WO2008134969A1 - Composés benzamides et leurs applications - Google Patents

Composés benzamides et leurs applications Download PDF

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Publication number
WO2008134969A1
WO2008134969A1 PCT/CN2008/070830 CN2008070830W WO2008134969A1 WO 2008134969 A1 WO2008134969 A1 WO 2008134969A1 CN 2008070830 W CN2008070830 W CN 2008070830W WO 2008134969 A1 WO2008134969 A1 WO 2008134969A1
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Prior art keywords
compound
halogen
alkyl
group
mmol
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PCT/CN2008/070830
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English (en)
French (fr)
Inventor
Bin Li
Dong Xiang
Baoshan Chai
Jing Yuan
Huibin Yang
Hong Zhang
Hongfei Wu
Haibo Yu
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Sinochem Corporation
Shenyang Research Institute Of Chemical Industry_Co., Ltd.
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Priority claimed from CN 200710011176 external-priority patent/CN101298451B/zh
Priority claimed from CN2008100571021A external-priority patent/CN101497602B/zh
Application filed by Sinochem Corporation, Shenyang Research Institute Of Chemical Industry_Co., Ltd. filed Critical Sinochem Corporation
Publication of WO2008134969A1 publication Critical patent/WO2008134969A1/zh

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D401/00Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/561,2-Diazoles; Hydrogenated 1,2-diazoles
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D231/00Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D231/00Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/16Halogen atoms or nitro radicals

Definitions

  • the invention belongs to the field of agricultural insecticides and fungicides. It relates to a benzamide compound and its use. Background technique
  • 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.
  • 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.
  • An object of the present invention is to provide a novel benzamide compound which can be applied to the control of pests and diseases.
  • the present invention provides a benzamide compound, as shown in Formula I:
  • 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;
  • R 2 and R 3 together with the attached carbon form a C 3 -C 6 cycloalkyl group
  • 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;
  • 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 is selected from white CH, CF, CC ⁇ N.
  • Ri is selected from H;
  • R 2 is selected from H or dC 3 alkyl
  • R 3 is selected from dC 3 alkyl
  • R 2 and R 3 together with the attached carbon form a C 3 -C 6 cycloalkyl group
  • R 5 is selected from halogen or CC 3 alkyl
  • R 7 is selected from H, halogen, CN or dC 3 haloalkyl
  • R 8 is selected from halogen
  • X selects white CH, CF, CC ⁇ N.
  • a still further preferred compound in the present invention is, 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
  • R 5 is selected from chlorine, bromine or methyl
  • R 7 is selected from H, chlorine or trifluoromethyl
  • X selects white CH, CF, CC ⁇ N.
  • 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:
  • 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;
  • R 2 and R 3 together with the attached carbon form a C 3 -C 6 cycloalkyl group
  • R 5 is selected from halogen or CC 3 alkyl.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a reducing agent such as iron, zinc or hydrogen
  • 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.
  • 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:
  • 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 us, 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.
  • a base such as triethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium hydrogencarbonate is advantageous for the reaction.
  • Table 1 lists the structural and physical properties of some of the compounds of formula I.
  • 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.
  • 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.
  • 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.
  • 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.
  • These chemicals can be formulated as wettable powders or creams.
  • at least one liquid or solid carrier is added, and a suitable surfactant may be added as needed.
  • 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.
  • 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.
  • 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.
  • 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,jjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj
  • N-(l-Cyanoethyl)-3-methyl-2-aminobenzamide (1.8 g, 8.9 mmol)
  • N-chlorosuccinimide N-chlorosuccinimide
  • NCS 1.2 g, 8.9 mmol
  • dimethylformamide 20 ml
  • 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%.
  • 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%.
  • 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%.
  • 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%.
  • 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%.
  • 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%.
  • 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.
  • compounds 1.1, 1.2, 1.14a, 1.14, 1.25a, 1.26 had a mortality rate of more than 90% against Plutella xylostella.
  • 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.
  • 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.
  • 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.
  • 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
  • Compound 1.17 has a control effect on rice blast of more than 90%.
  • 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: ⁇ 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.
  • Compound 1.14 has a control effect on cucumber downy mildew of more than 90%.

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  • Chemical & Material Sciences (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
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Description

苯甲酰胺类化合物及其应用 技术领域
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
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。
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。
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
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。
本发明的技术方案如下:
本发明提供了一种苯甲酰胺类化合物, 如通式 I所示:
Figure imgf000003_0001
式中:
选自 H或 d-C6烷基;
R2选自 H或 d-C6烷基;
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;
或者 R2和 R3同所连接的碳一起形成 C3-C6环烷基;
选自 H、 卤素或 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;
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;
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。
本发明中进一步优选的化合物为, 通式 I中:
Ri选自 H;
R2选自 H或 d-C3烷基;
R3选自 d-C3烷基;
或者 R2和 R3同所连接的碳一起形成 C3-C6环烷基;
选自 H、 卤素或 CN;
R5选自卤素或 C C3烷基;
选自卤素或 C C3卤烷基;
R7选自 H、 卤素、 CN或 d-C3卤烷基;
R8选自卤素;
X选白 CH、 CF、 CC^ N。
本发明中更进一步优选的化合物为, 通式 I中:
Ri选自 H;
R2选自 H或甲基;
R3选自甲基;
选自氯、 溴、 碘或 CN;
R5选自氯、 溴或甲基;
选自氯、 溴或三氟甲基;
R7选自 H、 氯或三氟甲基;
选自氯;
X选白 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:
Figure imgf000004_0001
式中:
选自 H或 d-C6烷基; R2选自 H或 d-C6烷基;
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;
或者 R2和 R3同所连接的碳一起形成 C3-C6环烷基;
选自 H、 卤素或 CN;
R5选自卤素或 C C3烷基。
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:
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。
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。
Figure imgf000005_0001
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
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。
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。
通式化合物 II的制备方法如下:
Figure imgf000005_0002
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。
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:
Figure imgf000006_0001
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, 4th 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。
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。
表 1列出了部分通式 I化合物的结构和物理性质。
表 1 部分通式 I化合物的结构
Figure imgf000007_0001
化合物 R2 R3 R4 R5 R« R7 ¾ X 外观 (熔点 (°c ) )
1.1a H CH3 H CH3 Br H CI N 白色固体 (146-150)
1.1 H CH3 CI CH3 Br H CI N 白色固体 (205 -207)
1.2 H CH3 CI CH3 CI H CI N 白色固体 (197-199)
1.3 H CH3 Br CH3 CI H CI N 白色固体 (138-140)
1.4 H CH3 Br CH3 Br H CI N 白色固体 (208-209)
1.5 H CH3 I CH3 CI H CI N 白色固体 (135-137)
1.6 H CH3 CI CI CI H CI N 白色固体 (165-168)
1.7 H CH3 Br CI CI H CI N 白色固体 (167-170)
1.8 H CH3 I CI CI H CI N 白色固体 (168-173)
1.9 H CH3 CI CI Br H CI N 白色固体 (153-156)
1.10 H CH3 Br CI Br H CI N 白色固体 (153-157)
1.11 H CH3 I CI Br H CI N 白色固体 (154-158)
1.12 H CH3 CN CI Br H CI N
1.13 H CH3 CN CH3 Br H CI N 白色固体 (210-213)
1.14a CH3 CH3 H CH3 Br H CI N 白色固体 (248-253)
1.14 CH3 CH3 CI CH3 Br H CI N 白色固体 (191-194)
1.15 CH3 CH3 CI CH3 CI H CI N 白色固体 (213-216)
1.16 CH3 CH3 Br CH3 Br H CI N 白色固体 (175-177)
1.17 CH3 CH3 CI CI CI H CI N 白色固体 (149-151)
1.18 CH3 CH3 CI CI Br H CI N 白色固体 (254-256)
1.19 CH3 CH3 CI CH3 CI H CI CH 白色固体 (252-254)
1.20 CH3 CH3 Br CH3 CI H CI CH 白色固体 (248-250)
1.21 CH3 CH3 Br Br CI H CI CH 白色固体 (177- 180)
1.22 CH3 CH3 CN CI Br H CI N
1.23 CH3 CH3 CN CH3 Br H CI N 白色固体 (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
-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
Figure imgf000008_0001
化合物 R3 R4 R5 外观 (熔点 (°c ) )
2.1 H CH3 H CH3 白色固体 (105-106)
2.2 H CH3 CI CH3 白色固体 (139-140)
2.3 H CH3 Br CH3 蜡状物
2.4 H CH3 I CH3 蜡状物
2.5 H CH3 H CI
2.6 H CH3 CI CI
2.7 H CH3 Br CI
2.8 H CH3 I CI
2.9 H CH3 CN CI
2.10 H CH3 CN CH3
2.11 CH3 CH3 H CH3 白色固体 (173-174)
2.12 CH3 CH3 CI CH3 白色固体 (199-201)
2.13 CH3 CH3 Br CH3
2.14 CH3 CH3 I CH3 蜡状物
2.15 CH3 CH3 CN CI
2.16 CH3 CH3 CN CH3
2.17 i-C3H7 CH3 H CH3 蜡状物
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)
2.20 i-C3H7 CH3 CI CI
2.21 CH2 CH2CH2CH2 H CH3 白色固体 (142-143)
2.22 CH2 CH2CH2CH2 CI CH3 蜡状物
2.23 CH2 CH2CH2CH2CH2 H CH3 白色固体 (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:
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)。
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)。
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)。
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)。
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,
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
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)。
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)。
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)。
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)。
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)。
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
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
(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)。
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,
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)。
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)。
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)。
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)。
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)。
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)。
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),
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)。
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)。
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)。
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,
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)。
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)。
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)。
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)。
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:
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)。
化合物 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)。
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)。
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)。
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。
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。
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。
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。
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。
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。
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。
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
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
实例 1、 化合物 1.2的制备
( 1 )、 2-氨基丙腈的合成
Figure imgf000012_0001
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%。
(2)、 3-甲基 -2-硝基苯甲酰氯的合成
Figure imgf000013_0001
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%。
(3 )、 N-(l-氰基乙基) -3-甲基 -2-硝基苯甲酰胺的合成
Figure imgf000013_0002
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 %。
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
Figure imgf000013_0003
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%。
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,
( 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
Figure imgf000014_0001
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%。
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)。
(6)、 3-氯 -2-肼基吡啶的合成
Figure imgf000014_0002
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%。
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)。
(7)、 l-(3-氯吡啶 -2-基) -3-吡唑烷酮 -5-羧酸乙酯的合成
Figure imgf000014_0003
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 %。
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
Figure imgf000015_0001
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%。
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
Figure imgf000015_0002
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%。
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
Figure imgf000015_0003
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%。
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
Figure imgf000016_0001
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 %。
( 12)、 化合物 1.2的合成
Figure imgf000016_0002
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 %。
实例 2、 化合物 1.14的制备
( 1 ) 2-氨基 -2-甲基丙腈的合成
Figure imgf000016_0003
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%。
(2)、 N-(l-甲基 -1-氰基乙基) -3-甲基 -2-硝基苯甲酰胺的合成
Figure imgf000017_0001
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%。
(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
Figure imgf000017_0002
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%。
(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
Figure imgf000017_0003
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%。
1H MR (300MHz, CDC13): 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
Figure imgf000018_0001
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%。
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
Figure imgf000018_0002
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%。
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
Figure imgf000018_0003
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%。
( 8)、 1-(3-氯吡啶 -2-基) -3-溴 -1H-吡唑 -5-甲酰氯的合成
Figure imgf000019_0001
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%。
(9)、 化合物 1.14的合成
Figure imgf000019_0002
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%。
实例 3、 化合物 1.17的制备
Figure imgf000019_0003
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
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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
Figure imgf000021_0001
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%。
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
Figure imgf000021_0002
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%。
1H MR(300MHz, 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
Figure imgf000021_0003
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:
(6)、 化合物 1.19的合成
Figure imgf000022_0001
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 %。
实例 5、 化合物 1.24的制备
( 1 )、 N'-(2-氯苯基 )-2,2,2-三氟乙酰肼的制备
Figure imgf000022_0002
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%。
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)。
(2) N'-(2-氯苯基 )-2,2,2-三氟乙酰甲基磺酸酯
F3C丫。
HNNH
Figure imgf000022_0003
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%。
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)。
( 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
Figure imgf000023_0001
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%。
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)。
(4) l-(2-氯苯基 )-3- (三氟甲基) -1H-吡唑 -5-甲酸乙酯的制备
Figure imgf000023_0002
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%。
1H MR(300MHz, CDC13): 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
Figure imgf000024_0001
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%。
1H MR(300MHz, CDC13): 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
Figure imgf000024_0002
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%。
(7) 化合物 1.24的制备
Figure imgf000024_0003
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 %。
生物活性测定结果
实例 6、 杀虫活性的测定
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%。
实例 6.1 、 杀小菜蛾活性的测定
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。
部分测试结果如下:
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。
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。
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
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。
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%。
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。
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。
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。
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, %)
Figure imgf000026_0001
Figure imgf000026_0002
实例 7、 杀菌活性的测定
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
%。
实例 7.1 、 对稻瘟病的离体杀菌活性的测定
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。
化合物 1.17对稻瘟病的防治效果在 90%以上。
实例 7.2 、 对黄瓜霜霉病的杀菌活性的测定
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。
化合物 1.14对黄瓜霜霉病的防治效果在 90%以上。

Claims

种苯甲酰胺类化合物, 如通式 I所示:
Figure imgf000027_0001
式中:
选自 H或 d-C6烷基;
R2选自 H或 d-C6烷基;
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;
或者 R2和 R3同所连接的碳一起形成 C3-C6环烷基;
选自 H、 卤素或 CN;
R5选自卤素或 C C3烷基;
选自卤素、 d-C3烷基、 d-C3卤烷基、 d-C3烷氧基或 d-C3卤烷氧基;
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;
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。
2、 按照权利要求 1所述的化合物, 其特征在于, 通式 I中:
Ri选自 H;
R2选自 H或 d-C3烷基;
R3选自 d-C3烷基;
或者 R2和 R3同所连接的碳一起形成 C3-C6环烷基;
选自 H、 卤素或 CN;
R5选自卤素或 CrC3烷基;
选自卤素或 C C3卤烷基;
R7选自 H、 卤素、 CN或 d-C3卤烷基;
选自卤素; X选白 CH、 CF、 CC^ N。
3、 按照权利要求 2所述的化合物, 其特征在于, 通式 I中:
Ri选自 H;
R2选自 H或甲基;
R3选自甲基;
选自氯、 溴、 碘或 CN;
R5选自氯、 溴或甲基;
选自氯、 溴或三氟甲基;
R7选自 H、 氯或三氟甲基;
选自氯;
X选白 CH、 CF、 CC^ N。
4、 一种制备权利要求 1所述的通式 I化合物的中间体, 如通式 II所示:
Figure imgf000028_0001
II
式中:
选自 H或 d-C6烷基;
R2选自 H或 d-C6烷基;
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;
或者 R2和 R3同所连接的碳一起形成 C3-C6环烷基;
选自 H、 卤素或 CN;
R5选自卤素或 CrC3烷基。
5、 一种按照权利要求 1所述的通式 I化合物用于控制虫害的用途。
6、 一种按照权利要求 1所述的通式 I化合物用于控制病害的用途。
7、 一种杀虫、 杀菌组合物, 含有如权利要求 1所述的通式 I所示化合物为活性 组分和农业、 林业、 卫生上可接受的载体, 组合物中活性组分的重量百分含量为 1-99%。
8、 一种控制虫害的方法, 其特征在于: 将权利要求 7所述的组合物以每公顷 10 克到 1000克的有效剂量施于需要控制的害虫或其生长的介质上。
9、一种控制病害的方法,其特征在于:将权利要求 7所述的组合物以每公顷 100 克到 2000克的有效剂量施于需要控制的病害或其生长的介质上。
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EP4140995A1 (en) 2021-08-27 2023-03-01 Basf Se Pyrazine compounds for the control of invertebrate pests
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EP4194453A1 (en) 2021-12-08 2023-06-14 Basf Se Pyrazine compounds for the control of invertebrate pests
EP4198033A1 (en) 2021-12-14 2023-06-21 Basf Se Heterocyclic compounds for the control of invertebrate pests
WO2023110656A1 (en) 2021-12-15 2023-06-22 Bayer Aktiengesellschaft Spectroscopic solution for non-destructive quantification of one or more chemical substances in a matrix comprising coating and bulk material in a sample, such as coated seeds, using multivariate data analysis
EP4198023A1 (en) 2021-12-16 2023-06-21 Basf Se Pesticidally active thiosemicarbazone compounds
EP4238971A1 (en) 2022-03-02 2023-09-06 Basf Se Substituted isoxazoline derivatives
WO2023203066A1 (en) 2022-04-21 2023-10-26 Basf Se Synergistic action as nitrification inhibitors of dcd oligomers with alkoxypyrazole and its oligomers
WO2023208447A1 (en) 2022-04-25 2023-11-02 Basf Se An emulsifiable concentrate having a (substituted) benzaldehyde-based solvent system
WO2024028243A1 (en) 2022-08-02 2024-02-08 Basf Se Pyrazolo pesticidal compounds
EP4342885A1 (en) 2022-09-20 2024-03-27 Basf Se N-(3-(aminomethyl)-phenyl)-5-(4-phenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-amine derivatives and similar compounds as pesticides
EP4389210A1 (en) 2022-12-21 2024-06-26 Basf Se Heteroaryl compounds for the control of invertebrate pests
CN117567417A (zh) * 2023-11-17 2024-02-20 山东绿霸化工股份有限公司 一组苯甲酰胺类化合物制备与应用
CN117567417B (zh) * 2023-11-17 2024-09-20 山东绿霸化工股份有限公司 一组苯甲酰胺类化合物制备与应用

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