TW393300B - 2-(O-(Pyrimidin-4-YL)Methylenoxy phenylessigsaure-derivate und ihre ver wendung zur bekampfung von schadpilzen und tierischen schadlingen - Google Patents

Description

A7 B7 V. Description of the invention (The present invention is based on the formula 2 · (〇-pyrimidin-4-yl] methyleneoxy) acetic acid, which expands the biological R ~~ NN NQ (I) • R3 and its salts And N-oxide ', in which R1 to R4 group and q have the following definitions: R1 is hydrogen or cvq-alkyl; R2 is hydrogen, Ci-CV alkyl or alkyl; R3 is hydrogen, amine, hydroxyl, thiol 'Halogen, Cl_C8_alkyl, and fluorenyl can be attached to phenyl' which can be attached to one or two of the following substituents: respectively And Crc4-alkoxy; CVC8-haloalkyl, crc8_alkoxy_Ci_c alkyl, CrC8-alkoxy, Ci-Cs-monoalkylamino, di-Ci-Cr alkylamine, CrC8-yard Sulfur group, Ci-Cg-Kenya-J wind group 'c ^ -Cg-fired stone wind group, C3_C8 · cycloalkyl group, tri-CrC8_ burning silyloxy group or the following, unsubstituted or substituted in the aromatic ring: benzene Group, phenoxy group, benzyloxymethyl group, benzyloxy group or heteroaryl group; R4 is hydrogen, cyano, autogen, crC4-alkyl, C 丨 -c4- alkynyl or C! -C4-alkoxy Base; Q is C (= NOCH3) -CONHCH3, C (= NOCH3) -COOCH3 or N (OCH3) -COOCH3. -4- This paper size applies to Chinese national standards CNS) Α4 specification (21〇 × 297 mm) -------- install --Γ ---- order -------- line (please read the precautions on the back before filling this page) Economy Printed by the Consumer Standards Cooperative of the Ministry of Standards of the People's Republic of China Printed by the Central Standards Bureau of the Ministry of Economic Affairs and printed by the Shellfish Consumer Cooperatives of the Ministry of Economic Affairs A7 _____________ B7 V. Description of the Invention (2) In addition, the present invention relates to a composition comprising the compound ί and its control of harmful maggots and animal pests The fungicidal and / or insecticidal and acaricidal active methyl α _ [2_ (heteroaryloxymethylene) phenyl] -methoxyimine acetamidamine has been revealed (ερ_α 398 629; £ Ρ- Α 477 631; JP-A 04/182 461; German Patent Application No. 195 26 661 7). In addition, let's set fungi and / or insecticidal and snail-killing activity β- [2_ (heteroaryloxymethylene) benzene Methyl] -or-methoxyiminoacetic acid methyl ester has been revealed (refer to Ep_A 254 426, EP-A 363 818, EP-A 407 873). In addition, fungicidal and / or insecticidal and acaricidal activity N -[2- (heteroaryloxymethylene) phenyl] -N-methoxycarbamic acid methyl ester. It has been revealed (refer to WO_A 93 / 15〇46). The activity of the compounds described in the above publications has not been Satisfactory. The subject is asked improved control harmful nature Zhen bacteria and animal pests of the novel compounds. We have found that the target compound can be defined at the outset via〗-containing compositions and their control of harmful fungi and animal pests Zhen achieved. Compound I was prepared in a similar manner to the literature mentioned at the outset. When synthesizing compound I, it doesn't matter who synthesized Q first or 2- (0- [pyrimidin-4-yl] fluorenoxy). For example, in a manner known per se, a fluorenyl derivative of the formula II and a pyrimidine-4-ol of the formula η are reacted in the presence of an inert organic solvent and a base to obtain the compound ί. -5- This paper is from the applicable Chinese national standard ^ 17 ^ 12 丨 〇X 297mm τ (. Read the precautions on the back before filling this page) ---------- k pack-^ ----- II ----------.------------- A7 B7 V. Description of the Invention (3 Yilingya)

N Ya N R3 II

III R2 R1

SrV O '-CH N Ya N R4

Q (Please read the notes on the back before filling this page)

V R3 (Q = C (= NOCH3) -CONHCH3), C (== NOCH3) -COOCH3 or n (och3) -cooch3) In Formula 111, X is a nucleophilic exchangeable leaving group such as fluorene (eg gas , Bromine or iodine) 'sulfonyl (for example, mesylsulfonyl or trifluoromethanesulfonyl) or arylsulfonyl (for example, phenylsulfanyl or 4-tolylsulfonyl) β This reaction is conventionally based on 0 ° C to 8 ° C, preferably at 20 ° C to 6 ° C. The appropriate solvents are aromatic hydrocarbons such as toluene, o-, m- and p-xylene, such as by gas-fired and gas-fired. Benzene, ethers such as diacetic acid, diisopropyl ether, tertiary butyl ether, dioxolane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol, n-propanol, isopropanol, N-butanol and tertiary butanol, ketones such as acetone and acetophenone, and dimethylene, dimethylformamide, dimethyl acetamide, i, 3, dimethylimidazolidine_2one and 1 , 3_ Dimethyltetrahydro · 2 (1Η) · Chestrone, especially preferred are dichloromethane, propane, and second-line. Printed by the shellfish consumer cooperation department of the China quasi-bureau of the Ministry of Economic Affairs-6-

Printed by A7 B7, Consumer Cooperative of the Central Government Bureau of the Ministry of Economic Affairs. 5. Description of the invention (4 Methylformamide-. Mixtures of the solvents can also be used. Appropriate bases are usually inorganic compounds with basic properties such as alkali metals and Earth metal hydroxides (such as lithium hydroxide, sodium hydride, potassium hydroxide, and calcium hydroxide), alkali metal and alkaline earth metal oxides (such as lithium oxide, sodium oxide, calcium oxide, and magnesium oxide), alkali metals and Alkaline earth metal hydrides (such as lithium hydride, sodium argon 'potassium hydride and calcium hydride), alkali metal amides (such as lithium amide, sodium amine and potassium amide), alkali metal and alkaline earth metal carbonates (such as carbonate And calcium carbonate) 'and alkali metal bicarbonates (such as sodium bicarbonate); organometallic compounds, especially alkali metal alkyl compounds (such as methyl lithium, butyl lithium, and phenyl lithium), 卣Alkyl magnesium (such as vaporized methylmagnesium), and alkali metal and soil metal alkoxides (such as sodium methoxide, sodium ethoxide, ethoxylate, potassium tert-butoxide and dimethoxymagnesium). Other suitable organic bases, such as tertiary amines Such as trimethylamine, triethylamine, triisopropylethylamine and N-fluorenylhexahydropyridine, pyridine, substituted pyridines such as trimethylpyridine, dimethylpyridine and 4-dimethylaminopyridine, and bicyclic amines. The best ones are sodium hydroxide, sodium hydride, potassium carbonate, and tert-butoxide. Their tests are generally used in mol or excessive amounts or as a solvent if appropriate. · For the reaction, a catalytic amount is added. Crown acid (such as 18-crown_6 or 15-crown-5). The reaction can also be in a two-phase system containing an aqueous solution of an alkali or alkaline earth metal hydroxide or carbonate and an organic phase (such as a hydrocarbon). The phase transfer catalyst added is ammonium chloride and ammonium tetrafluoroborate (for example, gasified fluorenyl triethyl is suitable for Zhongguanjiazhuan (c called (2 丨 ㈣ ^ public)) according to the paper size (please read the back first) (Notes for filling in this page)-,? Τ 丨 'line

II A7 B7 V. Description of the invention (5) First, brominated-tributylammonium, tetrabutylammonium vaporized 'hexadecyltrimethylammonium bromide or tetrabutylammonium tetrafluoroborate) and halogenated scales (such as gasification Four Ding scales and four bromide scales). It is advantageous for this reaction to treat the compound with a base at the beginning and to react with the resulting salt with compound III. In a similar manner to the known method [refer to j. Chem. Soc. (1946), page 5], the fluorenone ester VI is subjected to a condensation reaction with amidine, guanidine, urea, or thiourea VII to obtain compound II. R2

Rl —C0—CH—COOR + HN—C (NH2) —r3.VI VII (please read the notes on the back before filling this page),? Τ in formula VI is mainly Cl-C4_alkyl, especially Is methyl or ethyl. The reaction is usually performed at 0 to 120, preferably 20 to 80 ° C, and particularly preferably performed at the baboon point of the solvent. Commonly used solvents are alcohols, with methanol or ethanol being particularly preferred. Compound VII can also be used in its salt form, especially with its hydride (such as a hydride or hydrobromide) ^ If a salt is used, it is expected that the reaction can be carried out in a base (such as a 'earth metal' or an alkali metal alkoxide or Alkaline earth metals or alkali metal hydroxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide and calcium hydroxide) are carried out. Type II starting materials and their synthesis are generally known, especially from the following published documents: -8- The paper size is common Chinese National Standard (CNS) A4 specification (210X297 public director)-Central Bureau of Standards, Ministry of Economic Affairs Printed by employee consumer cooperative A7 B7 (II? R2 = «CH3) V. Description of invention (6 CH3

^ 〇H ΝγΝ R3

Justus Liebigs Ann, Cihem. 758, (1972), pages 125, 127, 130;

Chem. Pharm. Bull. 22, (1974), pages 1239, 1240, 1245-1247; J. Amer. Chem. Soc. 79 (1957) page 2230;

Bull Soc Chim. Fr (1965) / pages 2301-2306;

Bull Soc. Chim. Fr. (1963), page 673? BE-A 645062;

Reel Trav Chim. Pays-Bas 87, 10, (1968) 9 page 1089;

Chem. Pharm. Bull. 36f 5, (1988) f pages 1669-1675? * —

Tetrahedron 25, (1969), pages 5989, 5992; J. Org. Chem- 35, (1970), pages 3786, 3790, 3791; Z. Chem. F GE 25, 9f (1985), pages 328-329; J Chem. Soc. (1950), pages 452f 456, 458;

Am. Chem. J- 29 (1903), page 487;

Bull. Soc. Chim. Belg68 (1959), pages 30, 40; J. Biol ^ Chem. 3 (1907), page 303;

Arch. Pharm. (Weinheim Ger.) GE, 317, 5, (1984), pages 425-430; Am. Chem. J. 31 (1904) f page 595;

Am. Chem. J. 43 (1910), page 23; J. Amer · Chem- Soc. 51 (1929), page 1240;

Am. Chem. J. 42 (1909), page 368;

Rocz. Chem. 51, (1977), pages 1227, 1228f 1230?

Pol. J. Chem.EN, 55, 7/8, (1981), pages 1673-1676;

Org Mass Spectrom. 14, (1979), pages 405, 409, 412 ;.

AustJ. Chem. 41, 8, 1988, 1209-1219;

Pol · J- Chem: 57, 7-9, (1983 >, pages 1027-1031; ---; --- V --- ιί.Ά ------ Order ----- 'line ( Please read the note on the back # · Fill this page first.)

F

N Ya N CS-A 107166; BE-A 627342; US-A 3954759; US-A 3954758;

OH (II; R2 = F) -9- This paper size applies to Chinese National Standard (CNS) A4 specification (210 × 297 mm) A7 B7 V. Description of invention (CS-A 108806; SU-A 232975; BE-A 860309; JP-A 50150936; '

Gazz · Chim. Ital · 93 (1963) pages 1268, 1272;

Collect. Czech. Chem. Conunun. 27 (1962) pages 2250 -2560 J. Med. Chem. 8 (1965), page 253; J. Org. Chem. 27 (1962), page 2580; J. Chem. Soc C. (1967), page 1822; J. Chem. Soc. C. (1967), pages 2206-2207, J. Med. Chem. 36, 18 ^ (1993), pages 2627-2638; J. Chem. Soc. (1959), pages 3278, 3284; J. Am. Chem. Soc. 79 (1957), page 4559; —

Acta Chem. Scand. .23 (1969), page 294.

Cl (Please read the notes on the back before filling this page) vv t

OH (II; R2 = Cl) Order printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs BE-A 645062; GB-A-1174165;

Collect. Czech. Chem. Commun. 27 (1962), pages 2250 — 2560; J. Org. Chem. 27 (1962), pages 3507, 3510; J. Med. Chem. 6 (1963), pages 688-693; J. Med. Chem. 36, 18 (1993), pages 2627-2638. CF3 R1 vv Namma N R3

OH (II; R2 = * CF3)

Heterocycles 31, 3 (1990), pages 569-574. -10- This paper size applies to China National Standard (CNS) A4 specifications (210X 297 mm) A7 B7

R4

RG V. Description of the invention (8 Initialized compounds-III.1 (X = C1) and III.2 (X = Br), where Q is C (= NOCH3) -CONHCH3, refer to EP-A 477 631, table 1 No. 332 and

333. Successful preparation of compounds VII j ~ R4 from corresponding alkoxy or aryloxy groups

X—CH2 I

Q

III Unsubstituted or substituted alkyl or unsubstituted or substituted aryl (Please read the notes on the back before filling this page) No. RG X III.1 BC13 Cl III.2 ΗΒγ Br Order in an inert solvent (such as Halogenated hydrocarbons), prepared at -30 to 40 ° C by cracking boron trioxide (for III.1) or hydrogen bromide (for III.2). Examples 1 to 3 describe the advantageous synthesis of the corresponding compound VII (where R '= 2-tolyl (see EP-A 477 63 1, Table 1, number 94). Compound 111 (wherein Q is C (= NOCH3)) -COOCH3) is disclosed in EP-A 363 818. Compound 111 (wherein Q is N (OCH3) -COOCH3) is disclosed in WO-A 93/15046. _ Once prepared, compound I due to its C on Q = N double bond can be obtained as E / Z -11 This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -Linear Economic Ministry Central Standard Bureau Staff Consumer Cooperatives Printing Ministry of Economic Central Standard Bureau Bureau Consumer Cooperatives Print A7 -----— B * 7 V. Description of the invention (9) The structure mixture is in the form of ~, and these isomer mixtures can be separated into individual compounds by known methods (such as crystallization or color analysis). However, if a mixture of isomers is obtained once synthesized, it is generally not absolutely necessary to separate the isomers because in some cases the individual isomers can be transferred to each other for use during the manufacturing process (such as exposure, acid or inspection). Similar transformations It can also occur after travel ', e.g. for treated plants or for controlling harmful fungi or animals The treatment of the pest i. Compared to the C = N double bond in the Q group, the E isomer of compound I is better in terms of its activity (relative to the _c〇NHCH3 or -COOCH3 group of the 0CHi group. Part of the present invention is a salt of the acid-resistant compound I which contains a basic center, which is mainly a nitrogen atom and mineral acid (such as sulfuric acid and phosphoric acid) or Lewis acid (such as zinc chloride). Salt The nature is generally not relevant. The purpose of the present invention is preferably that these salts do not harm plants, areas, materials or spaces from harmful maggots or animal pests and do not adversely affect the activity of compound I. Particularly important are suitable for agricultural use The salts of the compound I can be known per se, mainly using the above-mentioned acid in water or an inert organic solvent 'at -80 to 120 ° C (preferably 0 to 60 ° C) with the corresponding compound I Reaction. _ Compounds of formula I can be converted into their N-oxides by known or similar methods (see e.g. A. Albini and S. Pietra, Heterocyclic N-oxides, CRC Publication, Boca

Raton, U.S.A. 1991; U.S. Moscher et al., Org. Synth. Coll. Vol. IV, 1963 'page 828; E.C. Taylor et al., Org. Synth. Coll.

Vol. IV, 1963, 704 pages' TW Bell et al., Synth. 69, 226 -12- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297) (Please read the precautions on the back before filling in (This page) Order '^

Printed by Shelley Consumers Cooperative of Central Bureau of Standards, Ministry of Economic Affairs, V. Invention Description (10 (1990)}.-An oxidant used to oxidize pyridoxine in the past, the examples are peracetic acid, trifluoroperacetic acid, Benzoic acid, methane perbenzoic acid, monopermaleic acid, magnesium monoperphthalate, sodium perborate, Oxone® (containing peroxy disulfate), pertungstic acid and hydrogen peroxide. Examples of suitable solvents Water, sulfuric acid, carboxylic acids such as acetic acid and trifluoroacetic acid, and halogenated hydrocarbons such as digas methane and gas imitation. Oxidation normally proceeds smoothly from 0 C to the boiling point of the reaction mixture. Emulsifiers normally use starting compounds as the main component. At least equal moles. However, usually excess oxidants have proven to be particularly advantageous. In the original definition of compound I, the collective terms used often represented the following groups: halogen: fluorine, gas, bromine, and hydrogen; tiger group: 1 to 4, 6 or 8 carbon atoms straight or branched chain alkyl, such as CrC6-fe group, such as fluorenyl, ethyl, propyl, methyl ethyl, butyl, 1-methylpropyl, 2-methyl Propylpropyl, ι, ι-dimethylethyl, pentyl, umethylbutyl, 2-fluorenylbutyl 3-methylbutyl, 2,2-diamidylpropyl, ^ ethylpropyl, hexyl, M-dimethylpropyl, 1,2-diamidylpropyl, 丨 methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, i, i-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl , 2,2-difluorenylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, i-ethylbutyl, ethylbutyl, 1,1,2-tri Methylpropyl, 1,2,2-trimethylpropyl, 1-ethyl- ^ methylpropyl and 1-ethyl · 2-methyl_propyl; alkylamino groups: monoamino groups, which It has been attached as above with 1 to 6 carbon atoms (read the notes on the back first and then fill in and write this page j-, 1T- Μ -13- This paper size applies to Chinese national standard () specifications (210X297) (%) A7 printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs -_____ B7_____ V. Description of the invention (11) Linear or branched chain dragon group; Dialkylamino group: Monoamine group, which has two linear or Branched alkyl, which are independent of each other and have 1 to 6 carbon atoms as described above; alkanesulfonyl: as CrC8-alkanesulfonyl: an alkyl group as defined above, via Benzyl (-S〇2)-bonded to the main bond; Benzyl group: WCi-Cg-Benzyl group: As defined above, it is bonded to sulfinyl group (-S0-) Main chain; trialkanosyloxy: such as tri-q-Cs-alkanosyloxy: silyloxy (-Si_〇_) which is attached to the silicon atom as defined above with three alkyl groups and is bonded via an oxygen atom j The main bond; a halogenated 1 group: a straight or branched alkyl group of 1 to 6 carbon atoms, wherein these groups or some or all of the hydrogen atoms can be replaced by the above halogen atoms, such as c 1 _c2_ haloalkyl, such as gas Methyl, difluoromethyl, trifluoromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, fluoromethyl, difluorofluoromethyl, fluorodifluoromethyl, 1-fluoroethyl ' 2-Gasethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-Gas-2-fluoroethyl, 2-Gas-2,2-difluoroethyl, 2 , 2-Digas-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl; Alkoxy: as described above, straight or branched chain having 1 to 4, 6 or 8 carbons Alkyl 'which is bonded to the main chain via an oxygen atom (-〇 ·), such as Crc6-alkoxy, such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy Methylpropoxy '2-fluorenylpropoxy, 1, i-dimethylethoxy, pentyloxy, 丨 methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2- Dimethylpropoxy, 丨 ethylpropoxy, hexyloxy, 1,1-difpropoxy, 1,2-dimethylpropoxy, dipentyloxy, 2-methylpentyloxy, 3-Methenyl, 4-Methenyloxy, ij-dif butoxy-14- This paper size applies to China National Standard (CNS) A4 (210X297 mm) I mm 1 HI In nmi 1-- --^^ 1 ^^ 1/1 0¾-e splash (please read the precautions on the back before filling this page) Printed by A7 B7 Du Shelley Consumer Cooperation of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (12) , 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy '3,3-dimethylbutoxy , 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1_methylpropoxy and 1 -Ethyl-2-methylpropoxy; Taiyuan oxygen pit group, such as C ^ -Cg-pit lactyl group-Ci-C *-alkynyl group: a fluorinated group having 1 to 4 carbon atoms as defined above, which Attach 1 to 8 carbon atoms as described above Oxygen: such as ^ 2-alkylene dioxy: straight or branched chain alkyl groups having 1 to 2 hard atoms, each via an oxygen source (-〇_) such as methylene dioxy. -O-CH ^ -O-) or ethylenedioxy (-OCH / HrO-) and to or bonded to two positions of the main chain; Sulfur group: as described above, the straight or branched chain has 1 to 4 Or a 6-carbon fluorenyl group, which is bonded to the main bond via a sulfur atom (-S-), such as Ci_Cg, a thio group such as methylthio, ethylthio, propylthio, 1-fluorene ethylthio, butyl Thio, 1-methylpropylthio, 2-methylpropylthio, 1,2-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio '3-methylbutylthio, 2,2- -methylpropylthio, 1-ethylpropylthio, hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio 1-pentylthio, 2-methylpentylthio Methyl, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2 ·, dimethylbutylthio < 1,3-dimethylbutylthio, 2,2- Dimethyl sulfanyl, 2,3-dibutylsulfanyl, 3,3-dimethylbutylsulfanyl, 1-ethylbutylsulfanyl, 2-ethylbutylsulfanyl, ι, ι, 2-trimethylpropylsulfanyl , 1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio, and 1-ethyl_2 · methylpropylthio; Cycloalkyl: such as C3-C8-cycloalkyl: single environmental groups with 3 to 8 carbon ring members such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; -15- This paper size applies to China Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)-Order 'Line' Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Printed A7 B7 V. Description of the invention (13) Base: The family of monocyclic or polycyclic radicals can contain one gas atom or one to three nitrogen atoms and one oxygen or sulfur atom or oxygen or sulfur atom in addition to the posterior member, such as gold. One to three_ A member of a heteroaromatic ring group of 2 nitrogen atoms, which may contain 1 to 3 nitrogen atoms in addition to carbon atoms, such as 2 ehaki, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazole , 5 · pyrazolyl, 2imidazolyl, 4-imidazolyl, 1,2,4-triazolyl-3, and 1,3,4-triazol_2_yl; • Boxes 1 to 4 nitrogens Atom or 1 to 3 nitrogen atoms and 1 weight oxygen oxo aryl heteroaryl: 5-membered ring heteroaryl, in addition to carbon atoms, may contain] to 4 nitrogen atoms or 1 to 3 nitrogen Atoms and 1 sulfur or oxygen atom are ring members, such as 2-furyl 3-furyl, 2-thienyl, 3-pyridyl, 2-p-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isopyrazolyl, 5-isoxazolyl, 3-iso Oxazolyl, 4-isopyrazolyl, 5-isopyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-humoxazolyl, 4-oxazolyl, 5- Peak group, 2-pyrazolyl, 4-oxazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl '1,2,4-humidazol-3-yl, 1,2,4 -Pyridin-5-yl, 1,2,4-pyrimidazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1 , 3,4-'^ di-2-hexyl, 1,3,4-pyrimidazol-2-yl and 1,3,4-triazole-2-yl;': ILL to 3 nitrogen atoms or 1 Of one nitrogen atom and / or one oxygen or sulfur atom— ~-pen sha ^^ 5-membered heteroaryl: a heteroaryl group with a 5-membered ring, which may contain 1 to 4 nitrogen atoms or 1 in addition to carbon atoms Up to 3 nitrogen atoms and 1 sulfur or oxygen atom as ring members, and two adjacent carbon ring members or 1 nitrogen and 1 adjacent carbon ring member may be d-1,3_- 二 晞 _1,4_ 二Base bridge; _ lotus-i-huang bond and a 5-membered heteroaryl group with 1 to 4 nitrogen atoms or via -16- This paper size applies Chinese National Standards (CNS) A regulations ^ (2) 7Gongguang) (Please read the notes on the back before filling in this page)

ST-line · Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 _______ B7 V. Description of the invention (14) ~ Benzene bonded with 1 to 3 nitrogen atoms and slightly more heteroaryl: 5 member ring Heteroaryl groups, in addition to carbon atoms, may contain 1 to 4 nitrogen atoms or 3 to 3 nitrogen atoms as ring members, and two adjacent carbocyclic members or 1 nitrogen and 1 adjacent carbocyclic members may be D-1 , 3-diphenyldiyl bridge, these rings are bonded to the main bond via one of the nitrogen ring members;-containing 1 to 3 or ... LA · 4 nitrogen atoms, 6 members of the winter miserable: JL 6 A heteroaryl group of a member ring may contain 1 to 3 or 4 to 4 nitrogen atoms in addition to the carbon atom, such as 2-pyridyl, 3-pyridyl, 4-pyridyl, and 3-tap. Phenyl, 4-pyridyl, 2-pyrimidyl, 4-pyrimidyl, 5-pyrimidyl, 2-ethoxyl., 1,3,5-di-well-2-yl, 1,2,4- Three-tillage _3_ and ι, 2,4,5-four-tillage_3_; One and four nitrogen atoms stupid and fused heteroaryl: 6-membered heteroaryl ring group, two of which are adjacent Blocking the ring members can be linked by Ding-U · Er 晞 _M · Erji Bridge! "Kui" «Lin, Yi Jun Lin, P Ku Tu Lin, and Jun Lin B Lin, the term " part or complete "All-Southernization" means that some or all of the hydrogen atoms in the group may be replaced by halogen atoms that are the same or different as described above. The term " unsubstituted or substituted " means that some or all of the nitrogen atoms in a group may be substituted with the same or different different groups such as those described in the collective terms above. In view of its biological activity against harmful maggots and animal pests, the preferred compound I 'has the following definitions alone or in combination: R1 is hydrogen; R1 is methyl; R2 is halogen, especially elephant and gas; R2 is methyl; -17- This paper size applies to the Chinese National Standard (CNS) Liu 4 Lai_ (210 > < 297 public broadcasting) (Please read the precautions on the back before filling in this page}, · ιτ 丨 line five Description of the invention (15) A7 B7 R2 is trifluoromethyl; R3 alkyl, these groups can be partially or completely halogenated; R3 is C3_C6-cycloalkyl; R3 is C 1 -C 8-thoxy; R3 Is Ci-Cg-sulfanyl; R3 is di-Ci-Cg-sulfanyl; R3 is Ci-C8-alkanesulfenyl; R3 is gadolinium-sulfanylsulfanyl; R3 is gas;- R3 is a phenyl group. This group may be connected to one to three of the following groups: halogen, Ci-C ^ r alkyl, cyano, CrC4-alkoxy, nitro, unhalogenated or partially or fully halogenated KCrC2-endane Dioxy; R3 is C iC ^ -Phenyl 'substituted by phenyl, the thiol moiety is unsubstituted, and the phenyl moiety can be attached to one or two of the following groups: from Phenyl, cyano, nitro, CpCV Base, CpC ^ -halo entertainment, base, crc4- Oxygen; R4 is hydrogen. From the above biological activity, the best compound I is the compound listed in the table below (please read the precautions on the back and fill in this page). Print

(1.1) | < installation -------- order ----- *, line one --- -18 This paper size is applicable to China National Standard (CNS) A4 specification (210X297) Standard Bureau Shellfish Consumer Cooperative Co., Ltd. printed A7 B7 V. Description of the invention (16) Table 1-Compound of formula 1.1 where Ri = hydrogen; R2 = methyl; R3 = one of the rows of table A in each case Table 2 of compound of formula 1.1 where Ri = hydrogen; R2 = fluorine; R3 = one of the rows of Table A in each case Table 3 of the compound of formula 1.1 where Ri = hydrogen; R2 = gas; R3 = one of the rows of Table A in each case Table 4 of the compound of formula 1.1 where Ri = Hydrogen; R2 = trifluoromethyl; R3 = one row of Table A in each case, except one row of number 1 except Table 5 Compounds of formula 1.1 where R1 = methyl; _ R2 = gas; (Please read the precautions on the back first (Fill in this page again) Order .—— Silk_ -19- This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) V. Description of the invention (17) R3 = In each case-line A7 of table A B7

The Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs printed Table 6 Compounds of formula 1.2 where R1 = hydrogen; R2 = fluorenyl; R3 = One of the rows in Table A in Table 7 Compounds of formula 1.2 where Ri = nitrogen; R2 = fluorine; R3 = one of the rows in Table A in each case Table 8 Compounds of formula 1.2 where R1 = nitrogen; R2 = gas; R3 = one of the rows in Table A in each case Table 9 compounds of formula 1.2 where -20- (please read first (Note 4 entries on the back then fill out this page)

, TT This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm). Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, A7 B7. 5. Description of the invention (18) Ri = nitrogen; -R2 = trifluoromethyl; R3 = one row of table A in each case, except one row of number 1 except for the compound of formula 1.2 where R1 = fluorenyl; R2 = gas; R3 = one row of table A in each case

R3 / 〇 Table 11 Compounds of formula 1.3 where R1 = hydrogen; R2 = methyl; R3 = one of the rows in Table A_ Table 12 Compounds of formula 1.3 where Ri = nitrogen; R2 = fluorine; R3 = in each case One line of table A-21----------- 1 IIII Order I —— I-I — Line (Please read the precautions on the front side and then fill out this page) This paper size applies to Chinese national standards. (CNS) A4 specifications (210X 297 mm) A7 B7 V. Description of the invention (19) Table 13-Compounds of formula 1.3 where R1 = nitrogen; R2 = chlorine; R3 = one of the rows of table A in each case. Table 14. Formula 1.3 Compounds where Ri = hydrogen; R2 = trifluoromethyl; R3 = one row of Table A in each case, except for one row of number 1 Table 15 Compounds of formula 1.3 where R1 = methyl; R2 = gas; R3 = each One line of table A in the example (please read the precautions on the back before filling this page) Printed by the Central Consumers Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperatives -22- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) ) A7 B7 Printed by the Consumer Co-operation of the Central Bureau of Standards of the Ministry of Economic Affairs V. Invention Description (20)

Table A

No. R3 1 lh 2 methyl 3 ethyl 4 n-propyl 5 iso-propyl 6 n-propyl 7 n-butyl 8 second-butyl 9 iso-butyl 10 third-butyl 11 cyclobutyl Group 12 n-pentyl 13 iso-pentyl 14 neo-pentyl 15 cyclofluorenyl 16 n-hexyl 17 n-heptyl 18 trifluoromethyl 19 chloromethyl 20 0-methyl 21 0-ethyl 22 0 -N-propyl 23 0-iso-propyl 24 0-n-butyl 25 0-second-butyl 26 0-true-butyl 27 0-third-butyl 28 0-n-pentyl 29 0 -Isopentyl 30 0 -_- pentyl 31 .0-n-hexyl 32 S-methyl 33 S-ethyl 34 S-n-propyl 35 -S-true-propyl 36 S-n-butyl 37 s (= o) -methyl 38 s (= o) -ethyl 39 s (= o) -n-propyl 40 s (= o) -iso-propyl 41 s (= o) -n- Butyl 42 s (= 0) 2-methyl 43 s (= o) 2-Ethyl 44 S (= 0) 2-n-if group 45 s (= o) 2-iso-¾ group 46 s (= o) 2 • n-butyl (please read the precautions on the back before filling this page)

、 1T 丨 -23- This paper size applies to Chinese National Standards (CNS) A4 specifications (210X297 mm) A7 B7 V. Description of invention (21) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economy

No. R3 47 nh2 48 N (Tomb) 2 49 N (ethyl) 2 50 N (n-propyl) 2 5 1 gas 52 0-benzyl 53 o-ch2-benzyl 54 0-CH2_ (4-gas Phenyl) 55 56 3-F-benzyl 58 4-F-benzyl 59 2-C1-benzyl tomb 60 3-Cbenzyl tomb 61 4-C1-benzyl 62 2-B r-rate 63 3_Br- Benzyl 64 4-Br-benzyl 65 2-tolyl. 66 3-methylbenzyl 67 4-methylbenzyl 68 2-CN-benzyl 69 3-CN-phenyl 70 4-CN-benzyl 71 2 -OMe-phenyl 72 3-OMe-benzyl 73 4-OMe-benzyl 74 2-CN-benzyl 75 3-CN-benzyl 76 4-CN-benzyl 77 2-nitrobenzyl 78 .3- Nitrobenzyl 79 4-Nitrobenzyl 80 2,4-Cl2-benzyl 81 2,4- (CH3) 2-benzyl 82 -3,4- (Cl2) -benzyl 83 3,4-methylene di Oxyphenyl 84 3,4- (difluoroiminodioxy) phenyl 85 2,4-F2-benzyl 86 CH2-benzyl 87 CH2- (3-Cl-phenyl) $ 8 CH2- (4- Cl-benzyl) 89 2-CF3-phenyl 90 3-CF3-benzyl 91 4-CF3-phenyl_ -24- (Please read the precautions on the back before filling this page) Order-Paper size Applicable to Chinese national standards (CNS> A4 specification (210X297 mm)

A7 B7 Printed by the staff of the Central Standards Bureau of the Ministry of Economic Affairs for consumer cooperation. 5. Description of the invention (22) In the above-mentioned special compound I, R3 is a compound other than hydrogen. Compound I is suitable for controlling harmful pinworms and animal pests. Depending on their chemical and physical properties, they can be blended with known blending aids, that is, the blending aids known to the artisan. The product of this method is called " composition ". Examples of suitable formulation auxiliaries are solid or liquid carriers, surfactants and tackifiers. It should be noted that liquid carriers such as liquid solvents such as water and organic solvents, and if the solvent used is water ', organic solvents are particularly used as auxiliary solvents. Useful organic solvents are aromatic hydrocarbons such as xylene, toluene, and alkyl fluorene, vaporized aromatic hydrocarbons or chlorinated fatty acids such as gas benzene, ethylene, and digas methane, and aliphatic hydrocarbons such as cyclohexane and chain hydrocarbons, such as mineral oil distillation. Parts, alcohols such as butanol, isobutanol, cyclohexanol, and ethylene glycol, and their corresponding bonds and lipids, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, nonionic bipolar solvents such as difluorenyl Formamidine, N-methyl-2-pyrrolidone and dimethylarsine. Suitable examples of solid carriers are: grinding natural minerals and minerals such as silica, silicates, kaolin, clay, red basalt, loess, talc, white powder, limestone, lime, dolomite, magnesium dioxide, Quartz, American activated white clay, montmorillonite and crushed soil; ground synthetic minerals such as high dispersibility; celite or synthetic Ming soil and powder of synthetic silicate. Examples of solid carriers particularly suitable for granules are: squeezed and fractionated natural ores such as calcite, marble, pumice, sepiolite; synthetic particles of inorganic and organic powders; organic particles such as sawdust, coconut, corn ears, or tobacco stems . Convenient surface active non-ionic and anionic pre-emulsifiers / foam formers and dispersants: -25- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -------- / ILd--r ----,? Τ ------ ά {Please read the notes on the back before filling this page) A7 A7 Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives ) 'Fatty acid-polyoxyethyl esters such as lauryl alcohol polyoxyethyl ether acetate,-alkyl polyoxyethyl ethers or alkyl polyoxypropyl ethers such as isotridecyl alcohol and fatty alcohol polyoxyethyl ethers,-polyaryl ethers such as octyl alcohol Phenyl polyoxyether,-Tributyl benzyl polyoxyether, 'Ethoxylated isooctylphenol, octylphenol or nonylphenol or castor oil,-Sorbitol vinegar, -Arylsulfonic acid' alkylsulfonic acid ' Alkyl sulfates, alkali metals, alkaline earth metals and ammonium salts of aromatic acids such as wood-, phenol-?-, And dibutylphosphonium sulfonic acids, alkyl sulfonic acids, alkylaryl acids, alkyl sulfuric acids, laurels Ether sulfuric acid and fatty alcohol sulfuric acid, fatty acids, sulfated hexadecyl, heptadecyl and octadecyl alcohol and fatty alcohol glycol ethers,-condensates of sulfonated sulfonium and its derivatives and formaldehyde, 'each continued The condensate of acid and pandemic acid, ~ protein hydrolysate and-. Especially as dispersant: lignin sulfite waste liquid and methyl salt vitamin. Suitable tackifiers: carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules, latex such as gum arabic, polyvinylacetate, polyvinyl acetate, natural phospholipids such as cerebrolipid and lecithin , Synthetic phospholipid lipid. The composition may additionally contain one or two representatives of the following: colorants, other known active ingredients, trace nutrients and other additives. Examples of synthetic dyes are inorganic pigments (such as iron oxide, titanium oxide, Prussian blue) and organic pigments (such as alizarin, azo), and metal anthocyanins. Note that other active ingredients such as other fungicides: insecticides, mothicides, _ -26- This paper size applies the Chinese National Standards (CNS) A4 Regulations £ 77 [" 〇 > < 297 cm) ----- (Please read the notes on the back before filling this page)-Order nickel A7 B7 V. Description of the invention (24) Herbicides and growth-growth regulators "Trace nutrients such as iron, ^ cat · , Rotten, copper, cobalt, molybdenum and zinc salts. Suitable additional additives are mineral oil and sprouts. In addition, the composition may be blended with other ingredients of practical importance, such as fertilizers or other finished compositions containing active ingredients. Depending on the physical and chemical properties of the substance used, the composition can be prepared by itself (e.g. mixing, accompanied by grinding, spraying, squeezing, granulating or dissolving water, the latter, assisted by organic solvents if necessary). Dispersible powders, substances and dusts are obtained by mixing with a solid carrier or by grinding Compound I together. Depending on the substance used, the composition may be, for example, a solution, emulsion, suspension powder, foam, paste, granules, aerosol or microcapsules as a polymer or coating composition for seed. Generally, the composition is commercially available as a concentrate. If necessary, it can be dissolved and diluted in a conventional manner. If it is used in the case of wet powders, hydrogels, emulsifiable concentrates, and dispersants, it is usually water. particle. The preparation of dusts, granules and dispersible solutions is usually not further diluted with other inert materials before use. The composition can be applied in a manner known per se such as spray spraying, atomizing dusting, scattering or pouring. Plants are typically sprayed or dusted with the composition. In addition, plant seeds are treated in a manner known per se. Printed by the Ministry of Economic Affairs of the Central Bureau of Standards for Consumer Product Cooperation 1 -—-— · I--I-II ^^ 1 Izn-n (Please read the notes on the back before filling this page) Example of ordering such preparations There are: I-90 weight wounds of the compound I of the present invention and 10 parts by weight of methyl-2-elorone, which are suitable for application in the form of very small droplets. II. 20 wt.% Of the damage, · 80 parts by weight of the compound, alkylated benzene, 10 parts by weight of 8 to 10 moles of ethylene oxide n mole of acid] ^ ethanolamine -27-

Printed by A7 B7, Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the Invention (25) Adduct product of amidine, 5 parts by weight of calcium dodecylbenzenesulfonate, 5 parts by weight of 40 mol ethylene oxide A solution in a mixture of alkane n mole castor oil adduct and the like; the formulation was finely dispersed in water to obtain a dispersion. III. 20 wt% Compound I of the present invention at 40 parts by weight of cyclohexanone / 30 parts by weight of isobutanol / 20 parts by weight of 40 moles of ethylene oxide and 1 mole of castor oil An aqueous dispersion of the product. IV. 20 parts by weight of the compound 1 of the present invention; 25 parts by weight of cyclohexanone / 65 parts by weight of stagnation point 210-280 C petroleum parts / 10 parts by weight 40 moles of ethylene oxide and 1 Mo. Aqueous dispersion of castor oil adduct. V. Add 80 parts by weight of the compound I of the present invention, 3 parts by weight of diisobutyl tea-1-sulfonic acid sodium salt, 10 parts by weight of lignin sulfonic acid sodium salt obtained from a sulfurous acid waste liquid and 7 A mixture of parts by weight of powdered silica gel ground in a hammer mill; finely dispersed in water to obtain a mixture; VI. 3 parts by weight of Compound I of the present invention and 97 parts by weight of finely divided kaolin Intimate mixture; this dusting composition contains 3% by weight of active compound; VII. 30% by weight of the compound I of the present invention, 92 parts by weight of powdered silica gel and 8 parts by weight of sprayed An intimate mixture of liquid paraffin on the surface of silicone gel; this preparation can make the active compound have good adhesion; VIII. 40 parts by weight of the present compound, 10 parts by weight of sodium benzoate / urea / Formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight 28- This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page) Order -Line- Shellfish Consumption Du printed A7 ______ ^ _ B7___ V. Description of the invention (26) A stable aqueous dispersion of parts of water, which can be re-diluted; IX. 20 parts by weight of D calcium salt, 8 parts by weight of fatty alcohol polyglycol Acid, a stable oil dispersion of 20 parts by weight of besylate sodium salt / urea / formaldehyde condensate and 68 parts by weight of paraffinic mineral oil. If compound I is used, its subdivision is very important. The compound I and the composition of the present invention can distinguish the competitive activity against a wide range of harmful fungi (phytophthora fungi), especially from-Ascomycetes, Basidiomycetes, •• Half Deute + romycetes and Phycomycetes. They have systemic activity and can be used as leaf and soil fungicides. They control various crops such as wheat, rye, barley, oats, rice, corn, grassland, cotton, soybeans, coffee, sugar cane, grapes, fruit trees, ornaments and vegetable plants such as cucumbers, beans and cucurbitaceae, as well as IL is particularly important on seeds. Compound I, its salts and N-oxides, and the composition of the present invention can be used to treat harmful fungi in the fungicidal active composition or its compound I. The environment, or seeds and plants to be protected against fungal infestation and damage , Materials, or soil. It can be applied before and after the infestation by maggots. & Specifically, the compositions and compounds of the present invention are suitable for controlling the following plant diseases: Cereal wheat powdery mildew, Cucurbitaceae powdery powdery mildew and red bean powdery mildew, Guguo apple powdery mildew, and grape white powder Disease, rust-like disease -29- This paper size applies Chinese National Standard (CNS) Α4 specification (21〇χ297 ^ ~ 5 --------- (Please read the precautions on the back before filling this page) Order-line V. Description of the invention (27) (Puccinias-es), cotton and grass canola stand 4, cereal and sweet black powder disease, rhizome apple black star disease, cereal black rot, wheat wheat Bacterial blight, Caulis cinerea and Grape Bean Botrytis, Peanut Brown Spot, Pseudosis of wheat and barley (Pseud〇e⑽Qsp (^ ia herp〇Stneh〇ides), Rice spasm of rice, Potato And Panyou ’s Phytophthora infestans, rice plant blight and verticillium wilt of various plants, grape downy mildew of grapes and rotaria of vegetables and fruits. The fungicidal composition usually includes 0.1-95, The active ingredient is preferably from 0.05 to 90% by weight. Quality, the application rate is from 0.01 to 20 kg of active ingredient per hectare. When treating seeds, usually 0.001 to 0.1 g, preferably 0.01 to 0.05 g of active ingredient per kg of seed. It is used as a fungicide In the use form, the composition of the present invention can also be used in combination with its active ingredients, such as herbicides, insecticides, growth regulators, fungicidal or other fertilizers. If they are mixed with fungicides, they often lead to widespread killing. The following fungicides and compounds of the present invention are intended to exemplify possible non-restrictive combinations of dragons: ° Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, M sulfur, dithiocarbamate, and derivatives thereof Substances such as iron (III) dimethyldithiophosphonate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, diethylene didithiocarbamate Manganese, ethylenediamine bisdiamidocarbamic acid manganese zinc 'tetramethylthiuram disulfide thiuram, (N, N ethylbisdithiocarbamate) zinc complex, (N ， N-Acryl di-30-30- This paper size Lai Jin Jia Jia (CNS) A4 specifications (21Gx297 male Printed by A7 B7, Shellfish Consumer Cooperative, Central Bureau of Procurement, Ministry of Economic Affairs 5. Description of the invention (28) ~ Amino-amino-carboxylic acid-) zinc ammonia complex, (N, N, -propanebisdithioamino) Formic acid) zinc and N, N'-poly (propylamino) bis (thioaminomethyl) disulfide; nitro derivatives such as dinitromethylheptylcrotonate) -phenyl ester, 3,3_di 2-second butyl-4,6-dinitrophenyl methacrylate, 2-second butyl-4,6-dinitrophenyl isopropyl carbonate, and 5-nitroisophthalic acid diiso Propyl esters; Heterocyclic substances such as 2-heptadecyl-2-imidazoline acetate, 2,4-digas-6- (orthobenzylamino) -s · Sangen, phthalimidoiminophosphonic acid group Thioacids 0,0-diethyl ester, 5-amino-1- [bis (diamidino) phosphino] -3-phenyltriazole, 2,3-dicyano-1,4-disulfide -Anthraquinone, 2-sulfan-1,3-dipyrimidine- [4,5-b] pyridine, 1- (butylaminomethylamidino)-. 2-benzimidazoleaminocarboxylic acid Methyl esters, 2-methoxy-aminopyridine, 2- (2-creanyl) benzimidol, 2 · (4 · ρ 塞 thiamine) · benzymidamine, N- (l, l, 2,2-tetrakisthylthio) tetrahydrog, Tyramine, N-trifluoromethylthiotetrahydrophthalimide, N-trifluoromethylthiophthalimide; N-difluorofluoromethylthio-N ', N'-difluorenyl · N-phenylsulfonylamine, 5-ethoxy-3-trifluoromethyl -1,2,3-pyrimadiazole, 2-cyanothiomethylthiobenzothiazole, 1,4-digas-2,5-dioxobenzene, 4- (2-gasphenylene) Hydrazino) -3-methyl-5-iso1 ^ 嗤 嗣,? Biyodo-2 -mercaptan-1-oxide, 8-meryl group V »Kui I» forest or its copper salt, 2,3-nitroaza-5-pyridinoamino-6-methyl-1, 4-17 oxathiine, 2,3-dihydro-5-benzylamino-6-methyl-1,4-hensacin 4,4-dioxide, 2-methyl -5,6-dihydro-4H-tripan-3-carboxamidobenzene, 2-methylfuran-3-chiamine aminobenzene, 2,5-dimethylfuran-3-carboxamido Benzene, 2,4,5-trimethylsuccin-3-carboxamidobenzyl, N-cyclohexyl-2,5-dimethyl-furan-3-carboxamido, N-cyclohexyl-N- Methoxy-2,5-difluorenylfuran-3-carboxamide, 2-methylbenzofluorenylbenzyl, 2-iodobenzofluorenaminobenzene, N-methylfluorenyl-N-morpholine " 2,2,2- -31-This paper size is applicable to China National Standard (CNS) A4 (210X297mm) (Please read the precautions on the back before filling this page) Staff of Central Standards Bureau, Ministry of Economic Affairs Printed by the consumer cooperative A7 B7 V. Description of the invention (29) Trichloroethyl acetaldehyde, hexahydropyracoxine], 4_diylbis (2,2 2_trigasethyl) _methanamine, 1- ( 3,4-Diaminoanilide formamido-2,2,2-trigasethane, 2,6-dimethyl-N-tridecylmorpholine or its salt, 2,6 Dimethylcyclododecylmorpholine and its salts, N- [3- (p-tert-butylphenyl) _2 • methylpropyl] _cis_26_dimethylmorphine, N- [3- ( For tertiary butylbenzyl) _2_fluorenyl-propyl] _hexahydropyridine, 1- [2- (2,4 · difluorophenyl) _4_ethyl_13_dioxolane_2 · yl Ethyl] _1H_ monofluorene 1- [2_ (2,4 -monophenyl) _4_n-propyl-i, 3-di.oxopentan-2_ylethyl] -1fluorene-1,2,4-tri Azole, N- (n-propyl) -N- (2,4,6 · trigasphenoxyethyl) -N'-imidyl urea, 1- (4-gasphenoxy_3,3_di Methyl-1- (ιη-1,2,4: triazole-butyl) -2-butanone, (2-Gaphenyl) _ (4-Gaphenyl) -5-pyrimidinemethanol, 5- Butyl-2-diamidino-4-hydroxy-6-methylpyrimidine, di-p-phenylphenyl > 3-pyridinemethanol, 1,2-bis- (3 · ethoxycarbonyl_2_thioureido) Benzene and 1,2-bis (3-methoxycarbonyl-2-thioureido) -benzene, and various pesticides such as dodecylguanidine acetate, 3_ [3_ (3,5-dimethyl-2- Oxycyclohexyl) -2-hydroxyethyl] -pentamethyleneimine, hexakisbenzene, DL-N- (2,6-xylyl) -N-furanmethylmethylpropionate, DL-N -(2,6-xylyl) -N- (2 · -methoxyethoxyl) alanine, N- (2,6-difluorene Benzene) -N-Acetomethyl-D, L-2-aminobutyrolactone, DL-N- (2,6-xylyl) -N- (phenethylethyl) -alanine methyl Ester, 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-humazidine, 3- [3,5-digasbenzene Yl) -5-methyl-5-methoxymethyl] -1,3-oxazolidin-2,4-dione, 3- (3,5-diphenylphenyl) -1-isopropylamine Formamidinehydantoin, N- (3,5-difluorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboxyamidoimine, 2-cyano- [N- ( Ethylaminocarbonyl) -2-methoxyimino] -acetamidamine, 1- [2- (2,4-diaminophenyl) -pentyl] -1H-1,2,4-triazole, 2 , 4-Difluoro-a-(1H- -32- This paper size applies to Chinese National Standards (CNS) Α4 grid (210 × 297 mm) (Please read the precautions on the back before filling out this page) Order * Line A7 B7 V. Description of the invention (3,1,2,4-triazol-4-ylmethyl) dibenzyl alcohol, n- (3-gas-2,6-dinitro-4-trifluorotolyl)- 5-trifluoromethyl-3-amino-2-pyridine and ι ((bis- (4-fluorophenyl) -silyl) -methyl) -1H-1,2,4-triazole.

Strobilurins such as E-methoxyimino [α-(〇-tolyloxy) -〇-tolyl] methyl acetate 'E-2- {2- [6- (2-cyanophenoxy) pyrimidine_4 -Methoxy] phenyl} methyl 3-methoxyacrylate'methyl-E-methoxyimino [α- (2-phenoxyphenyl)] acetamide, methyl- £ -methoxy Imino [Han- (2,5-xylyloxy) -0-tolyl] Acetylamine. Aniline such as N- (4,6-dimethylpyrimidin · 2 · yl) aniline, N- [4-methyl-6- (1-propynyl) pyrimidin-2-yl] aniline, N- (4- Methyl-6-cyclopropylpyrimidin-2-yl) aniline. Phenylelopol is such as 4- (2,2-difluoro-1,3-phenylhydrazone dioxolane-4-yl) pyrrole-3-carbonitrile. Cinnamon amines such as [3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) propanyl]? (2118,38 Chinese) -1- [3- (2-Gaphenyl) -2- [4-fluorophenyl] ethylene oxide-2-ylmethyl] -1H-1,2,4-tri Jun. The compounds of formula I are also effective in controlling animal pests, especially insects, spiders and nematodes. They can be used in crop protection and hygiene, material protection, and veterinary departments as pesticides. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). Insect pests include: Order of the butterfly (Lepidoptera) such as small silkworm, yellow tiger, Alabama argilacea), Li Dou Ye, E. chinensis, Spodoptera frugiperda, Pine-clover, Scirpus cylindrica, Capua ru ... ⑽, Cheimatobia brumata, Spruce Leaf Leaf E, Western Spruce Leaf Leaf E. americana , Crocidolomia binotalis, Codling moth, European pine caterpillar -33- Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, printed A7 B7 V. Description of the invention (31) Corn borer, Eupoecilia ambiguella, Evetria bouliana, Grain-spotted tiger, Large soil borer, Prunella borer, Papaver borer's cotton bollworm, Spodoptera frugiperda, Spodoptera littoralis, cabbage snail; Hibernia defoliaria, American white moth, Apple nest moth, tomato moth, hemlock scale moth, beet armyworm, coffee spot moth, spiny leaf moth, Lithocolletis blancardella, Lobesia botrana, yellow-green stripe moth, gypsy moth, monk poison Moth, narrow-winged leaf miner, canopy caterpillar, Kale Yee, Orgyia pseudotsugate, European corn fillet, Panolis flammea, red bollworm, potato tuber moth, citrus leafworm, large-vegetable meal _ pot, clover green leafworm , .Platynota stultana 'Plutella xylostella, Orange flower nest moth, Grease nest moth, Prodenia sunia, Yellow stripe armyworm, Soybean night moth, Pine leaf leaf moth, Scrobialpula absoluta, Chess, Grape Cinnamon Moth, Grasshopper, Egyptian cotton Trichomonas, Spodoptera litura 'Thaumatopoea pityocampa, Quercus spp., Spodoptera litura, and Spruce leaf curl moths; Spodoptera (Scalyoptera) such as strip beetle, Agriotes obscurus, wild cotton weevil, apple flower Weevil, Apion vorax, Atomaria linearis, Large pine cockles, beet turtles, bean leaf beetles, kale pod weevil, Ceuthorhynchus napi, beet tibialis, tobacco needle needles, asparagus twelve star leaf beetles, spruce red wing small蠹 'Longhorn leaf beetle, twelve star melon leaf beetle, corn root leaf beetle, Mexican bean ladybug, tobacco jumping beetle, Eutinobothrus brasiliensis, Hylobius abietis, Egyptian alfalfa weevil, alfalfa leaf weevil Lemabilineata, Lema melanopus, potato beetle, gold beetles, rice elephant sting, Melanotus communis, Miligethes aeneus, Melolontha hippocastani, total horn beetle, rice negative mudworm, -34- This paper size applies Chinese National Standard (CNS) A4 Specifications (210X297 mm) (Please read the notes on the back before filling out this page) -6 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Silk Economy Α7 Β7 V. Description of the invention (32)

Ortiorrhynchus sulcatus 'Ortiorrhynchus ovatus, Pheasant ape leaf worm, Garden beetle, Phyllophaga sp., Brassica jumping beetle., Turnip light foot beetle, Yellow curve bar beetle' Yamoto Reaper, Psylliodes napi, Intricate little stupid , Bowl bean leaf weasel, and broad bean elephant, bowl bean elephant, Bruchus lentis, valley elephant, tobacco stealer, saw (chest) valley burglar, valley gluten, rice elephant, red quail valley robber, valley spotted cormorant and sitona lineatus, Sitophilus granaria; Diptera such as Egyptian streaks, Wix mosquitoes, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellarla, Contariniia sorghicola, Cordylobia anthropophaga, Culex picuroles, Dacus , Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericalis, Mayor musioola pectoral mestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbla coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea, Tipula paludosa. Hymenoptera, such as tobacco brown thrips, alfalfa thrips, thrips, wheat skin thrips, orange thrips, box thrips, Thrips palmi and cotton thrips; Hymenoptera such as Xinjiang leafy bee, Atta cephalotes , Atta sexdens, Texas leaf moth, Hoplocampa minuta, Apple leaf bee, A-35- This paper size applies to Chinese National Standard (CNS) Α4ί_1 grid (210 × 297 mm) (Notes on the back of the poem before reading (Fill in this page again.) Order A7 B7 printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Nickel. 5. Description of the invention (33) Genting ants, kitchen ants, fire ants, red fire ants and black fire ants; Heteroptera The order of the eyes is such as the green magpie, hairy long magpie, tobacco black spot magpie, cotton red insect spring, Dysdercus intermedius 'Eurygaster integriceps' cotton brown wall, leaf foot bee, pod blind binding, forage blindfold (Lygus lineolaris), Forage blind bee (Lygus pratensis), rice green bee, beet stingray, Solubea insularis and Thyanta perditor; Homoptera orders such as Acyrthosiphon onobrychis, worm tooth, larch ball pair, red round valence, Aphidula nasturtii, silkworm Seals, cottonworm teeth, apple aphids, potato aphids, bemisia tabaci, thistle short-tailed aphids, sweet IL aphids, 'Dalbulus maidis' Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, broad bean microleaf glow, rhizome cotton wool teeth, rice Gray planthopper, long tube pair of wheat, long tube pair of euphorbia, long tube pair of rosette, broad bean aphid, rose wheat aphid, peach (red) aphid, cherry black tumor front aphid, black tail leafhopper, rice brown fly Qi, Fei Fengfeng, Phorodon humuli 'Fruit Orange, Yunmu S *, Psylla sylvestris, Corn aphid, Aphis gossypii, wheat aphid, white-backed planthopper, orange aphid, wheat whitefly, greenhouse white powder Ticks and grape nodule aphids; Amaranths (Isoptera.) Such as Calotermes flavicollis, Leucotermes flavipes, Macrotermes subhyalinus, Reticulitermes lucifu-gus and Termes natalensis; Orthoptera such as European salamanders, Tibetan migratory locusts, double-banded grasshoppers' red-legged grasshoppers ., Mexico Kun Meng, Migratory Grasshopper Meng, Luoji Mountain Kun Meng, Red Wing Jun, American Worm, Schistocerca peregrina, Stauronotus maroccanus, Heath grasshopper, and family salamander, Eastern goatfish, German small And American giant salamanders; orders of the arachnid class such as plant-feeding chigger mites such as tomato leaf-scarred chigger mites and apple-spin chigger mites -36- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297); ^ --- ----- ΓΙΜ ^ .------ Order ------ 0 (Please read the notes on the back before filling out this page) Employees of the Prospective Bureau of the Ministry of Economic Affairs, Consumer Co-operation, Society ¥ system Α7 Β7 Five 'invention description (34), Brevipaljms phoenicis, clover snail, hormonal oriental leaf snail, Texas orange leaf snail, Eriophyes sheldoni, grass small snail, rhizome , Orange gourd concealer, Orange rust snail, Polygonum spp., Vermillion leaf worm, Tetranychus kanzawai, Pacific Red leaf concealer, Snail, Ticks such as American flower stele, Amblyomma variegatum, Persian cynophagus 1, with loop Square head ticks, Boophilus decoloratus 'Small Missing Monument, Dermacentor silvarum, Hyalomma truncatum' Ixodes rubicundus, Ornithodorus moubata, Ear Residual Ticks, Rhipicephalus appendiculatus and Rhipicephalus evertsi and-zoo parasitic ticks such as chicken skin mites, sheep Itch and chigger mites; nematodes Such as root-knot nematodes such as horseradish nematodes, peanut root-knot nematodes, and cotton root-worm nematodes, forming cyst nematodes such as Globodera rostochiensis, Heterodera avenae, soybean nematodes and Heterodera schachtii, Heterodera trifolii stems and leaf nematodes such as Belonolaimus longicaudatus, destructive stem nematodes, corn Stem nematodes, Heliocotylenchus multicinctus, Longidorus elongatus, Radopholus similis, Rotylenchus robustus, Trichodorus primitivus' Tylenshorhynchus claytoni, Tylenchorhynchus dubius, Pratylenchus neglectus, Pratylenchus pensuanivitamins can be used in concentrations Subject to change. Generally, they are 0.0001 to 10%, preferably 0.01 to 1%. The active ingredient can also be successfully used in the ultra-low-volume method (ULV). It may use -37-degrees applicable to China National Standard (CNS) A4 specifications (210X297 mm) III i I. ^ 1 I Order r, line (please first Read the notes on the back and fill in this page again) A 7 B7 V. Description of the invention (35 greater than 95% by weight is a formulation with specific active ingredients, or even active ingredients without additives. The application rate of active ingredients to control pests under field conditions 〇 丨 to 2 〇, preferably 0.2 to 1.0 kg / ha. Synthetic Examples The procedure of the following synthetic examples can change the starting compound to obtain other representatives of compound I or III. The physical data of the prepared product are shown in each case In the table below: The chemical shift (in ppm) of the NMR spectrum is measured in terms of tetramethylsilane (br = broadcast, s = single peak, m = multiple ··). I) where Q is C (= NOCH3) -Preparation of Compound I of CONHCH3. For example, the starting compound III can be prepared as described below (Examples 1 to 3) from E-2-methoxyimino-2-[(2-tolyloxy) phenyl] acetic acid methyl ester using methylamine It can be easily obtained by ammonolysis followed by pyrolysis with boron trioxide or hydrogen bromide (£ ^. £? _ A 493 711). Example 1 N-methyl-E-2-methoxyimino · 2-[(2-tolyloxymethyl) phenyl] acetamidine 250 g of E-2-amidoimino-2- [(2-Tolyloxenyl) phenyl] methyl acetate was suspended in 1 liter of a 40 ° / ❶ strength aqueous methylamine solution, and the suspending agent was heated at 40 ° C for 4 hours. The mixture was cooled to room temperature (20x), the solid was filtered with suction, washed repeatedly with water and dried at 50 ° C to give 229.8 g of the title compound as colorless crystals. Melting point: 109-112 ° C; 4 NMR (CDC13): 2.20 (s, 3H); 2.85 (d, 3H); 3.95 (s, 3H); 4.9J) (s, 2H); 6.7 (NH); 6.8 -7.6 (m, 8H) Example 2 -38 This paper is from Shicai Guanjia County (CNS) A4 size (21QX297 male thin) (Please read the precautions on the back before filling this page_) | 髻. VS vs Economy Printed by the Central Standards Bureau of the Ministry of Industry and Labor Cooperatives of the Ministry of Economic Affairs. Printed by the Central Standards Bureau of the Ministry of Economic Affairs. Printed by A7 B7. V. Description of the invention (36) N-methyl-E--2-methoxyimino-2-[( 2-Gas methyl) benzyl] acetamide in HTC will be 2 grams of N-methyl_E_2-methoxyimino_2-[(2.tolyloxymethyl) phenyl] acetamide in Example 1 30 ml of anhydrous dichloromethane were introduced. 9.4 g of boron trioxide (eg, 1 mole of solution in n-hexane) was added dropwise, the mixture was refluxed for 1.5 hours and cooled to 10 ° C, 9.4 g of boron trioxide was added, and the mixture was stirred at room temperature (20.0 overnight). After 8.2 g of methanol was added dropwise, the batch was evaporated on a rotary evaporator. The residue was taken up in 100 ml of digas methane and washed with 5% sodium hydroxide solution and water. The organic phase was then dried over sodium sulfate. After the solvent was stripped, 1.2 g of the title compound as an oil body remained. ~ _'H NMR (CDC13): 2.95 (d, 3H); 3.90 (s, 3H); 4.45 (s, 2H); 6.8 (NH); 7.1-7.6 (m , 4H) Example 3 N-methyl-E-2 -methoxyimino-2-[(2-bromomethyl) phenyl] ethanamine 10 g of N-methyl-E-2 of Example 1 -Phenoxyimino_2-[(2-tolyloxymethyl) phenyl] acetamidine was introduced into 50 ml of anhydrous digas methane. Pass hydrogen bromide to the solution until the saturation point (about 9 grams of HBr ). The mixture was stirred at room temperature for 68 hours to react all the starting materials. An additional 50 ml of Digas 1 was added, and the mixture was treated as in Example 2. 7.0 g of the title compound as an oily body remained, which crystallized upon standing. Melting point: 128-129 ° C; 4 NMR (CDC13): 2 .95 (d, 3H); 3.95 (s, 3H); 4.35 (s, 2H); 6.85 (NH); 7.1-7.5 (m, 4H) Example 4 N-methyl-E-2-methoxyimine Phenyl-2-t (2- [2-n-propyl-5 -methyl p · myden, 4-yl)] oxymethyl) phenyl] acetamidamine-39- This paper is applicable to China's national standard (〇 呢) 6 4 specifications (2 丨 0 father 297 male Chu) (Please read the precautions on the back before filling this page) Order-line-A7 B7 V. Description of the invention (37) 1.52 grams 2_ 正-丙The methyl-5-methyl-4-hydroxypyrimidine was dissolved in 25 ml of dimethylformamide. Add 1.38 g of finely divided potassium carbonate and 2.85 g of N-methyl-E-2-methoxyimino-2-[(2-bromomethyl) phenyl] acetamidamine. The mixture was stirred at 50 ° C for 4 hours and concentrated. The residue was taken up in 300 ml of a semi-concentrated aqueous sodium vaporization solution and extracted three times each with 100 ml of methyl tertiary butyl ether. The combined organic phases were then washed with water and dried over sodium sulfate. After the solvent was stripped, the residue was chromatographed on silica gel with cyclohexane / ethyl acetate 1: 2. This gave 0.6 g of the title compound as a colorless solid. Melting point: 60-62 ° C, (Please read the precautions on the back before filling this page) Order ------ Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -40- This paper size applies to Chinese national standards ( CNS) A4 specification (210X297 mm) 5. Invention description (38) f ^ h—T ^ # -3 驷

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S 5® I s 7W I 77 97 I 9 must wear down ^^ mpfc], IR [cm 丨 二 丨 line 4 This paper size applies to China National Standard (CNS) Α4 specification (210X 297 mm) V. Description of the invention (39) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs NJ 〇 h- * Ο ►— CO — H— ON — cn — ▲ 1— · u > — ro H- ♦ — h- .0 3;-pt put pi «Sr -a tt -9 Η Office-9 a \ n μ- Ι and Ι» ι 1 H = s: X = s = = = Ln 1 Μ Office σ \ σ \ 1 σ »U1 U) 1 tn Ln CD I— 1 CD U > 0 Ln 1 I- * O σ \ σ \ 1 σ \ vo u »Ui 1 H- U) — NJ 〇1 μ- N > fO • Ck.! -Nj Ln ON N > 1 σ \ a —h- U > < Nj > — · M VO \ 〇 »-* K- ro Ln h- VO CO AH *»-* O l / »C \ vo Ln ►—» — 〇 ^ »« »Cn VO •« H- · & · KJ C3 o Race 3, 1¾ 3 • ρ I— ^ b- < (Please read the notes on the back before filling this page). Binder-book-line-42- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 ____ -_B7 _______ V. Description of the invention (4〇) II) of which " Q 系 C (= N0CH3) -C00CH32 Compound 1 Production Example 5 E · 2-methoxyimino-2-[(2- [2-ethyl-5-methylpyrimidin-4-yl)] oxymethyl) benzyl] formic acid Esters (Table 2) 2-17 grams of 2-ethyl-5-methyl-4-hydroxypyrimidine were dissolved in 40 ml of dimethylformamide. To this solution were added 3.1 g of fine powdered potassium carbonate and 4.29 g of E-2-methoxyimino-2-[(2-bromomethyl) phenyl] acetic acid methyl acetate. The mixture was stirred at 50 ° C for 4 hours, then at room temperature overnight and concentrated. The residue was taken up in 300 ml of a dilute sodium gas solution and extracted three times with methyl tert-butyl ether. First rinse with sodium bicarbonate solution and then with water. Combine the organic phases and then dry the combined organic phases over sodium sulfate. After stripping the solvent ', the residue remaining was recrystallized from n-hexane / methyl tert-butyl ether. 1.3 g of the title was obtained as a colorless solid.

Melting point: 75-77 ° C (please read the precautions on the back before filling this page) "-丨 Printed by Beige Consumer Cooperative, Central Bureau of Standards of the Ministry of Economic Affairs-43- This paper size applies to Chinese national standards (CNS M4 specifications (210X297 mm) A7 B7 printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (41)

-ί _Nulw " '口 一 i * a ^ I ^-状 衣 --.---- ^ ------- 0 (洧 Read the precautions on the back before filling this page) 97 1673,1593 , 1564, 1525, 1450, 142'1319, 979. 70 丨 ^ 1-73 174 128-130 60 丨 62 105 丨 107 13 Still 137 wear dill garlic {? Ρ · 【OCJ; I'-cm-One two -44- This paper size is applicable to Chinese National Standard (CNS) A4 (2 丨 0 '乂 297mm) V. Description of the invention (42) A7B7 Printed by Shellfish Consumer Cooperative, Zhongda Standards Bureau, Ministry of Economic Affairs

-45- This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm) I ------- installation-- (Please read the precautions on the back before filling this page),-= 5 -line _ Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperatives, A7 _ _ B7 V. Description of the Invention (43) Examples of use-1. Examples of anti-harmful fungi, emulsified with 10% by weight active agent and 90% by weight mixture The following experiments were carried out on the fungicidal activity of compound I. The mixture was 70% by weight of cyclohexanone, 20% by weight of Nekanil® LN (Lutensol® AP6, with ethoxylated as the matrix. It has the function of emulsifier and dispersant. Wetting agent) and 10% by weight of Uniperol® EL (a non-ionic emulsifier based on ethoxylated castor oil) are diluted with water to adjust the desired concentration of the active ingredient. Activity against Pyricularia oryzae (rice blast) The leaves of rice seedlings (Tai Nong 67 variant) are sprayed with an aqueous emulsion containing 80% of active compound and 20% of emulsifier in dry matter until dripping wet '24 hours later ' It was inoculated with a spore suspension of Pyricularia oryzae and the plants were placed in a 22-24T environmental control room and 95-99% atmospheric humidity. The extent of the disease was determined visually after 6 days. Containing 6] ppm The following compounds of the present invention were tested with aqueous formulations of Active Ingredients 1, 3, 5, 7, 8, 9, 10, and 11 of Table S1. When these compounds were applied, 0 to 5% of the leaf area was visually infected by the fungus. 80% of untreated plants were affected. 2. Examples of activity against animal pests_ The following test can be used to confirm the effect of compounds of formula I against animal pests: — · 46_ This paper's standard (cns) a_4 specifications (2iGx297 public-(Please read the precautions on the back before filling (This page),?! _ A7 _ B7_ V. Description of the invention (44) Preparation of active ingredients-a) 0.1% strength solution in acetone, or b) 70% by weight of cyclohexanone, 20% by weight of Nekanil® LN ( Lutensol® AP6, based on ethoxylated sintered base as a emulsifier and dispersant, and 10% by weight of Uniperol® EL (non-ionic emulsifier based on ethoxylated hemp oil) Concentration emulsion. It is diluted with acetone in case a) and with water in case b) according to the desired concentration. -At the end of the test, determine the lowest concentration (lower limit of activity or lowest concentration) at which the lowest concentration of the compound in each case can still cause 80 to 100% inhibition or lethality compared to the untreated control test. (Please read the notes on the back before filling this page)

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Claims (1)

Bulletin No. 85115212 Patent Application Supplementary Specification (January 89) I. Test compounds: ⑻ According to this case (85115212) no. 7, table S2 (b) according to Wenderoth et al. (EP 363 818) Comparative compound A (similar to Wenderoth no. 156) No. 156 compound having the structure shown below: P: \ PTS \ GAN \ ATYPE \ B \ 45937SUPDOaWCK Bulletin i 8551 1f 2 12 2 How many ?: Please call the document to add the text, also supplement the data 1. Example of fungicidal activity Example 1 · The effect on pisain opara viticola is sprayed with an aqueous solution made of a preservation solution composed of 10% active ingredient, 63% cyclohexanone and 27% emulsifier " Mullet " (Muler Thurgan) variety of potted grape leaves. In order to assess the duration of the effect, when the spray layer was dried, the plants were placed in a greenhouse for 8 days and then the leaves were infected with a phylococcus aureus (Polymanium sp In a small room, then in a greenhouse at 20 to 30 ° C for 5 days. To accelerate and strengthen the discharge of sporangial stalks, the bryophytes' plants were placed in a humid chamber for 16 hours. The extent of the infestation of the maggots was evaluated on the back of the leaves. U: \ TYPE \ EN \ ENG \ 0337G.OOC 8 393300 2 1 No. 2 patent application scope amendment (February 89) A8 B8 C8 D8 Type I 2- (0-Call Bite-4-Base) (Methoxy) phenylacetic acid derivative R2 R1 Namma N R3 〇-CH (I) The Central Government Bureau of the Ministry of Economic Affairs, the Consumers ’Cooperative of India and its N-oxides, where the R1 to R4 groups and Q have the following definitions: R1 is hydrogen or cvcv alkyl; R2 is southin or crc2- Alkyl; R3 is hydrogen, amine, hydroxy, mercapto, halogen, C ^ -Cs-alkyl, and alkynyl can be attached to phenyl, which can be attached to one or two of the following substituents: halogen, cyan Group, nitro, c ^ -cv alkyl, q-cv haloalkyl &CrC4-alkoxy; CrCV alkyl, Ci-Cg-alkoxy-Ci-C4-alkyl, crc8-alkoxy Group, crc8-monoalkylamino, di-Crc8-alkylamino, crc8-alkylthio, crc8-alkylsulfoxide, CrC8-alkylfluorenyl, c3-c8-cycloalkyl'tri-C ^ -Cs -Alkanosilyloxy or the following, unsubstituted or substituted in the aromatic ring: phenyl, phenoxy, phenoxymethyl, fluorenyl- or heteroaryl; r4 hydrogen, cyano, halogen, crc4 -Alkyl, halide or Cj-Cj-carboxy; and Q is C (= NOCH3) _CONHCH3, or C (= NOCH3) -COOCH3. 2. —A composition suitable for controlling harmful fungi ', which contains an effective amount of a compound of formula I according to item 1 of the scope of the patent application, or a salt thereof, or N_oxidized paper, using China National Tree Rate (CNS) A4 Specifications (210 > < 297 public teaching) -------- I order ------- line {Please read the note # ^ on the back before filling in this page} Compound Table / No. Source R3 Υ Application ··· ι Regulate ge .63 > pm activity Θ * Invasion after inoculation 16 L Water damage% 4. 1/3 OZ 46435 Methyl ethyl NΗ 5 5/6 / 3 OZ 46435 methyl ethyl 0 25 40 / 1/6 OZ 46435 methylcyclopropyl ΝΗ 5 0 / 6/6 OZ 46435 methyl cyclopropyl 0 25 40 / 1/7 OZ 46435 methyl n-butyl ΝΗ 0 5 5 6/7 OZ 46435 fluorenyl n-butyl 0 0 20 60 1/12 OZ 46435 fluorenyl n-pentyl N Η 0 0 25 6/12 OZ 46435 fluorenyl n-pentyl 0 0 5 65 1/16 OZ 46435 Methyl n-hexyl NΗ 0 0 25 6/16 OZ 46435 Methyl n-hexyl 0 0 15 65 1/55 OZ 46435 Methyl n-phenyl 25Η 6/55 OZ 46435 Methyl phenyl 0 40 40/3 / 3 0 · Z. 46435 Chloroethyl NΗ / 0 5 8/3 Ο.Z. 46435 Gas ethyl 0/0 40 3/7 〇.Z. 46435 Gas n-butyl NΗ / 0 5 8/7 〇.Z 46435 Chloro-n-butyl 0/0 40 3/12 〇.Z. 46435 Gas n-pentyl NΗ / 0 0 8/12 〇.Z. 46435 Gas-n-pentyl 0/0 25 3/55 Ο.Z. 46435 Chlorophenyl N 25 25 / 8/55 0.Z. 46435 Chlorophenyl 0 50 50 / Untreated 65 1 Example 2: Effect on wheat brown rust (Puccinia recondita) The seedlings of potted wheat seedlings were sown with the spores of Puccinia recondita (Kanzler). Plants are placed in a high humidity (90 to 95%) chamber at 20 to 22 ° C and left in the dark for 24 hours. Spray with U: \ TYPE \ EN \ ENG \ 0337G.DOC 8 -2-Sprinkle the inoculated plant until it drips wet with a preservation solution made of 10% active ingredient, 63% cyclohexanone and 27% emulsifier. . After the spray layer has dried, the plants are placed in a greenhouse at 20 to 24 ° C and a relative humidity of 60 to 80%. After 7 days, the distribution of phytophthora was evaluated. Compound Table / No. Source R1 R2 R3 Y Application · 250 ppm live, f sex after the sex 63 t ingredient water worry% 16 1/3 OZ 46435 曱 ethyl ethyl NH 15 40 / 6/3 OZ 46435 Η Methyl ethyl 0 25 85 / 1/4 OZ 46435 Η Methyl n-propyl NH 15 // 6/4 OZ 46435 Η Methyl n-propyl 0 25 // 1/5 OZ 46435 曱 Methyl isopropyl Propyl NH 15 25 / 6/5 OZ 46435 Η fluorenyl isopropyl 0 40 85 / 1/7 OZ 46435 Η methyl n-butyl NH 0 5 15 6/7 OZ 46435 Η methyl n-butyl 0 0 5 60 1/10 OZ 46435 甲基 methyl tertiary butyl NH 15 40 / 6/10 OZ 46435 第三 methyl tertiary butyl 0 60 85 / 1/12 OZ 46435 Η fluorenyl n-pentyl NH 0 0 5 6 / 12 OZ 46435 Η Methyl n-pentyl 0 0 5 50 1/16 OZ 46435 Η Methyl n-hexyl NH 0 0 3 6/16 OZ 46435 Η Methyl n-hexyl 0 15 40 40 3/4 OZ 46435 Η Gas n-propyl NH 15 25 / 8/4 OZ 46435 Η chloro-n-propyl 0 40 85 / 3/2 OZ 46435 气 Gas methyl NH 0 15 / 8/2 OZ 46435 Η Gas methyl 0 85 85 / 3/3 OZ 46435 Η Gas ethyl NH 0 / / 8/3 OZ 46435 Gas ethyl 0 85 // 5/4 OZ 46435 methyl chloro n-propyl NH / 25 40 10/4 OZ 46435 methyl gas n-propyl 0/65 65 untreated 85 U: \ TYPE \ EN \ ENG \ 0337G .DOC 8 -3- Example 3: Effect on Pyriculariaoryzae (protective effect) Spraying with an aqueous suspension containing (dry matter) 80% active ingredient and 20% emulsifier "Tai Nong 67" ; (Tai-Nong 67) varieties of potted rice seedling leaves. After 24 hours, the plants were inoculated with an aqueous bramble suspension of Pyricularia oryzae. The plants were then placed in a steam-saturated chamber for 6 days at 20 to 24 ° C. The distribution of Ascaris spp. Was evaluated and expressed as% of invasion area. U: \ TYPE \ EN \ ENG \ 0337G.DOC 8 -4- Compound table / Να Source of literature R1 R2 R3 Y Application · · Saliva _ 250 ppm Live seven sex, 4 63 fc ingredients after water damage% 16 1/3 〇.Z. 46435 Η ethyl ethyl NH 0 / / 6/3 〇.Z. 46435 Η Methyl ethyl 0 5 / / 1/4 〇.Z. 46435 Η Methyl n-propyl NH 0 0 / 6/4 〇.Z. 46435 Η 正 正Propyl 0 0 5 / 1/5 〇.Z. 46435 Η Methyl isopropyl NH 0 0 / 6/5 〇.Z. 46435 Η Methyl isopropyl 0 25 40 / 1/6 Ο. 46.435 Η Methylcyclopropyl NH 0 /// 6/6 〇.Z. 46435 Η Methylcyclopropyl 0 5 // 1/7 〇.Z. 46435 Η Methyl n-butyl NH 0 5 15 6/7 Ο .Z. 46435 Η methyl n-butyl 0 0 5 25 1/10 〇. 46. 435 Η methyl tert-butyl NH 5 40 / 6/10. 46435 Η methyl tert-butyl 0 69 60 / 1/12 〇.Z. 46435 Η methyl n-pentyl NH 0 0 5 6/12 .n-pentyl 0 0 5 60 1/16 〇.Z. 46435 Η methyl n-hexyl NH 0 0 5 6/16 〇.Z. 46435 Η methyl n-hexyl 0 5 15 60 3/4 〇.Z. 46435 Η n-propyl NH 0 5 15 8/4 〇.Z. 46435 Η chloro-n Propyl 0 15 25 35 3/3 〇.Z. 46 435 Η chloroethyl NH 25 40 / 8/3 Ο.Z. 46. 435 气 ethyl ethyl 0 80 80 / 5/4 〇. 46. 46435 曱 chlorochloro n-propyl NH 0 / / 10/4. 46435 Benzene gas n-propyl 0 15 // Untreated 80 Supplementary data 2 Examples of activity against animal pests U: \ TYPE \ EN \ ENG \ 0337G.DOC 7 -5- Prepared according to the application method on page 39 Active ingredient. 1. Cotton spider mite (Tetranychusurticae) (spray treatment, contact activity) In a spray box ', individually spray a potted legume plant (Phaseolus) which has grown a pair of fully developed leaves. Therefore, the plants are sent to the rotating disc in the spray box via the track, and are sprayed with 3 nozzles adjusted at three angles. During spraying for 20 seconds, 30 ml of the active ingredient solution was applied to each host plant that had been infected by snails and had many adult and insect marks in the greenhouse for 5 days, and then the success of the treatment was evaluated using a binocular microscope. The circular paper was treated with an aqueous formulation of the active ingredient; then 5 adult leafleaders were placed on the paper. Determining extinction rate after 24 hours U: \ TYPE \ EN \ ENG \ 0337G.DOC 7 -6- 3. Sangdou 4 teeth (entering 1 ^ £ 3536) ’contact effect The active ingredient is more miscellaneous than kidney beans (heart 3 f faba) 〇 The elimination rate is measured after 24 hours Supplementary data 3. Comparison with EP 363 818 (D1) and EP 407 873 (D2) Test Example 1: The effect on piasmoparaparaviticola from 10% active ingredients, 63% An aqueous solution of cyclohexanone and a 27% emulsifier made from a preservation solution. Spraying "MulerThurgan" varieties of potted grape leaves. To assess the useful life 'when the spray layer was dried, the plants were placed in a greenhouse for 8 days. The leaves were then infected with a spore suspension of P. viticolae, which was first placed in a steam-saturated chamber at 24 ° C and then at 20 to 30. (: 5 days in the greenhouse. To accelerate and strengthen the spore discharge from the cystic stalks, the plant U: \ TYPE \ EN \ ENG \ 0337G.DOC -7- is placed in a wet chamber for 16 hours. It is evaluated on the back of the leaves 眞Degree of bacterial infestation. Deng Compound Table / No. Source R1 Injury% after application of 63ppm active ingredient aqueous formulation Table. S2 # 7 OZ 46435 ch3 Gas n-propyl 5-EP 363 818 ch3 Hydro-n-propyl 40 Logic 85 Compound No. 156, RLCHs; R2 = hydrogen; R3 = Isopropyl Example 2: Effect on Erysiphe graminis forma specialis fric (Triticum aestivum) made from a preservation solution composed of 10% active ingredient, 63% cyclohexanone and 27 ° / ❶ emulsifier A solution of Chengzhi was sprayed with "Fruhgold" (Fruhgold) varieties of potted wheat seedlings until dripping. Twenty-four hours after the spray layer had dried, plants were sown with wheat spores (Triticum aestivum) spores. Plants are placed in a greenhouse at 20 to 22 ° C and a relative humidity of 75 to 80%. After 7 days, the degree of distribution of powdery mildew was evaluated and expressed as a percentage of total leaf surface damage. U: \ TYPE \ EN \ ENG \ 0337G.DOC 8 -8- Compound table / No. Domain source R1 R2 R3% damage after applying 4ppm active ingredient aqueous formulation Table. S2 # 7 OZ46435 ch3 Phenylpropyl 5 -EP 407 873 ch3 Gas n-propyl 40 Nucleation ™ ~ so. ~ 1: 1 1 丨 Consistent Example 3: Long-term effect on Phytophthorainfestans caused by 10% active ingredient, 63% cyclohexan A four-leaf stage of potted Fanyou (GroBe Fleischtomate) was sprayed with an aqueous solution made of a preservation solution consisting of ketone and 27% emulsifier. After 7 days, the leaves were infected with a zoospore suspension of Phytophthora infestans The plants were placed in a steam-saturated chamber for 6 days. After 6 days, when the disease of the untreated plants had spread to a considerable extent, the fungicidal activity of the test substances could be evaluated. Compound table / No. :: Source R1, R2, R3, Shijia 6ppm active ingredient aqueous __. Advantages and benefits of the formulation Table. S2 # 7 OZ 46435 CH3 Gas n-propyl 15. · EP 363 818 ch3 hydrogen N-propyl 40 7 ^ 90 ^ * \ .... 1 1 ”In DH compound No. 156, R ^ CH;; R2 = hydrogen; R3 = isopropyl U: \ TYPE \ EN \ ENG \ 0337G.0OC β -9- Example 4: Effect on Phytophthorainfestans, an aqueous solution made of a preservation solution composed of 10% active ingredient, 63% cyclohexanone and 27% emulsifier Spray > Li "GroBe Fleischtomate" varieties of potted Fanyou seedling leaves. After 24 hours, the leaves were infected with a zoospore suspension of Phytophthora infestans. The plants were placed in a chamber saturated with steam for 6 days. After 6 days, when the disease of the untreated plants has spread to a considerable extent, the fungicidal activity of the test substance can be evaluated. Compound: Table / No. Source R1 Surface: Fiber:% of damage after applying 16ppm active ingredient leech formulations, S2 # 7 OZ 46435 CH3 Airborne propyl 5 ^--EP 407 873 ch3 Airborne propyl Base 55 ~~~----- ~~~-. Principle -----_, 90 I ~ --- UATYPe \ EN \ ENG \ 0337G.DOC 8 * 10- Announcement Supplementary Specification of Patent Application No. 85115212 (January 89) I. Test compounds: ⑻ According to the present case (85115212) no. 7, table S2 (b) according to Wenderoth et al. (EP 363 818) Comparative compound A (similar to Wenderoth no. 156) No. 156 compound having the structure shown below: P: \ PTS \ GAN \ ATYPE \ B \ 45937SUPDOaWCK Comparative Compound B (No. 188 of Wenderoth) II. Experimental content: Comparative Experiment 1: The effect on Botrytis Cinerea is made from a preservation solution composed of 10% active ingredient, 63% cyclohexanone and 27% emulsifier Spray several dishes of green pepper pods into the aqueous solution of Chengzhi f. After spray drying, spray spore suspension of Botrytis cinerea (1.7 x 106 spores per milliliter of fortified biological malt solution) into the dish, and store it at 20 to 24 ° C 'high relative humidity 5 day. The results were evaluated visually. Compound table _ / Νο · Source R1 Damage after application of 500 ppm active ingredient aqueous formulation Table. S2 # 7 85115212 ch3 Gas-n-propyl 40 ~~-·), A EP 363 818 ch3 Hydron-propyl 100 , 3 100 1 in compound EP 363 818 no. 156, R3 = isopropyl P: \ PTS \ GAN \ ATYPE \ B \ 45937SUP.DOCWCK -2- 3 inhibitor 300 Comparative experiment 2 Erysiphe graminis forma The effect of specialis fric (wheat flour mold) is sprayed with an aqueous solution made of a preservation solution composed of 10% active ingredients, 63% cyclohexanone and 27% emulsifier "Fruhgold" potted wheat seedlings Until dripping. Twenty-four hours after the spray layer had dried, plants were sporeed with wheat spores (Triticum aestivum). Plants are placed in a greenhouse at 20 to 22 C and a relative humidity of 75 to 80%. After 7 days, the degree of distribution of powdery mildew was evaluated and expressed as a percentage of total leaf surface damage. Compound table./No. Source R1 R2 R3% damage after application of 250 ppm active ingredient aqueous formulation Table. S2 # 7 85115212 ch3 gas-n-propyl 5-*), A EP 363 818 ch3 hydrogen-n-propyl 40 Untreated 85 1 1 compound in EP 363 818 no. 156, R3 = isopropyl. Comparative experiment 3: The effect on piasmoparaparatica (piasm〇para vitic〇ia) by 10% active ingredient, 63% cyclohexyl An aqueous solution made from a preservation solution consisting of a ketone and a 27% emulsifier spray pot "Muler Thurgan" variety of potted grape leaf β In order to evaluate the period of action 'When the spray layer is dried, the plant is placed in a greenhouse In 8 days. The leaves were then infected with a spore suspension of the genus Plasmopara viticola fungus, which was first placed at 24. 〇Steam-saturated chamber, then at 20-30. (: 5 days in the greenhouse. In order to accelerate and strengthen P: «» TS \ GAN \ ATYPE \ B \ 45937SUP.D0aWCK 393300 spore stalks discharge spores, the plants are placed in a humid chamber for 16 hours. Then in the leaves The extent of fungal attack was assessed on the back. Compound table./No. Where: ': ΐ; Rim damage after applying 63 ppm active ingredient epidermal formulation " I.— 表 _S2 # 7 85115212 ch3 Chloro-propyl 5′-,), A EP 363 818 ch3 hydrogen price n-propyl 40 188, B EP 363 818 cf3 chloro n-propyl 25 t treatment 85 ~ 1 in EP 363 818 no. 156 compound, R3 = isopropyl comparison experiment 4: for tomato The long-term effect of Phytophthora infestans is sprayed with an aqueous solution made of a preservation solution composed of 10% active ingredient, 63% cyclohexanone and 27% emulsifier "GroBeFleischtomate" variety Potted tomato four-leaf stage seedlings. After 7 days, the leaves were infected with a zoospore suspension of Phytophthora infestans. Plants were placed in a steam-saturated chamber for 6 days. After 6 days, the fungicidal activity of the test substance can be evaluated when the disease in the untreated plant has spread to a considerable extent. P: \ PTS \ GAN \ ATYPE \ B \ 45M7SUP.DOC \ WCK -4- 393300 Compound table./No. Source R1 R2% of damage after application of 16 ppm active ingredient aqueous formulation Table. S2 # 7 85115212 ch3 Chlorine -Propyl 15 :), A EP 363 818 ch3 hydrogen n-propyl 40 188, B EP 363 818 cf3 chloro n-propyl 80 hexed 90 in EP 363 818 no. 156 compound, R3 = isopropyl from the above The experimental results can clearly prove that the compound according to the present case (85115212) has excellent progress and improved activity in controlling the effects of undesired fungi. P: \ PTS \ GANUTYPE \ B \ 45937SUPDOC \ WCK 393300 2 1 Patent Application Scope Amendment (February 89) A8 B8 C8 D8 Type I 2- (0-Call Bite-4-Base) Methyleneoxy) phenylacetic acid derivative R2 R1 Namma N R3 〇-CH (I) The Central Government Bureau of the Ministry of Economic Affairs, the Consumers ’Cooperative of India and its N-oxides, where the R1 to R4 groups and Q have the following definitions: R1 is hydrogen or cvcv alkyl; R2 is southin or crc2- Alkyl; R3 is hydrogen, amine, hydroxy, mercapto, halogen, C ^ -Cs-alkyl, and alkynyl can be attached to phenyl, which can be attached to one or two of the following substituents: halogen, cyan Group, nitro, c ^ -cv alkyl, q-cv haloalkyl &CrC4-alkoxy; CrCV alkyl, Ci-Cg-alkoxy-Ci-C4-alkyl, crc8-alkoxy Group, crc8-monoalkylamino, di-Crc8-alkylamino, crc8-alkylthio, crc8-alkylsulfoxide, CrC8-alkylfluorenyl, c3-c8-cycloalkyl'tri-C ^ -Cs -Alkanosilyloxy or the following, unsubstituted or substituted in the aromatic ring: phenyl, phenoxy, phenoxymethyl, fluorenyl- or heteroaryl; r4 hydrogen, cyano, halogen, crc4 -Alkyl, halide or Cj-Cj-carboxy; and Q is C (= NOCH3) _CONHCH3, or C (= NOCH3) -COOCH3. 2. —A composition suitable for controlling harmful fungi ', which contains an effective amount of a compound of formula I according to item 1 of the scope of the patent application, or a salt thereof, or N_oxidized paper, using China National Tree Rate (CNS) A4 Specifications (210 > < 297 public teaching) -------- I order ------- line {please read the note # ^ on the back before filling in this page} 393300 A8 C8 D8, patent application scope and At least one formulation adjuvant. 3. A composition suitable for controlling animal pests, which contains an effective amount of a compound of formula j according to item i of the scope of patent application, or a salt or oxide thereof, and at least one formulation adjuvant. 4. Two methods of preparing a composition according to item 2 of the scope of the patent application, comprising treating the compound of formula I with at least one formulation adjuvant. 5. A method for preparing a composition according to item 3 of the scope of patent application, comprising treating a compound of formula I with at least one formulation adjuvant. 6. A method for controlling harmful fungi, which comprises treating the harmful compound with an effective amount of a compound of formula I or a salt or oxide thereof according to item 1 of the scope of patent application or a composition according to item 2 of the scope of patent application Fungi whose environment is or are free of-plants, seeds, areas, materials or spaces that are harmed by harmful fungi. 7. —A method for controlling animal pests, which includes treating the animal pests with an effective amount of a compound of formula I according to item 1 of the scope of patent application, or a salt or N-oxide thereof, or a composition according to item 2 of the scope of patent application , Plants, seeds, areas, materials or spaces whose environment or is protected from animal pests. 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