WO2008134969A1

WO2008134969A1 - Benzamide compounds and applications thereof

Info

Publication number: WO2008134969A1
Application number: PCT/CN2008/070830
Authority: WO
Inventors: Bin Li; Dong Xiang; Baoshan Chai; Jing Yuan; Huibin Yang; Hong Zhang; Hongfei Wu; Haibo Yu
Original assignee: Shenyang Research Institute of Chemical Industry Co Ltd; Sinochem Corp
Current assignee: Shenyang Research Institute of Chemical Industry Co Ltd; Sinochem Corp
Priority date: 2007-04-30
Filing date: 2008-04-28
Publication date: 2008-11-13
Anticipated expiration: 2009-10-30

Abstract

Novel benzamide compounds and intermediate compounds thereof, as shown by formula I and II respectively, wherein the definition of each substituent see the description. Compounds with formula I has excellent insecticidal and fungicidal activities and can be used to control insect pest and diseases.

Description

苯甲酰胺类化合物及其应用技术领域 Benzoamide compounds and their applications

本发明属于农用杀虫、杀菌剂领域。涉及一种苯甲酰胺类化合物及其应用。背景技术 The invention belongs to the field of agricultural insecticides and fungicides. It relates to a benzamide compound and its use. Background technique

由于杀虫剂、杀菌剂在使用一段时间后，害虫、病菌会对其产生抗性，因此，需要不断发明新型的和改进的具杀虫、杀菌活性的化合物和组合物。 Since insecticides and fungicides are resistant to pests and germicides after a period of use, it is necessary to continuously invent new and improved insecticidal and bactericidal active compounds and compositions.

WO03/015518A1报道了某些苯甲酰胺类化合物具有杀虫活性，在 50 ppm的浓度下对黏虫具有高的防治效果。 WO 03/015518 A1 reports that certain benzamide compounds have insecticidal activity and have a high control effect on armyworms at a concentration of 50 ppm.

在现有技术中，如本发明所示的含烷基腈类苯甲酰胺化合物的制备及其杀虫、杀菌活性未见公开。发明内容 In the prior art, the preparation of the alkylnitrile-containing benzamide compound as shown in the present invention and its insecticidal and bactericidal activity have not been disclosed. Summary of the invention

本发明的目的在于提供一种结构新颖的苯甲酰胺化合物，它可应用于虫害、病害的防治。 SUMMARY OF THE INVENTION An object of the present invention is to provide a novel benzamide compound which can be applied to the control of pests and diseases.

本发明的技术方案如下： The technical solution of the present invention is as follows:

本发明提供了一种苯甲酰胺类化合物，如通式 I所示： The present invention provides a benzamide compound, as shown in Formula I:

式中：

In the formula:

选自 H或 d-C₆烷基； DC ₆ is selected from H or alkyl;

R₂选自 H或 d-C₆烷基； R _{2 is} selected from H or dC ₆ alkyl;

R₃选自 d-C₆烷基或 C₃-C₆环烷基，所述基团上的氢还可以被以下基团进一步取代：卤素、 N0₂、 d-C₃烷氧基、苯氧基、 d-C₃烷硫基、 d-C₃烷基亚磺酰基或 d-C₃ 烷基磺酰基； R _{3 is} selected from dC ₆ alkyl or C ₃ -C ₆ cycloalkyl, and the hydrogen on the group may be further substituted by the following groups: halogen, N0 ₂ , dC ₃ alkoxy, phenoxy, dC _{a 3} -alkylthio group, a dC ₃ alkylsulfinyl group or a dC ₃ alkylsulfonyl group;

或者 R₂和 R₃同所连接的碳一起形成 C₃-C₆环烷基； Or R ₂ and R ₃ together with the attached carbon form a C ₃ -C ₆ cycloalkyl group;

选自 H、卤素或 CN; Selected from H, halogen or CN;

R₅选自卤素或 C C₃烷基； Re选自卤素、 CrC₃烷基、 d-C₃卤烷基、 d-C₃烷氧基或 d-C₃卤烷氧基； R _{5 is} selected from halogen or CC ₃ alkyl; Re is selected from halogen, CrC ₃ alkyl, dC ₃ haloalkyl, dC ₃ alkoxy or dC ₃ haloalkoxy;

R₇选自 H、卤素、 CN、 d-C₃烷基、 d-C₃卤烷基、 d-C₃烷氧基、 d-C₃烷硫基、 Ci-C₃烷基亚磺酰基或 d-C₃烷基磺酰基； R _{7 is} selected from H, halogen, CN, dC ₃ alkyl, dC ₃ haloalkyl, dC ₃ alkoxy, dC ₃ alkylthio, Ci-C ₃ alkylsulfinyl or dC ₃ alkylsulfonyl;

R₈选自卤素、 CN、 d-C₃烷基、 d-C₃卤烷基、 d-C₃烷氧基或 d-C₃烷硫基； X选白 CH、 CF、 CC^ N。 R _{8 is} selected from halogen, CN, dC ₃ alkyl, dC ₃ haloalkyl, dC ₃ alkoxy or dC ₃ alkylthio; X is selected from white CH, CF, CC^N.

本发明中进一步优选的化合物为，通式 I中： Further preferred compounds of the invention are those of formula I:

Ri选自 H; Ri is selected from H;

R₂选自 H或 d-C₃烷基； R _{2 is} selected from H or dC ₃ alkyl;

R₃选自 d-C₃烷基； R _{3 is} selected from dC ₃ alkyl;

选自 H、卤素或 CN; Selected from H, halogen or CN;

R₅选自卤素或 C C₃烷基； R _{5 is} selected from halogen or CC ₃ alkyl;

选自卤素或 C C₃卤烷基； Selected from halogen or CC ₃ haloalkyl;

R₇选自 H、卤素、 CN或 d-C₃卤烷基； R _{7 is} selected from H, halogen, CN or dC ₃ haloalkyl;

R₈选自卤素； R _{8 is} selected from halogen;

X选白 CH、 CF、 CC^ N。 X selects white CH, CF, CC^ N.

本发明中更进一步优选的化合物为，通式 I中： A still further preferred compound in the present invention is, in the formula I:

Ri选自 H; Ri is selected from H;

R₂选自 H或甲基； R _{2 is} selected from H or methyl;

R₃选自甲基； R _{3 is} selected from a methyl group;

选自氯、溴、碘或 CN; Selected from chlorine, bromine, iodine or CN;

R₅选自氯、溴或甲基； R _{5 is} selected from chlorine, bromine or methyl;

选自氯、溴或三氟甲基； Selected from chlorine, bromine or trifluoromethyl;

R₇选自 H、氯或三氟甲基； R _{7 is} selected from H, chlorine or trifluoromethyl;

选自氯； Selected from chlorine;

X选白 CH、 CF、 CC^ N。 X selects white CH, CF, CC^ N.

本发明还包括直接用于制备通式 I化合物的中间体，该中间体此前未见报道，结构如通式 II所示： The invention also includes intermediates which are directly employed in the preparation of compounds of formula I which have not previously been reported and which have the structure shown in formula II:

式中：

In the formula:

选自 H或 d-C₆烷基; R₂选自 H或 d-C₆烷基； Selected from H or dC ₆ alkyl; R _{2 is} selected from H or dC ₆ alkyl;

选自 H、卤素或 CN; Selected from H, halogen or CN;

R₅选自卤素或 C C₃烷基。 R _{5 is} selected from halogen or CC ₃ alkyl.

上面给出的通式 I化合物的定义中，汇集所用术语一般定义如下： In the definitions of the compounds of formula I given above, the terms used in the collection are generally defined as follows:

烷基是指直链或支链形式，例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、特丁基、正戊基、异戊基、正己基等基团。环烷基是指包括环状链形式，例如环丙基、环丁基、环戊基、环己基等基团。卤烷基是指烷基被一个或多个卤原子取代的基团。烷氧基是指烷基末端连有氧原子的基团，例如甲氧基、乙氧基、正丙氧基、异丙氧基、特丁氧基等。卤烷氧基是指烷基被一个或多个卤原子取代，末端连有氧原子的基团。烷硫基是指烷基末端连有硫原子的基团，例如甲硫基、乙硫基等。烷基亚磺酰基指的是烷基末端为（SO-) 的基团，如甲基亚磺酰基。烷基磺酰基指的是烷基末端为（so₂-) 的基团，如甲基磺酰基。卤素是指氟、氯、溴、碘。 Alkyl means straight or branched form, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, A group such as n-hexyl. The cycloalkyl group means a group including a cyclic chain such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or the like. Haloalkyl means a group in which an alkyl group is substituted by one or more halogen atoms. The alkoxy group means a group having an oxygen atom bonded to the terminal of the alkyl group, such as a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a t-butoxy group or the like. A haloalkoxy group means a group in which an alkyl group is substituted by one or more halogen atoms and an oxygen atom is bonded to the terminal. The alkylthio group means a group having a sulfur atom bonded to the terminal of the alkyl group, such as a methylthio group, an ethylthio group or the like. The alkylsulfinyl group refers to a group having an alkyl group terminal (SO-) such as a methylsulfinyl group. Alkylsulfonyl refers to a group having a terminal (so ₂ -) at the alkyl group, such as a methylsulfonyl group. Halogen means fluorine, chlorine, bromine or iodine.

本发明的通式化合物 I可由如下的方法制备，反应式中各基团定义同前。 The compound of the formula I of the present invention can be produced by the following method, wherein each group in the reaction formula is as defined above.

II III II与 III在适宜的溶剂中、温度为 -10°C到沸点下反应 0.5-48小时制得目标化合物 II III II and III are reacted in a suitable solvent at a temperature of from -10 ° C to the boiling point for 0.5 to 48 hours to obtain the target compound.

I。适宜的溶剂选自二氯甲烷、氯仿、四氯化碳、己烷、苯、甲苯、乙酸乙酯、乙腈、 THF、二氧六环、 DMF或二甲基亚砜等。 I. Suitable solvents are selected from the group consisting of dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, THF, dioxane, DMF or dimethyl sulfoxide.

加入适宜的碱类物质对反应有利。适宜的碱选自有机碱如甲醇钠、叔丁醇钠、叔丁醇钾、三乙胺、 N， N-二甲基苯胺或吡啶等，或无机碱如碳酸钠、碳酸钾、碳酸氢钠、氢氧化钠或氢氧化钾等。 The addition of a suitable base material is advantageous for the reaction. Suitable bases are selected from organic bases such as sodium methoxide, sodium t-butoxide, potassium t-butoxide, triethylamine, N,N-dimethylaniline or pyridine, or inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate. , sodium hydroxide or potassium hydroxide.

通式化合物 II的制备方法如下： The preparation method of the general compound II is as follows:

IV II

硝基化合物 IV与还原剂如铁、锌或氢等反应（参见专利 EPA0083055A2中描述的方法），在适宜的溶剂中，温度为 -10°C到沸点下反应 0.5-48小时制得化合物 II。溶剂可选自水、乙酸、丙酮、二氯甲烷、氯仿、四氯化碳、己烷、苯、甲苯、乙酸乙酯、乙醇、 DMF、 THF 或二氧六环；也可以选用由上述两种或三种溶剂组成的混合溶剂为卤原子的化合物 II也可以用为氢的化合物 II与卤化试剂在适宜的溶剂中，温度为 -10°C到沸点下反应 0.5-48小时制得。卤化试剂为卤素、卤代丁二酰亚胺等；溶剂可选自二氯甲烷、氯仿、四氯化碳、 DMF、 THF,二氧六环或二甲基亚砜等。卤素选自碘、溴或氯。 The nitro compound IV is reacted with a reducing agent such as iron, zinc or hydrogen (see the method described in the patent EPA 0 083 055 A2), and a compound II is obtained by reacting in a suitable solvent at a temperature of from -10 ° C to a boiling point for 0.5 to 48 hours. The solvent may be selected from the group consisting of water, acetic acid, acetone, dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, ethanol, DMF, THF or dioxane; The compound II in which the mixed solvent of the three solvents is a halogen atom can also be obtained by reacting the compound II which is hydrogen with a halogenating agent in a suitable solvent at a temperature of -10 ° C to the boiling point for 0.5 to 48 hours. The halogenating agent is halogen, halogenated succinimide or the like; the solvent may be selected from the group consisting of dichloromethane, chloroform, carbon tetrachloride, DMF, THF, dioxane or dimethyl sulfoxide. Halogen is selected from the group consisting of iodine, bromine or chlorine.

为 CN的化合物 II也可以由为卤原子的化合物 II与氰基化试剂在适宜的溶剂中，温度为 -10°C到沸点下反应 0.5-48小时制得。氰基化试剂为氰化钠、氰化钾或氰化亚铜等；溶剂可选自 DMF、 THF, 二氧六环或二甲基亚砜等。卤素选自碘、溴通式化合物 IV的制备方法如下: The compound II which is CN can also be obtained by reacting the compound II which is a halogen atom with a cyanating agent in a suitable solvent at a temperature of from -10 ° C to a boiling point for 0.5 to 48 hours. The cyanation reagent is sodium cyanide, potassium cyanide or cuprous cyanide; the solvent may be selected from the group consisting of DMF, THF, dioxane or dimethyl sulfoxide. Halogen is selected from the group consisting of iodine and bromine. The preparation method of the compound IV is as follows:

V VI IV V VI IV

苯甲酰氯 V (有市售，也可按已知通用的方法制备，参见 March J, Advanced Organic Chemistry, 4^th Ed, John Wiley & sons, 1992)在适宜的溶剂中、与氨基烷基乙腈 VI (有市售，也可自制、制备方法参见 J. Peptide Res. 56, 2000, 283-297)在温度为 -10°C 到沸点下反应 0.5-48小时制得化合物 IV。溶剂可选自氯仿、二氯甲烷、四氯化碳、己烷、苯、甲苯、乙酸乙酯、 DMF、 THF或二氧六环等。加入碱类物质，如三乙胺、吡啶、氢氧化钠、氢氧化钾、碳酸钠、碳酸钾或碳酸氢钠等对反应有利。 Benzoyl chloride V (commercially available, can also be prepared by known general methods, see, March J, Advanced Organic Chemistry, 4 th Ed, John Wiley & sons, 1992) in a suitable solvent, acetonitrile with an aminoalkyl VI (Commercially available, can also be prepared by ourselves, and the preparation method is described in J. Peptide Res. 56, 2000, 283-297). The compound IV is obtained by reacting at a temperature of -10 ° C to the boiling point for 0.5 to 48 hours. The solvent may be selected from the group consisting of chloroform, dichloromethane, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, DMF, THF or dioxane. The addition of a base such as triethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium hydrogencarbonate is advantageous for the reaction.

通式化合物 III (吡唑甲酰氯及其相应的原料羧酸）的制备可以参考 Bioorganic fe Medicinal Chemistry Letters, 2005, 15, 4898-4906中的操作进行。 The preparation of the compound of the formula III (pyrazolyl chloride and its corresponding starting carboxylic acid) can be carried out in accordance with the procedure in Bioorganic fe Medicinal Chemistry Letters, 2005, 15, 4898-4906.

表 1列出了部分通式 I化合物的结构和物理性质。 Table 1 lists the structural and physical properties of some of the compounds of formula I.

表 1 部分通式 I化合物的结构 Table 1 Structure of a part of the compound of formula I

化合物 R₂ R₃ R4 R₅ R« R7 ¾ X 外观（熔点（°c ) )Compound R ₂ R ₃ R4 R ₅ R« R7 3⁄4 X Appearance (melting point (°c ) )

1.1a H CH₃ H CH₃ Br H CI N 白色固体 (146-150)1.1a H CH ₃ H CH ₃ Br H CI N White solid (146-150)

1.1 H CH₃ CI CH₃ Br H CI N 白色固体 (205 -207)1.1 H CH ₃ CI CH ₃ Br H CI N White solid (205 -207)

1.2 H CH₃ CI CH₃ CI H CI N 白色固体 (197-199)1.2 H CH ₃ CI CH ₃ CI H CI N White solid (197-199)

1.3 H CH₃ Br CH₃ CI H CI N 白色固体 (138-140) _{_{1.3 H CH 3 Br CH 3 CI}} H CI N as a white solid (138-140)

1.4 H CH₃ Br CH₃ Br H CI N 白色固体 (208-209) _{_{1.4 H CH 3 Br CH 3 Br}} H CI N as a white solid (208-209)

1.5 H CH₃ I CH₃ CI H CI N 白色固体 (135-137)1.5 H CH ₃ I CH ₃ CI H CI N White solid (135-137)

1.6 H CH₃ CI CI CI H CI N 白色固体 (165-168)1.6 H CH ₃ CI CI CI H CI N White solid (165-168)

1.7 H CH₃ Br CI CI H CI N 白色固体 (167-170)1.7 H CH ₃ Br CI CI H CI N White solid (167-170)

1.8 H CH₃ I CI CI H CI N 白色固体 (168-173)1.8 H CH ₃ I CI CI H CI N White solid (168-173)

1.9 H CH₃ CI CI Br H CI N 白色固体 (153-156)1.9 H CH ₃ CI CI Br H CI N White solid (153-156)

1.10 H CH₃ Br CI Br H CI N 白色固体 (153-157) _{1.10 H CH 3 Br CI Br H} CI N as a white solid (153-157)

1.11 H CH₃ I CI Br H CI N 白色固体 (154-158)1.11 H CH ₃ I CI Br H CI N White solid (154-158)

1.12 H CH₃ CN CI Br H CI N 1.12 H CH ₃ CN CI Br H CI N

1.13 H CH₃ CN CH₃ Br H CI N 白色固体 (210-213)1.13 H CH ₃ CN CH ₃ Br H CI N White solid (210-213)

1.14a CH₃ CH₃ H CH₃ Br H CI N 白色固体 (248-253)1.14a CH ₃ CH ₃ H CH ₃ Br H CI N White solid (248-253)

1.14 CH₃ CH₃ CI CH₃ Br H CI N 白色固体 (191-194)1.14 CH ₃ CH ₃ CI CH ₃ Br H CI N White solid (191-194)

1.15 CH₃ CH₃ CI CH₃ CI H CI N 白色固体 (213-216)1.15 CH ₃ CH ₃ CI CH ₃ CI H CI N White solid (213-216)

1.16 CH₃ CH₃ Br CH₃ Br H CI N 白色固体 (175-177)1.16 CH ₃ CH ₃ Br CH ₃ Br H CI N White solid (175-177)

1.17 CH₃ CH₃ CI CI CI H CI N 白色固体 (149-151)1.17 CH ₃ CH ₃ CI CI CI H CI N White solid (149-151)

1.18 CH₃ CH₃ CI CI Br H CI N 白色固体 (254-256)1.18 CH ₃ CH ₃ CI CI Br H CI N White solid (254-256)

1.19 CH₃ CH₃ CI CH₃ CI H CI CH 白色固体 (252-254)1.19 CH ₃ CH ₃ CI CH ₃ CI H CI CH White solid (252-254)

1.20 CH₃ CH₃ Br CH₃ CI H CI CH 白色固体 (248-250)1.20 CH ₃ CH ₃ Br CH ₃ CI H CI CH White solid (248-250)

1.21 CH₃ CH₃ Br Br CI H CI CH 白色固体 (177- 180)1.21 CH ₃ CH ₃ Br Br CI H CI CH White solid (177- 180)

1.22 CH₃ CH₃ CN CI Br H CI N 1.22 CH ₃ CH ₃ CN CI Br H CI N

1.23 CH₃ CH₃ CN CH₃ Br H CI N 白色固体 (140-142)1.23 CH ₃ CH ₃ CN CH ₃ Br H CI N White solid (140-142)

1.24 CH₃ CH₃ CI CI CF₃ H CI CH 白色固体 (246-248) -C₃H₇ CH₃ H CH₃ Br H CI N 白色固体 (186-188) -C₃H₇ CH₃ CI CH₃ Br H CI N 白色固体 (204-208) -C₃H₇ CH₃ CI CH₃ CI H CI N 油1.24 CH ₃ CH ₃ CI CI CF ₃ H CI CH White solid (246-248) -C ₃ H ₇ CH ₃ H CH ₃ Br H CI N White solid (186-188) -C ₃ H ₇ CH ₃ CI CH ₃ Br H CI N White solid (204-208) -C ₃ H ₇ CH ₃ CI CH ₃ CI H CI N oil

-C₃H₇ CH₃ CI CH₃ Br H CI CH 白色固体 (120-125) H2 CH2 CH2 CH2 CI CH₃ CI H CI N 白色固体 (165-167) H2 CH2 CH2 CH2 CI CH₃ Br H CI N 白色固体 (252-256) H2 CH2 CH2 CH2 CH2 CI CH₃ CI H CI N 白色固体 (226-228) H2 CH2 CH2 CH2 CH2 CI CH₃ Br H CI N 白色固体 (225-227) 部分通式 II化合物的结构 -C ₃ H ₇ CH ₃ CI CH ₃ Br H CI CH White solid (120-125) H2 CH2 CH2 CH2 CI CH ₃ CI H CI N White solid (165-167) H2 CH2 CH2 CH2 CI CH ₃ Br H CI N White solid (252-256) H2 CH2 CH2 CH2 CH2 CI CH ₃ CI H CI N White solid (226-228) H2 CH2 CH2 CH2 CH2 CI CH ₃ Br H CI N White solid (225-227) Partially compound of formula II Structure

化合物 R3 R4 R₅ 外观 (熔点（°c ) )

Compound R3 R4 R ₅ appearance (melting point (°c ) )

2.1 H CH₃ H CH₃ 白色固体 (105-106)2.1 H CH ₃ H CH ₃ white solid (105-106)

2.2 H CH₃ CI CH₃ 白色固体 (139-140)2.2 H CH _₃ CI CH ₃ as a white solid (139-140)

2.3 H CH₃ Br CH₃ 蜡状物 2.3 H CH ₃ Br CH ₃ wax

2.4 H CH₃ I CH₃ 蜡状物 2.4 H CH _₃ I CH ₃ wax

2.5 H CH₃ H CI 2.5 H CH ₃ H CI

2.6 H CH₃ CI CI 2.6 H CH ₃ CI CI

2.7 H CH₃ Br CI 2.7 H CH ₃ Br CI

2.8 H CH₃ I CI 2.8 H CH ₃ I CI

2.9 H CH₃ CN CI 2.9 H CH ₃ CN CI

2.10 H CH₃ CN CH₃ 2.10 H CH _₃ CN CH ₃

2.11 CH₃ CH₃ H CH₃ 白色固体 (173-174)2.11 CH ₃ CH ₃ H CH ₃ white solid (173-174)

2.12 CH₃ CH₃ CI CH₃ 白色固体 (199-201)2.12 CH ₃ CH ₃ CI CH ₃ white solid (199-201)

2.13 CH₃ CH₃ Br CH₃ 2.13 CH ₃ CH ₃ Br CH ₃

2.14 CH₃ CH₃ I CH₃ 蜡状物 2.14 CH ₃ CH ₃ I CH ₃ wax

2.15 CH₃ CH₃ CN CI 2.15 CH ₃ CH ₃ CN CI

2.16 CH₃ CH₃ CN CH₃ 2.16 CH ₃ CH ₃ CN CH ₃

2.17 i-C₃H₇ CH₃ H CH₃ 蜡状物 2.17 iC ₃ H ₇ CH ₃ H CH ₃ wax

2.18 i-C₃H₇ CH₃ CI CH₃ 白色固体 (125-127) 2.19 i-C₃H₇ CH₃ H H 白色固体 (129-130) 2.18 iC ₃ H ₇ CH ₃ CI CH ₃ white solid (125-127) 2.19 iC ₃ H ₇ CH ₃ HH white solid (129-130)

2.20 i-C₃H₇ CH₃ CI CI 2.20 iC ₃ H ₇ CH ₃ CI CI

2.21 CH2 CH2CH2CH2 H CH₃ 白色固体 (142-143)2.21 CH2 CH2CH2CH2 H CH ₃ white solid (142-143)

2.22 CH2 CH2CH2CH2 CI CH₃ 蜡状物 2.22 CH2 CH2CH2CH2 CI CH ₃ wax

2.23 CH2 CH2CH2CH2CH2 H CH₃ 白色固体 (136-138)2.23 CH2 CH2CH2CH2CH2 H CH ₃ white solid (136-138)

2.24 CH2 CH2CH2CH2CH2 CI CH₃ 白色固体 (131-133) 部分化合物的 1H MR(300MHz, CDC1₃)数据如下： 2.24 CH2 CH2CH2CH2CH2 CI CH ₃ White solid (131-133) The 1H MR (300MHz, CDC1 ₃ ) data for some compounds are as follows:

化合物 1.1a: 9.855 (s, IH), 8.476-8.454 (q, IH), 7.879-7.847 (q, IH), 7.407-7.316 (m, 3H), 7.243-7.169 (m, IH), 7.036 (s, IH), 7.626-7.635 (d, IH), 4.973-4.924 (m, IH), 2.205 (s, 3H), 1.576-1.552 (d, 3H)。 Compound 1.1a: 9.855 (s, IH), 8.476-8.454 (q, IH), 7.879-7.847 (q, IH), 7.407-7.316 (m, 3H), 7.243-7.169 (m, IH), 7.036 (s , IH), 7.626-7.635 (d, IH), 4.973-4.924 (m, IH), 2.205 (s, 3H), 1.576-1.552 (d, 3H).

化合物 1.1： 9.663 (s, IH), 8.463-8.443 (d, IH), 7.878-7.845 (d, IH), 7.402-7.359 (m, IH), 7.280-7.241 (m, 2H), 7.070 (s, IH), 6.716-6.692 (d, IH), 4.958-4.908 (m, IH), 2.175 (s, 3H), 1.589-1.564 (d, 3H)。 Compound 1.1: 9.663 (s, IH), 8.463-8.443 (d, IH), 7.878-7.845 (d, IH), 7.402-7.359 (m, IH), 7.280-7.241 (m, 2H), 7.070 (s, IH), 6.716-6.692 (d, IH), 4.958-4.908 (m, IH), 2.175 (s, 3H), 1.589-1.564 (d, 3H).

化合物 1.2： 9.654 (s, IH), 8.470-8.448 (d, IH), 7.884-7.853 (d, IH), 7.410-7.368 (m, IH), 7.275-7.252 (m, 2H), 6.973 (s, IH), 6.584-6.558 (d, IH), 4.986-4.937 (m, IH), 2.195 (s, 3H), 1.603-1.593 (d, 3H)。 Compound 1.2: 9.654 (s, IH), 8.470-8.448 (d, IH), 7.884-7.853 (d, IH), 7.410-7.368 (m, IH), 7.275-7.252 (m, 2H), 6.973 (s, IH), 6.584-6.558 (d, IH), 4.986-4.937 (m, IH), 2.195 (s, 3H), 1.603-1.593 (d, 3H).

化合物 1.3： 9.627 (s, IH), 8.445-8.424 (d, IH), 7.870-7.837 (d, IH), 7.408-7.343 (m, 3H), 6.992 (s, IH), 6.830-6.804 (d, IH), 4.919-4.871 (m, IH), 2.151 (s, 3H), 1.556-1.532 (d, 3H)。 Compound 1.3: 9.627 (s, IH), 8.445-8.424 (d, IH), 7.870-7.837 (d, IH), 7.408-7.343 (m, 3H), 6.992 (s, IH), 6.830-6.804 (d, IH), 4.919-4.871 (m, IH), 2.151 (s, 3H), 1.556-1.532 (d, 3H).

化合物 1.4： 9.613 (s, IH), 8.450-8.428 (d, IH), 7.870-7.832(d, IH), 7.413-7.345 (m, Compound 1.4: 9.613 (s, IH), 8.450-8.428 (d, IH), 7.870-7.832 (d, IH), 7.413-7.345 (m,

3H), 7.069 (s, IH), 6.755-6.731 (d, IH), 4.929-4.880 (m, IH), 2.157 (s, 3H), 1.564-1.532 (d, 3H)。 3H), 7.069 (s, IH), 6.755-6.731 (d, IH), 4.929-4.880 (m, IH), 2.157 (s, 3H), 1.564-1.532 (d, 3H).

化合物 1.5： 9.632 (s, IH), 8.463-8.441 (d, IH), 7.878-7.847(d, IH), 7.696-7.597 (m, 2H), 7.402-7.359(m, IH), 6.948 (s, IH), 6.443 (s, IH), 4.996-4.945 (m, IH), 2.174 (s, 3H), 1.633-1.581 (d, 3H)₀ Compound 1.5: 9.632 (s, IH), 8.463-8.441 (d, IH), 7.878-7.847 (d, IH), 7.696-7.597 (m, 2H), 7.402-7.359 (m, IH), 6.948 (s, IH), 6.443 (s, IH), 4.996-4.945 (m, IH), 2.174 (s, 3H), 1.633-1.581 (d, 3H) ₀

化合物 1.6: 8.856 (s, IH), 8.483-8.461 (d, IH), 7.958-7.927(d, IH), 7.548-7.541 (m, IH), 7.390-7.382(m, 2H), 6.971 (s, IH), 6.485-6.443 (d, IH), 4.956-4.905 (m, IH), 1.560 (s, 3H)。 Compound 1.6: 8.856 (s, IH), 8.483-8.461 (d, IH), 7.958-7.927 (d, IH), 7.548-7.541 (m, IH), 7.390-7.382 (m, 2H), 6.971 (s, IH), 6.485-6.443 (d, IH), 4.956-4.905 (m, IH), 1.560 (s, 3H).

化合物 1.7： 8.867 (s, IH), 8.467-8.458 (d, IH), 7.928-7.907(d, IH), 7.688-7.675 (m, IH), 7.527-7.520(m, IH), 7.428-7.400 (m, IH), 6.971 (s, IH), 6.483-6.254(m, IH), 4.965-4.896 (m, IH), 1.556 (s, 3H)。 Compound 1.7: 8.867 (s, IH), 8.467-8.458 (d, IH), 7.928-7.907 (d, IH), 7.688-7.675 (m, IH), 7.527-7.520 (m, IH), 7.428-7.400 ( m, IH), 6.971 (s, IH), 6.483-6.254 (m, IH), 4.965-4.896 (m, IH), 1.556 (s, 3H).

化合物 1.8： 8.957 (s, IH), 8.453-8.448 (d, IH), 7.904-7.871(d, IH), 7.832 (s, IH), 7.663 (s,lH), 7.415-7.396 (m, IH), 6.992 (s, IH), 6.455 (s, IH), 4.955-4.932 (m, IH), 1.563 (s, 3H)。 Compound 1.8: 8.957 (s, IH), 8.453-8.448 (d, IH), 7.904-7.871 (d, IH), 7.832 (s, IH), 7.663 (s, lH), 7.415-7.396 (m, IH) , 6.992 (s, IH), 6.455 (s, IH), 4.955-4.932 (m, IH), 1.563 (s, 3H).

化合物 1.9： 8.875 (s, IH), 8.465-8.318 (d, IH), 7.923-7.895 (m, IH), 7.556 (s, IH), 7.394-7.376 (m, 2H), 7.056 (s, IH), 6.523 (s, IH), 4.958-4.939 (m, IH), 1.571 (s, 3H)。 Compound 1.9: 8.875 (s, IH), 8.465-8.318 (d, IH), 7.923-7.895 (m, IH), 7.556 (s, IH), 7.394-7.376 (m, 2H), 7.056 (s, IH) , 6.523 (s, IH), 4.958-4.939 (m, IH), 1.571 (s, 3H).

化合物 1.10： 9.141 (s, IH), 8.450-8.434 (d, IH), 7.881-7.855 (d, IH), 7.543-7.536 (d IH), 7.420-7.353 (m, 2H), 7.119 (s, IH), 6.817-6.791 (d, IH), 4.885-4.837 (m, IH), 1.510-1.487 (d, 3H)。 Compound 1.10: 9.141 (s, IH), 8.450-8.434 (d, IH), 7.881-7.855 (d, IH), 7.543-7.536 (d IH), 7.420-7.353 (m, 2H), 7.119 (s, IH) ), 6.817-6.791 (d, IH), 4.885-4.837 (m, IH), 1.510-1.487 (d, 3H).

化合物 1.11 : 8.978 (s, IH), 8.489-8.464 (d, IH), 7.923-7.845 (m, 2H), 7.673 (s, IH), 7.425-7.386 (m, IH), 7.069 (s, IH), 6.493 (s, IH), 4.956-4.913 (m, IH), 1.569-1.548 (d, 3H) o Compound 1.11: 8.978 (s, IH), 8.489-8.464 (d, IH), 7.923-7.845 (m, 2H), 7.673 (s, IH), 7.425-7.386 (m, IH), 7.069 (s, IH) , 6.493 (s, IH), 4.956-4.913 (m, IH), 1.569-1.548 (d, 3H) o

化合物 1.13： 10.346 (s, IH), 8.556-8.452 (d, IH), 7.866-7.834 (m, IH), 7.749-7.746 Compound 1.13: 10.346 (s, IH), 8.556-8.452 (d, IH), 7.866-7.834 (m, IH), 7.749-7.746

(m, IH), 7.636 (m, IH), 7.407-7.380 (m, IH), 7.267 (br, IH), 7.047 (s, IH), 4.970 (m, IH), 2.262 (s, 3H), 1.627-1.614 (d, 3H)。 (m, IH), 7.636 (m, IH), 7.407-7.380 (m, IH), 7.267 (br, IH), 7.047 (s, IH), 4.970 (m, IH), 2.262 (s, 3H), 1.627-1.614 (d, 3H).

化合物 1.14a: 9.876 (s, IH), 8.459-8.445 (d, IH), 7.863-7.837 (d, IH), 7.397-7.371 (m, 3H), 7.267-7.230 (m, IH), 7.155 (s, IH), 6.427 (s, IH), 2.206 (s, 3H), 1.620 (s, 6H)。 Compound 1.14a: 9.876 (s, IH), 8.459-8.445 (d, IH), 7.863-7.837 (d, IH), 7.397-7.371 (m, 3H), 7.267-7.230 (m, IH), 7.155 (s , IH), 6.427 (s, IH), 2.206 (s, 3H), 1.620 (s, 6H).

化合物 1.14: 9.699 (s, IH), 8.435-8.414 (d, IH), 7.860-7.829 (d, IH), 7.387-7.345 (m, Compound 1.14: 9.699 (s, IH), 8.435-8.414 (d, IH), 7.860-7.829 (d, IH), 7.387-7.345 (m,

2H), 7.311 (s, IH), 7.192-7.139 (m, IH), 6.591 (s, IH), 2.161 (s, 3H), 1.675 (s, 6H)。 2H), 7.311 (s, IH), 7.192-7.139 (m, IH), 6.591 (s, IH), 2.161 (s, 3H), 1.675 (s, 6H).

化合物 1.15: 9.666 (s, IH), 8.436-8.421 (d, IH), 7.866-7.833 (d, IH), 7.392-7.349 (m, IH), 7.256-7.164 (m, 3H), 6.438 (s, IH), 2.171 (s, 3H), 1.680 (s, 6H)。 Compound 1.15: 9.666 (s, IH), 8.436-8.421 (d, IH), 7.866-7.833 (d, IH), 7.392-7.349 (m, IH), 7.256-7.164 (m, 3H), 6.438 (s, IH), 2.171 (s, 3H), 1.680 (s, 6H).

化合物 1.16: 9.722 (s, IH), 8.428-8.407 (d, IH), 7.855-7.822 (d, IH), 7.379-7.324 (m, 3H), 7.264 (s, IH), 6.651 (s, IH), 2.130 (s, 3H), 1.649 (s, 6H)。 Compound 1.16: 9.722 (s, IH), 8.428-8.407 (d, IH), 7.855-7.822 (d, IH), 7.379-7.324 (m, 3H), 7.264 (s, IH), 6.651 (s, IH) , 2.130 (s, 3H), 1.649 (s, 6H).

化合物 1.17(CDC1+DMS0): 10.152 (s, IH), 8.375-8.355 (d, IH), 8.210 (s, IH), 7.799-7.767 (d, IH), 7.451-7.409 (m, IH), 7.346-7.304 (m, 2H), 7.217 (s, IH), 1.550 (s, 6H)。 Compound 1.17 (CDC1 + DMS0): 10.152 (s, IH), 8.375-8.355 (d, IH), 8.210 (s, IH), 7.799-7.767 (d, IH), 7.451-7.409 (m, IH), 7.346 -7.304 (m, 2H), 7.217 (s, IH), 1.550 (s, 6H).

化合物 1.18: 9.469 (s, IH), 8.512-8.493 (d, IH), 7.938-7.906 (d, IH), 7.434-7.370 (m, 2H), 7.034-7.297 (d, IH), 7.239-7.232 (d, IH), 7.214 (s, IH), 1.735 (s, 6H)。 Compound 1.18: 9.469 (s, IH), 8.512-8.493 (d, IH), 7.938-7.906 (d, IH), 7.434-7.370 (m, 2H), 7.034-7.297 (d, IH), 7.239-7.232 ( d, IH), 7.214 (s, IH), 1.735 (s, 6H).

化合物 1.19: 9.424 (s, IH), 7.517-7.486 (m, IH), 7.425-7.326 (m, 3H), 7.109-7.101 (d 2H), 7.040 (s, IH), 6.713 (s, IH), 2.051 (s, 3H), 1.678 (s, 6H)。 Compound 1.19: 9.424 (s, IH), 7.517-7.486 (m, IH), 7.425-7.326 (m, 3H), 7.109-7.101 (d 2H), 7.040 (s, IH), 6.713 (s, IH), 2.051 (s, 3H), 1.678 (s, 6H).

化合物 1.20： 9.459 (s, IH), 7.519-7.487 (m, IH), 7.435-7.273 (m, 5H), 7.051 (s, IH), 6.602 (s, IH), 2.083 (s, 3H), 1.688 (s, 6H)。 Compound 1.20: 9.459 (s, IH), 7.519-7.487 (m, IH), 7.435-7.273 (m, 5H), 7.051 (s, IH), 6.602 (s, IH), 2.083 (s, 3H), 1.688 (s, 6H).

化合物 1.21： 9.011 (s, IH), 7.528-7.497 (m, IH), 7.388-7.271 (m, 5H), 7.167 (s, IH), Compound 1.21: 9.011 (s, IH), 7.528-7.497 (m, IH), 7.388-7.271 (m, 5H), 7.167 (s, IH),

7.025 (s, IH), 2.175 (s, 3H), 1.621 (s, 6H)。 7.025 (s, IH), 2.175 (s, 3H), 1.621 (s, 6H).

化合物 1.24： 8.415 (br s, IH), 8.234 (d, IH), 7.915 (d, IH), 7.518-7.310 (m, 5H), 7.310 (br s, IH), 1.646 (s, 6H)。 Compound 1.24: 8.415 (br s, IH), 8.234 (d, IH), 7.915 (d, IH), 7.518-7.310 (m, 5H), 7.310 (br s, IH), 1.646 (s, 6H).

化合物 1.25a: 8.497-8.476 (q, IH), 8.173-8.141 (q, IH), 7.621-7.579 (q, IH), 7. 405-7.390 (m, 3H), 7.281 (s, IH), 2.192-2.094 (m, 4H), 1.402 (s, 3H), 1.027-1.004 (d, 3H), 0.884-0.863 (d, 3H)。 Compound 1.25a: 8.497-8.476 (q, IH), 8.173-8.141 (q, IH), 7.621-7.579 (q, IH), 7. 405-7.390 (m, 3H), 7.281 (s, IH), 2.192 -2.094 (m, 4H), 1.402 (s, 3H), 1.027-1.004 (d, 3H), 0.884-0.863 (d, 3H).

化合物 1.25: 8.494-8.482 (d, IH), 8.175-8.149 (d, IH), 7.627-7.585 (m, IH), 7.528 (s, IH), 7.392 (s, IH), 7.316 (s, IH), 2.260-2.193 (m, 4H), 1.410 (s, 3H), 1.024-1.002 (d, 3H), 0.877-0.858 (d, 3H)。 Compound 1.25: 8.494-8.482 (d, IH), 8.175-8.149 (d, IH), 7.627-7.585 (m, IH), 7.528 (s, IH), 7.392 (s, IH), 7.316 (s, IH) , 2.260-2.193 (m, 4H), 1.410 (s, 3H), 1.024-1.002 (d, 3H), 0.877-0.858 (d, 3H).

化合物 1.26: 9.784 (s, IH), 8.441-8.421 (q, IH), 7.862-7.831 (q, IH), 7.404-7.353 (m, Compound 1.26: 9.784 (s, IH), 8.441-8.421 (q, IH), 7.862-7.831 (q, IH), 7.404-7.353 (m,

3H), 7.216 (s, IH), 6.396 (s, IH), 2.271-2.188 (m, IH), 2.166 (s, 3H), 1.562 (s, 3H), 1.110-1.087 (d, 3H), 1.019-0.996 (d, 3H)。 3H), 7.216 (s, IH), 6.396 (s, IH), 2.271-2.188 (m, IH), 2.166 (s, 3H), 1.562 (s, 3H), 1.110-1.087 (d, 3H), 1.019 -0.996 (d, 3H).

化合物 1.27： 9.555 (s, IH), 7.501-7.350 (m, 4H), 7.282-7.274 (m, IH), 7.230-7.222 (d IH), 7.178 (s, IH), 7.150-7.142 (d, IH), 2.148-2.109 (m, 4H), 1.601 (s, 3H), 1.150-1.128 (d, 3H), 1.048-1.027 (d, 3H)。 Compound 1.27: 9.555 (s, IH), 7.501-7.350 (m, 4H), 7.282-7.274 (m, IH), 7.230-7.222 (d IH), 7.178 (s, IH), 7.150-7.142 (d, IH ), 2.148-2.109 (m, 4H), 1.601 (s, 3H), 1.150-1.128 (d, 3H), 1.048-1.027 (d, 3H).

化合物 1.28： 9.688 (s, IH), 8.446-8.425 (m, IH), 7.865-7.832 (m, IH), 7.389-7.346 (m, IH), 7.234-7.228 (m, IH), 7.181-7.163 (m, 2H), 6.541 (s, IH), 2.458-2.414 (m, 2H), 2.169 (s, 3H), 2.045-1.977 (m, 2H), 1.878-1.748 (m, 4H)。 Compound 1.28: 9.688 (s, IH), 8.446-8.425 (m, IH), 7.865-7.832 (m, IH), 7.389-7.346 (m, IH), 7.234-7.228 (m, IH), 7.181-7.163 ( m, 2H), 6.541 (s, IH), 2.458-2.414 (m, 2H), 2.169 (s, 3H), 2.045-1.977 (m, 2H), 1.878-1.748 (m, 4H).

化合物 1.29 (DMSO)： 10.209 (s, IH), 8.615 (s, IH), 8.454-8.434 (m, IH), 7.927-7.895 (m, IH), 7.667 (s, IH), 7.478-7.436 (m, IH), 7.386-7.378 (d, IH), 7.320 (s, IH), 2.310-2.102 (m, 7H), 1.816-1.719 (m, 4H)。 Compound 1.29 (DMSO): 10.209 (s, IH), 8.615 (s, IH), 8.454-8.434 (m, IH), 7.927-7.895 (m, IH), 7.667 (s, IH), 7.478-7.436 (m , IH), 7.386-7.378 (d, IH), 7.320 (s, IH), 2.310-2.102 (m, 7H), 1.816-1.719 (m, 4H).

化合物 1.30: 9.725 (s, IH), 8.435-8.420 (d, IH), 7.863-7.831 (m, IH), 7.389-7.346 (m: IH), 7.260-7.150 (m, 3H), 6.471 (s, IH), 2.400-2.318 (m, 2H), 2.164 (s, 3H), 1.706-1.452 (m, 8H)。 Compound 1.30: 9.725 (s, IH), 8.435-8.420 (d, IH), 7.863-7.831 (m, IH), 7.389-7.346 (m: IH), 7.260-7.150 (m, 3H), 6.471 (s, IH), 2.400-2.318 (m, 2H), 2.164 (s, 3H), 1.706-1.452 (m, 8H).

化合物 1.31 : 9.692 (s, IH), 8.446-8.432 (d, IH), 7.865-7.834 (m, IH), 7.394-7.351 (m: Compound 1.31 : 9.692 (s, IH), 8.446-8.432 (d, IH), 7.865-7.834 (m, IH), 7.394-7.351 (m:

IH), 7.260-7.250 (m, 2H), 7.184 (s, IH), 6.326 (s, IH), 2.401-2.356 (m, 2H), 2.170 (s, 3H)_: 1.725-1.564 (m, 8H)。 IH), 7.260-7.250 (m, 2H), 7.184 (s, IH), 6.326 (s, IH), 2.401-2.356 (m, 2H), 2.170 (s, 3H) _: 1.725-1.564 (m, 8H) .

化合物 2.3： 7.327-7.319 (d, IH), 7.275-7.271 (d, IH), 6.251-6.227 (d, IH), 5.049-4.999 (m, IH), 2.148 (s, 3H), 1.685-1.660 (m, 3H)。 Compound 2.3: 7.327-7.319 (d, IH), 7.275-7.271 (d, IH), 6.251-6.227 (d, IH), 5.049-4.999 (m, IH), 2.148 (s, 3H), 1.685-1.660 ( m, 3H).

化合物 2.4： 7.483-7.476 (d, IH), 7.431-7.426 (d, IH), 6.231-6.214 (d, IH), Compound 2.4: 7.483-7.476 (d, IH), 7.431-7.426 (d, IH), 6.231-6.214 (d, IH),

5.048-4.999 (m, IH), 2.125 (s, 3H), 1.685-1.651 (m, 3H)。 5.048-4.999 (m, IH), 2.125 (s, 3H), 1.685-1.651 (m, 3H).

化合物 2.14： 7.429-7.423 (d, IH), 7.381-7.379 (d, IH), 6.145 (s, IH), 2.097 (s, 3H), 1.809 (s, 6H)。 Compound 2.14: 7.429-7.423 (d, IH), 7.381-7.379 (d, IH), 6.145 (s, IH), 2.097 (s, 3H), 1.809 (s, 6H).

化合物 2.22: 7.132-7.126 (d, IH), 7.028 (d, IH), 6.492 (s, IH), 5.389 (s, 2H), 2.499-2.434 (m, 2H), 2.222-2.144 (m, 2H), 1.907-1.876 (m,4H)。 Compound 2.22: 7.132-7.126 (d, IH), 7.028 (d, IH), 6.492 (s, IH), 5.389 (s, 2H), 2.499-2.434 (m, 2H), 2.222-2.144 (m, 2H) , 1.907-1.876 (m, 4H).

在有机分子中，用甲基或其它烷基取代氢原子后，可以提高有机分子的脂溶性。分子的脂溶性与分子在昆虫、植物等生物体内的输导性密切相关。生物活性分子合适的输导性能对药效的发挥起着重要的作用。生物活性分子输导性能的合适性是不可预知的，而是需要大量的创造性劳动才能获知的。 In the organic molecule, after the hydrogen atom is replaced by a methyl group or another alkyl group, the fat solubility of the organic molecule can be improved. The fat solubility of molecules is closely related to the transport of molecules in organisms such as insects and plants. The appropriate transport properties of biologically active molecules play an important role in the efficacy of the drug. The suitability of bioactive molecular transport properties is unpredictable, but requires a large amount of creative labor to be known.

现已发现，同已知的苯甲酰胺基乙腈类化合物相比，本发明通式 I所示的苯甲酰胺基烷基乙腈类化合物具有意想不到的高杀虫活性，同时具有高的杀菌活性。因此，本发明还包括通式 I化合物用于控制虫害、病害的用途。 It has now been found that the benzoyl group of the formula I of the present invention is compared to the known benzamidoacetonitrile compounds. Aminoalkyl acetonitrile compounds have unexpectedly high insecticidal activity while having high bactericidal activity. Accordingly, the present invention also encompasses the use of a compound of formula I for controlling pests and diseases.

本发明还包括以通式 I化合物作为活性组分的杀虫、杀菌组合物。该杀虫、杀菌组合物中活性组分的重量百分含量在 1-99%之间。该杀虫、杀菌组合物中还包括农业、林业、卫生上可接受的载体。 The present invention also encompasses insecticidal and bactericidal compositions having a compound of formula I as an active ingredient. The weight percent of active ingredient in the insecticidal, bactericidal composition is between 1 and 99%. The insecticidal and bactericidal compositions also include agricultural, forestry, and hygienic acceptable carriers.

本发明的组合物可以制剂的形式施用。通式 I化合物作为活性组分溶解或分散于载体中或配制成制剂以便作为杀虫或杀菌剂使用时更易于分散。例如：这些化学制剂可被制成可湿性粉剂或乳油。在这些组合物中，至少加入一种液体或固体载体，并且当需要时可以加入适当的表面活性剂。 The compositions of the invention may be administered in the form of a formulation. The compound of the formula I is dissolved or dispersed in the carrier as an active ingredient or formulated into a formulation for easier dispersion when used as an insecticide or bactericide. For example: These chemicals can be formulated as wettable powders or creams. In these compositions, at least one liquid or solid carrier is added, and a suitable surfactant may be added as needed.

本发明的技术方案还包括防治虫害的方法：将本发明的杀虫组合物施于所述的害虫或其生长介质上。通常选择的较为适宜有效量为每公顷 10克到 1000克，优选有效量为每公顷 20克到 500克。 The technical solution of the present invention also includes a method of controlling pests by applying the pesticidal composition of the present invention to the pest or the growth medium thereof. A more suitable effective amount is usually selected from 10 grams to 1000 grams per hectare, preferably from 20 grams to 500 grams per hectare.

本发明的技术方案还包括防治病害的方法：将本发明的杀菌组合物施于所述的病害或其生长介质上。通常选择的较为适宜有效量为每公顷 100克到 2000克，优选有效量为每公顷 200克到 1000克。 The technical solution of the present invention also includes a method of controlling a disease by applying the bactericidal composition of the present invention to the disease or its growth medium. A more suitable effective amount is usually selected from 100 grams to 2000 grams per hectare, preferably from 200 grams to 1000 grams per hectare.

对于某些应用，例如在农业上可在本发明的杀虫、杀菌组合物中加入一种或多种其它的杀菌剂、杀虫剂、除草剂、植物生长调节剂或肥料等，由此可产生附加的优点和效果。 For certain applications, for example, one or more other fungicides, insecticides, herbicides, plant growth regulators or fertilizers may be added to the pesticidal and bactericidal compositions of the invention, for example, in agriculture. Produces additional advantages and effects.

应明确的是，在本发明的权利要求所限定的范围内，可进行各种变换和改动。具体实施方式 It is to be understood that various changes and modifications may be made within the scope of the appended claims. detailed description

下列合成实例、生测试验结果可用来进一步说明本发明，但不意味着限制本发明。合成实例 The following synthetic examples, bioassay results can be used to further illustrate the invention, but are not meant to limit the invention. Synthesis example

实例 1、化合物 1.2的制备 Example 1. Preparation of Compound 1.2

( 1 )、 2-氨基丙腈的合成

(1) Synthesis of 2-aminopropionitrile

在 500毫升的反应瓶中加入氰化钠（4.95克， 100毫摩尔）和氨水（60 毫升），常温搅拌至氰化钠完全溶解，加入乙醛（11.00克， 100毫摩尔）和氯化铵（5.38克， 100毫摩尔），常温反应 48小时，用二氯甲烷萃取三次（依次 50毫升、 10毫升、 10 毫升）反应液，合并有机相，用无水硫酸镁干燥，减压脱溶，得 2.57克浅绿色油，收率： 32%。 Add sodium cyanide (4.95 g, 100 mmol) and ammonia water (60 ml) to a 500 ml reaction flask, stir at room temperature until the sodium cyanide is completely dissolved, and add acetaldehyde (11.00 g, 100 mmol) and ammonium chloride. (5.38 g, 100 mmol), reacted at room temperature for 48 hours, extracted three times with dichloromethane (50 ml, 10 ml, 10 ml), and the organic phases were combined, dried over anhydrous magnesium sulfate Obtained 2.57 g of light green oil, yield: 32%.

(2)、 3-甲基 -2-硝基苯甲酰氯的合成

(2) Synthesis of 3-methyl-2-nitrobenzoyl chloride

在 500毫升的反应瓶中加入 2-硝基 -3-甲基苯甲酸（20.0克， 110毫摩尔）、 100 毫升二氯甲烷和草酰氯（21.0克， 165毫摩尔），再滴入 5滴二甲基甲酰胺，有大量气体放出。室温搅拌下反应 8小时后将反应液减压浓缩，加入 100毫升甲苯，减压浓缩后得 22克白色固体，收率： 100%。 Add 2-nitro-3-methylbenzoic acid (20.0 g, 110 mmol), 100 ml of dichloromethane and oxalyl chloride (21.0 g, 165 mmol) to a 500 ml reaction vial, then add 5 drops Dimethylformamide, a large amount of gas is released. After reacting for 8 hours at room temperature, the reaction mixture was concentrated under reduced pressure.

(3 )、 N-(l-氰基乙基) -3-甲基 -2-硝基苯甲酰胺的合成

Synthesis of (3), N-(l-Cyanoethyl)-3-methyl-2-nitrobenzamide

在 500毫升的反应瓶中依次加入 2-硝基 -3-甲基苯甲酰氯（21.0克， 105毫摩尔）、 200毫升二氯甲烷和 2-氨基丙腈（7.0克， 100毫摩尔），再滴加入三乙胺（12.0克， 120毫摩尔），室温下搅拌反应 3小时。将反应液倒入 200毫升水中，用 3x 100毫升乙酸乙酯萃取，合并有机相，经饱和碳酸钠溶液、食盐水洗涤后，用无水硫酸镁干燥，浓缩后得 21.5克深棕色油状物。通过柱色谱分离（淋洗液：乙酸乙酯：石油醚 = 1 ： 1 ) 得 18.5克橙黄色固体，收率： 75 %。 2-Nitro-3-methylbenzoyl chloride (21.0 g, 105 mmol), 200 ml of dichloromethane and 2-aminopropionitrile (7.0 g, 100 mmol) were added sequentially to a 500 ml reaction flask. Further, triethylamine (12.0 g, 120 mmol) was added dropwise, and the reaction was stirred at room temperature for 3 hours. The reaction mixture was poured into EtOAc (3 mL, EtOAc). Separation by column chromatography (eluent: ethyl acetate: petroleum ether = 1 : 1 ) yielded 18.5 g of an orange solid, yield: 75 %.

1H MR (300MHz, CDCI3+CD3OD): 9.025-9.001 (d, IH), 7.520-7.439 (m, 3H), 5.044-4.972 (m, IH), 2.409 (s, 3H), 1.632-1.608 (d, 3H)。 1H MR (300MHz, CDCI3+CD3OD): 9.025-9.001 (d, IH), 7.520-7.439 (m, 3H), 5.044-4.972 (m, IH), 2.409 (s, 3H), 1.632-1.608 (d, 3H).

(4)、 N-(l-氰基乙基; )-3-甲基 -2-氨基苯甲酰胺（化合物 2.1 ) 的合成

Synthesis of (4), N-(l-Cyanoethyl; )-3-methyl-2-aminobenzamide (Compound 2.1)

在 250毫升的反应瓶中依次加入 N-(l-氰基乙基) -3-甲基 -2-硝基苯甲酰胺 (4.0克， 17.2毫摩尔）、 40毫升四氢呋喃、 40毫升水和锌粉（5.6克， 86毫摩尔），室温搅拌下在 30分钟内滴加浓盐酸（5.2克， 51.6毫摩尔），控制反应温度不超过 30°C。室温下继续反应 3小时。滤出反应液中不溶物，滤液用 2x 100毫升乙酸乙酯萃取，有机相经水、饱和碳酸钠溶液和饱和食盐水洗涤后，用无水硫酸镁干燥，浓缩后得 2.8克浅黄色固体，收率 80%。 N-(l-Cyanoethyl)-3-methyl-2-nitrobenzamide (4.0 g, 17.2 mmol), 40 ml of tetrahydrofuran, 40 ml of water and zinc were sequentially added to a 250 ml reaction flask. The powder (5.6 g, 86 mmol) was added dropwise with concentrated hydrochloric acid (5.2 g, 51.6 mmol) over 30 minutes with stirring at room temperature, and the reaction temperature did not exceed 30 °C. The reaction was continued at room temperature for 3 hours. The insoluble material in the reaction mixture was filtered, and the filtrate was evaporated,jjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj The yield was 80%.

1H MR (300MHz, CDC1₃): 7.246-7.220 (d, IH), 7.160-7.137 (d, IH), 6.667-6.641 (d, IH), 6.591-6.541 (t, IH), 5.659 (s, 2H), 5.048-4.997 (m, IH), 2.144 (s, 3H), 1.633-1.608 (d, 1H MR (300MHz, CDC1 ₃ ): 7.246-7.220 (d, IH), 7.160-7.137 (d, IH), 6.667-6.641 (d, IH), 6.591-6.541 (t, IH), 5.659 (s, 2H ), 5.048-4.997 (m, IH), 2.144 (s, 3H), 1.633-1.608 (d,

( 5 )、 N-(l-氰基乙基) -5-氯 -3-甲基 -2-氨基苯甲酰胺（化合物 2.2) 的合成

Synthesis of (5), N-(l-cyanoethyl)-5-chloro-3-methyl-2-aminobenzamide (Compound 2.2)

在 50毫升的反应瓶中依次加入 N-(l-氰基乙基) -3-甲基 -2-氨基苯甲酰胺（1.8克， 8.9毫摩尔）、 N-氯代丁二酰亚胺（简称： NCS) (1.2克， 8.9毫摩尔）和 20毫升二甲基甲酰胺，升温至 100-110°C下搅拌 30分钟。冷却至室温，将反应液倾入 100毫升水中，用 2x100毫升乙酸乙酯萃取，有机相经水、饱和食盐水洗涤后，用无水硫酸镁干燥，浓缩后得 1.8克浅黄色油状物， HPLC分析无明显杂质，收率 86%。 N-(l-Cyanoethyl)-3-methyl-2-aminobenzamide (1.8 g, 8.9 mmol), N-chlorosuccinimide (N-chlorosuccinimide) was added in a 50 ml reaction flask. Abbreviation: NCS) (1.2 g, 8.9 mmol) and 20 ml of dimethylformamide, and the mixture was heated to 100-110 ° C for 30 minutes. After cooling to room temperature, the reaction mixture was poured into 100 ml of water and extracted with 2×100 ml of ethyl acetate. The organic phase was washed with water and brine, and dried over anhydrous magnesium sulfate. The analysis showed no significant impurities, and the yield was 86%.

1H MR (300MHz, CDC1₃): 7.535 (s, 1H), 7.331-7.324 (d, 1H), 7.104-7.102 (d, 1H): 5.040-5.016 (m, 1H), 2.131 (s, 3H), 1.671-1.647 (d, 3H)。 1H MR (300MHz, CDC1 ₃ ): 7.535 (s, 1H), 7.331-7.324 (d, 1H), 7.104-7.102 (d, 1H): 5.040-5.016 (m, 1H), 2.131 (s, 3H), 1.671-1.647 (d, 3H).

(6)、 3-氯 -2-肼基吡啶的合成

(6) Synthesis of 3-chloro-2-mercaptopyridine

在 1000毫升的反应瓶中依次加入 2,3-二氯吡啶（74克， 500毫摩尔）、 50%水合肼（250克， 2.5摩尔）和 300毫升二氧六环，回流温度下搅拌 20小时。反应液冷却过夜，有白色晶体析出，过滤，干燥后得固体 51克，收率： 71%。 2,3-dichloropyridine (74 g, 500 mmol), 50% hydrazine hydrate (250 g, 2.5 mol) and 300 ml of dioxane were sequentially added to a 1000 ml reaction flask, and stirred at reflux temperature for 20 hours. . The reaction solution was cooled overnight, and white crystals were precipitated, filtered, and dried to give a solid, 51 g, yield: 71%.

1H MR (300MHz, CDC1₃): 8.113-8.092 (d, 1H), 7.493-7.463 (d, 1H), 6.672-6.630 (q: 1H), 6.237 (s, 1H), 3.905 (s, 2H)。 1H MR (300MHz, CDC1 ₃ ): 8.113-8.092 (d, 1H), 7.493-7.463 (d, 1H), 6.672-6.630 (q: 1H), 6.237 (s, 1H), 3.905 (s, 2H).

(7)、 l-(3-氯吡啶 -2-基) -3-吡唑烷酮 -5-羧酸乙酯的合成 Synthesis of (7), l-(3-Chloropyridin-2-yl)-3-pyrazolidinone-5-carboxylic acid ethyl ester

在 1000毫升反应瓶内加入 300毫升无水乙醇和乙醇钠 (15.6克， 0.229摩尔）， 3- 氯 -2-肼基吡啶 (30.0克， 0.208摩尔)，混合物加热回流 5分钟，滴加马来酸二乙酯 (36.0 克， 0.250摩尔)。继续加热回流 10分钟。待冷却到 65°C后将反应混合物用冰乙酸 (25.2 克， 0.420摩尔)中和。混合物用 300毫升水稀释，冷至室温，有固体析出。过滤收集固体，用 3x50毫升 40%的乙醇水溶液洗涤。干燥后得到橙色固体 26.3克，收率 42 %。 300 ml of absolute ethanol and sodium ethoxide (15.6 g, 0.229 mol), 3-chloro-2-mercaptopyridine (30.0 g, 0.208 mol) were added to a 1000 ml reaction flask, and the mixture was heated under reflux for 5 minutes, and the mixture was added dropwise. Diethyl acid (36.0 g, 0.250 mol). Continue to heat and reflux for 10 minutes. After cooling to 65 ° C, the reaction mixture was neutralized with glacial acetic acid (25.2 g, 0.420 mol). The mixture was diluted with 300 ml of water, cooled to room temperature, and solid precipitated. The solid was collected by filtration and washed with 3×50 ml of 40% aqueous ethanol. After drying, 26.3 g of an orange solid was obtained, yield 42%.

1H MR(300MHz, DMSO): 8.289-8.269 (q, 1H), 7.956-7.190 (q, 1H), 7.231-7.190 (q: 1H), 4.862-4.816 (q, 1H), 4.236-4.165 (q, 2H), 2.967-2.879 (q, 1H), 2.396-2.336 (q, 1H), 1.250-1.202 (t, 3H)。 1H MR (300MHz, DMSO): 8.289-8.269 (q, 1H), 7.956-7.190 (q, 1H), 7.231-7.190 (q: 1H), 4.862-4.816 (q, 1H), 4.236-4.165 (q, 2H), 2.967-2.879 (q, 1H), 2.396-2.336 (q, 1H), 1.250-1.202 (t, 3H).

(8)、 l-(3-氯吡啶 -2-基) -3-氯 -2-吡唑啉 -5-羧酸乙酯的合成

Synthesis of (8), l-(3-chloropyridin-2-yl)-3-chloro-2-pyrazoline-5-carboxylic acid ethyl ester

在 100毫升反应瓶内加入 65毫升乙腈、 1-(3-氯吡啶 -2-基) -3-吡唑烷酮 -5-羧酸乙酯 (6.5克， 24毫摩尔)和三氯氧磷 (4.4克， 28.8毫摩尔)。加热回流 2小时，蒸熘除去 30毫升溶剂。将上述浓缩反应混合物加到碳酸氢钠 (10.1克， 120毫摩尔)和 40毫升水形成的混合物中，搅拌 20分钟至不再有气体逸出。混合物用 100毫升二氯甲烷稀释，然后搅拌 50分钟。再用二氯甲烷 3x 100毫升萃取。有机相水洗、无水硫酸镁干燥后利用旋转蒸发仪浓缩。产物为 4.7克深琥珀色油状物，收率： 68%。 Add 65 ml of acetonitrile, ethyl 1-(3-chloropyridin-2-yl)-3-pyrazolidinone-5-carboxylate (6.5 g, 24 mmol) and phosphorus oxychloride in a 100 ml reaction flask. (4.4 g, 28.8 mmol). The mixture was heated under reflux for 2 hours, and 30 ml of solvent was evaporated. The above concentrated reaction mixture was added to a mixture of sodium hydrogen carbonate (10.1 g, 120 mmol) and 40 ml of water, and stirred for 20 minutes until no more gas evolved. The mixture was diluted with 100 ml of dichloromethane and then stirred for 50 minutes. It was extracted with dichloromethane 3 x 100 ml. The organic phase was washed with water, dried over anhydrous magnesium sulfate and evaporated. The product was 4.7 g of amber oil, yield: 68%.

1H MR(300MHz, DMSO): 8.129-8.108 (q, 1H), 7.866-7.834 (q, 1H), 7.017-6.975 (q: 1H), 5.275-5.207 (q, 1H), 4.150-4.078 (q, 2H), 3.648-3.504 (m, 1H), 3.298-3.211 (m, 1H), 1.174-1.127 (t, 3H；)。 1H MR (300MHz, DMSO): 8.129-8.108 (q, 1H), 7.866-7.834 (q, 1H), 7.017-6.975 (q: 1H), 5.275-5.207 (q, 1H), 4.150-4.078 (q, 2H), 3.648-3.504 (m, 1H), 3.298-3.211 (m, 1H), 1.174-1.127 (t, 3H;).

(9)、 l-(3-氯吡啶 -2-基) -3-氯 -1H-吡唑 -5-羧酸乙酯的合成 Synthesis of (9), l-(3-Chloropyridin-2-yl)-3-chloro-1H-pyrazole-5-carboxylate

在 100毫升反应瓶内加入 l-O氯 -2-吡啶基 )-3-氯 -2-吡唑啉 -5-羧酸乙酯 C4.0克， 13.9毫摩尔)、 10毫升乙腈和 98 %的硫酸（2.8克， 27.8毫摩尔）。搅拌数分钟后，加入过硫酸钾 (6.0克， 22.2毫摩尔)。加热回流 5小时。趁热（50-65°C ) 过滤生成的橙色浆液以移去白色细小沉淀物。滤饼用 10毫升乙腈洗涤。在旋转蒸发仪上浓缩滤液至大约 10毫升，加入 50毫升水，过滤收集固体产物，产物用 3x 15毫升 25 %的乙腈水溶液洗涤，干燥后得到橙色固体 3.2克，收率： 80%。 Add 100 mg of ethyl chloro-2-pyridyl)-3-chloro-2-pyrazol-5-carboxylate (13.9 mmol), 10 ml of acetonitrile and 98% sulfuric acid in a 100 ml reaction flask. (2.8 g, 27.8 mmol). After stirring for a few minutes, potassium persulfate (6.0 g, 22.2 mmol) was added. Heat to reflux for 5 hours. The resulting orange slurry was filtered while hot (50-65 ° C) to remove the fine white precipitate. The filter cake was washed with 10 ml of acetonitrile. The filtrate was concentrated on a rotary evaporator to approx. 10 ml, 50 ml of water was added, and the solid product was collected by filtration. The product was washed with 3 x 15 ml of 25% aqueous acetonitrile, and dried to give an orange solid, 3.2 g, yield: 80%.

1H MR(300MHz, DMSO): 8.521-8.500 (d, 1H), 7.963-7.930 (d, 1H), 7.511-7.469 (q: 1H), 6.950 (s, 1H), 4.258-4.187 (q, 2H), 1.242-1.195 (t, 3H)。 1H MR (300MHz, DMSO): 8.521-8.500 (d, 1H), 7.963-7.930 (d, 1H), 7.511-7.469 (q: 1H), 6.950 (s, 1H), 4.258-4.187 (q, 2H) , 1.242-1.195 (t, 3H).

( 10)、 l-(3-氯吡啶 -2-基) -3-氯 -1H-吡唑 -5-羧酸的合成 Synthesis of (10), l-(3-chloropyridin-2-yl)-3-chloro-1H-pyrazole-5-carboxylic acid

在 100毫升反应瓶内加入 l-O氯 -2-吡啶基 3-氯 -1H-吡唑 -5-羧酸乙酯 (1.8克， 6.3 毫摩尔)、甲醇、水各 10毫升和氢氧化钠 (0.3克， 6.9毫摩尔)。室温搅拌 1小时后，所有起始原料都已溶解。在旋转蒸发仪上浓缩形成的深棕橙色溶液到大约 10毫升，然后加水 40毫升。水溶液用 50毫升乙醚萃取，用浓盐酸酸化至 pH=4。过滤收集生成的固体产物，用 2x50毫升水洗涤，干燥后得到白色固体 1.4克，收率： 88%。 Add 10% chloro-2-pyridyl 3-chloro-1H-pyrazole-5-carboxylic acid ethyl ester (1.8 g, 6.3) in a 100 ml reaction flask. Millimol), 10 ml each of methanol and water and sodium hydroxide (0.3 g, 6.9 mmol). After stirring at room temperature for 1 hour, all starting materials were dissolved. The resulting dark brown orange solution was concentrated on a rotary evaporator to approximately 10 mL, then 40 mL of water was added. The aqueous solution was extracted with 50 ml of diethyl ether and acidified to pH = 4 with concentrated hydrochloric acid. The resulting solid product was collected by filtration, washed with 2×50 ml of water, and dried to give a white solid, 1.4 g, yield: 88%.

1H MR(300MHz, DMSO): 8.578-8.566 (d, 1H), 8.278-8.251 (d, 1H), 7.719-7.677 (q: 1H), 7.234 (s, 1H)。 1H MR (300MHz, DMSO): 8.578-8.566 (d, 1H), 8.278-8.251 (d, 1H), 7.719-7.677 (q: 1H), 7.234 (s, 1H).

( 11 )、 l-(3-氯吡啶 -2-基) -3-氯 -1H-吡唑 -5-甲酰氯的合成 Synthesis of (11), l-(3-chloropyridin-2-yl)-3-chloro-1H-pyrazole-5-formyl chloride

在 100毫升的反应瓶中加入 l-O氯吡啶 -2-基;) -3-氯 -1H-吡唑 -5-羧酸（15.0克， 58.1 摩尔）、 100毫升二氯甲烷和草酰氯（11.1克， 87.2毫摩尔），再滴入 5滴二甲基甲胺，有大量气体生成。室温搅拌反应 8小时后将反应液减压浓缩至干，再加入 100 升甲苯，减压浓缩后得 16克绿色固体，收率： 100 %。 Add 10O chloropyridin-2-yl in a 100 ml reaction flask;) -3-chloro-1H-pyrazole-5-carboxylic acid (15.0 g, 58.1 mol), 100 ml dichloromethane and oxalyl chloride (11.1 g) , 87.2 mmol, and 5 drops of dimethylmethylamine were added dropwise, and a large amount of gas was formed. After the reaction was stirred at room temperature for 8 hours, the reaction mixture was evaporated to dryness.

( 12)、化合物 1.2的合成 (12), Synthesis of Compound 1.2

8.4毫摩尔）、 20毫升二氯甲烷、 l-O氯吡啶 -2-基;) -3-氯 -1H-吡唑 -5-甲酰氯（2.8克， 10.1毫摩尔）和三乙胺（1.1克， 10.9毫摩尔），室温搅拌 3小时。将反应液倾入 100 毫升水中，用 2x 100毫升乙酸乙酯萃取，有机层用饱和碳酸钠溶液、饱和食盐水洗涤，无水硫酸镁干燥后浓缩，残余物柱色谱提纯（淋洗液：乙酸乙酯：石油醚 = 1 :2)，得 2.3克白色固体化合物 1.2，收率: 58 %。 8.4 mmol, 20 ml of dichloromethane, 10O chloropyridin-2-yl;) -3-chloro-1H-pyrazole-5-formyl chloride (2.8 g, 10.1 mmol) and triethylamine (1.1 g, 10.9 mmol), stirred at room temperature for 3 hours. The reaction solution was poured into 100 ml of water, and extracted with 2×100 ml of ethyl acetate. The organic layer was washed with saturated sodium carbonate and brine, dried over anhydrous magnesium sulfate and evaporated. Ethyl ester: petroleum ether = 1 : 2) gave 2.3 g of white solid compound 1.2. Yield: 58 %.

实例 2、化合物 1.14的制备 Example 2. Preparation of Compound 1.14

( 1 ) 2-氨基 -2-甲基丙腈的合成

(1) Synthesis of 2-amino-2-methylpropionitrile

在 250毫升的反应瓶中加入氰化钠（4.95克， 100毫摩尔）和氨水（60 毫升），常温搅拌至氰化钠完全溶解，加入丙酮（5.84克， 100毫摩尔）和氯化铵（5.38克， 100毫摩尔），常温反应 48小时，反应液用二氯甲烷萃取三次（依次 50毫升、 10毫升、 10毫升），合并有机相，用无水硫酸镁干燥、减压脱溶，得 5.25g无色油，收率: 57%。 Add sodium cyanide (4.95 g, 100 mmol) and ammonia water (60 ml) to a 250 ml reaction flask, stir at room temperature until the sodium cyanide is completely dissolved, and add acetone (5.84 g, 100 mmol) and ammonium chloride ( 5.38 g, 100 mmol), reacted at room temperature for 48 hours, and the reaction solution was extracted three times with dichloromethane (50 ml, 10 m in order) The organic phase was combined, dried over anhydrous magnesium sulfate and evaporated to dryness.

(2)、 N-(l-甲基 -1-氰基乙基) -3-甲基 -2-硝基苯甲酰胺的合成

(2) Synthesis of N-(l-methyl-1-cyanoethyl)-3-methyl-2-nitrobenzamide

在 500毫升的反应瓶中依次加入 2-硝基 -3-甲基苯甲酰氯（21.0克， 105毫摩尔）、 200毫升二氯甲烷和 2-氨基 -2-甲基丙腈（8.8克， 105毫摩尔），再滴加入三乙胺（12.6 克， 126毫摩尔），室温下搅拌反应 3小时。将反应液倒入 200毫升水中，用 3x 100 毫升乙酸乙酯萃取，合并有机相，经饱和碳酸钠溶液、食盐水洗涤后，用无水硫酸干燥，浓缩后得 19.2克白色固体。收率： 74%。 2-Nitro-3-methylbenzoyl chloride (21.0 g, 105 mmol), 200 ml of dichloromethane and 2-amino-2-methylpropionitrile (8.8 g) were placed in a 500 ml reaction flask. 105 mmol), triethylamine (12.6 g, 126 mmol) was added dropwise, and the reaction was stirred at room temperature for 3 hours. The reaction mixture was poured into EtOAc (3 mL, EtOAc) Yield: 74%.

(3 )、 N-(l-甲基 -1-氰基乙基) -3-甲基 -2-氨基苯甲酰胺（化合物 2.11 ) 的合成

Synthesis of (3), N-(l-Methyl-1-cyanoethyl)-3-methyl-2-aminobenzamide (Compound 2.11)

在 250毫升的反应瓶中依次加入 N-(l-甲基 -1-氰基乙基) -3-甲基 -2-硝基苯甲酰胺 (6.4克， 25.9毫摩尔）、 80毫升醋酸和铁粉（5.8克， 103.6毫摩尔），控制反应温度不超过 80°C，反应 3小时。冷至室温后加入 100毫升水，用 3x 100毫升乙酸乙酯萃取，有机相经水、饱和碳酸钠溶液和饱和食盐水洗涤后，用无水硫酸镁干燥，浓缩后得 4.5克棕黄色固体，收率 80%。 N-(l-Methyl-1-cyanoethyl)-3-methyl-2-nitrobenzamide (6.4 g, 25.9 mmol), 80 ml of acetic acid and then sequentially were placed in a 250 ml reaction flask. Iron powder (5.8 g, 103.6 mmol), the reaction temperature was controlled to not exceed 80 ° C, and the reaction was carried out for 3 hours. After cooling to room temperature, 100 ml of water was added, and the mixture was extracted with EtOAc EtOAc EtOAc. The yield was 80%.

(4)、 N-(l-甲基 -1-氰基乙基) -5-氯 -3-甲基 -2-氨基苯甲酰胺（化合物 2.12) 的合成 (4) Synthesis of N-(l-methyl-1-cyanoethyl)-5-chloro-3-methyl-2-aminobenzamide (Compound 2.12)

在 150毫升的反应瓶中依次加入 N-(l-甲基 -1-氰基乙基) -3-甲基 -2-氨基苯甲酰胺 (4.3克， 19.8毫摩尔）、 NCS (2.7克， 19.8毫摩尔）和 50毫升二甲基甲酰胺，升温至 100-110°C下搅拌 30分钟。冷却至室温，将反应液倾入 100毫升水中，用 3x 100 毫升乙酸乙酯萃取，有机相经水、饱和食盐水洗涤后，用无水硫酸镁干燥，浓缩后得 4.0克黑色固体，收率 80%。 N-(l-Methyl-1-cyanoethyl)-3-methyl-2-aminobenzamide (4.3 g, 19.8 mmol), NCS (2.7 g, was added sequentially to a 150 ml reaction flask. 19.8 mmol) and 50 ml of dimethylformamide were stirred and heated to 100-110 ° C for 30 minutes. After cooling to room temperature, the reaction mixture was poured into 100 ml of water and extracted with 3×100 ml of ethyl acetate. The organic phase was washed with water and brine, dried over anhydrous magnesium sulfate 80%.

1H MR (300MHz, CDC1₃): 7.145-7.126 (m, 2H), 6.054 (s, 1H), 2.143 (s, 3H), 1.807 (s, 6H)。 1H MR (300MHz, CDC1 ₃ ): 7.145-7.126 (m, 2H), 6.054 (s, 1H), 2.143 (s, 3H), 1.807 (s, 6H).

( 5 )、 l-(3-氯吡啶 -2-基) -3-溴 -2-吡唑啉 -5-羧酸乙酯的合成

Synthesis of (5), l-(3-chloropyridin-2-yl)-3-bromo-2-pyrazoline-5-carboxylic acid ethyl ester

在 150毫升反应瓶内加入 65毫升乙腈、 1-(3-氯吡啶 -2-基) -3-吡唑烷酮 -5-羧酸乙酯 (5.0克， 18.5毫摩尔)和三溴氧磷 (3.4克， 11.9毫摩尔)。加热回流 2小时，蒸熘除去 30毫升溶剂。将上述浓缩反应混合物加到碳酸氢钠 (10.1克， 120毫摩尔;)和 40毫升水形成的混合物中，搅拌 20分钟至不再有气体逸出。混合物用 100毫升二氯甲烷稀释，然后搅拌 50分钟。再用二氯甲烷 3x 100毫升萃取。有机相水洗、无水硫酸镁干燥后利用旋转蒸发仪浓缩。产物为 6.0克琥珀色油状物，收率： 97%。 Into a 150 ml reaction flask was added 65 ml of acetonitrile, ethyl 1-(3-chloropyridin-2-yl)-3-pyrazolidinone-5-carboxylate (5.0 g, 18.5 mmol) and phosphorus bromide. (3.4 g, 11.9 mmol). The mixture was heated under reflux for 2 hours, and 30 ml of solvent was evaporated. The above concentrated reaction mixture was added to a mixture of sodium hydrogencarbonate (10.1 g, 120 mmol;) and 40 ml of water, and stirred for 20 minutes until no more gas evolved. The mixture was diluted with 100 ml of dichloromethane and then stirred for 50 minutes. It was extracted with dichloromethane 3 x 100 ml. The organic phase was washed with water, dried over anhydrous magnesium sulfate and concentrated using a rotary evaporator. The product was 6.0 g of amber oil, yield: 97%.

1H MR: 8.093-8.073 (q, 1H), 7.681-7.650 (q, 1H), 6.892-6.851 (q, 1H), 5.293-5.224 (q, 1H), 4.220-4.150 (q, 2H), 3.502-3.404 (q, 1H), 3.291-3.202 (q, 1H), 1.226-1.179 (t, 3H)。 1H MR: 8.093-8.073 (q, 1H), 7.681-7.650 (q, 1H), 6.892-6.851 (q, 1H), 5.293-5.224 (q, 1H), 4.220-4.150 (q, 2H), 3.502- 3.404 (q, 1H), 3.291-3.202 (q, 1H), 1.226-1.179 (t, 3H).

1-(3-氯吡啶 -2-基) -3-溴 -1H-吡唑 -5-羧酸乙酯的合成 Synthesis of ethyl 1-(3-chloropyridin-2-yl)-3-bromo-1H-pyrazole-5-carboxylate

在 100毫升反应瓶内加入 1-(3-氯 -2-吡啶基 )-3-溴 -2-吡唑啉 -5-羧酸乙酯 (4.0克， 12.0毫摩尔)、 10毫升乙腈和 98 %的硫酸（2.4克， 24.0毫摩尔）。搅拌数分钟后，加入过硫酸钾 (5.2克， 19.2毫摩尔)。加热回流 5小时。趁热（50-65°C ) 过滤生成的橙色浆液以移去白色细小沉淀物。滤饼用 10毫升乙腈洗涤。在旋转蒸发仪上浓缩滤液至大约 10毫升，加入 50毫升水，过滤收集固体产物，产物用 3x 15毫升 25 %的乙腈水溶液洗涤，干燥后得到橙色固体 3.8克，收率： 95%。 Add 1-(3-chloro-2-pyridyl)-3-bromo-2-pyrazoline-5-carboxylic acid ethyl ester (4.0 g, 12.0 mmol), 10 ml of acetonitrile and 98 in a 100 ml reaction flask. % sulfuric acid (2.4 g, 24.0 mmol). After stirring for a few minutes, potassium persulfate (5.2 g, 19.2 mmol) was added. Heat to reflux for 5 hours. The resulting orange slurry was filtered while hot (50-65 ° C) to remove the fine white precipitate. The filter cake was washed with 10 ml of acetonitrile. The filtrate was concentrated on a rotary evaporator to approx. 10 ml, 50 ml of water was added, and the solid product was collected by filtration. The product was washed with 3 x 15 ml of 25% aqueous acetonitrile and dried to give 3.8 g of an orange solid. Yield: 95%.

1H MR(300MHz, CDC1): 8.522-8.501 (q, 1H), 7.927-7.895 (q, 1H), 7.465-7.424 (q, 1H), 7.034 (s, 1H), 4.262-4.190 (q, 2H), 1.240-1.192 (t, 3H)。 1H MR (300MHz, CDC1): 8.522-8.501 (q, 1H), 7.927-7.895 (q, 1H), 7.465-7.424 (q, 1H), 7.034 (s, 1H), 4.262-4.190 (q, 2H) , 1.240-1.192 (t, 3H).

(7)、 l-(3-氯吡啶 -2-基) -3-溴 -1H-吡唑 -5-羧酸的合成 Synthesis of (7), l-(3-chloropyridin-2-yl)-3-bromo-1H-pyrazole-5-carboxylic acid

在 100毫升反应瓶内加入 1-(3-氯 -2-吡啶基 )-3-溴 -1H-吡唑 -5-羧酸乙酯 (1.4克， 4.2 毫摩尔)、甲醇、水各 10毫升和氢氧化钠 (0.2克， 4.6毫摩尔)。室温搅拌 1小时后，所有起始原料都已溶解。在旋转蒸发仪上浓缩形成的深棕橙色溶液到大约 10毫升，然后加水 40毫升。水溶液用 50毫升乙醚萃取，用浓盐酸酸化至 pH=4。过滤收集生成的固体产物，用 2x50毫升水洗涤，干燥后得到白色固体 1.1克，收率： 85%。 Add 1-(3-chloro-2-pyridyl)-3-bromo-1H-pyrazole-5-carboxylic acid ethyl ester (1.4 g, 4.2) to a 100 ml reaction vial Millimol), 10 ml each of methanol and water and sodium hydroxide (0.2 g, 4.6 mmol). After stirring at room temperature for 1 hour, all starting materials were dissolved. The resulting dark brown orange solution was concentrated on a rotary evaporator to approximately 10 mL, then 40 mL of water was added. The aqueous solution was extracted with 50 ml of diethyl ether and acidified to pH = 4 with concentrated hydrochloric acid. The resulting solid product was collected by filtration, washed with 2×50 ml of water and dried to give a white solid (1.1 g, yield: 85%).

( 8)、 1-(3-氯吡啶 -2-基) -3-溴 -1H-吡唑 -5-甲酰氯的合成 Synthesis of (8), 1-(3-chloropyridin-2-yl)-3-bromo-1H-pyrazole-5-formyl chloride

在 100毫升的反应瓶中加入 1-(3-氯吡啶 -2-基) -3-溴 -1H-吡唑 -5-羧酸（0.9克， 2.8 毫摩尔）、 10毫升二氯甲烷和草酰氯（0.7克， 5.6毫摩尔），再滴入 2滴二甲基甲酰胺，有大量气体生成。室温搅拌反应 8小时后将反应液减压浓缩至干，再加入 50毫升甲苯，减压浓缩后得 0.9克油状物，收率： 100%。 Add 1-(3-chloropyridin-2-yl)-3-bromo-1H-pyrazole-5-carboxylic acid (0.9 g, 2.8 mmol), 10 ml of dichloromethane and grass to a 100 mL reaction flask The acid chloride (0.7 g, 5.6 mmol) was added dropwise to 2 drops of dimethylformamide, and a large amount of gas was formed. After the reaction was stirred at room temperature for 8 hours, the reaction mixture was concentrated to dryness, and then evaporated.

(9)、化合物 1.14的合成 (9) Synthesis of Compound 1.14

在 100毫升的反应瓶中加入 N-(l-甲基 -1-氰基乙基) -5-氯 -3-甲基 -2-氨基苯甲酰胺 (0.64克， 2.0毫摩尔）、 20毫升二氯甲烷、 1-(3-氯吡啶 -2-基) -3-溴 -1H-吡唑 -5-甲酰氯 (0.5克， 2.0毫摩尔）和三乙胺（0.24克， 2.4毫摩尔），室温搅拌 3小时。将反应液倾入 100毫升水中，用 2x 100毫升乙酸乙酯萃取，有机层用饱和碳酸钠溶液、饱和食盐水洗涤，无水硫酸镁干燥后浓缩，残余物柱色谱提纯（淋洗液：乙酸乙酯：石油醚 = 1 :2)，得 0.4克白色固体化合物 1.14，收率: 40%。 Add N-(l-methyl-1-cyanoethyl)-5-chloro-3-methyl-2-aminobenzamide (0.64 g, 2.0 mmol) in 20 ml vial, 20 ml Dichloromethane, 1-(3-chloropyridin-2-yl)-3-bromo-1H-pyrazole-5-carbonyl chloride (0.5 g, 2.0 mmol) and triethylamine (0.24 g, 2.4 mmol) Stir at room temperature for 3 hours. The reaction mixture was poured into 100 ml of water and extracted with 2×100 ml of ethyl acetate. The organic layer was washed with saturated aqueous sodium sulfate and brine, dried over anhydrous magnesium sulfate and evaporated. Ethyl ester: petroleum ether = 1 : 2), 0.4 g of a white solid compound 1.14, yield: 40%.

实例 3、化合物 1.17的制备 Example 3. Preparation of Compound 1.17

在 100 毫升的反应瓶中加入 N-(l-甲基 -1-氰基乙基) - 3,5-二氯 -2-氨基苯甲酰胺 81 Add N-(l-methyl-1-cyanoethyl)-3,5-dichloro-2-aminobenzamide to a 100 ml reaction vial 81

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0C80.0/800ZN3/X3d 696 /800Z OAV (3) l-(2-氯苯基 )-3-氯 -1H-吡唑 -5-羧酸乙酯的合成 0C80.0/800ZN3/X3d 696 /800Z OAV (3) Synthesis of ethyl l-(2-chlorophenyl)-3-chloro-1H-pyrazole-5-carboxylate

在 100毫升反应瓶内加入 l-O氯苯基 )-3-氯 -2-吡唑啉 -5-羧酸乙酯 C2.8克， 10.0毫摩尔)、 30毫升乙腈和 98 %的硫酸（2.0克， 20.0毫摩尔）。搅拌数分钟后，加入过硫酸钾 (4.3克， 16.0毫摩尔)。加热回流 5小时。趁热（50-65°C ) 过滤生成的橙色浆液以移去白色细小沉淀物。滤饼用 10毫升乙腈洗涤。在旋转蒸发仪上浓缩滤液至大约 10毫升，加入 50毫升水，过滤收集固体产物，产物用 3x 15毫升 25 %的乙腈水溶液洗涤，干燥后得到橙色固体 1.6克，收率： 56%。 Add 100 g of ethyl chlorophenyl)-3-chloro-2-pyrazol-5-carboxylate (10.0 mmol), 30 ml of acetonitrile and 98% sulfuric acid (2.0 g) in a 100 ml reaction flask. , 20.0 mmol). After stirring for a few minutes, potassium persulfate (4.3 g, 16.0 mmol) was added. Heat to reflux for 5 hours. The resulting orange slurry was filtered while hot (50-65 ° C) to remove the white fine precipitate. The filter cake was washed with 10 ml of acetonitrile. The filtrate was concentrated to about 10 ml on a rotary evaporator, 50 ml of water was added, and the solid product was collected by filtration. The product was washed with 3 x 15 ml of 25% aqueous acetonitrile, and dried to give an orange solid, 1.6 g, yield: 56%.

1H MR(300MHz, DMSO): 7.528-7.438 (m, 4H), 6.930 (s, 1H), 4.177-4.132 (q, 2H), 1.207-1.159 (t, 3H；)。 1H MR (300MHz, DMSO): 7.528-7.438 (m, 4H), 6.930 (s, 1H), 4.177-4.132 (q, 2H), 1.207-1.159 (t, 3H;).

(4)、 l-(2-氯苯基 )-3-氯 -1H-吡唑 -5-羧酸的合成 Synthesis of (4), l-(2-chlorophenyl)-3-chloro-1H-pyrazole-5-carboxylic acid

在 100毫升反应瓶内加入 1-0氯苯基 )-3-氯 -1H-吡唑 -5-羧酸乙酯 C1.6克， 5.6毫摩尔)、甲醇、水各 10毫升和氢氧化钠 (0.27克， 6.7毫摩尔)。室温搅拌 1小时后，所有起始原料都已溶解。在旋转蒸发仪上浓缩形成的深棕橙色溶液到大约 10毫升，然后加水 40毫升。水溶液用 50毫升乙醚萃取，用浓盐酸酸化至 pH=4。过滤收集生成的固体产物，用 2x50毫升水洗涤，干燥后得到白色固体 1.1克，收率： 79%。 Add 1-0 chlorophenyl)-3-chloro-1H-pyrazole-5-carboxylic acid ethyl ester C1.6 g, 5.6 mmol, 100 ml of methanol and water, and sodium hydroxide in a 100 ml reaction flask. (0.27 g, 6.7 mmol). After stirring at room temperature for 1 hour, all of the starting materials were dissolved. The resulting dark brown orange solution was concentrated on a rotary evaporator to approximately 10 mL, then 40 mL of water was added. The aqueous solution was extracted with 50 ml of diethyl ether and acidified to pH = 4 with concentrated hydrochloric acid. The resulting solid product was collected by filtration, washed with 2×50 ml of water, and dried to give a white solid, 1.1 g, yield: 79%.

1H MR(300MHz, DMSO): 7.623-7.049 (m, 4H), 7.049 (s, 1H)。 1H MR (300 MHz, DMSO): 7.623-7.049 (m, 4H), 7.049 (s, 1H).

(5)、 l-(2-氯苯基 )-3-氯 -1H-吡唑 -5-甲酰氯的合成 Synthesis of (5), l-(2-chlorophenyl)-3-chloro-1H-pyrazole-5-formyl chloride

在 50毫升的反应瓶中加入 l-O氯苯基 )-3-氯 -1H-吡唑 -5-羧酸（1.1克， 4.3毫摩尔）、 20毫升二氯甲烷和草酰氯（0.8克， 6.4毫摩尔），再滴入 1滴二甲基甲酰胺，有大量气体生成。室温搅拌反应 8小时后将反应液减压浓缩至干，再加入 20毫升甲苯，减压浓缩后得 1.2克油状物，收率: Add 10 chlorophenyl)-3-chloro-1H-pyrazole-5-carboxylic acid (1.1 g, 4.3 mmol), 20 ml of dichloromethane and oxalyl chloride (0.8 g, 6.4 m) to a 50 ml reaction flask. Molar), another drop of dimethylformamide was added dropwise, and a large amount of gas was formed. After stirring the reaction for 8 hours at room temperature, the reaction solution was concentrated to dryness under reduced pressure, then 20 ml Benzene, concentrated under reduced pressure to give 1.2 g of oil, yield:

(6)、化合物 1.19的合成 (6), synthesis of compound 1.19

在 50毫升的反应瓶中加入 N-(l-甲基 -1-氰基乙基) -5-氯 -3-甲基 -2-氨基苯甲酰胺 (0.3克， 1.2毫摩尔）、 10毫升二氯甲烷、 l-O氯苯基 3-氯 -1H-吡唑 -5-甲酰氯（0.33 克， 1.2毫摩尔）和三乙胺（0.14克， 1.4毫摩尔），室温搅拌 3小时。将反应液倾入 50毫升水中，用 2x50毫升乙酸乙酯萃取，有机层用饱和碳酸钠溶液、饱和食盐水洗涤，无水硫酸镁干燥后浓缩，残余物柱色谱提纯（淋洗液：乙酸乙酯：石油醚 = 1 :2)，得 0.4克白色固体化合物 1.19，收率 :68 %。 Add N-(l-methyl-1-cyanoethyl)-5-chloro-3-methyl-2-aminobenzamide (0.3 g, 1.2 mmol) in a 50 ml reaction vial, 10 ml Dichloromethane, lOchlorophenyl 3-chloro-1H-pyrazole-5-formyl chloride (0.33 g, 1.2 mmol) and triethylamine (0.14 g, 1.4 mmol) were stirred at room temperature for 3 hours. The reaction solution was poured into 50 ml of water, and extracted with 2×50 ml of ethyl acetate. The organic layer was washed with saturated aqueous sodium sulfate and brine, dried over anhydrous magnesium sulfate and evaporated. Ester: petroleum ether = 1 : 2), 0.4 g of a white solid compound 1.19, yield: 68%.

实例 5、化合物 1.24的制备 Example 5. Preparation of Compound 1.24

( 1 )、 N'-(2-氯苯基 )-2,2,2-三氟乙酰肼的制备 Preparation of (1), N'-(2-chlorophenyl)-2,2,2-trifluoroacetylhydrazine

向三口瓶中依次加入 2-氯苯肼（10.0克， 70.4毫摩尔）、四氢呋喃 (80 毫升)，滴加三氟乙酸酐（14.6克， 70.4毫摩尔）的四氢呋喃溶液（20毫升），室温反应 3小时，减压蒸尽溶剂，加入乙酸乙酯（100 毫升），水（50毫升）分液萃取，有机层用分别用饱和碳酸氢钠溶液（50毫升），氯化钠溶液（50毫升）洗涤，无水硫酸镁干燥，减压蒸尽溶剂，得微黄色固体 15.7克，收率 93%。

2-Chlorobenzoquinone (10.0 g, 70.4 mmol), tetrahydrofuran (80 ml) was added to a three-necked flask, and a solution of trifluoroacetic anhydride (14.6 g, 70.4 mmol) in tetrahydrofuran (20 ml) was added dropwise at room temperature. After 3 hours, the solvent was evaporated under reduced pressure. ethyl acetate (100 ml), water (50 ml) was evaporated, and the organic layer was applied with saturated sodium hydrogen carbonate solution (50 ml), sodium chloride solution (50 ml) The mixture was washed with anhydrous magnesium sulfate and evaporated.]]]]]]

1H MR(300MHz, CDC1₃): 8.750 (br s, 1H), 7.306 (dd, 1H), 7.145 (dd, 1H), 6.947 (dd, 1H), 6.815 (dd, 1H), 6.590 (br s, 1H)。 1H MR (300MHz, CDC1 ₃ ): 8.750 (br s, 1H), 7.306 (dd, 1H), 7.145 (dd, 1H), 6.947 (dd, 1H), 6.815 (dd, 1H), 6.590 (br s, 1H).

(2) N'-(2-氯苯基 )-2,2,2-三氟乙酰甲基磺酸酯 (2) N'-(2-chlorophenyl)-2,2,2-trifluoroacetylmethanesulfonate

F₃C丫。 F ₃ C丫.

H^N、_NH

向三口瓶中依次加入 N'-(2-氯苯基 )-2,2,2-三氟乙酰肼（5.00克， 29.1 毫摩尔）、乙酸乙酯 (50 毫升)， 0°C下滴加甲基磺酰氯（3.8克， 32.5毫摩尔）， 30分钟滴加完毕。继续搅拌反应 30分钟后，滴加三乙胺（4.11克， 40.6毫摩尔），有白色固体析出，室温搅拌，反应完全，加入乙酸乙酯（100毫升），水（50毫升）分液萃取，有机层用分别用饱和氯化钠溶液 (50 毫升)洗涤，无水硫酸镁干燥，减压蒸尽溶剂，得粘稠黄色固体 4.2克，收率 59%。 H ^N , _NH

N'-(2-chlorophenyl)-2,2,2-trifluoroacetyl hydrazine (5.00 g, 29.1 mmol), ethyl acetate (50 ml) was added to a three-necked flask, and the mixture was added dropwise at 0 °C. Methanesulfonyl chloride (3.8 g, 32.5 mmol) was added dropwise over 30 minutes. After stirring the reaction for 30 minutes, triethylamine (4.11 g, 40.6 mmol) was added dropwise, and a white solid was precipitated, and the mixture was stirred at room temperature, and the reaction was completed, and ethyl acetate (100 ml) and water (50 ml) The organic layer was washed with a saturated aqueous solution of sodium chloride (50 ml), dried over anhydrous magnesium sulfate, and evaporated.

1H MR(300MHz, CDC1₃): 8.854 (br s, 1H), 7.526 (dd, 1H), 7.327-7.231 (m, 2H), 6.944 (dd, 1H), 3.402 (s, 3H)。 1H MR (300MHz, CDC1 ₃ ): 8.854 (br s, 1H), 7.526 (dd, 1H), 7.327-7.231 (m, 2H), 6.944 (dd, 1H), 3.402 (s, 3H).

( 3 ) l-(2-氯苯基 )-3- (三氟甲基) -4,5-二氢 -1H-吡唑 -5-甲酸乙酯的制备 (3) Preparation of ethyl l-(2-chlorophenyl)-3-(trifluoromethyl)-4,5-dihydro-1H-pyrazole-5-carboxylate

向三口瓶中依次加入上步产物（2.00克， 7.60毫摩尔）、甲苯溶液 (20 毫升)、丙烯酸乙酯（1.53克， 15.2毫摩尔）， 0°C下滴加三乙胺（0.92克， 9.14毫摩尔）， 10分钟滴完，室温反应过夜，溶液由黄色变为棕黄色，反应完全。加入乙酸乙酯 (100 毫升)，水（50毫升）分液萃取，有机层分别用饱和碳酸氢钠溶液（50毫升）、氯化钠溶液 (50 毫升)洗涤，无水硫酸镁干燥，减压蒸尽溶剂，残余物柱色谱提纯得黄色油状物 0.8克，收率 36%。 The above product (2.00 g, 7.60 mmol), a toluene solution (20 ml), ethyl acrylate (1.53 g, 15.2 mmol) were added to a three-necked flask, and triethylamine (0.92 g) was added dropwise at 0 °C. 9.14 mmol), after 10 minutes of dropwise addition, the reaction was allowed to proceed overnight at room temperature, and the solution turned from yellow to brownish yellow, and the reaction was completed. Ethyl acetate (100 ml), water (50 ml), EtOAc (EtOAc m. The solvent was evaporated, and the residue was purified mjjjjjjjj

1H MR(300MHz, CDC1₃): 7.439 (br s, 1H), 7.349 (dd, 1H), 7.261 (dd, 1H), 7.118 (dd, 1H), 5.463 (dd, 1H), 3.966 (q, 2H), 3.449-3.384 (m, 2H), 0.993 (t, 3H)。 1H MR (300MHz, CDC1 ₃ ): 7.439 (br s, 1H), 7.349 (dd, 1H), 7.261 (dd, 1H), 7.118 (dd, 1H), 5.463 (dd, 1H), 3.966 (q, 2H ), 3.449-3.384 (m, 2H), 0.993 (t, 3H).

(4) l-(2-氯苯基 )-3- (三氟甲基) -1H-吡唑 -5-甲酸乙酯的制备 (4) Preparation of ethyl l-(2-chlorophenyl)-3-(trifluoromethyl)-1H-pyrazole-5-carboxylate

向三口瓶中依次加入 1-(2-氯苯基 )-3- (三氟甲基) -4,5-二氢 -1H-吡唑 -5-甲酸乙酯 ( 1.00克， 3.48毫摩尔）、四氢呋喃（10 毫升)，室温下分批加入 N-氯代丁二酰胺（0.51 克， 3.48毫摩尔），室温反应 10分钟，溶液由黄色变为黑色，反应 4小时，加入乙酸乙酯 (100 毫升)、水（50 毫升）分液萃取，有机层分别用饱和碳酸氢钠溶液（50 毫升）、氯化钠溶液 (50 毫升)洗涤，无水硫酸镁干燥，减压蒸尽溶剂，残余物柱色谱提纯得 0.6克黄色油状物，收率 61%。 To a three-necked bottle was added 1-(2-chlorophenyl)-3-(trifluoromethyl)-4,5-dihydro-1H-pyrazole-5-carboxylic acid ethyl ester (1.00 g, 3.48 mmol). , tetrahydrofuran (10 ml), N-chlorosuccinamide (0.51 g, 3.48 mmol) was added portionwise at room temperature, reacted at room temperature for 10 minutes, the solution changed from yellow to black, reacted for 4 hours, and ethyl acetate (100) was added. ML), water (50 ml), and the organic layer was washed with saturated sodium bicarbonate solution (50 ml), sodium chloride solution (50 ml), dried over anhydrous magnesium sulfate, and evaporated in vacuo. Purification by column chromatography gave 0.6 g of a yellow oil, yield 61%.

1H MR(300MHz, CDC1₃): 7.548-7.397 (m, 4H), 7.285 (s, 1H), 4.231 (q, 2H), 1.238 (t, 3H)_C 1H MR (300MHz, CDC1 ₃ ): 7.548-7.397 (m, 4H), 7.285 (s, 1H), 4.231 (q, 2H), 1.238 (t, 3H) _C

( 5 ) l-(2-氯苯基 )-3- (三氟甲基) -1H-吡唑 -5-甲酸的制备 (5) Preparation of l-(2-chlorophenyl)-3-(trifluoromethyl)-1H-pyrazole-5-carboxylic acid

向单口瓶中依次加入 1-(2-氯苯基 )-3- (三氟甲基) -1H-吡唑 -5-甲酸乙酯（1.20克， 3.72毫摩尔）、四氢呋喃 (10毫升)，加入氢氧化钠（0.16克， 3.72毫摩尔）水溶液（10 毫升），升温至 30°C， TLC监测 (乙酸乙酯：石油醚 = 1： 1作展开剂)至反应完全。加入乙酸乙酯 (100 毫升)、水（100毫升）分液萃取，水层用浓盐酸调 pH值 2~3，加入乙酸乙酯 (150毫升)萃取，有机层用饱和氯化钠溶液 (3X50毫升)洗涤，无水硫酸镁干燥，减压蒸尽溶剂，得白色固体 0.89克，收率 82%。 1-(2-Chlorophenyl)-3-(trifluoromethyl)-1H-pyrazole-5-carboxylic acid ethyl ester (1.20 g, 3.72 mmol), tetrahydrofuran (10 ml) was added sequentially to a single-necked flask. An aqueous solution of sodium hydroxide (0.16 g, 3.72 mmol) (10 ml) was added and the mixture was warmed to 30 <0>C. Add ethyl acetate (100 ml), water (100 ml), and extract with water. The aqueous layer is adjusted to pH 2~3 with concentrated hydrochloric acid, and extracted with ethyl acetate (150 ml). The mixture was washed with MgSO.sub.4.

1H MR(300MHz, CDC1₃): 7.543-7.418 (m, 4H), 7.348 (s, 1H)。 1H MR (300MHz, CDC1 ₃ ): 7.543-7.418 (m, 4H), 7.348 (s, 1H).

(6) l-(2-氯苯基 )-3- (三氟甲基) -1H-吡唑 -5-甲酰氯的制备 (6) Preparation of l-(2-chlorophenyl)-3-(trifluoromethyl)-1H-pyrazole-5-formyl chloride

将 1-(2-氯苯基 )-3- (三氟甲基) -1H-吡唑 -5-甲酸（0.40克， 1.36毫摩尔）、二氯甲烷 (10毫升)、草酰氯（0.34克， 2.72毫摩尔）依次加入到单口瓶中，室温搅拌 1小时左右,气体放出量减少；加入一滴 DMF，有大量气体放出，继续搅拌 4-6小时至无气体放出。待反应完全，减压蒸尽溶剂，加入甲苯继续脱溶得目标物 0.6克，黄色固体，收率 100%。 1-(2-Chlorophenyl)-3-(trifluoromethyl)-1H-pyrazole-5-carboxylic acid (0.40 g, 1.36 mmol), dichloromethane (10 ml), oxalyl chloride (0.34 g) , 2.72 mmol) was added to a single-mouth bottle in turn, stirred at room temperature for about 1 hour, and the amount of gas released was reduced; a small amount of DMF was added, a large amount of gas was released, and stirring was continued for 4-6 hours until no gas evolved. After the reaction was completed, the solvent was distilled off under reduced pressure, and toluene was added to afford to afford to afford to afford to afford to afford to afford to afford 0.6 g as a yellow solid.

(7) 化合物 1.24的制备 (7) Preparation of compound 1.24

在 100 毫升的反应瓶中加入 N-(l-甲基 -1-氰基乙基; )-3,5-二氯 -2-氨基苯甲酰胺 (0.52克， 1.1毫摩尔）、20毫升二氯甲烷、 1-(2-氯苯基 )-3-三氟 -1H-吡唑 -5-甲酰氯（0.6 克， 1.1毫摩尔）和吡啶（0.15克， 1.1毫摩尔），室温搅拌反应 3小时。将反应液倾入 100毫升水中，用 2x 100毫升乙酸乙酯萃取，有机层用饱和碳酸钠溶液、饱和食盐水洗涤，无水硫酸镁干燥后浓缩，残余物柱色谱提纯（淋洗液：乙酸乙酯：石油醚 = 1 :2)，得 0.4克白色固体化合物 1.24，收率: 38 %。 Add N-(l-methyl-1-cyanoethyl; )-3,5-dichloro-2-aminobenzamide (0.52 g, 1.1 mmol) in a 100 ml reaction vial, 20 ml two Methyl chloride, 1-(2-chlorophenyl)-3-trifluoro-1H-pyrazole-5-formyl chloride (0.6 g, 1.1 mmol) and pyridine (0.15 g, 1.1 mmol). hour. Pour the reaction solution Into 100 ml of water, extracted with 2×100 ml of ethyl acetate. The organic layer was washed with saturated aqueous sodium sulfate and brine, dried over anhydrous magnesium sulfate and evaporated. Ether = 1 : 2) gave 0.4 g of white solid compound 1.24, yield: 38%.

生物活性测定结果 Biological activity assay result

实例 6、杀虫活性的测定 Example 6. Determination of insecticidal activity

根据待测化合物的溶解性，原药用丙酮或二甲亚砜溶解，然后用 1%。的吐温 80 溶液配制成所需浓度的待测液 50 毫升，丙酮或二甲亚砜在总溶液中的含量不超过 10%。 Depending on the solubility of the test compound, the original pharmaceutically acceptable acetone or dimethyl sulfoxide is dissolved, and then 1% is used. The Tween 80 solution is formulated into a desired concentration of 50 ml of test solution, and the content of acetone or dimethyl sulfoxide in the total solution is not more than 10%.

实例 6.1 、杀小菜蛾活性的测定 Example 6.1, Determination of the activity of Plutella xylostella

将甘蓝叶片用打孔器打成直径 1 厘米的叶碟，用 Airbrush喷雾处理，一定浓度的测试化合物在每叶碟正反面喷雾，喷液量为 0.5 毫升，阴干后每处理接入 10头试虫（2龄），每处理 3次重复。处理后放入 24 °C、相对湿度 60%〜70%、无光照的室内培养， 96小时后调查存活虫数，计算死亡率。 The cabbage leaves were punched into a 1 cm diameter leaf disc with a puncher and sprayed with Airbrush. A certain concentration of the test compound was sprayed on the front and back of each leaf disc. The spray volume was 0.5 ml. After the dry operation, 10 shots were applied per treatment. Insects (2 years old), repeated 3 times per treatment. After the treatment, the cells were cultured at 24 ° C, relative humidity of 60% to 70%, and exposed to light. After 96 hours, the number of viable animals was investigated and the mortality was calculated.

部分测试结果如下： Some test results are as follows:

药液浓度为 150 ppm时，化合物 1.1、 1.2、 1.14a、 1.14、 1.25a、 1.26对小菜蛾的死亡率在 90%以上。 At a concentration of 150 ppm, compounds 1.1, 1.2, 1.14a, 1.14, 1.25a, 1.26 had a mortality rate of more than 90% against Plutella xylostella.

药液浓度为 40 ppm时，化合物 1.1、 1.2、 1.14a、 1.26对小菜蛾的死亡率在 90% 以上。 At a concentration of 40 ppm, the mortality of compounds 1.1, 1.2, 1.14a, 1.26 against Plutella xylostella was above 90%.

药液浓度为 lO ppm时，化合物 1.1， 1.14， 1.16对小菜蛾的死亡率在 90%以上。实例 6.2 、杀甜菜夜蛾活性的测定 At a concentration of 10 ppm, the mortality of compounds 1.1, 1.14, 1.16 against Plutella xylostella was above 90%. Example 6.2, Determination of the activity of killing beet armyworm

将甘蓝叶片用打孔器打成直径 1 厘米的叶碟，用 Airbrush喷雾处理，一定浓度的测试化合物在每叶碟正反面喷雾，喷液量为 0.5 毫升，阴干后每处理接入 8头试虫 ( 3龄），每处理 3次重复。处理后放入 24°C、相对湿度 60%〜70%、无光照的室内培养， 96小时后调查存活虫数，计算死亡率。 The cabbage leaves were punched into a 1 cm diameter leaf disc with a puncher and sprayed with Airbrush. A certain concentration of the test compound was sprayed on the front and back of each leaf dish, and the spray volume was 0.5 ml. After the dry operation, 8 passes per treatment were applied. Insects (3 years old), repeated 3 times per treatment. After the treatment, the cells were cultured at 24 ° C, relative humidity of 60% to 70%, and without light. After 96 hours, the number of surviving insects was investigated, and the mortality was calculated.

药液浓度为 20 ppm时，化合物 1.23 等对甜菜夜蛾的防治效果为 100%。 When the concentration of the drug solution is 20 ppm, the control effect of compound 1.23 on beet armyworm is 100%.

部分供试的化合物中，下列化合物在浓度为 1 ppm时对甜菜夜蛾的防治效果较好，死亡率在 90%以上： 1.1、 1.2、 1.3、 1.4、 1.5、 1.6、 1.7、 1.8、 1.9、 1.10、 1.11、 1.14、 1.15、 1.16、 1.17、 1.18、 1.19、 1.20、 1.21、 1.24、 1.27。 Among the compounds tested, the following compounds had better control effect on beet armyworm at a concentration of 1 ppm, and the mortality rate was above 90%: 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.10, 1.11, 1.14, 1.15, 1.16, 1.17, 1.18, 1.19, 1.20, 1.21, 1.24, 1.27.

部分供试的化合物中，下列化合物在浓度为 0.2 ppm时对甜菜夜蛾的防治效果较好，死亡率在 90%以上： 1.1、 1.4、 1.14、 1.15、 1.18、 1.19、 1.21、 1.24。 Among the compounds tested, the following compounds had better control effect on Spodoptera exigua at a concentration of 0.2 ppm, and the mortality rate was above 90%: 1.1, 1.4, 1.14, 1.15, 1.18, 1.19, 1.21, 1.24.

按照以上方法，选取化合物 1.14和已知化合物 KC ( WO03/015518A1中的化合物 D477 ) 进行了杀甜菜夜蛾活性的平行测定。结果见表 3。 According to the above method, Compound 1.14 and the known compound KC (Compound D477 in WO03/015518A1) were selected for parallel determination of the activity of Spodoptera exigua. The results are shown in Table 3.

表 3 : 化合物 1.14与已知化合物 KC杀甜菜夜蛾活性平行比较（死亡率，％) Table 3: Parallel comparison of compound 1.14 with known compound KC killing beet armyworm activity (mortality, %)

实例 7、杀菌活性的测定 Example 7. Determination of bactericidal activity

根据待测化合物的溶解性，原药用丙酮或二甲亚砜溶解，然后用 1%。的吐温 80 溶液配制成所需浓度的待测液 50毫升，丙酮或二甲亚砜在总溶液中的含量不超过 10 Depending on the solubility of the test compound, the original pharmaceutically acceptable acetone or dimethyl sulfoxide is dissolved, and then 1% is used. The Tween 80 solution is formulated into a desired concentration of 50 ml of the test solution, and the content of acetone or dimethyl sulfoxide in the total solution is not more than 10

%。 %.

实例 7.1 、对稻瘟病的离体杀菌活性的测定 Example 7.1 Determination of in vitro bactericidal activity against rice blast

将熔好的 AEA培养基冷却至 60°C〜70°C, 按所设浓度加入定量药剂，制成含有不同药量的含毒培养基，测试化合物的浓度为 25 ppm, 待其充分冷却后，接种直径为 0.5cm的稻瘟病菌菌片，放置培养箱中培养。在培养箱中培养 10天后进行调查，调查时分别测量每个处理的菌落生长直径，并计算抑菌率。 Cool the melted AEA medium to 60 ° C ~ 70 ° C, add the quantitative agent according to the set concentration, make a toxic medium containing different doses, the concentration of the test compound is 25 ppm, after it is fully cooled , inoculate a 0.5 cm diameter rice blast fungus, and place it in an incubator for cultivation. The culture was carried out for 10 days in an incubator, and the diameter of colony growth of each treatment was measured and the inhibition rate was calculated.

化合物 1.17对稻瘟病的防治效果在 90%以上。 Compound 1.17 has a control effect on rice blast of more than 90%.

实例 7.2 、对黄瓜霜霉病的杀菌活性的测定 Example 7.2 Determination of bactericidal activity against cucumber downy mildew

选择生长整齐一致的盆栽黄瓜幼苗剪去生长点保留二片真叶，测试化合物的喷雾浓度为 400 ppm，进行喷雾处理。处理后的试验材料在第二天接种黄瓜霜霉病孢子悬浮液，然后放置人工气候室（温度：昼 25 °C、夜 20°C，相对湿度： 95〜100%)培养，保湿培养 6天后调查防治效果，按发病程度分 6级记载，以病指计算防效。 The potted cucumber seedlings with uniform growth were selected to cut off the growth point and two true leaves were retained. The test compound was sprayed at a concentration of 400 ppm and sprayed. The treated test material was inoculated with the cucumber downy mildew spore suspension on the next day, and then placed in an artificial climate chamber (temperature: 昼25 °C, night 20 °C, relative humidity: 95~100%), and cultured for 6 days after moisturizing. Investigate the prevention and treatment effect, record according to the degree of disease, and calculate the control effect by disease index.

化合物 1.14对黄瓜霜霉病的防治效果在 90%以上。 Compound 1.14 has a control effect on cucumber downy mildew of more than 90%.

Claims

a benzamide compound, as shown in Formula I:

In the formula:

DC ₆ is selected from H or alkyl;

R _{2 is} selected from H or dC ₆ alkyl;

R _{3 is} selected from dC ₆ alkyl or C ₃ -C ₆ cycloalkyl, and the hydrogen on the group may be further substituted by the following groups: halogen, N0 ₂ , dC ₃ alkoxy, phenoxy, dC _{a 3} -alkylthio group, a dC ₃ alkylsulfinyl group or a dC ₃ alkylsulfonyl group;

Or R ₂ and R ₃ together with the attached carbon form a C ₃ -C ₆ cycloalkyl group;

Selected from H, halogen or CN;

R _{5 is} selected from halogen or CC ₃ alkyl;

Selected from halogen, dC ₃ alkyl, dC ₃ haloalkyl, dC ₃ alkoxy or dC ₃ haloalkoxy;

R _{7 is} selected from H, halogen, CN, dC ₃ alkyl, dC ₃ haloalkyl, dC ₃ alkoxy, dC ₃ alkylthio, Ci-C ₃ alkylsulfinyl or dC ₃ alkylsulfonyl;

R _{8 is} selected from halogen, CN, dC ₃ alkyl, dC ₃ haloalkyl, dC ₃ alkoxy or dC ₃ alkylthio;

X selects white CH, CF, CC^ N.

2. A compound according to claim 1 wherein, in formula I:

Ri is selected from H;

R _{2 is} selected from H or dC ₃ alkyl;

R _{3 is} selected from dC ₃ alkyl;

Selected from H, halogen or CN;

R _{5 is} selected from halogen or CrC ₃ alkyl;

Selected from halogen or CC ₃ haloalkyl;

R _{7 is} selected from H, halogen, CN or dC ₃ haloalkyl;

Selected from halogen; X selects white CH, CF, CC^N.

3. A compound according to claim 2, characterized in that, in the formula I:

Ri is selected from H;

R _{2 is} selected from H or methyl;

R _{3 is} selected from a methyl group;

Selected from chlorine, bromine, iodine or CN;

R _{5 is} selected from chlorine, bromine or methyl;

Selected from chlorine, bromine or trifluoromethyl;

R _{7 is} selected from H, chlorine or trifluoromethyl;

Selected from chlorine;

X selects white CH, CF, CC^ N.

4. An intermediate for the preparation of a compound of formula I according to claim 1, as shown in formula II:

II

In the formula:

DC ₆ is selected from H or alkyl;

R _{2 is} selected from H or dC ₆ alkyl;

Selected from H, halogen or CN;

R _{5 is} selected from halogen or CrC ₃ alkyl.

5. Use of a compound of formula I according to claim 1 for controlling pests.

6. Use of a compound of formula I according to claim 1 for the control of diseases.

7. An insecticidal and bactericidal composition comprising the compound of the formula I according to claim 1 as an active ingredient and an agricultural, forestry, hygienic acceptable carrier, the weight of the active ingredient in the composition The content is from 1 to 99%.

A method of controlling pests, characterized in that the composition of claim 7 is applied to a pest to be controlled or a medium for growth thereof at an effective dose of from 10 g to 1000 g per hectare.

A method for controlling a disease, characterized in that the composition of claim 7 is applied to a disease to be controlled or a medium for growth thereof at an effective dose of from 100 g to 2000 g per hectare.