes. After dropping, cool in an ice bath. The solution is initially colorless and becomes yellow and a white solid precipitates out. After placing in an ice bath for 1 hour, the reaction mixture is left warm at room temperature and stirred for 2 hours. The mixture is washed successively with water, diluted hydrochloric acid, water, aqueous sodium carbonate, and aqueous sodium chloride and concentrated to dryness to afford 3- (chloromethyl) thiophene (14.50 g, 63% yield) as a yellow liquid. ^l H nmr: delta 4.62 (2H, s) ppm.

A solution of phenol (13.16 g) in DMF (10 ml) is added in portions over 10 minutes to a stirred suspension of sodium anhydride (3.12 g) in DMF (100 ml). After 2 hours, a solution of 3- (chloromethyl) thiophene (14.50 g) in DMF (30 ml) is added in portions and the resulting mixture is stirred at room temperature for 3 hours, then poured into water and extracted with ether. The extract was washed successively with water, dilute sodium hydroxide and aqueous sodium chloride, and then concentrated to dryness to afford 3- (waste oxymethyl) thiophene (18.86 g, 91% yield) as a white solid. Recrystallization with methanol gives mp 49-50 ° C.

n -butyl-lithium (11.56 ml of a 2.5M solution in n -hexane) is added dropwise to a stirring solution of 3- (phenoxymethyl) thiophene (5.0 g) in THF (50 ml) at a temperature of about -70 ° C. After dropping, the reaction mixture is left to warm at room temperature and stirred for 1 hour. To a stirred solution of dimethyl oxalate (6.2 g) in THF (75 ml) was added dropwise at a temperature of about -10 ° C. The resulting mixture is stirred at room temperature for 2 hours, poured into water and extracted with ether. The extract was washed with water, dried, concentrated and chromatographed using a 1: 1 mixture of ether and petrol as eluent to afford an orange oil (2.71 g) which was then fixed and crystallized.

The solid is triturated with petrol, filtered and dried to give methyl 2- (3-phenoxymethyl-2-thienyl) -2-oxoacetate (770 mg, 11% yield) as a yellow solid. mp 98-99 ° C. ^l H nmr: Delta 3.97 (3H, s), 5.47 (2H, s) ppm.

Potassium t -butoxide (844 mg) is added in portions to a stirred suspension of (methoxymethyl) triphenylphosphonium chloride (2.86 g) in ether (30 ml). The reaction mixture turned red.

After 2 minutes, a solution of methyl 2- (3-phenoxymethyl-2-thienyl) 2-oxoacetate (770 mg) in THF (10 ml) is added in portions. Red color disappears The reaction mixture is stirred for 30 minutes at room temperature and poured into water. The organic layer and the aqueous layer are separated and the aqueous layer is extracted with ether. The combined organic layers were washed with water, dried, concentrated and chromatographed (1: 1 mixture of eluent ether and petrol) to give: (i) ( Z ) -isomer (230,27%) pale yellow oil of the title compound , IR (film) 1710, 1625 cm ^-1 ,

¹ H nmr: see Table 7: and (ii) (E) title compound isomer (80mg, 9% yield), also a pale yellow oil, IR (film), see 1700, 1620cm ^{-1 l} H nmr Table 7.

(Example 6)

( E )-and ( Z ) -isomers of methyl 3- (methylthio) -2- (3-phenoxymethyl-2-thienyl) propenoate (compounds 37 and 11 in Table 1).

Potassium t -butoxide (0.49 g) is added in one portion to a stirred solution of (methylthiomethyl) triphenylphosphonium chloride (1.82 g) in ether (30 ml). The resulting mixture was lemon colored. After 30 minutes, a solution of methyl 2- (3-phenoxymethyl-2-thienyl-2-oxo-acetate (0.80 g, prepared in Example 5) in THF (10 ml) is added in one portion. Stir and pour into water The organic and aqueous layers are separated and the aqueous layer is extracted with ether The combined organic layers are washed with water, dried and concentrated and chromatographed (20% ether in eluent petrol) to give (1) of the title compound. ( E ) -isomer (89 mg), containing 10% starting ketoester according to oil form G. ¹ H nmr See Table 7. (ii) ( Z ) -isomer (240 mg), oil form ^l H nmr of the title compound See Table 7.

(Example 7)

( E ) -Methyl 3-methoxy-2- [4- (proro-1-yloxycarbonyl) -3-thienyl] -propenoate (Compound No. 40 in Table 2).

Methyl (4-carboxy-3-thienyl) acetate is prepared from 4-bromothiophene-3-carboxylic acid and methyl acetoacetate (for corresponding ethyl esters, DE Ames and O Ribeiro, J. Chem. Soc. , Perkin I , 1975, 1930). A solid was obtained and had 121-122 ° C. after recrystallization with aqueous methanol. ^l Hnmr delta 3.72 (3H, s), 3.95 (2H, s), 7.18 (1H, d J 3Hz), 8.27 (1H, d J 3Hz) ppm.

Potassium carbonate (670 mg), and after 15 minutes, 1-iodopropane (0.26 ml) is added continuously to a stirred solution of methyl (4-carboxy-3-thienyl) acetate (490 ml) in DMF (10 ml). After 3 hours, the resulting mixture is diluted with water and extracted with ether. The extract was washed with water, dried and concentrated to give yellow liquid methyl [4- (prop-1-yloxycarbonyl) -3-thienyl] acetate (600 mg, quantitative yield). GC purification, IR (film): 1735, 1710 cm ^-1 , ^l H nmr: delta 1.00 (3H, t), 1.75 (2H, g), 3.69 (3H, s), 3.92 (2H, s), 4.20 (2H , t), 7.13 (1H, d J 3.5 Hz), 8.12 (1H, d J 3.5 Hz) pprn.

Triethylamine (0.34 ml) and trimethylsilyl triflate (0.47 ml) were stirred in methyl [4- (prop-1-yloxycarbonyl) -3-thienyl] acetate (600 mg) in ether (7.5 ml). Add continuously to and cool to 0 ° C. The resulting mixture is stirred overnight at room temperature. During this time, red oil precipitates out. Along with the ethereal solution, get 'A solution'. Titanium tetrachloride (0.27 ml) is added dropwise to a solution of trimethylorthoformate (0.27 ml) in dichloromethane (10 ml) and cooled to -70 ° C to give a yellow suspension. 'A solution' is added dropwise to this suspension over 10 minutes and then cooled to -70 ° C. The resulting mixture is left to warm, then stirred overnight at room temperature, diluted with aqueous potassium potassium and extracted with ether.

The extract was washed with water, dried and concentrated to give an orange oil (450 mg) consisting mainly of the title compound and starting acetate (62% and 31%, respectively, by GC). The use of a 1: 1 mixture of ether and petrol on silica gel afforded the pure title compound (202 mg, 29% yield) as an almost colorless oil by HPLC. IR (film): 1710, 1635 cm ⁻¹ , ^l H nmr: see Table 7.

(Example 8)

( E , E ) -Methyl-3-methoxy-2- (3-styryl-2-furyl) propenoate (Compound No. 17 in Table 3)

Potassium t -butoxide (35.7 g) is added in one portion to the benzyltriphenylphosphonium chloride (41.6 g) stirred suspension in ether (1ι). After 1 hour a solution of 3-popmilfuran (17.5 g) in ether (60 ml) is added to the resulting orange mixture, stirred for 2 hours, then poured into water and extracted with ether. The extract was washed with water, dried and concentrated to give a solid. The solid was triturated with ether to give a large amount of weak solid triphenylphosphine oxide, the excess phosphonium salt was separated, and the ether-soluble portion (37.06 g) was chromatographed (eluent: ether) to give 3- as a yellow solid. Obtain a mixture of ( E- and ( Z ) -isomers of styrylfuran (27 g), crystallized twice with methanol to give ( E ) -3-styrylfuran (5.12 g) as a yellow solid, mp 96 ° C.

A solution of methyl oxalyl chloride (4.05 g) in THF (35 ml) is added dropwise over 15 minutes into ( E ) -3-styrylfuran (5.12 g) stirred solution in THF (50 ml). Two drops of boron trifluorolide etherate are added and the resulting mixture is heated at 60 ° C. for 44 hours, then cooled, poured into water and extracted with ether. The extract is washed with water, dried and concentrated to give ( E ) -methyl 2- (3-styryl-2-furyl) -2-oxoacetate (1.65 g, 21% yield) as a yellow solid. mp 116 ° C., IR (Newsol) 1735 cm ^−l .

( E ) -Methyl 2- (3-styryl-2-furyl) -2 by using the method described in Example 5 from an (methoxymethyl) triphenylphosphonium chloride and potassium t -butoxide Oxoacedate converts the title compound (41% yield). The title compound has mp 107 ° C. as a white solid. ^l H nmr: Delta 3.76 (3H, s), 3.92 (3H, s), 6.66-6.83 (3H, m), 7.18-7.48 (6H, m), 7.70 (lH, s) ppm.

(Example 9)

( E ) -Methyl 2- (3-furyl) -3-methoxypropenoate (Compound No. 1 in Table 4).

A mixture of 3-formylfuran (50.0 g), methyl (methylthiomethyl) sulfoxide (7.lg) and triton B [(40% by weight of benzyltrimethylammonium hydroxide solution in methanol) 4.8 g in THF (7 ml) was added. Heat under reflux for 5 hours. After cooling, it is poured into water and extracted with ether. The extract is washed with water (X3), washed with aqueous sodium chloride, dried and concentrated to give brown oil (4.0 g). 1R (film) 1610, 1060cm- ¹ acetyl chloride (1.4 ml) is added into dry methanol (25 ml) with gentle stirring and cooled to 0 ° C. After addition, the resulting mixture is left at room temperature to warm up and then a portion of brown oil (2.0 g) is added with stirring at once. After 30 minutes, the resulting mixture is heated at reflux for 2 hours at reflux, poured into water and extracted with ether. The extracts are washed successively with water (X3), aqueous bicarbonate sodium and sodium chloride, dried, concentrated and eluted through a silica gel short column using a 1: 1 mixture of ether and petrol. Methyl (3-furyl) acetate as yellow oil (36% yield from 1.3 g, 3-formylfuran), IR (film) 1736 cm ^-l

Methyl (3-furyl) acetate can be converted to the title compound in two steps as described in Example 2. That is, (1) react with sodium anhydride and methyl formate, and (ii) treat the resulting formyl acetate with potassium carbonate and dimethyl sulfate. The title compound is a yellow oil. IR (film) 1705, 1628 cm ⁻¹ and ¹ H nmr are as described in Table 7.

(Example 10)

( E ) -Methyl 2- (2-formyl-3-furyl) -3-methoxypropenoate (Compound No. 37 in Table 4).

( E ) -Methyl 2- (3-furyl) -3-methoxypropenoate is converted to the title compound (56% yield) by treatment with Vilsmeier reagent as described for the corresponding thiophene of Example 3 . The title compound is a solid at mp 124 ° C. IR (new sol); 1685, 1625 cm ^-1 , ^l H nmr: Delta 3.77 (3H, s), 3.93 (3H, s), 6.59 (1H, d, J 1.5Hz), 7.62 (1H, d J 1.5Hz), 7.68 (1H, s), 9.59 (1 H, s) ppm.

(Example 11)

( e ) -Methyl 2- (1-benzyl-5-methylpyrrole-2-yl) -3-methoxy propenoate (Compound No. 57 in Table 5).

A solution of potassium t -butoxide (1.34 g, 12 mmol) in DMF (30 ml) is added dropwise to a methyl (5-methylpyrrole-2-yl) octoacetate (2.0 g, 12 mmol) solution in DMF (5 ml). The reaction mixture is stirred for 2 hours, then cooled to 0 ° C. and treated dropwise with benzyl chloride solution (1.4 ml, 12 mmol) in DMF (5 ml). The mixture is stirred for 6 hours, poured into water (150 ml) and extracted with ether (2 × 100 ml). The organic layer is washed with brine (2 x 150 ml), dried and evaporated under reduced pressure to give an orange oil. Chromatography (eluent: diethyl ether and hexane 1: 1) yields methyl (1-benzyl-5-methylpyrrole-2-yl) octoacetate (2.0 g) as a yellow oil. ^l H nmr: delta 2.22 (3H, s), 3.87 (3H, s), 5.65 (2H, s), 6.1 (1H, d), 7.9 (2H, d), 7.2 -7.4 (4H, m) ppm.

A mixture of (methoxymethyl) triphenylphosphonium chloride and sodium amide (3.41 g of 1: 1 molar mixture) is stirred in THF (90 ml) at 0 ° C. under nitrogen atmosphere for 3 hours. A solution of methyl 2- (1-benzyl-5-methyl-pyrrole-2-yl) octoacetate (1 g) in THF (5 ml) is added dropwise at 0 ° C. and the resulting mixture is stirred for 16 hours. Water (5 ml) is added and THF is depressurized. The residue is extracted with ether (150 ml), washed with brine and dried. Evaporation under reduced pressure gave an orange oil which was chromatographed (eluent: ether and hexane 1: 1) to give the title compound (0.35 g) as a pale yellow solid. mp 102-3 ° C. ^l H nmr: Delta 2.12 (3H, s), 3.58 (3H, s), 3.71 (3H, s), 4.90 (2H, s), 6.04 (2H, m), 6.9 (2H, m ), 7.2 (3H, m), 7.52 (1H, s) ppm.

(Example 12)

( E ) -Methyl 3-methoxy-2- (1-methylpyrrole-2-yl) propenoate (Compound No. 38 in Table 5).

Sodium anhydride (3.05 g, 50% dispersion in oil, 64 mmol) is washed with 40-60 ° C. petroleum ether and suspended in dry DNF (30 ml) under nitrogen atmosphere. Methyl (1-methylpyrrole-2-yl) acetate (5 g, 32 mmol) and methyl formate (39.5 ml, 64 mmol) in DMF (10 ml) were added dropwise with vigorous stirring at room temperature. After 3 hours, the reaction mixture is poured into 10% aqueous potassium carbonate (100 ml) and extracted with ether (2 × 100 ml). The aqueous layer is treated with concentrated hydrochloric acid and reextracted with ether (2 x 100 ml). The combined ether layers were dried and evaporated to afford methyl 3-hydroxy-2- (1-methylpyrrole-2-yl) propenoate (5.4 g) as an orange oil which was used without further purification.

Methyl 3-hydroxy-2- (1-methylpyrrole-2) propenoate (5.4 g, 30 mmol) in DMF (10 ml) was added dropwise into potassium carbonate stirred solution (8.24 g, 60 mmol) in DMF (75 ml). do. After stirring for 2 hours at room temperature, dimethyl sulfate (2.8 ml, 29 mmol) is added dropwise and stirring is continued for 6 hours. The reaction mixture is poured into saturated sodium carbonate and extracted with diethyl ether (2 x 10 ml). The combined organic layer was washed with brine, dried and evaporated under reduced pressure to give a viscous orange oil. Chromatography (eluent: ether and hexane 1: 1) afforded the title compound (450 mg) as a yellow crystalline solid: mp 58 ° C .; ^l H nmr: delta 3.45 (3H, s), 3.72 (3H, s), 3.86 (3H, s), 6.08 (1H, m), 6.17 (1H, m), 6.67 (1H, m), 7.62 (1H , s) ppm.

(Example 13)

( E ) -Methyl 3-methoxy-2- [ N- (2-phenylethyl) pyrrol-2-yl] -propenoate (Compound No. 34 in Table 5).

Pyrrole (5.00 g) is added dropwise over 5 minutes to a stirred mixture of potassium t -butoxide (9.20 g) and 18-crown-6 (1.96 g) in ether (250 ml). After 30 minutes phenethyl bromide (15.16 g) is added and the resulting mixture is stirred overnight, poured into water and extracted with ether. The extract was washed with water, dried and concentrated to give a red liquid (22.4 g), followed by distillation by short passage. As a pale yellow liquid containing 10% of phenethyl bromide by GC, N- (2-phenylethyl) pyrrole (1.23 g ) (Oven temperature 170 ° C., pressure ca 100 mmHg). ^l H nmr: delta 3.04 (2H, t), 4. 10 (2H, t), 6.12 (2H, m), 6.60 (2H, m) ppm.

A solution of pyrrole (0.15 g) in dichloromethane (5 ml), and after 15 minutes N- (2-phenylethyl) pyrrole (1.00 g) in dichloromethane (5 ml) was added methyl oxalyl chloride (0.79 g) in dichloromethane (10 ml). Add dropwise to the stirred solution and cool to -70 ° C. After one hour at −70 ° C., the reaction mixture is warmed to room temperature, poured into water and extracted with ether. The extract was successively volumed with water, dried hydrochloric acid, water, aqueous sodium bicarbonate, aqueous sodium chloride, dried, concentrated and chromatographed (eluent: 1: 1 mixture of ether and petrol) to give methyl 2- [ N- . (2-phenylethyl) pyrrole-2-yl] -2-oxoacetate (0.94 g, 63% yield) was obtained. IR (film) 1735, 1640 cm ^-1 , ¹ H nmr: Delta 3.02 (2H, t), 3.95 (3H, s), 4.51 (2H, t) ppm.

Under the conditions described in Example 5, alpha-ketoester is converted to the title compound (24% yield) using phospholane derived from (methoxymethyl) triphenylphosphonium chloride and potassium t -butoxide. The title compound is a solid that is mp 72-73 ° C.

^l H nmr: delta 2.94 (2H, t), 3.72 (3H, s), 3.86 (3H, s), 3.91 (2H, t), 6.06 (1H, m), 6.18 (1H, m), 6.64 (1H m), 7.66 (1H, s) ppm.

(Example 14)

( E ) -Methyl 3-methoxy-2- ( N -methylpyrrole-3-yl) propenoate (Compound No. 1 in Table 6).

Pyrrole (2.9 ml, 42 mmol) is added dropwise to potassium t -butoxide (4.66 g, 42 mmol) and 18-crown-6 (0.2 g, 0.76 mmol) suspension in ether (300 ml) at room temperature. After 1 hour, tri-isopropylsilyl chloride (8.0 g, 42 mmol) is added and the reaction mixture is stirred for 16 hours and then filtered. The residue is washed with ether and the combined filtrate and washings are washed with brine, dried and concentrated to give N -triisopropylsilyl pyrrole (8.0 g, 86% yield) as a clear oil. ^l H nmr: delta 1.04 (18H, d), 1.38 (3H, m), 6.22 (2H, m), 6.72 (2H, m) ppm.

A pyridine (10.9 ml, 135 mmol) solution in dichloromethane (50 ml) was added dropwise to a solution of methyl oxalyl chloride (12.4 ml, 135 mmol) in dichloromethane (200 ml) and then cooled to -60 ° C. The reaction mixture is stirred for 15 minutes and a solution of N -triisopropylsilylpyrrole (10.0 g, 45 mmol) in dichloromethane (10 ml) is added dropwise and the reaction mixture is kept at -60 ° C. The reaction mixture is stirred for 2 days and treated with 0.5 molar hydrochloric acid (100 ml). The organic phase was separated, washed with brine, dried and concentrated to give a viscous, brown oil [IR (thin film) 1730, 1660 cm ^-1 ], dissolved in THF, and then dissolved in tetrabutyl ammonium fluoride (25 ml, 25 mmol, THF). 1.0M solution). After 10 minutes, the reaction mixture is concentrated and partitioned between water and ethyl acetate. The organic phase is washed with brine, dried and concentrated to give a semicrystalline material. This is recrystallized from a 60-80 ° C. petrol and chloroform mixture to give methylpyrrole-3-yloxoacetate (3.3 g, 50% yield) as a light brown solid. mp 112 ° C., IR (Newsol-Mule) 2800, 1735, 1620 cm ^−l , ^l H nmr: Delta 3.92 (3H, s), 6.79 (2H, m), 7.82 (1H, m), 10.7 (H, br s ppm.

A solution of methyl pyrrole-3-yloxoacetate (3.3 g, 22 mol) in THF (70 ml) was added to potassium T -butoxide (2.7 g, 24 mmol) and 18-crown-6 (0.1 g, in ether (250 ml) at room temperature. 0.39 mmol) pour into the stirring suspension. The reaction mixture is stirred for 30 minutes and iodomethane (1.6 ml, 26 mmol) in ether (50 ml) is added dropwise. The reaction mixture was stirred for 16 h, filtered through Hyflo Supercell, washed with brine, dried and concentrated to afford methyl N -methyl-pyrrole-3-yloxoacetate (2.84 g, 79% yield) as a clear oil. Get IR (thin film) 1725, 1645 cm ⁻¹ , ^l Hnmr delta 3.64 (3H, s), 3.85 (3H, s), 6.5 (1H, m), 6.7 (1H, m), 7.6 (1H, m) ppm.

A sodium hydride (0.815 g, 35 mmol) suspension in DMSO (30 ml) is heated at 75 ° C. for 1 hour, diluted with THF (30 ml) and cooled in an ice bath. A solution of (methoxymethyl) triphenylphosphonium chloride (12.8 g, 34 mmol) in DMSO (25 ml) is added and the reaction mixture is exothermic to 20 ° C. to produce a dark red color. A solution of methyl N -methylpyrrole-3-yloxoacetate (2.84 g, 17 mm) in DMSO (10 ml) was added and the reaction mixture was stirred at room temperature for 1 hour, then poured into brine (15 ml) and ethyl acetate (2 × 150 ml). The organic phase is washed with brine, dried and concentrated to give an orange oil which is purified by HPLC (eluent: ether) to give the title compound (1.57 g, 47% yield) as a permeable pale yellow oil. IR (thin film) 1715, 1640 cm ⁻¹ , ^l H nmr: see Table 7.

(Example 15)

( E ) -Methyl 3-methoxy-2- ( N -methyl-2-formylpyrrole-4-yl) propenoate and ( E ) -methyl 3-methoxy2- ( N -methyl-2-prop Milpyrrole-4-yl) propenoate (compounds 60 and 62 of Table 6).

To the mixture obtained by adding phosphoryl chloride (1.74 ml, 18.7 mmol) in DMF (1.45 ml, 18.7 mmol) while cooling, ( E ) -methyl 3-methoxy-2- in 1,2-dichloroethane (25 ml) A solution of ( N -methylpyrrole-3-yl) propenoate (1.82 g, 9.3 mmol, described in Example 14) is added dropwise with stirring at room temperature. After 3 hours at room temperature, saturated aqueous sodium acetate solution (70 ml) is added and the resulting mixture is heated to reflux for 20 minutes. Cool the mixture and extract with dichloromethane (2 x 100 ml). The extract is washed with water, dried and concentrated to give an orange oil which is purified by HPLC (ether eluent) on silica gel to give: (i) ( E ) -Methyl-3-methoxy-2- ( N -methyl-2-formylpyrrole-4-yl) propenoate (0.43 g, 21% yield). Clear oil ¹ H nmr: see Table 7. First melt, (ii) ( E ) -methyl3-methoxy-2- ( N -methyl-2-formylpyrrole-3-yl) -propenoate (1.43 g, 69% yield), crystalline solid , mp 82-84 ° C. ^l H nmr: see Table 7, second eluate.

(Example 16)

( E ) -Methyl 3-methoxy-2- ( N -methyl-2- ( Z ) -styrylpyrrole-3-yl) -propenoate (Compound No. 11 in Table 6).

Sodium hydride suspension (0.215 g, 9 mmol) in DMSO is heated at 75 ° C. for 1 h, cooled, diluted with dry THF (20 ml) and cooled in an ice bath. Benzyltriphenylphosphonium chloride (3.5 g, 9 mmol) was added with stirring and the resulting bright red mixture was stirred for 10 minutes and ( E ) -methyl 3-methoxy-2- ( N -methyl-2) in THF (20 ml). A solution of -formylpyrrole-3-yl) -propenoate (1.0 g 4.5 mmol, as described in Example 15) is added. The reaction mixture is stirred for 3 hours, poured into brine (100 ml) and extracted with ethyl acetate (2 × 200 ml). The extract was washed with brine, dried and concentrated to give an orange oil which was then purified by HPLC on silica gel using ether as eluent to give the title compound as a yellow oil (0.75 g, 56% yield) ^l H nmr: see Table 7 Next The compositions of are examples of compositions suitable for agriculture and horticulture formulated with the compounds of the present invention. Such compositions belong to the present invention, with percentages by weight.

(Example 17)

The following components were mixed and stirred until dissolved to form an emulsion concentrate.

10% compound 4 in Table 1

Benzyl Alcohol 30%

Calcium Doneshylbenzenesulfonate 5%

Nonylphenol ethoxylate (13 mol ethylene oxide) 10%

Alkyl Benzene 45%

(Example 18)

The active ingredient is dissolved in methylene dichloride and the resulting liquid is sprayed onto attapulgite clay granules. The solvent is left to evaporate to produce a granule composition.

5% compound 4 of Table 1

Attapulgite Granule 95%

(Example 19)

A composition suitable for seed dressing was prepared by grinding and mixing the following three components.

Compound 57 (Table 5) 50%

Mineral oil 2%

China clay 48%

(Example 20)

Powder was prepared by talc, milling and mixing the active ingredient.

5% compound 5 in Table 5

Dalk 95%

(Example 21)

Suspension concentrates are prepared by ball milling the components to form an aqueous suspension of water and milling mixture.

Compound 57 (Table 5) 40%

Sodium lignosulfate 10%

Bentonite Clay 1%

49% of water

This preparation is used by spraying with dilution with water or directly on the seed.

(Example 22)

The wettable powder formulation was mixed and ground until the ingredients were thoroughly mixed.

25% compound 57 in Table 5

Sodium Lauryl Sulfate 2%

Sodium lignosulfate 5%

Silica 25%

China Clay 43%

Other compounds up to Tables 1-6 are formulated similarly, based on their physical properties.

(Example 23)

The compounds listed in Table 8 were tested for leaf fungal disease of plants. The technique used is as follows.

Plants are grown in John Innes Potting Compost (number 1 or 2) in a 40 cm diameter minipot. The test compound is made as a solution in acetone or acetone / ethanol which is bead milled with aqueous dispersol T or immediately diluted to the required concentration before use. The formulation (100 ppm active ingredient) is sprayed onto the leaves or applied to plant roots in the soil. Spraying is applied at maximum retention and root uptake up to the same final concentration on up to 40 ppm a.i./dry soil. When spraying is applied to the grains, Tween 20 is added to a final concentration of 0.05%.

In most tests, compounds are applied to soil (roots) and leaves (sprays) one or two days before the disease is injected. Erysiphe graminis is courtesy and the plant is infused 24 hours before treatment. Leaf pathogens are added by spraying a spore suspension onto the leaves of the test plant. After injection, the plants are placed in a suitable environment to allow for transmission and incubate until the disease is sufficient for evaluation. The time period between infusion and assessment can vary from 4 days to 14 days depending on the disease and environment.

Disease suppression is recorded in the following grades.

4 = no disease

3 = trace-5% disease on untreated plants

2 = 6-25% disease on untreated flora

1 = 26-59% disease on untreated flora

0 = 60-100% disease on untreated flora

The results are shown in Table 8.

TABLE 8

(Example 24)

This example illustrates the plant growth regulating properties of compound 1 of Table 1, compound 3 and 58 of Table 4, compound 38 and 57 of Table 5 and compound 57 of Table 6.

These compounds are tested on celestial plant screens for the plant growth species used, which are listed in Table 9 along with the leaf locations to be sprayed.

Each chemical formulation is applied at 4000 ppm (4 kg / ha in 10001 / ha forest volume) using a track sprayer and a SS8004E (Teejet) nozzle. Addition tests are done on 2000 and 500 ppm tomatoes. After spraying, the plants are grown in greenhouses at temperatures of 25 ° C. day / 22 ° C. night. An exception for grain wheat and barley is grown at 13-16 ° C. day / 11-13 ° C. night temperatures. A supplementary light is supplied to provide an average photoperiod of 16 hours (minimum of 14 hours).

After two to six weeks in the greenhouse, depending on the number of species and the number of species, the plants visually assess the morphological properties of the control plants sprayed with the blank formulation. The results are shown in Table 10.

TABLE 9

TABLE 10

* 2000ppm

+ 500 ppm

Suppression 1-3: 1 = 10-30% G = Greening Effect

2 = 2l-60% A = breaking peak

3 = 61-100% T = Sprout or Sprout

Blank means less than 10% effect.

NT compounds that have not been tested for these species.

Claims (7)

Compound of the following general formula (1) and its stereoisomer

Wherein, W is _{CH 3 O 2 CC = CHOCH 3} ; A is O, S or NR ³ (R ³ is H, C _1-4 alkyl, phenyl (C _1-4 ) alkyl or C ₆ H ₅ CH (OCOCH ₃ ) CH ₂ ); W is adjacent to X is H, halo, C _1-4 alkyl, halo (C _l-4) alkyl, phenyl (C _2-4) alkenyl, pyenok City, C _1-4 alkanoyl, benzoyl, C _1-4 Alkoxycarbonyl or CH ₃ ON = CH: Y is H or C _1-4 alkyl: and Z ¹ is H, or Y and Z ¹ are fused together with the carbon atoms to which they are attached when they are adjacent To form benzene ring. The compound of formula (1A) according to claim 1, wherein:

Wherein X is (located adjacent to the acrylate group) halogen, C _1-4 alkyl, halo (C _1-4 ) alkyl, phenyl (C _1-4 ) alkyl, phenoxy (C _1-4 ) alkyl, Phenyl (C _2-4 ) alkenyl, waste oxy, C _1-4 alkanoyl or benzoyl The compound of formula (1B) according to claim 1, wherein:

Wherein, R ³ is hydrogen, C _1-4 alkyl or phenyl (C _l-4) alkyl: X another hydrogen, C _l-4 alkyl, phenyl (C _1-4) alkyl, phenyl (C _2-4) alkenyl , C _1-4 alkanoyl or benzoyl, and Y and Z ¹ are hydrogen, or when X is hydrogen, Y and Z ¹ together form a fused benzene ring. Chemical Intermediate of Formula (2)

Wherein A, X, Y and Z ¹ are as described in claim 1 A bactericidal composition comprising, as an active ingredient, a bactericidal effective amount of the compound of claim 1 and an acceptable carrier or diluent for sterilization. A composition for regulating plant growth, comprising as an active ingredient an effective amount of the compound of claim 1 and an acceptable carrier or diluent. Chemical Intermediate of Formula (13)

Wherein A, X, Y and Z ¹ are as described in claim 1 and R ¹³ is hydrogen or a metal atom