WO2012034403A1 - Fluoromethoxypyrazole anthranilamide compounds, synthesization methods and uses thereof - Google Patents

Fluoromethoxypyrazole anthranilamide compounds, synthesization methods and uses thereof Download PDF

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WO2012034403A1
WO2012034403A1 PCT/CN2011/073810 CN2011073810W WO2012034403A1 WO 2012034403 A1 WO2012034403 A1 WO 2012034403A1 CN 2011073810 W CN2011073810 W CN 2011073810W WO 2012034403 A1 WO2012034403 A1 WO 2012034403A1
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alkyl
formula
compound
represented
cyano
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PCT/CN2011/073810
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French (fr)
Chinese (zh)
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窦花妮
陈杰
郑昀红
许天明
邢家华
郑志文
彭伟立
许勇华
董德臻
魏优昌
孔小林
袁静
刘刚
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中化蓝天集团有限公司
浙江省化工研究院有限公司
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Publication of WO2012034403A1 publication Critical patent/WO2012034403A1/en

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    • 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
    • C07D231/18One oxygen or sulfur atom
    • C07D231/20One oxygen atom attached in position 3 or 5
    • C07D231/22One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
    • 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
    • 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
    • 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
    • C07D401/14Heterocyclic 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 three or more hetero rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D413/00Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D413/00Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • R CF 3 , Cl, Br or OCH 2 CF 3
  • A is N or CH
  • n is an integer from 0 to 4.
  • R 2 is halogen, cyano, d-Ce alkyl or halogenated dC 3 alkyl.
  • R 1 is hydrogen, halogen, cyano, methyl or trifluoromethyl
  • R 2 is a halogen or a cyano group.
  • an isomer such as an optical isomer or a geometric isomer may be present, and the present invention encompasses various forms. Both the conformation and the mixture of isomers. Further, the present invention also encompasses various isomers other than the above within the scope of technical knowledge in the technical field. Further, although a chemical structure different from the above structural formula (I) may be formed depending on the kind of the isomer, as long as those skilled in the art can fully recognize that the isomer exists, it is apparent that Within the scope of the invention.
  • A is N or CH
  • R 1 is hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, cyanoalkyl, alkenyl, haloalkenyl, block, halo block, alkoxy, cyanoalkoxy , alkoxy, alkylthio, alkylthio, alkylsulfonyl, alkylcarbonyl, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonyl or aminoalkyl;
  • R 1 is hydrogen, halogen, cyano, methyl or trifluoromethyl
  • R 2 is a halogen or a cyano group.
  • Step (1) The post-treatment of the compound represented by the structural formula (W) is: filtration, the filter cake is washed with a small amount of an organic solvent, and the filtrate is combined and concentrated.
  • the hydrolysis reaction is carried out directly in the step (2) without isolation and purification.
  • the post-treatment of the monofluoromethoxypyrazolecarboxylic acid represented by the structural formula (III) in the step (2) is: after evaporating the organic solvent, adding water, extracting with diethyl ether, and then adding acidic hydrochloric acid to the aqueous phase to make it acidic. A large amount of solid precipitated, filtered, washed with water, and dried by an infrared lamp to give the above formula (III) a solid containing a monofluoromethoxypyrazolecarboxylic acid.
  • the base is an organic base, and the organic base is further preferably one selected from the group consisting of triethylamine, pyridine or 3-methylpyridine. Or a combination of two or more; the reaction temperature is -30 to 80 ° C, and more preferably -15 to 30 ° C.
  • the volume of the organic base is 1 to 4 times (ml/g), preferably 1 to 2 times (ml/g), based on the mass of the monofluoromethoxypyrazolecarboxylic acid represented by the structural formula (III).
  • the amount of the compound to be represented by IV) is 1:1 to 5, more preferably 1:1 to 2;
  • the aprotic solvent is selected from the group consisting of tetrahydrofuran, acetonitrile, 1, 4-dioxane, diethyl ether, toluene One or a combination of two or more of dichloromethane or chloroform.
  • the volume of the aprotic solvent is 5 to 60 times the mass of the 4H-benzo[1,3]oxazin-4-one compound containing the monofluoromethoxypyrazole represented by the structural formula ( ⁇ ) (ml/ g ) is preferably 5 to 20 times (ml/g).
  • the present invention also provides the use of a monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I) or an agriculturally applicable salt thereof, a pesticide preparation for controlling pests, and a control The method of pests.
  • a pest control agent containing a fluoromethoxypyrazole-containing orthoformylbenzamide compound represented by the structural formula (I) of the present invention or an agriculturally applicable salt thereof can be used for pest control on agricultural crops, for example It is particularly useful as a control agent for various pests that is a problem in the field of agriculture and horticulture, that is, an agricultural and horticultural pest control agent, or a pest control agent that is parasitic on animals, that is, an animal parasite control agent.
  • a pesticidal or acaricide for controlling plant parasitism such as two-spotted spider mites, red leafhopper, citrus scorpion, and whole claw scorpion.
  • the agricultural and horticultural pest control agent containing the compound of the present invention is particularly effective for agricultural pests and the like. Further, the agricultural or horticultural pest control agent containing the fluoromethoxypyrazole-containing orthoformylaminobenzamide compound represented by the structural formula (I) of the present invention or an agriculturally applicable salt thereof Various resistant pests of an agent such as an organophosphorus agent, a carbamate agent, or a pyrethroid agent are effective.
  • pest control agent containing the monofluoroamidobenzamide compound containing the monofluoromethoxypyrazole represented by the structural formula (I) of the present invention or an agriculturally applicable salt thereof may be mentioned.
  • a pest control agent for agricultural and horticultural pest control such as plant parasitic mites, agricultural pests, and soil pests.
  • Various forms of preparation are used, but as long as it is suitable for the purpose of the present invention, it can be made into all preparation forms which are generally used in the field.
  • Examples of the adjuvant used in the preparation include diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, kaolinite and sericite mixture, clay, sodium carbonate, baking soda, thenardite, zeolite, starch.
  • auxiliary agents can be used singly or in combination of two or more kinds as long as they do not deviate from the object of the present invention. Further, it may be appropriately selected from those known in the art in addition to the above-mentioned auxiliary agents.
  • Various adjuvants commonly used such as extenders, thickeners, dustproofing agents, antifreeze agents, dispersion stabilizers, phytotoxicity reducing agents, and antifungal agents, can also be used.
  • composition of the formula (I) represents a weight ratio of the compound and the various adjuvants, that is, the carrier, usually 0. 1: 99. 9 ⁇ 90: 10.
  • these preparations can be used directly or diluted with a diluent to a prescribed concentration.
  • Use various developing agents surfactants, vegetable oils, mineral oils, etc.) as needed.
  • the application of the agricultural and horticultural pest control agent containing the compound represented by the structural formula (I) of the present invention varies depending on the meteorological conditions, the form of the preparation, the application period, the application site, the type of the pest or the occurrence state, and the like, and cannot be generalized.
  • the application is generally carried out at a concentration of the active ingredient of 0.05 to 800 ppm, preferably 0.5 to 500 ppm, and the application amount per unit is 1 to 5000 g, preferably 10 to 1000 g per 1 hectare of the compound of the invention.
  • the application of the agricultural and horticultural pest control agent containing the other preferred embodiment of the pest control agent of the present invention can be carried out according to the application of the above-mentioned pest control agent.
  • the present invention also encompasses a method for controlling pests using such an application method, particularly a method for controlling plant parasitic mites and agricultural pests.
  • the application of various preparations, or dilutions thereof, of the agricultural and horticultural pest control agent containing the compound of the formula (I) of the present invention can be generally carried out by a usual application method such as spreading, spraying, misting, misting.
  • by mixing the above-mentioned active ingredients into the feed to the livestock it is also possible to hinder the occurrence and growth of pests, particularly harmful insects, in the excrement, and it is also possible to use the so-called ultra low volume.
  • Administration in this method, may contain 100% of the active ingredient.
  • the structural formula (I) according to the present invention can be used in combination with one or two or more kinds of conventional insecticidal, bactericidal or herbicidal pesticides, and exhibits more advantageous effects and functions.
  • one or more mixed pest control compositions of the compound of the formula (I) and the other active ingredients of the pesticidal compound of the present invention may be used in combination or in combination, and the scope of application, the period of treatment of the drug, and the control activity may be applied. Wait for a good direction to improve.
  • the compound of the present invention and other active ingredient compounds of the agricultural chemical may be used by mixing the separately prepared preparations at the time of dispersion, or may be used together as a preparation, and the present invention also encompasses such a mixed pest control composition. .
  • the structural formula (I) of the present invention represents a compound and a preparation thereof, and has the following advantages:
  • the present invention introduces a monofluoromethoxy group for the first time in a pyrazole ring, and the structure of the compound is novel;
  • the compound of the present invention and its preparation have a broad spectrum of insecticidal activity: against lepidopteran pests (Plutella xylostella, Spodoptera frugiperda and Helicoverpa armigera), Hemipteran pests (Peach and aphid), and the same wing
  • lepidopteran pests Plutella xylostella, Spodoptera frugiperda and Helicoverpa armigera
  • Hemipteran pests Pieric and aphid
  • the target pests rice planthopper
  • the dipteran pests Lepidoptera: Trifolium
  • the leaf-like pests Haorse genus
  • the compound of the present invention and its preparation have an extremely high insecticidal activity: at a dose of 0.16 mg/L, it has a good effect on Plutella xylostella, Spodoptera frugiperda and Helicoverpa armigera; at a dose of 4 mg/L
  • the lower aphids, trifolium and horseradish have also showed good results; at 20mg/L, the rice brown planthopper showed good effect;
  • the compound of the present invention and its preparation have good safety, and are safe to some crops such as wheat, soybean, cotton, rice, etc., and are environmentally friendly;
  • the compound of the present invention and its preparation have reasonable toxicity, ecotoxicity and environmental compatibility, and are low-toxic environmental friends. Good pesticides.
  • the examples of the present invention are described below, but the present invention is not limited thereto, and a synthesis example of the compound of the present invention will be described first. detailed description
  • the insecticidal activity evaluation test was carried out according to the following methods:
  • test targets were Plutella xylostella, Spodopterem f rug i per da), Helicoverpa armigera, Aphis medicaginis ⁇ Myzus persicae ⁇ Ta lugens), Liriomyza trifolii (r /o ) and horseradish (Phaedon cochleariae).
  • Mortality ( % ) number of live insects ⁇ ⁇ )0
  • Potted cotton (2-3 leaf ages) was sprayed with the drug and allowed to dry. Put in the culture room and continue normal culture. After 5, 12, 19d, cut the leaves with scissors, place them in a 09cm plastic petri dish, connect the cotton bollworm larvae, put a piece of filter paper, and cover. Place in the observation room and check the results after 6 days. Mortality was calculated according to the above mortality calculation formula. Abnormal worms are also seen as dead. Compounds 3, 8, 10, 33, 36, 49, 51 in Table 1 gave 100% mortality at 20 mg/L. Compounds 8, 10, 33, and 51 gave 100% mortality at 4 mg/L.
  • Potted cabbage (3-4 leaf ages) was sprayed with the drug and allowed to dry. Put in the culture room and continue normal culture. After 5, 12, 19d, use the nymphs respectively. Place in the observation room and check the results after 7-10d. Mortality is calculated according to the above mortality calculation formula. Abnormal worms are also seen as death. Compounds 3, 8, 10, 33, 51 in Index Table 1 achieved 100% mortality at 20 mg/L. Compounds 3, 8, 33, 51 gave at least 90% mortality at 4 mg/L.
  • Example 12 Effect test on rice brown planthopper Nilaparvata lugens
  • Potted cabbage (3-4 leaf ages) was sprayed with the drug and allowed to dry. Put in the culture room and continue normal culture. After 5, 12, 19d, cut the leaves with scissors, place them in a 09cm plastic petri dish, and connect the 2nd instar larvae of horseradish or Plutella xylostella, put a piece of filter paper, and cover. Place in the observation room and check the results after 6-7 days. Mortality was calculated according to the above mortality calculation formula. Abnormal worms are also seen as death. Compounds 3, 8, 10, 33, 36, 49, 51 in Table 1 gave 100% mortality at 20 mg/L. Compounds 3, 8, 33, 51 gave at least 90% mortality at 4 mg/L. Compound 8 gave at least 90% mortality at 0.8 mg/L. According to the above method, compound 8 and the known compound chlorantraniliprole were selected for killing the diamondback moth, cockroach and rice brown fly fruit as shown in Table 3.

Abstract

Fluoromethoxypyrazole anthranilamide compounds of formula (I) or agrochemical salts thereof, as well as synthesization methods and uses thereof. The compounds of formula (I) have broad-spectrum insecticidal activities and are effective to pests of lepidopteron (such as Plutella xylostella), hemipteran (such as Aphis medicaginis), homopteran (such as Nilaoarvata lugens) and the like. Agricultural preparations including compounds of formula (I) and methods of preventing and controlling pests are involved.

Description

说明书  Instruction manual
一种含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类化合物、 其合成方法及应用 技术领域  O-formylaminobenzamide compound containing monofluoromethoxypyrazole, synthesis method and application thereof
本发明提供了一种邻甲酰氨基苯甲酰胺类化合物。 背景技术  The present invention provides an o-formylaminobenzamide compound. Background technique
邻甲酰氨基苯甲酰胺类化合物 (鱼尼丁受体抑制剂类) 是近几年开发的防治无脊锥动物 害虫的有效杀虫剂。  O-formylaminobenzamides (Finedine Receptor Inhibitors) are effective insecticides developed in recent years to control pests without ridges.
PCT专利申请 WO2003/015519 公开了如下具有杀虫活性的化合物:  The PCT patent application WO2003/015519 discloses the following compounds having insecticidal activity:
Figure imgf000003_0001
Figure imgf000003_0001
R=CF3,Cl,Br或 OCH2CF3 R=CF 3 , Cl, Br or OCH 2 CF 3
PCT专利申请 WO2004/033468公开了如下具有杀虫活性的化合物:  The PCT patent application WO2004/033468 discloses the following compounds having insecticidal activity:
Figure imgf000003_0002
Figure imgf000003_0002
PCT专利申请 WO2004/067528公开了如下具有杀虫活性的化合物:  PCT patent application WO2004/067528 discloses the following compounds having insecticidal activity:
Figure imgf000003_0003
Figure imgf000003_0003
PCT专利申请 WO2006/080311公开了如下具有杀虫活性的化合物: PCT patent application WO2006/080311 discloses compounds having insecticidal activity as follows:
Figure imgf000004_0001
Figure imgf000004_0002
Figure imgf000004_0001
Figure imgf000004_0002
PCT专利申请 WO2008/134969公开了如下具有杀虫活性的化合物:  The PCT patent application WO 2008/134969 discloses the following compounds having insecticidal activity:
Figure imgf000004_0003
Figure imgf000004_0003
上述 PCT专利申请中所有公开的化合物虽与本发明所述化合物有一定的相似之处, 但都没有记载具有相当于本发明所述式 ( I ) 表示的含一氟甲氧基吡唑的邻甲酰氨基苯甲 酰胺类化合物。 尽管用于防治无脊椎害虫的许多产品可以购买, 但仍然需要更有效、 低毒、 低成本、 对环境安全的新化合物。 发明内容  All of the compounds disclosed in the above PCT patent application have certain similarities with the compounds of the present invention, but none of them have a homologous one containing a fluoromethoxypyrazole represented by the formula (I) of the present invention. Formylaminobenzamides. Although many products for controlling invertebrate pests can be purchased, there is still a need for new compounds that are more effective, less toxic, less costly, and environmentally safe. Summary of the invention
本发明的目的在于提供一种新的有害生物防除剂, 可防除在农业园艺领域中成为问题 的各种有害生物, 或寄生于动物的有害生物, 在低药量下具有对有害生物超高的防治效果。  The object of the present invention is to provide a novel pest control agent which can prevent various pests which are problems in the field of agriculture and horticulture, or pests which are parasitic on animals, and which have high pests at low doses. Control effect.
为实现上述目的, 本发明提供如下技术手段:  To achieve the above object, the present invention provides the following technical means:
一种结构式(I )表示的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类化合物或其农业上适 用的盐,
Figure imgf000005_0001
A fluoromethoxypyrazole-containing orthoamidobenzamide compound represented by the formula (I) or an agriculturally applicable salt thereof,
Figure imgf000005_0001
其巾:  Its towel:
A为 N或 CH;  A is N or CH;
R1为氢、 卤素、 氰基、 硝基、 烷基、 卤代烷基、 氰基烷基、 链烯基、 卤代链烯基、 块基、 卤代块基、 烷氧基、 氰基烷氧基、 ^代烷氧基、 烷硫基、 ^代烷硫基、 烷基磺酰基、 烷基羰 基、 ^代烷基羰基、 烷氧基羰基、 ^代烷氧基羰基或氨基烷基; R 1 is hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, cyanoalkyl, alkenyl, haloalkenyl, block, halo block, alkoxy, cyanoalkoxy , alkoxy, alkylthio, alkylthio, alkylsulfonyl, alkylcarbonyl, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonyl or aminoalkyl;
R2为氢、 卤素、 烷基、 卤代烷基、 烷氧基、 卤代烷氧基或氰基; R 2 is hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or cyano;
R3为氢、 烷基或烷氧基; R 3 is hydrogen, alkyl or alkoxy;
R4为氢、 氰基、 烷基、 烷氧基、 烷氨基、 ^代烷基、 ^代烷氧基、 ^代烷氨基、 氰基烷 基、 环烷基、 ^代环烷基、 羟烷基、 烷氧羰基甲基、 烷氧基酰胺基、 烷基酰胺基、 ^代烷基 酰胺基、 氰基取代的烷基酰胺基或芳杂环甲基; R 4 is hydrogen, cyano, alkyl, alkoxy, alkylamino, alkyl, alkoxy, alkylamino, cyanoalkyl, cycloalkyl, cycloalkyl, hydroxy An alkyl group, an alkoxycarbonylmethyl group, an alkoxyamide group, an alkylamido group, an alkylalkylamide group, a cyano substituted alkylamido group or an arylheterocyclic methyl group;
或者 R3和 R4与所连接的 N—起形成三元、 四元、 五元或六元环; Or R 3 and R 4 form a ternary, quaternary, five- or six-membered ring with the N-linked group;
m为 0〜4的整数;  m is an integer from 0 to 4;
n为 0〜4的整数。 作为优选的方式, 结构式 (I ) 表示的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类化合物 中:  n is an integer of 0 to 4. In a preferred embodiment, the monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I):
R1为氢、 卤素、 氰基、 硝基、 d-Ce浣基、 d-Ce卤代烷基、 氰基 d-Ce烷基、 C2_C6链烯基、R 1 is hydrogen, halogen, cyano, nitro, d-Ce fluorenyl, d-Ce haloalkyl, cyano d-Ce alkyl, C 2 _C 6 alkenyl,
C2_C6卤代链烯基、 C2-C6块基、 卤代 C3-C6块基、 ( -(:6烷氧基、 d-C6氰基烷氧基、 d-C6卤代烷 氧基、 d-Ce烷硫基、 d-Ce卤代烷硫基、 d-Ce烷基磺酰基、 CfCe烷基羰基、 卤代 CfCe烷基羰 基、 ( Ce烷氧基羰基、 ^代 d-C6烷氧基羰基或氨基 d-C6烷基; C 2 -C 6 haloalkenyl, C 2 -C 6 block, halo C 3 -C 6 block, (-(: 6 alkoxy, dC 6 cyanoalkoxy, dC 6 haloalkoxy) , d-Ce alkylthio, d-Ce haloalkylthio, d-Ce alkylsulfonyl, CfCe alkylcarbonyl, halogenated CfCe alkylcarbonyl, (ce alkoxycarbonyl, ^dC 6 alkoxycarbonyl) Or an amino dC 6 alkyl group;
R2为氢、 卤素、 d-Ce烷基、 卤代 d-Ce烷基、 d-Ce烷氧基、 卤代 CfCe烷氧基或氰基;R 2 is hydrogen, halogen, d-Ce alkyl, halogenated d-Ce alkyl, d-Ce alkoxy, halogenated CfCe alkoxy or cyano;
R3为氢或 烷基; R 3 is hydrogen or an alkyl group;
R4为氢、 氰基、 d-Ce烷基、 d-Ce烷氧基、 d-Ce烷氨基、 卤代 CfCe烷基、 卤代 CfCe烷氧 基、 卤代 ( -(:6烷氨基、 氰基 d-C6烷基、 (:3_(:6环烷基、 卤代(:3_(:6环烷基、 羟( -(:6烷基、 d-c6 烷氧羰基甲基、 (^-(:6烷氧基酰胺基、 d-c6烷基酰胺基、 ^代 d-c6烷基酰胺基、 氰基取代的 d-c6烷基酰胺基或芳杂环甲基; R 4 is hydrogen, cyano, d-Ce alkyl, d-Ce alkoxy, d-Ce alkylamino, halogenated CfCe alkyl, halogenated CfCe alkoxy, halo (-(: 6 alkylamino, Cyano dC 6 alkyl, (: 3 _(: 6 cycloalkyl, halo (: 3 _: 6 cycloalkyl, hydroxy (-(: 6 alkyl, dc 6 alkoxycarbonylmethyl, (^ -(: 6 alkoxyamido group, dc 6 alkyl amide group, ^ dc 6 alkyl amide group, cyano substituted dc 6 alkyl amide group or aryl heterocyclic methyl group;
m为 2;  m is 2;
n为 1。 作为进一步优选的方式, 结构式 (I ) 表示的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺 类化合物中: n is 1. In a further preferred embodiment, the monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I):
A为 N;  A is N;
R1为氢、 卤素、 氰基、 CfCe烷基、 d- 卤代烷基或 d- 烷基羰基; R 1 is hydrogen, halogen, cyano, CfCe alkyl, d-haloalkyl or d-alkylcarbonyl;
R2为卤素、 氰基、 d-Ce烷基或卤代 d-C3烷基。 R 2 is halogen, cyano, d-Ce alkyl or halogenated dC 3 alkyl.
作为更进一步优选的方式, 结构式 (I ) 表示的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰 胺类化合物中:  In a still further preferred mode, the monofluoroamidobenzoylamine compound containing a monofluoromethoxypyrazole represented by the formula (I):
R1为氢、 卤素、 氰基、 甲基或三氟甲基; R 1 is hydrogen, halogen, cyano, methyl or trifluoromethyl;
R2为卤素或氰基。 R 2 is a halogen or a cyano group.
作为最为优选的方式, 结构式 (I ) 表示的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类 化合  As a most preferred mode, the fluoroformylpyrazole-containing o-formylaminobenzamide represented by the formula (I)
Figure imgf000006_0001
Figure imgf000006_0001
在上述 A、 R R2、 R3、 R4和 R5基团中: In the above A, RR 2 , R 3 , R 4 and R 5 groups:
作为 R R2或 R4中的卤素或作为取代基的卤素, 可列举出, 氟、 氯、 溴或碘的各原子。 作为取代基的卤素的数可以为 1或 2以上, 在 2以上的场合, 各卤素可以相同也可以不同。 另外, 卤素的取代位置可以在任一位置。 Examples of the halogen in the RR 2 or R 4 or the halogen as the substituent include each atom of fluorine, chlorine, bromine or iodine. The number of halogens as a substituent may be 1 or 2 or more, and when it is 2 or more, each halogen may be the same or different. In addition, the halogen substitution position can be at any position.
R R2、 R3或 R4中的烷基或烷基部分, 可以是直链也可以是支链。 作为其具体例, 可列 举出, 甲基、 乙基、 丙基、 异丙基、 丁基、 叔丁基、 戊基、 己基这样的 d— 6的烷基等。 The alkyl or alkyl moiety in RR 2 , R 3 or R 4 may be straight or branched. Specific examples thereof include a d- 6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group or a hexyl group.
R1中的链烯基或链烯基部分,可以是直链或支链的任一一种。作为其具体例,可列举出, 乙烯基、 1-丙烯基、 烯丙基、 异丙烯基、 1-丁烯基、 1, 3-丁二烯基、 1-己烯基这样的 C26的 R1中的块基或块基部分, 可以是直链或支链的任一一种。 作为其具体例, 可列举出乙块 基、 2-丁块基、 2-戊块基、 3-己块基这样的 C26的块基等。 The alkenyl or alkenyl moiety in R 1 may be either a straight chain or a branched chain. Specific examples thereof include C 2 such as a vinyl group, a 1-propenyl group, an allyl group, an isopropenyl group, a 1-butenyl group, a 1, 3-butadienyl group, and a 1-hexenyl group. 6 The block group or the block group portion in R 1 may be either a straight chain or a branched chain. Specific examples thereof include acetylene group, 2-block group, 2-block basis, a block group such as 3-hexyl C 2 - 6 group of blocks.
在上述结构式(I )表示的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类化合物中, 有时存 在光学异构体、几何异构体这样的异构体, 本发明包含各异构体及异构体混合物这两者情况。 此外, 在该技术领域的技术常识的范围内, 本发明也包含上述以外的各种异构体。 另外, 虽 然有时因异构体的种类导致形成与上述结构式 (I )不同的化学结构的情况, 但只要是本领 域技术人员就能充分认识这是存在异构体的关系, 因此很明显是在本发明的范围内。  In the orthoformylaminobenzamide compound containing a monofluoromethoxypyrazole represented by the above structural formula (I), an isomer such as an optical isomer or a geometric isomer may be present, and the present invention encompasses various forms. Both the conformation and the mixture of isomers. Further, the present invention also encompasses various isomers other than the above within the scope of technical knowledge in the technical field. Further, although a chemical structure different from the above structural formula (I) may be formed depending on the kind of the isomer, as long as those skilled in the art can fully recognize that the isomer exists, it is apparent that Within the scope of the invention.
本发明还提供一种用于制备上述结构式(I )表示的含一氟甲氧基吡唑的邻甲酰氨基苯甲 酰胺类化合物, 具有以下结构式 (Π ):  The present invention also provides an orthoylaminobenzamide compound containing a monofluoromethoxypyrazole represented by the above structural formula (I), which has the following structural formula (Π):
Figure imgf000007_0001
Figure imgf000007_0001
其中 A、 R1和 R2基团及!!!和!!与结构式 (I ) 表示的含一氟甲氧基吡唑的邻甲酰氨基苯甲 酰胺类化合物中基团相对应, 即: Among them, A, R 1 and R 2 groups and! ! ! with! Corresponding to a group in the o-formylaminobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I), namely:
A为 N或 CH;  A is N or CH;
R1为氢、 卤素、 氰基、 硝基、 烷基、 卤代烷基、 氰基烷基、 链烯基、 卤代链烯基、 块基、 卤代块基、 烷氧基、 氰基烷氧基、 ^代烷氧基、 烷硫基、 ^代烷硫基、 烷基磺酰基、 烷基羰 基、 ^代烷基羰基、 烷氧基羰基、 ^代烷氧基羰基或氨基烷基; R 1 is hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, cyanoalkyl, alkenyl, haloalkenyl, block, halo block, alkoxy, cyanoalkoxy , alkoxy, alkylthio, alkylthio, alkylsulfonyl, alkylcarbonyl, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonyl or aminoalkyl;
R2为氢、 卤素、 烷基、 卤代烷基、 烷氧基、 卤代烷氧基或氰基; R 2 is hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or cyano;
m为 0〜4的整数;  m is an integer from 0 to 4;
n为 0〜4的整数。  n is an integer of 0 to 4.
作为优选的方式, 结构式 (Π ) 表示的化合物中:  In a preferred embodiment, the compound represented by the structural formula (Π) is:
A为 N;  A is N;
R1为氢、 卤素、 氰基、 硝基、 CrC6烷基、 CrC6卤代烷基、 氰基 CrC6烷基、 C2-C6链烯 基、 C2-C6卤代链烯基、 C2-C6块基、 卤代 C3-C6块基、 -C6烷氧基、 d-C6氰基烷氧基、 -C6 卤代烷氧基、 ^-^烷硫基、 C C6 ^代烷硫基、 CrC6烷基磺酰基、 CrC6烷基羰基、 ^代 CrC6 烷基羰基、 -C6烷氧基羰基、 ^代 -C6烷氧基羰基或氨基 -C6烷基; R 1 is hydrogen, halogen, cyano, nitro, C r C 6 alkyl, C r C 6 haloalkyl, cyano C r C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 Haloalkenyl, C 2 -C 6 block, halogenated C 3 -C 6 block, -C 6 alkoxy, dC 6 cyanoalkoxy, -C 6 haloalkoxy, ^-alkyl thio, CC 6 ^ substituting alkylthio, C r C 6 alkylsulfonyl group, a C r C 6 alkylcarbonyl, C r C 6 substituting ^ alkylcarbonyl, -C 6 alkoxycarbonyl group, -C ^ substituting 6 alkoxycarbonyl or amino-C 6 alkyl;
R2为氢、 卤素、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基、 卤代 CrC6烷氧基或氰基; m为 2; n为 1。 R 2 is hydrogen, halogen, C r C 6 alkyl, halogenated C r C 6 alkyl, C r C 6 alkoxy, halogenated C r C 6 alkoxy or cyano; m is 2; n is 1.
作为进一步优选的方式, 结构式 (Π ) 表示的化合物中:  As a further preferred mode, among the compounds represented by the structural formula (Π):
R1为氢、 卤素、 氰基、 d-C6烷基、 d-C6卤代烷基或 d-C6烷基羰基; R 1 is hydrogen, halogen, cyano, dC 6 alkyl, dC 6 haloalkyl or dC 6 alkylcarbonyl;
R2为卤素、 氰基、 CfCe烷基或卤代 d-C3烷基。 R 2 is halogen, cyano, CfCe alkyl or halogenated dC 3 alkyl.
作为更为优选的方式, 结构式 (Π ) 表示的化合物中:  In a more preferred manner, among the compounds represented by the structural formula (Π):
R1为氢、 卤素、 氰基、 甲基或三氟甲基; R 1 is hydrogen, halogen, cyano, methyl or trifluoromethyl;
R2为卤素或氰基。 R 2 is a halogen or a cyano group.
本发明还提供上述结构式(I )表示的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类化合物 的合成方法。  The present invention also provides a method for synthesizing a monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole represented by the above structural formula (I).
一种结构式 (I ) 表示的的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类化合物合成方法, 包括如下步骤:  A method for synthesizing a monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I), comprising the steps of:
( 1 ) 在非质子性溶剂中, 结构式 (VI) 表示的化合物与一氟一溴甲烷在缚酸剂作用下, 反应得到结构式 (W) 表示化合物;  (1) In an aprotic solvent, a compound represented by the formula (VI) is reacted with a monofluoromethane bromide under an action of an acid binding agent to give a structural formula (W) to represent a compound;
(2) 在质子性溶剂中, 结构式 (W) 表示化合物在碱作用下水解得到结构式 (III) 表 示的含一氟甲氧基吡唑羧酸; (2) In a protic solvent, the structural formula (W) indicates that the compound is hydrolyzed under a base to give a monofluoromethoxypyrazolecarboxylic acid represented by the formula (III);
CHPF  CHPF
Yesterday
Figure imgf000008_0001
Figure imgf000008_0001
(VI) (VD) (III)  (VI) (VD) (III)
(3) 在非质子性溶剂中, 加入碱和烷基磺酰氯, 结构式 (III) 表示的含一氟甲氧基吡 唑羧酸和结构式 (V ) 表示的取代邻氨基苯甲酸反应得结构式 (Π ) 表示的含一氟甲氧基吡 唑的 4H-苯并 [1, 3]噁嗪 -4-酮类化合物;  (3) In a non-protic solvent, a base and an alkylsulfonyl chloride are added, and the monofluoro-aminopyrazolecarboxylic acid represented by the formula (III) and the substituted anthranilic acid represented by the formula (V) are reacted to obtain a structural formula ( 4 ) represented by a monofluoro-pyridazole-containing 4H-benzo[1,3]oxazin-4-one compound;
Figure imgf000008_0002
Figure imgf000008_0002
( 4 ) 在非质子性溶剂中, 结构式 (Π )表示的含一氟甲氧基吡唑的 4Η-苯并 [1, 3]噁嗪 -4-酮类化合物和结构式 (IV)表示的化合物反应得结构式 (I )表示的含一氟甲氧基吡唑的 邻甲酰氨基苯甲酰胺类化合物;
Figure imgf000009_0001
(4) A 4-fluorenyl-benzo[Z,3-oxazin-4-one-based compound containing a monofluoromethoxypyrazole represented by the formula (Π) and a compound represented by the formula (IV) in an aprotic solvent Reacting the o-formylaminobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I);
Figure imgf000009_0001
(II) (IV) ( I )  (II) (IV) (I)
结构式 (II) 至 (YD) 表示的化合物中 A、 R R2、 R3、 R4和 R5基团以及 m和 n的定义及 优选方式如上述结构式(I)表示的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类化合物, 其中 结构式 (VI) 表示的化合物中!^为^— 6烷基。 The definitions and preferred forms of the A, RR 2 , R 3 , R 4 and R 5 groups and m and n in the compounds represented by the formulae (II) to (YD) are as defined above for the monofluoromethoxy group represented by the formula (I). An orthoformylbenzamide compound of pyrazole, wherein the compound represented by the formula (VI) is in the compound! ^ is ^ -6 alkyl.
上述结构式 (VI) 表示的化合物为公知化合物, 其制备方法可以参照 PCT 专利申请 WO03015519和 WO2006023783。  The compound represented by the above formula (VI) is a known compound, and its preparation method can be referred to PCT Patent Application No. WO03015519 and WO2006023783.
作为优选的实施方式, 前述合成方法步骤 (1) 中, 结构式 (VI)表示的化合物与一氟一 溴甲烷和缚酸剂的投料物质的量比为 1: 1.1〜2: 1.1〜2, 进一步优选 1: 1.1〜1.5: 1.1〜 1.5; 所述非质子性溶剂选自四氢呋喃、 乙腈、 1, 4-二氧六环或丙酮中的一种或两种以上 组合; 反应温度为 10〜90°C, 进一步优选 20〜80° (:。  In a preferred embodiment, in the step (1) of the synthesis method, the ratio of the compound represented by the formula (VI) to the material of the monofluoromethane bromide and the acid binding agent is 1: 1.1 to 2: 1.1 to 2, further preferably 1: 1.1~1.5: 1.1~1.5; The aprotic solvent is selected from one or a combination of two or more of tetrahydrofuran, acetonitrile, 1,4-dioxane or acetone; the reaction temperature is 10 to 90 ° C Further preferably 20 to 80° (:.
步骤 (1) 结构式 (W)表示的化合物的后处理是: 过滤, 滤饼用少量的有机溶剂进行淋 洗, 滤液合并, 浓縮。 不必进行分离纯化直接进行步骤 (2) 所述水解反应。  Step (1) The post-treatment of the compound represented by the structural formula (W) is: filtration, the filter cake is washed with a small amount of an organic solvent, and the filtrate is combined and concentrated. The hydrolysis reaction is carried out directly in the step (2) without isolation and purification.
作为优选的实施方式, 前述合成方法步骤(2) 中, 结构式 (W)表示化合物与碱的投料 物质的量比为 1: 1〜1.5, 进一步优选 1: 1〜1.2; 所述质子性溶剂为甲醇和 /或乙醇; 反 应温度为 10〜90°C, 进一步优选 20〜80° (:。  In a preferred embodiment, in the step (2) of the above synthesis method, the structural formula (W) represents an amount ratio of the compound to the base material to be 1:1 to 1.5, further preferably 1:1 to 1.2; and the protic solvent is Methanol and/or ethanol; reaction temperature is 10 to 90 ° C, further preferably 20 to 80 ° (:.
步骤 (2) 中结构式 (III) 表示的含一氟甲氧基吡唑羧酸的后处理是: 蒸除有机溶剂后, 加水, 用乙醚进行萃取, 然后水相中加稀盐酸使呈酸性, 大量固体析出, 过滤, 水洗, 红外 灯干燥, 得所述结构式 (III) 表示含一氟甲氧基吡唑羧酸固体。  The post-treatment of the monofluoromethoxypyrazolecarboxylic acid represented by the structural formula (III) in the step (2) is: after evaporating the organic solvent, adding water, extracting with diethyl ether, and then adding acidic hydrochloric acid to the aqueous phase to make it acidic. A large amount of solid precipitated, filtered, washed with water, and dried by an infrared lamp to give the above formula (III) a solid containing a monofluoromethoxypyrazolecarboxylic acid.
作为优选的实施方式, 前述合成方法步骤(3) 中, 结构式 (III)表示的含一氟甲氧基吡 唑羧酸和结构式(V)表示的取代邻氨基苯甲酸及烷基磺酰氯的投料物质的量比为 1: 1〜1.5: 2〜3, 进一步优选 1: 1〜1.2: 2〜2.5; 所述烷基磺酰氯为甲基磺酰氯; 所述非质子性溶剂 选自四氢呋喃、 乙腈、 1, 4-二氧六环、 乙醚或甲苯中的一种或两种以上组合; 所述碱为 有机碱, 有机碱进一步优选自三乙胺、 吡啶或 3-甲基吡啶中的一种或两种以上组合; 反 应温度为 -30〜80°C, 进一步优选 -15〜30°C。 其中有机碱的体积用量为结构式(III)表示的 含一氟甲氧基吡唑羧酸质量的 1~4倍 (ml/g), 优选为 1~2倍 (ml/g)。  In a preferred embodiment, in the step (3) of the above synthesis method, the fluorine-containing methoxypyrazolecarboxylic acid represented by the formula (III) and the substituted anthranilic acid and alkylsulfonyl chloride represented by the structural formula (V) are charged. The amount ratio of the substance is 1:1 to 1.5: 2 to 3, further preferably 1:1 to 1.2: 2 to 2.5; the alkylsulfonyl chloride is methylsulfonyl chloride; and the aprotic solvent is selected from tetrahydrofuran and acetonitrile. One or a combination of two or more of 1, 4-dioxane, diethyl ether or toluene; the base is an organic base, and the organic base is further preferably one selected from the group consisting of triethylamine, pyridine or 3-methylpyridine. Or a combination of two or more; the reaction temperature is -30 to 80 ° C, and more preferably -15 to 30 ° C. The volume of the organic base is 1 to 4 times (ml/g), preferably 1 to 2 times (ml/g), based on the mass of the monofluoromethoxypyrazolecarboxylic acid represented by the structural formula (III).
步骤(3) 的后处理为: 反应结束, 过滤, 滤饼先后用水、 有机溶剂与水的混合溶剂及少 量有机溶剂洗后得第一批固体; 滤液蒸除溶剂后, 加有机溶剂萃取, 无水硫酸钠干燥后, 过 滤, 浓縮, 用乙醇进行重结晶, 得第二批固体; 两批固体合并, 得所述结构式 (II) 表示的 化合物。 The post-treatment of the step (3) is: the end of the reaction, filtration, the filter cake is washed with water, a mixed solvent of an organic solvent and water, and a small amount of an organic solvent to obtain a first solid; the filtrate is distilled off, and then extracted with an organic solvent, After the sodium sulfate is dried, Filtration, concentration, recrystallization from ethanol to give a second crop of solids; and two batches of solids combined to give the compound of formula (II).
其中结构式 (V) 表示的取代邻氨基苯甲酸是一种已知化合物, 可以通过许多方法进行 制备, 可参照以下文献: Organic Synthesis, Coll.Vol.79,pl96(2002) ; Vol.l0,p23(2004) ; Adv.Heterocycl.Chem.1975, 18, 1 -58 ; Journal of the Brazilian Chemical Society 2001,12(3),273-324; Angew.Chem.Int.Ed.Engl.1980, 19,222-223。  The substituted anthranilic acid represented by the structural formula (V) is a known compound and can be produced by a number of methods, and can be referred to the following literature: Organic Synthesis, Coll. Vol. 79, pl 96 (2002); Vol. l0, p23 (2004); Adv. Heterocycl. Chem. 1975, 18, 1-58; Journal of the Brazilian Chemical Society 2001, 12(3), 273-324; Angew. Chem. Int. Ed. Engl. 1980, 19, 222-223 .
作为优选的实施方式, 前述合成方法步骤(4 ) 中, 结构式 (Π )表示的含一氟甲氧基吡 唑的 4H-苯并 [ 1, 3]噁嗪 -4-酮类化合物和结构式(IV )表示的化合物的投料物质的量比为 1 : 1〜5, 进一步优选 1 : 1〜2; 所述非质子性溶剂选自四氢呋喃、 乙腈、 1, 4-二氧六环、 乙 醚、 甲苯、 二氯甲烷或氯仿中的一种或两种以上组合。 其中非质子性溶剂的体积用量为 结构式 (Π ) 表示的含一氟甲氧基吡唑的 4H-苯并 [ 1, 3]噁嗪 -4-酮类化合物质量的 5~60 倍 ( ml/g ) , 优选为 5~20倍 (ml/g)。  In a preferred embodiment, in the step (4) of the above synthesis method, a tetrafluoromethoxypyrazole-containing 4H-benzo[1,3]oxazin-4-one compound represented by the formula (Π) and a structural formula ( The amount of the compound to be represented by IV) is 1:1 to 5, more preferably 1:1 to 2; the aprotic solvent is selected from the group consisting of tetrahydrofuran, acetonitrile, 1, 4-dioxane, diethyl ether, toluene One or a combination of two or more of dichloromethane or chloroform. The volume of the aprotic solvent is 5 to 60 times the mass of the 4H-benzo[1,3]oxazin-4-one compound containing the monofluoromethoxypyrazole represented by the structural formula (Π) (ml/ g ) is preferably 5 to 20 times (ml/g).
下面, 将本发明所涉  Below, the invention is involved
Figure imgf000010_0001
Figure imgf000010_0001
以下的索引表 1中采用的縮写如下: t是叔、 n是正、 i是异、 s是仲、 Me 是甲基、 Et是乙基、 Pr是丙基、 Bu是丁基;相应的 i-Pr是异丙基等。索引表 1中 R2=3_C1, n=l, R: 和 R4可以为独立的取代基, 也可以连接成一个整体。 The following abbreviations used in the following Table 1 are as follows: t is unterminated, n is positive, i is hetero, s is secondary, Me is methyl, Et is ethyl, Pr is propyl, Bu is butyl; corresponding i- Pr is an isopropyl group or the like. In the index table 1, R 2 = 3_C1, n = 1, R : and R 4 may be independent substituents, or may be connected as a whole.
Figure imgf000010_0002
Figure imgf000010_0002
Figure imgf000011_0001
Figure imgf000012_0001
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000011_0001
Figure imgf000012_0001
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000018_0001
以下索引表 2为索引表 1所述部分化合物的物化性能及核磁数据。 注:索引表 2所述的编号与索引表 1所述的化合物编号相对应。其中 s为单峰, d为双峰, t 为三重峰, q为四重峰, m为多重峰, brs为宽单峰。 索引表 2 The following index table 2 shows the physical and chemical properties and nuclear magnetic data of some of the compounds described in Table 1. Note: The numbers described in Index Table 2 correspond to the compound numbers described in Table 1. Where s is a single peak, d is a doublet, t is a triplet, q is a quartet, m is a multiplet, and brs is a broad singlet. Index table 2
编号 熔点 /°c ¾NMR (除非另有说明, 试剂均为 CDC13) No. Melting point / °c 3⁄4 NMR (Reagents are CDC1 3 unless otherwise stated)
0. 95-0. 98 (m, 3H) , 1. 58-1. 62 (m, 2H) , 2. 19 (s, 3H) ,  0. 95-0. 98 (m, 3H) , 1. 58-1. 62 (m, 2H) , 2. 19 (s, 3H) ,
3. 32-3. 37 (m, 2H) , 5. 83— 5. 96 (d, 2H) , 6. 12 (s, 1H) ,  3. 32-3. 37 (m, 2H), 5. 83— 5. 96 (d, 2H), 6. 12 (s, 1H),
1  1
6. 66 (s, 1H) , 7. 22 (s, 1H) , 7. 33-7. 37 (m, 1H) ,  6. 66 (s, 1H) , 7. 22 (s, 1H) , 7. 33-7. 37 (m, 1H) ,
7. 82-7. 84 (d, 1H) , 8· 45- 8· 46 (d, 1H) , 10. 00 (s, 1H)  7. 82-7. 84 (d, 1H) , 8· 45- 8· 46 (d, 1H) , 10. 00 (s, 1H)
1. 20-1. 22 (d, 6H) , 2. 18 (s, 3H) , 4. 15-4. 20 (m, 1H) ,  1. 20-1. 22 (d, 6H) , 2. 18 (s, 3H) , 4. 15-4. 20 (m, 1H) ,
5. 83-5. 96 (d, 2H) , 5. 92-5. 94 (d, 1H) , 6. 71 (s, 1H) ,  5. 83-5. 96 (d, 2H), 5. 92-5. 94 (d, 1H), 6. 71 (s, 1H),
2  2
7. 19-7. 36 (m, 3H) , 7· 82- 7· 84 (d, 1H) , 8. 46 (s, 1H) ,  7. 19-7. 36 (m, 3H) , 7· 82- 7· 84 (d, 1H) , 8. 46 (s, 1H),
10. 06 (s, 1H)  10. 06 (s, 1H)
2. 16 (s, 3H) , 2. 67 (s, 3H) , 5. 85-5. 99 (d, 1H), 6. 93 (brs, 2. 16 (s, 3H) , 2. 67 (s, 3H) , 5. 85-5. 99 (d, 1H), 6. 93 (brs,
3 (实施例 2 ) 236-237 1H) , 7. 34 (s, 1H) , 7. 45 (s, 1H) , 7. 54-7. 57 (m, 1H) , 3 (Example 2) 236-237 1H), 7. 34 (s, 1H), 7. 45 (s, 1H), 7. 54-7. 57 (m, 1H),
8. 10-8. 47 (m, 3H) , 10. 18 (brs, 1H)  8. 10-8. 47 (m, 3H) , 10. 18 (brs, 1H)
1. 16-1. 20 (t, 3H) , 2. 17 (s, 3H) , 3. 37-3. 44 (m, 2H) ,  1. 16-1. 20 (t, 3H) , 2. 17 (s, 3H) , 3. 37-3. 44 (m, 2H) ,
4 5. 83-5. 96 (d, 2H) , 6. 15 (s, 1H) , 6. 75 (s, 1H) , 7. 19—7. 36 4 5. 83-5. 96 (d, 2H) , 6. 15 (s, 1H) , 6. 75 (s, 1H) , 7. 19-7. 36
(m, 3H) , 7. 82-7. 84 (d, 1H) , 8. 44-8. 46 (m, 1H) ,  (m, 3H) , 7. 82-7. 84 (d, 1H) , 8. 44-8. 46 (m, 1H) ,
10. 00 (s, 1H)  10. 00 (s, 1H)
0. 91-0. 95 (m, 3H) , 1. 34-1. 60 (m, 4H) , 2. 18 (s, 3H) ,  0. 91-0. 95 (m, 3H) , 1. 34-1. 60 (m, 4H) , 2. 18 (s, 3H) ,
3. 34-3. 39 (m, 2H), 5. 82-5. 96 (d, 2H) , 6. 12 (s, 1H) , 3. 34-3. 39 (m, 2H), 5. 82-5. 96 (d, 2H), 6. 12 (s, 1H),
5 6. 71 (s, 1H) , 7. 19-7. 36 (m, 3H) , 7· 81— 7· 83 (d, 1H) , 5 6. 71 (s, 1H) , 7. 19-7. 36 (m, 3H), 7·81—7· 83 (d, 1H),
8. 44-8. 45 (d, 1H) ,  8. 44-8. 45 (d, 1H),
10. 00 (s, 1H)  10. 00 (s, 1H)
1. 14-1. 96 (m, 10H) , 1. 59 (s, 3H) , 2. 18 (s, 3H) , 3. 85-3. 87 (d, 1H) , 5, 82-5. 96 (d, 2H) , 5. 96 (s, 1H), 6. 69 (s, 1H) ,  1. 14-1. 96 (m, 10H), 1. 59 (s, 3H), 2. 18 (s, 3H), 3. 85-3. 87 (d, 1H), 5, 82-5. 96 (d, 2H) , 5. 96 (s, 1H), 6. 69 (s, 1H) ,
6 252-253  6 252-253
7. 19-7. 36 (m, 3H) , 7. 81-7· 83 (d, 1H) , 8. 44-8· 45 (d, 1H) , 10. 03 (s, 1H)  7. 19-7. 36 (m, 3H) , 7. 81-7· 83 (d, 1H) , 8. 44-8· 45 (d, 1H) , 10. 03 (s, 1H)
2. 34 (s, 3H) , 4. 54-4. 56 (d, 2H) , 5. 83-5. 97 (d, 2H) ,  2. 34 (s, 3H) , 4. 54-4. 56 (d, 2H) , 5. 83-5. 97 (d, 2H) ,
6. 28-6. 64  6. 28-6. 64
7  7
(m, 3H) , 7. 34-7. 36 (d, 2H) , 7· 81- 7· 83 (d, 1H) ,  (m, 3H) , 7. 34-7. 36 (d, 2H) , 7· 81- 7· 83 (d, 1H) ,
8. 44-8. 45 (d, 1H) , 9. 89 (s, 1H) (Ηΐ 's)28 "6 '(Ηΐ 'P)ff S-Z "8 8. 44-8. 45 (d, 1H) , 9. 89 (s, 1H) (Ηΐ 's)28 "6 '(Ηΐ 'P)ff SZ "8
'(Ηΐ 'Ρ)98 "Z-S8 'ί '(HS '^) 9S 'ί-ίΖ 'ί ' (Η2 '^) Ζ9 "9-09 "9  '(Ηΐ 'Ρ)98 "Z-S8 'ί '(HS '^) 9S 'ί-ίΖ 'ί ' (Η2 '^) Ζ9 "9-09 "9
'ΟΕ 'Ρ)96 -9-£8 "9  'ΟΕ 'Ρ)96 -9-£8 "9
'ΟΕ 'Ρ)8ΐ ·卜 9ΐ '(HS 's)08 Τ '(HS ^)\Ζ 'Ζ 06ΐ 8ΐ 'ΟΕ 'Ρ) 8ΐ ·卜 9ΐ '(HS 's)08 Τ '(HS ^)\Ζ 'Ζ 06ΐ 8ΐ
(Ηΐ 's)09 "6 '(Ηΐ 'Ρ)9 8- S 8 '(Ηΐ 'Ρ)98 "Ζ (Ηΐ 's)09 "6 '(Ηΐ 'Ρ)9 8- S 8 '(Ηΐ 'Ρ)98 "Ζ
'(Η2 'ω) S " -εε "Ζ '(HI 'S)99 "9 '(HI ^)ίΖ "9 '(ΙΕ'Ρ) '(Η2 'ω) S " -εε "Ζ '(HI 'S)99 "9 '(HI ^)ίΖ "9 '(ΙΕ'Ρ)
96 -9-£8 "9 96 -9-£8 "9
ΐ ΐ
'(Η2 's)g Τ '(HS 's)T6 τ '(HS 's)T2 '(H9'S)S9"T '(Η2 's)g Τ '(HS 's)T6 τ '(HS 's)T2 '(H9' S )S9"T
(Ηΐ 's)T6 ·6 '(Ηΐ 'Ρ) 9f ·8- ·8  (Ηΐ 's)T6 ·6 '(Ηΐ 'Ρ) 9f ·8- ·8
' (Η2 'Ρ) 8 Ί-ZS 'ί ' (Η2 9S 'L-7Z Ί ' (Ηΐ 's) U ·9  ' (Η2 'Ρ) 8 Ί-ZS 'ί ' (Η2 9S 'L-7Z Ί ' (Ηΐ 's) U ·9
9ΐ '(Η2 'Ρ)96 -9-£8 "9 ' (HS ^) Ζ ' (HS 's)TT '(H9's)^l 9ΐ '(Η2 'Ρ)96 -9-£8 "9 ' (HS ^) Ζ ' (HS 's)TT '(H9' s )^l
(Ηΐ 's)66 ·6  (Ηΐ 's)66 ·6
'(HT 's)9 ·8 '(Ηΐ 'Ρ)98 'ί ' (Η9 '^) 9S "Ζ-06 "9  '(HT 's)9 ·8 '(Ηΐ 'Ρ)98 'ί ' (Η9 '^) 9S "Ζ-06 "9
9ΐ ' (Η2 'ΡΡ) S6 '9 ' (Η8 ΐθ -6ΐ Τ ' (HS 's) ΐθ ·Ζ  9ΐ ' (Η2 'ΡΡ) S6 '9 ' (Η8 ΐθ -6ΐ Τ ' (HS 's) ΐθ ·Ζ
(Ηΐ 's) '6 '(Ηΐ 'P)S ·8- ·8 '(Ηΐ 'Ρ) 8 ·Ζ  (Ηΐ 's) '6 '(Ηΐ 'P)S ·8- ·8 '(Ηΐ 'Ρ) 8 ·Ζ
' (Η^ 'ω) S "Ζ-06 "9 '(Η2 'Ρ)96 "9-28 "9 ' (Η^ '^) 9 SO Έ  ' (Η^ 'ω) S "Ζ-06 "9 '(Η2 'Ρ)96 "9-28 "9 ' (Η^ '^) 9 SO Έ
'(Η£ 's)80 'Ζ '(HS 'ω)02 "ΐ-Ζΐ "ΐ ' (HS '^) 86 Ό-96 Ό  '(Η£ 's)80 'Ζ '(HS 'ω)02 "ΐ-Ζΐ "ΐ ' (HS '^) 86 Ό-96 Ό
(Ηΐ 's)98 "6 '(Ηΐ 'P)S ·8- ·8 '(Ηΐ 'Ρ)  (Ηΐ 's)98 "6 '(Ηΐ 'P)S ·8- ·8 '(Ηΐ 'Ρ)
S8 "Ζ-Ϊ8 "Ζ '(Ηΐ 'ω)9ε " -2S "Ζ '(Ηΐ 's)90 "Ζ ' (Η2 's)96 "9  S8 "Ζ-Ϊ8"Ζ '(Ηΐ 'ω)9ε " -2S "Ζ '(Ηΐ 's)90 "Ζ ' (Η2 's)96 "9
'(Η2 'Ρ)½ "9-Ϊ8 "9 '(HS 's)ZO Τ ' (HS 's)9Z 7 ' (HS 's)^07  '(Η2 'Ρ)1⁄2 "9-Ϊ8 "9 '(HS 's)ZO Τ ' (HS 's)9Z 7 ' (HS 's)^07
(Ηΐ 's)OT Όΐ ' (Ηΐ 'Ρ) ff S-£ "8 ' (Ηΐ 'Ρ) 28 "Ζ-08 Ί ' (Η2  (Ηΐ 's)OT Όΐ ' (Ηΐ 'Ρ) ff S-£ "8 ' (Ηΐ 'Ρ) 28 "Ζ-08 Ί ' (Η2
'冚)  '冚)
9S "Ζ ' (HS 'ω) 20 "Ζ-86 "9 ' (Η2 'Ρ)06 "9-ΖΖ "9 ' (Η2 '^) 2ΐ w, 'm) z τ-ιζ τ '(HS 's)go τ '(m <IU)T61-WT 9S "Ζ ' (HS 'ω) 20 "Ζ-86 "9 ' (Η2 'Ρ) 06 "9-ΖΖ "9 ' (Η2 '^) 2ΐ w, ' m ) z τ-ιζ τ '(HS ' s)go τ '(m <IU )T61-WT
(Ηΐ 's)^8 "6 '(Ηΐ 'Ρ) ·8- ·8 '(Ηΐ 'Ρ)98 " -S8 Ί  (Ηΐ 's)^8 "6 '(Ηΐ 'Ρ) ·8- ·8 '(Ηΐ 'Ρ)98 " -S8 Ί
' (HS 'ω) 9£ "Ζ ' (Η2 99 "9-69 ·9 ' (Η2 'Ρ)  ' (HS 'ω) 9£ "Ζ ' (Η2 99 "9-69 ·9 ' (Η2 'Ρ)
ΐΐ Ϊ́ΐ
96 -9-£8 "9 96 -9-£8 "9
'(Η 'Ρ)8Ζ · - ΐ · '(HS 's)T2 '(Η£ '冚)££ ·ΐ- 62 ·ΐ  '(Η 'Ρ)8Ζ · - ΐ · '(HS 's)T2 '(Η£ '冚)££ ·ΐ- 62 ·ΐ
(Ηΐ 'Ρ)00 Όΐ-96 ·6 '(Ηΐ 'Ρ)ε ·8- '(Ηΐ 'Ρ) (Ηΐ 'Ρ)00 Όΐ-96 ·6 '(Ηΐ 'Ρ)ε ·8- '(Ηΐ 'Ρ)
8 "Ζ-08 "Ζ '(Η ' εΉ6·9 '(Η2 'P)f6 "9-ΐ8 "9 ' (Η^ '^) 8 "Ζ-08 "Ζ '(Η ' εΉ6·9 '(Η2 'P)f6 "9-ΐ8 "9 ' (Η^ '^)
98ΐ- 8ΐ Οΐ 98ΐ- 8ΐ Οΐ
'(HS 's)207 '(Η2 'ω)ΐ9 "ΐ- ε 'ΐ ' (HS '^) 96 Ό-Τ6 Ό '(HS 's)207 '(Η2 'ω)ΐ9 "ΐ- ε 'ΐ ' (HS '^) 96 Ό-Τ6 Ό
(Ηΐ 's)20 Όΐ '(Ηΐ 'Ρ)9 ·8- ·8 ' (Ηΐ 'Ρ) 8 ·Ζ  (Ηΐ 's)20 Όΐ '(Ηΐ 'Ρ)9 ·8- ·8 ' (Ηΐ 'Ρ) 8 ·Ζ
'(Η2 'ω) ε "Ζ '(Ηΐ 's)89 "9 ' (Ηΐ 's) £ "9 ' (Η2 'Ρ)  '(Η2 'ω) ε "Ζ '(Ηΐ 's)89 "9 ' (Ηΐ 's) £ "9 ' (Η2 'Ρ)
6 6
96 -9-£8 "9 96 -9-£8 "9
'(HS 's)6T 7 '(H9 )6S ·ΐ-εε ·ΐ ' (Η£ ' ) 06 ·0-68 Ό  '(HS 's)6T 7 '(H9 )6S ·ΐ-εε ·ΐ ' (Η£ ' ) 06 ·0-68 Ό
(Ηΐ 's)OT Όΐ '(Ηΐ 'Ρ)9 8—  (Ηΐ 's)OT Όΐ '(Ηΐ 'Ρ)9 8—
'(Ηΐ ·8-0ΐ ·8 ' (Η^ 'ω) 89 "Ζ ' (Ηΐ 's)S6 "9  '(Ηΐ ·8-0ΐ ·8 ' (Η^ 'ω) 89 "Ζ ' (Ηΐ 's)S6 "9
822- LZZ  822- LZZ
'(Η2 'Ρ)Ζ6 "9-^8 "9 ' (HS 's)9T 7 '(H6's)92 "ΐ :9Ρ— OSMI '(Η2 'Ρ)Ζ6 "9-^8 "9 ' (HS 's)9T 7 '(H6' s )92 "ΐ :9 Ρ - OSMI
L\ L\
OT8C.0/llOZN3/X3d co o Ζ OAV OT8C.0/llOZN3/X3d co o Ζ OAV
Figure imgf000020_0001
Figure imgf000020_0001
81  81
Ol8C.0/llOZN3/X3d co o Ζ OAV 6. 73-6. 74 (d, IH), 7. 27-7. 86 (m, 5H), 8. 44-8. 45 (d, IH) ,Ol8C.0/llOZN3/X3d co o Ζ OAV 6. 73-6. 74 (d, IH), 7. 27-7. 86 (m, 5H), 8. 44-8. 45 (d, IH),
7. 77-7. 79 (d, IH) 7. 77-7. 79 (d, IH)
214-215  214-215
DMS0-d6 : 0. 81-0. 85 (m, 3H) , 1. 40-1. 45 (m, 2H) , 2. 16DMS0-d 6 : 0. 81-0. 85 (m, 3H) , 1. 40-1. 45 (m, 2H) , 2. 16
(s, 3H) , 3. 06-3. 09 (m, 2H) , 5. 85— 5. 98 (d, 2H) , 6. 93 (s, IH) ,(s, 3H) , 3. 06-3. 09 (m, 2H) , 5. 85— 5. 98 (d, 2H) , 6. 93 (s, IH) ,
7. 44-7. 59 (m, 3H) , 8. 10-8. 46 (m, 3H) , 10. 14 (s, IH) 7. 44-7. 59 (m, 3H) , 8. 10-8. 46 (m, 3H) , 10. 14 (s, IH)
0. 95-2. 22 (m, 10H) , 2. 11 (s, 3H) , 3. 32-3· 75 (m, 2H) , 0. 95-2. 22 (m, 10H) , 2. 11 (s, 3H) , 3. 32-3· 75 (m, 2H) ,
4. 62-5. 02 (m, 2H) , 5. 82-5. 95 (d, 2H) , 6. 91-7. 35 (m, 4H) ,4. 62-5. 02 (m, 2H) , 5. 82-5. 95 (d, 2H) , 6. 91-7. 35 (m, 4H) ,
7. 80-7. 82 (d, IH) , 8. 42 (s, IH) , 9. 88 (s, IH) 7. 80-7. 82 (d, IH) , 8. 42 (s, IH) , 9. 88 (s, IH)
0. 64-2. 43 (m, 14H) , 2. 05 (s, 3H) , 3. 39-3. 75 (m, 2H) , 0. 64-2. 43 (m, 14H) , 2. 05 (s, 3H) , 3. 39-3. 75 (m, 2H) ,
135-136 135-136
4. 69-5. 03 (m, 2H) , 5. 81-5. 94 (d, 2H) , 6. 88-7. 35 (m, 4H) , 4. 69-5. 03 (m, 2H) , 5. 81-5. 94 (d, 2H) , 6. 88-7. 35 (m, 4H) ,
7. 80-7. 82 (d, IH) , 8. 42 (s, IH) , 9. 69 (s, IH) 7. 80-7. 82 (d, IH) , 8. 42 (s, IH) , 9. 69 (s, IH)
2. 23 (s, 3H) , 2. 62 (s, 3H) , 2. 89 (s, 3H) , 5. 85— 5. 99 (d, 2H) , 6. 92 (s, IH) , 7. 58-8. 49 (m, 5H) , 10. 46 (s, IH)  2. 23 (s, 3H) , 2. 62 (s, 3H) , 2. 89 (s, 3H) , 5. 85— 5. 99 (d, 2H) , 6. 92 (s, IH) , 7 58-8. 49 (m, 5H) , 10. 46 (s, IH)
DMS0-d6: . 89-0. 95 (m, 3H) , 1. 11-1. 97 (m, 9H) , 2. 20 (s, 3H) ,DMS0-d 6 : . 89-0. 95 (m, 3H) , 1. 11-1. 97 (m, 9H) , 2. 20 (s, 3H) ,
3. 60-3. 62 (m, IH) , 5. 83-5. 97 (d, 2H) , 6· 67- 6· 68 (d, IH) , 7. 21-7. 37 (m, 3H) , 7· 82- 7· 84 (d, IH) , 8· 45- 8· 46 (d, IH) , 10. 05 (s, IH) 3. 60-3. 62 (m, IH) , 5. 83-5. 97 (d, 2H) , 6· 67- 6· 68 (d, IH) , 7. 21-7. 37 (m, 3H ) , 7· 82- 7· 84 (d, IH) , 8· 45- 8· 46 (d, IH) , 10. 05 (s, IH)
DMS0-d6: . 71-0. 79 (m, 3H) , 0· 99- 1· 79 (m, 9H) , 2. 22 (s, 3H) ,DMS0-d 6 : . 71-0. 79 (m, 3H) , 0·99- 1· 79 (m, 9H) , 2. 22 (s, 3H) ,
252-253 252-253
3. 26-3. 33 (m, IH) , 5. 85- 5. 98 (d, 2H) , 6. 95- 6. 97 (d, IH), 7. 54-8. 45 (m, 5H) , 10. 05 (s, IH)  3. 26-3. 33 (m, IH) , 5. 85- 5. 98 (d, 2H) , 6. 95- 6. 97 (d, IH), 7. 54-8. 45 (m, 5H ) , 10. 05 (s, IH)
DMS0-d6: 1. 08-1. 74 (m, 10H) , 2. 22 (s, 3H) , 3. 59-3. 61 (m, IH) , 5. 86-5. 99 (d, 2H) , 6. 99 (s, IH) , 7. 56-8. 46 (m, 5H) , DMS0-d 6 : 1. 08-1. 74 (m, 10H) , 2. 22 (s, 3H) , 3. 59-3. 61 (m, IH) , 5. 86-5. 99 (d, 2H) , 6. 99 (s, IH) , 7. 56-8. 46 (m, 5H) ,
10. 38 (s, IH)  10. 38 (s, IH)
DMS0-d6 : 0. 83-0. 86 (m, 3H) , 1. 25-1. 45 (m, 6H) , 2. 21 (s, 3H) , 3. 11-3. 16 (m, 2H) , 5. 86—5. 99 (d, 2H) , 6. 95 (s, IH) , 7. 55-8. 47 (m, 6H) , 10. 42 (s, IH) DMS0-d 6 : 0. 83-0. 86 (m, 3H) , 1. 25-1. 45 (m, 6H) , 2. 21 (s, 3H) , 3. 11-3. 16 (m, 2H) , 5. 86—5. 99 (d, 2H) , 6. 95 (s, IH) , 7. 55-8. 47 (m, 6H) , 10. 42 (s, IH)
DMS0-d6: 1. 27 (s, 9H) , 2. 21 (s, 3H) , 5. 85— 5. 98 (d, 2H) ,DMS0-d 6 : 1. 27 (s, 9H) , 2. 21 (s, 3H) , 5. 85— 5. 98 (d, 2H) ,
233-237 233-237
6. 96 (s, IH) , 7. 55-8. 47 (m, 6H) , 10. 33 (s, IH) 6. 96 (s, IH) , 7. 55-8. 47 (m, 6H) , 10. 33 (s, IH)
DMS0-d6: 2. 22 (s, 3H) , 4. 34-4. 36 (d, 2H) , 5· 86- 5· 99 (d, 2H) ,DMS0-d 6 : 2. 22 (s, 3H) , 4. 34-4. 36 (d, 2H) , 5· 86- 5· 99 (d, 2H) ,
142-143 142-143
6. 26-6. 37 (d, 2H) , 6. 92 (s, IH) , 7. 53- 8. 85 (m, 7H),  6. 26-6. 37 (d, 2H) , 6. 92 (s, IH) , 7. 53- 8. 85 (m, 7H),
10. 41 (s, IH)  10. 41 (s, IH)
DMS0-d6 : l. 41-1. 50 (m, 4H) , 2. 30 (s, 3H) , 2. 91-3. 47 (m, 6H) , 5. 85-5. 98 (d, 2H) , 6. 97 (s, IH) , 7. 57- 7. 82 (m, 3H), 8. 13-8. 15 (d, IH) , 8· 46- 8· 47 (d, IH) DMS0-d 6 : l. 41-1. 50 (m, 4H) , 2. 30 (s, 3H) , 2. 91-3. 47 (m, 6H) , 5. 85-5. 98 (d, 2H) , 6. 97 (s, IH) , 7. 57- 7. 82 (m, 3H), 8. 13-8. 15 (d, IH) , 8· 46- 8· 47 (d, IH)
181-182  181-182
0. 91-0. 96 (m, 3H) , 1. 37-1. 64 (m, 2H) , 2. 03 (s, 3H) ,  0. 91-0. 96 (m, 3H) , 1. 37-1. 64 (m, 2H) , 2. 03 (s, 3H) ,
2. 92-3. 39 (m, 4H) , 5. 81-5. 94 (d, 2H) , 6. 93-7. 35  2. 92-3. 39 (m, 4H) , 5. 81-5. 94 (d, 2H) , 6. 93-7. 35
(m, 4H) , 7. 80-7. 82 (d, IH) , 8. 42- 8. 43 (d, IH) (m, 4H) , 7. 80-7. 82 (d, IH) , 8. 42- 8. 43 (d, IH)
234. 5-24 1. 14-1. 96 (m, 10H) , 2. 36 (s, 3H) , 3. 82-3. 87 (m, IH) , 0 5. 83-5. 96 (d, 2H) , 6. 67 (s, IH) , 7. 33-7. 40 (m, 3H) , 234. 5-24 1. 14-1. 96 (m, 10H) , 2. 36 (s, 3H) , 3. 82-3. 87 (m, IH) , 0 5. 83-5. 96 (d , 2H) , 6. 67 (s, IH) , 7. 33-7. 40 (m, 3H) ,
7. 81-7. 83 (d, IH) , 8· 44- 8· 46 (d, IH) , 10. 04 (s, IH)  7. 81-7. 83 (d, IH) , 8· 44- 8· 46 (d, IH) , 10. 04 (s, IH)
223-224 2. 17 (s, 3H) , 2. 93-2. 94 (d, 3H) , 5· 83- 5· 96 (d, 2H) ,  223-224 2. 17 (s, 3H) , 2. 93-2. 94 (d, 3H) , 5· 83- 5· 96 (d, 2H) ,
6. 16 (s, IH) , 99 τ 6. 16 (s, IH), 99 τ
S9 S9
(H2 'ω) ζζ τ-οζ τ (m <s)so 'ζ (m ")99 "ΐ-ΐ9 "ΐ 902-^02 (H2 'ω) ζζ τ-οζ τ (m <s )so '' (m ")99 "ΐ-ΐ9 "ΐ 902-^02
(Ηΐ 's)06 "6 '(Ηΐ cP)Z S-Zf "8 '(Ηΐ 'Ρ) 28 "Ζ-08 "Ζ (Ηΐ 's)06 "6 '(Ηΐ c P)Z S-Zf "8 '(Ηΐ 'Ρ) 28 "Ζ-08 "Ζ
' (Η2 'ω) 9£ ·Ζ- "Ζ ' (Ηΐ 's) 0ΐ "Ζ ' (Ηΐ 's) 6 ·9 ' (Η2 'Ρ)  ' (Η2 'ω) 9£ ·Ζ- "Ζ ' (Ηΐ 's) 0ΐ "Ζ ' (Ηΐ 's) 6 ·9 ' (Η2 'Ρ)
f6 "9-08 "9  F6 "9-08 "9
29 29
(Η ' ) 8 ε-εο ·ε '(HS 's)go 7 '(Η9 6ΐ ·ΐ- ε6·ο 99Τ-29Ϊ (Η ' ) 8 ε-εο ·ε '(HS 's)go 7 '(Η9 6ΐ ·ΐ- ε6·ο 99Τ-29Ϊ
(Ηΐ 'Ρ) 90 ΌΙ-fO Όΐ ' (Ηΐ 9 S- ·8  (Ηΐ 'Ρ) 90 ΌΙ-fO Όΐ ' (Ηΐ 9 S- ·8
' (Ηΐ 'ω) S8 "Ζ-Ϊ8 "Ζ ' (HS 'ω) 0 ' ' (Ηΐ 'Ρ) £L '9-2 ·9  ' (Ηΐ 'ω) S8 "Ζ-Ϊ8 "Ζ ' (HS 'ω) 0 ' ' (Ηΐ 'Ρ) £L '9-2 ·9
' (Η2 'Ρ) 96 "9-28 "9 ' (Ηΐ 'Ρ) 09 Τ-89 Τ ' (HS 's) 8ΐ ·Ζ  ' (Η2 'Ρ) 96 "9-28 "9 ' (Ηΐ 'Ρ) 09 Τ-89 Τ ' (HS 's) 8ΐ ·Ζ
ΐ9 (Ηΐ 'Ρ) 6 ·ΐ- 06 ·ΐ '(Η6 'm)SL 'l-6fl ' (HS '^) S6 Ό-98 Ό Ϊ́9 (Ηΐ 'Ρ) 6 ·ΐ- 06 ·ΐ '(Η6 ' m )SL 'l-6fl ' (HS '^) S6 Ό-98 Ό
(Ηΐ 's)ZO Όΐ  (Ηΐ 's) ZO Όΐ
(Ηΐ 'P)S ·8- ·8  (Ηΐ 'P)S ·8- ·8
(Η2 'Ρ)£8 "Ζ-Ϊ8 "Ζ '(Ηΐ 's) ·9  (Η2 'Ρ) £8 "Ζ-Ϊ8 "Ζ '(Ηΐ 's) ·9
(Ηΐ 's)8T ·9 '(Η2 'Ρ)96 "9-28 "9 {wz 'm)i£ τ-ζ£ τ (Ηΐ 's)8T ·9 '(Η2 'Ρ)96 "9-28 "9 {wz ' m )i£ τ-ζ£ τ
09 09
'OK 's)9T ·Ζ (Η9 ")99 ·ΐ— ΐε ·ΐ (HS ' ΐ6 Ό-88 Ό 'OK 's)9T ·Ζ (Η9 ")99 ·ΐ— ΐε ·ΐ (HS ' ΐ6 Ό-88 Ό
(Ηΐ 's)00 Όΐ '(Ηΐ 'Ρ)9 ·8- ·8 (Ηΐ 'Ρ) 8 "Ζ-Ϊ8 ·ί  (Ηΐ 's)00 Όΐ '(Ηΐ 'Ρ)9 ·8- ·8 (Ηΐ 'Ρ) 8 "Ζ-Ϊ8 ·
(HS 'ω) If ' -εε ' '(HI 's^q)80 "9 {W, 'Ρ)96 "9-28 "9 9 "Ζ  (HS 'ω) If ' -εε ' '(HI 's^q)80 "9 {W, 'Ρ)96 "9-28 "9 9 "Ζ
69 (HS '^)£Ζ ·ΐ- 6ΐ ·ΐ  69 (HS '^)£Ζ ·ΐ- 6ΐ ·ΐ
(Ηΐ 's)ZO Όΐ '(Ηΐ 'Ρ)9^ S-ff "8 ' (Ηΐ 'Ρ) S8 "Ζ-ΐ8 "Ζ  (Ηΐ 's)ZO Όΐ '(Ηΐ 'Ρ)9^ S-ff "8 ' (Ηΐ 'Ρ) S8 "Ζ-ΐ8"Ζ
' (HS 'ω) S "Ζ ' (Ηΐ 's) fL ·9 ' (Ηΐ 's) 96 "9 ' (Η2 'Ρ)  ' (HS 'ω) S "Ζ ' (Ηΐ 's) fL ·9 ' (Ηΐ 's) 96 "9 ' (Η2 'Ρ)
96 "9-28 "9 9  96 "9-28" 9 9
89 89
(Ηΐ 'ω)6ΐ 'f-fl 'f '(HS 's) T τ '(Η9'Ρ)0Ζ ·ΐ-6ΐ ·ΐ "9ΐ2-9ΐ2 (Ηΐ 'ω)6ΐ 'f-fl 'f '(HS 's) T τ '(Η9'Ρ)0Ζ ·ΐ-6ΐ ·ΐ "9ΐ2-9ΐ2
(Ηΐ 's)8T Όΐ  (Ηΐ 's)8T Όΐ
(Ηΐ 'P)ff S-Z ·8  (Ηΐ 'P)ff S-Z ·8
(Η2 'Ρ)28 "Ζ-08 "Ζ (HS 'ω)9ε - - 6 '9 '(Ηΐ 'sjq)TO ·9  (Η2 'Ρ)28 "Ζ-08"Ζ (HS 'ω)9ε - - 6 '9 '(Ηΐ 'sjq)TO ·9
Ζ9 {W, 'Ρ)96 "9-28 "9 '(H6'S)9S ·ΐ Z-9ZZ Ζ9 {W, 'Ρ)96 "9-28 "9 '(H6' S )9S ·ΐ Z-9ZZ
(Ηΐ 'sjq)T2 Όΐ '(Ηΐ 'Ρ)8 ·8- '(Ηΐ 'Ρ)9ΐ '8-εΐ "8 '(HS 'ω)69 " -SS ' ' (Ηΐ 's)06 "9 9  (Ηΐ 'sjq)T2 Όΐ '(Ηΐ 'Ρ)8 ·8- '(Ηΐ 'Ρ)9ΐ '8-εΐ "8 '(HS 'ω)69 " -SS ' ' (Ηΐ 's)06 "9 9
99 (Η2 'Ρ)86 "9-^8 "9 ' (HS 's)88 'Ζ ' (HS 's)297 :9Ρ- OSMI '9 -ε 99 (Η2 'Ρ)86 "9-^8 "9 ' (HS 's)88 'Ζ ' (HS 's)297 : 9 Ρ- OSMI '9 -ε
(Ηΐ 's)W ·0ΐ '(Ηΐ 'Ρ)9 8— S 8 '(Ηΐ :s)8T ·8 (Ηΐ 's)W ·0ΐ '(Ηΐ 'Ρ)9 8—S 8 '(Ηΐ : s)8T ·8
:(Ηΐ 'Ρ)Οΐ ·8- 60 ·8 ' (HS '^) 89 'L-£ "Ζ '(Ηΐ :s)26 ·9 :(Ηΐ 'Ρ)Οΐ ·8- 60 ·8 ' (HS '^) 89 'L-£ "Ζ '(Ηΐ : s)26 ·9
' (Η2 'Ρ) 86 "9-98 "9 ' (Η2 9ΐ ·ε- Όΐ '£ :(Η£ 's) ' (Η2 'Ρ) 86 "9-98 "9 ' (Η2 9ΐ ·ε- Όΐ '£ :(Η£ 's)
ΐ 'Ζ (m <lu) W\-ZZ '\ ' (HS 'ω) 98 Ό-28 Ό : 99 ΐ 'Ζ (m <lu ) W\-ZZ '\ ' (HS 'ω) 98 Ό-28 Ό : 99
'P-OSHQ 1 Ζ  'P-OSHQ 1 Ζ
(Ηΐ 'Ρ)8 ·8- 9 ·8  (Ηΐ 'Ρ)8 ·8- 9 ·8
(Ηΐ 'ΡΡ)9ΐ ·8- Π ·8 ' (Η£ ' ) £8 ·Ζ ' (Ηΐ 'Ρ) 9ΐ ·8- Π ·8  (Ηΐ 'ΡΡ)9ΐ ·8- Π ·8 ' (Η£ ' ) £8 ·Ζ ' (Ηΐ 'Ρ) 9ΐ ·8- Π ·8
' (HS 'ω) S8 "Ζ-Ζ9 "Ζ ' (Ηΐ 's) Ζ6 ·9 ' (Η2 'Ρ) 86 "9-98 "9 ζ  ' (HS 'ω) S8 "Ζ-Ζ9 "Ζ ' (Ηΐ 's) Ζ6 ·9 ' (Η2 'Ρ) 86 "9-98 "9 ζ
(Η^ 'ω)οε -ε-ζο τ '(HS'S)9 '(Η '冚) ·Ϊ- 9 ·Ϊ:9Ρ- OS I LZ- 'ΟΙΖ (Η^ 'ω)οε -ε-ζο τ '(HS'S)9 '(Η '冚) ·Ϊ- 9 ·Ϊ: 9 Ρ- OS I LZ- 'ΟΙΖ
(Ηΐ 'Ρ)9 ·8- ·8  (Ηΐ 'Ρ)9 ·8- ·8
'(Ηΐ 'Ρ)ΖΙ "8-0ΐ "8 ' (Η£ ' ) 06 ·Ζ— ·Ζ '(Ηΐ 's)Z6 "9  '(Ηΐ 'Ρ)ΖΙ "8-0ΐ "8 ' (Η£ ' ) 06 ·Ζ— ·Ζ '(Ηΐ 's)Z6 "9
S9 (Η2 'Ρ)66 "9-98 "9 ' (HS 's)29 Τ ' (HS 's)6T 7 :9Ρ- OSMI S9 (Η2 'Ρ) 66 "9-98 "9 ' (HS 's)29 Τ ' (HS 's)6T 7 : 9 Ρ- OSMI
(Ηΐ 's) ·0ΐ ' (Ηΐ 'Ρ) Lf ·8- 9 ·8 ' (Ηΐ 'Ρ) fl '8~ΖΙ ·8  (Ηΐ 's) ·0ΐ ' (Ηΐ 'Ρ) Lf ·8- 9 ·8 ' (Ηΐ 'Ρ) fl '8~ΖΙ ·8
(HS 'ω) S8 "Ζ-99 'ί ' (Ηΐ 's) £6 ·9 ' (Η2 'Ρ) Ζ6 "9-£8 "9 ' (Η 9  (HS 'ω) S8 "Ζ-99 'ί ' (Ηΐ 's) £6 ·9 ' (Η2 'Ρ) Ζ6 "9-£8 "9 ' (Η 9
Ζ  Ζ
ίΖ ·ε— ΐ6 ·Ζ ' (HS 's) 02 ·Ζ ' (Η9 ) W) ·Η8 Ό : 9Ρ- OSMI '0ΖΖ-ί\Ζ Ζ ε ε ΐ 6 · Ζ ' (HS 's) 02 · Ζ ' (Η9 ) W) · Η 8 Ό : 9 Ρ - OSMI '0ΖΖ-ί\Ζ
(Ηΐ 's)86 ·6 (Ηΐ 'Ρ)  (Ηΐ 's)86 ·6 (Ηΐ 'Ρ)
8- ·8  8- ·8
(Ηΐ 'Ρ) 8 Ί-Ζ8 'ί (Ηε 'ω)6ε '(ΗΤ S)0Z ·9(Ηΐ 'Ρ) 8 Ί-Ζ8 'ί (Ηε 'ω)6ε '(ΗΤ S )0Z ·9
Figure imgf000022_0001
Figure imgf000022_0001
Ol8C.0/llOZN3/X3d co o ζ OAV Ol8C.0/llOZN3/X3d co o ζ OAV
Figure imgf000023_0001
Figure imgf000023_0001
Ol8C.0/llOZN3/X3d co o Ζ OAV Ol8C.0/llOZN3/X3d co o Ζ OAV
Figure imgf000024_0001
Figure imgf000024_0001
(Ηΐ 's) l ·6 (Ηΐ 's) l ·6
' (Ηΐ ' ) '(Ηΐ 'ω)^8 Ί-ZS 'ί ' (Η2 '^) Ιζ Ί~η 'ί  ' (Ηΐ ' ) '(Ηΐ 'ω)^8 Ί-ZS 'ί ' (Η2 '^) Ιζ Ί~η 'ί
'(Ηΐ 's)92 'I '(Ηΐ 's) 8 '9 ' (Ηΐ 'Ρ) 80 ·9_90 ·9  '(Ηΐ 's)92 'I '(Ηΐ 's) 8 '9 ' (Ηΐ 'Ρ) 80 ·9_90 ·9
'(Η2 'Ρ)96 "9-28 "9 ' (Ηΐ '^)^8 '£~Ζ8 '£ ' (Η2 '^) 06 "ΐ-Ζ8 "ΐ  '(Η2 'Ρ)96 "9-28 "9 ' (Ηΐ '^)^8 '£~Ζ8 '£ ' (Η2 '^) 06 "ΐ-Ζ8"ΐ
'(Η£ ' ) ^ΐ- 99 ·ΐ '(Η2 'ω) "ΐ-^ε "ΐ '(Η£ ' )8ΐ ·ΐ- 80 ·ΐ S6 '(Η£ ' ) ^ΐ- 99 ·ΐ '(Η2 'ω) "ΐ-^ε "ΐ '(Η£ ' )8ΐ ·ΐ- 80 ·ΐ S6
(Ηΐ 's)g0 Όΐ '(Ηΐ 'Ρ)9 ·8- ·8 (Ηΐ 'Ρ)ΖΙ ·8- Οΐ ·8 (Ηΐ 's)g0 Όΐ '(Ηΐ 'Ρ)9 ·8- ·8 (Ηΐ 'Ρ)ΖΙ ·8- Οΐ ·8
'(Ηΐ 's)Z6 "Ζ '(Ηΐ 'ω)89 "Ζ-99 "Ζ (Ηΐ 'P)S -L-£ 'I  '(Ηΐ 's)Z6 "Ζ '(Ηΐ 'ω)89 "Ζ-99"Ζ (Ηΐ 'P)S -L-£ 'I
'(Ηΐ 'P)2S ' -θε "Ζ '(HI 'S)96 "9 (Η2 'Ρ)66 "9-98 "9  '(Ηΐ 'P)2S ' -θε "Ζ '(HI 'S)96 "9 (Η2 'Ρ)66 "9-98 "9
'(Ηΐ ' )09·ε '(HS 's)027 (Η^ '^) l "ΐ-99 "ΐ  '(Ηΐ ' )09·ε '(HS 's)027 (Η^ '^) l "ΐ-99 "ΐ
(Ηΐ 'ω)89 "ΐ-99 "ΐ '(Η9 "ΐ-ΖΟ "ΐ :9Ρ- OSMI 26 (Ηΐ 'ω)89 "ΐ-99 "ΐ '(Η9 "ΐ-ΖΟ "ΐ : 9 Ρ - OSMI 26
(Ηΐ 's)0T Όΐ '(Ηΐ 'Ρ)9 ·8- ·8  (Ηΐ 's)0T Όΐ '(Ηΐ 'Ρ)9 ·8- ·8
'(Ηΐ 'Ρ)ΖΙ "8-ΐΐ "8 '(Ηΐ 's)T0 '8 ' (Ηΐ 's)g '  '(Ηΐ 'Ρ)ΖΙ "8-ΐΐ "8 '(Ηΐ 's)T0 '8 ' (Ηΐ 's)g '
(Η2 'ω) 9 " -½ "Ζ '(HT 's) 96 "9 ' (Η2 'Ρ) 86 "9-98 "9  (Η2 'ω) 9 " -1⁄2 "Ζ '(HT 's) 96 "9 ' (Η2 'Ρ) 86 "9-98 "9
'(Ηΐ 'ω)09 Τ-89 '£ '(HS 's)gT '(Η ) εΖ'ΐ-99 'ΐ  '(Ηΐ 'ω)09 Τ-89 '£ '(HS 's)gT '(Η ) εΖ'ΐ-99 'ΐ
'(Ηΐ 'ω)89 "ΐ-99 "ΐ '(Η9 LZ "ΐ-ΖΟ "ΐ :9Ρ- OSMI ΐ6 '(Ηΐ 'ω)89 "ΐ-99 "ΐ '(Η9 LZ "ΐ-ΖΟ "ΐ : 9 Ρ - OSMI ΐ 6
(Ηΐ 's)Tg ΐ '(Η2 'ω)ΐ9 ·8- ^ "8  (Ηΐ 's)Tg ΐ '(Η2 'ω)ΐ9 ·8- ^ "8
'(Ηΐ 'Ρ)06 "Ζ-88 "Ζ ' (Η£ ' ) 6£ ·Ζ '(Ηΐ 'ω)ΐΐ 'Z-80 "Ζ  '(Ηΐ 'Ρ)06 "Ζ-88 "Ζ ' (Η£ ' ) 6£ ·Ζ '(Ηΐ 'ω)ΐΐ 'Z-80 "Ζ
'(Ηΐ 's)99 "9 '(Ηΐ 'P)fl -9-ΖΙ "9 '(Η2 'Ρ) 86 "9-98 "9  '(Ηΐ 's)99 "9 '(Ηΐ 'P)fl -9-ΖΙ "9 '(Η2 'Ρ) 86 "9-98 "9
(Ηΐ ' )ΐΟ ·卜 66 Έ ' (Η2 'ω) ΖΟ 7-90 'Ζ ' (Η2 '^) 28 "ΐ-6Ζ "ΐ (Ηΐ ' )ΐΟ ·卜 66 Έ ' (Η2 'ω) ΖΟ 7-90 'Ζ ' (Η2 '^) 28 "ΐ-6Ζ"ΐ
'(Η2 'ω)2 "ΐ-Ζ9 "ΐ '(1Ε ·τ— '(Η2 ·ΐ- 02 ·ΐ 06 '(Η2 'ω)2 "ΐ-Ζ9 "ΐ '(1Ε · τ — '(Η2 ·ΐ- 02 ·ΐ 06
(Ηΐ 's)06 "6 '(Ηΐ 'Ρ) ·8  (Ηΐ 's)06 "6 '(Ηΐ 'Ρ) ·8
-£f ·8  -£f ·8
'(ΗΪ 'ρ)^8 -L-ZS · ' ΟΕ '冚) 9ε ·ζ-οε ·Ζ '(Ηΐ 's)\Z 'I  '(ΗΪ 'ρ)^8 -L-ZS · ' ΟΕ '冚) 9ε ·ζ-οε ·Ζ '(Ηΐ 's)\Z 'I
(HT 's) 86 ·9 ' (Ηΐ 's)ZO "9 '(Η2 'P)f6 "9-ΐ8 "9 '(H6'S)SS "ΐ 68 (HT 's) 86 ·9 ' (Ηΐ 's)ZO "9 '(Η2 'P)f6 "9-ΐ8 "9 '(H6' S )SS "ΐ 68
(Ηΐ 's)0^ Όΐ  (Ηΐ 's)0^ Όΐ
(Ηΐ 'P)S ·8- ·8 '(Ηΐ 'P)S8 "Ζ-Ϊ8 "Ζ '(Ηΐ  (Ηΐ 'P)S ·8- ·8 '(Ηΐ 'P)S8 "Ζ-Ϊ8 "Ζ '(Ηΐ
(Ηΐ 'Ρ) 02 "Ζ-8ΐ ·ί ' (Ηΐ 'Ρ) ΖΟ "Ζ-90 ·ί ' (Ηΐ 's) 26 ·9 (Ηΐ 'Ρ) 02 "Ζ-8ΐ ·ί ' (Ηΐ 'Ρ) ΖΟ "Ζ-90 ·ί ' (Ηΐ 's) 26 ·9
'(Ηΐ 's)96 "9  '(Ηΐ 's)96 "9
'(Η2 'Ρ)96 "9-28 "9 ' (HS 's)9T '(H6'S)9S "ΐ 88 '(Η2 'Ρ)96 "9-28 "9 ' (HS 's)9T '(H6' S )9S "ΐ 88
(Ηΐ 's)T2 ΐ '(Η2 'Ρ)ΐ9 "8-6^ "8  (Ηΐ 's)T2 ΐ '(Η2 'Ρ)ΐ9 "8-6^ "8
(Ηΐ 'Ρ)06 "Ζ-88 "Ζ ' (Η£ ' ) 9£ ·Ζ '(Ηΐ 'ω) 60 "Ζ-90 "Ζ  (Ηΐ 'Ρ) 06 "Ζ-88 "Ζ ' (Η£ ' ) 9£ ·Ζ '(Ηΐ 'ω) 60 "Ζ-90"Ζ
' (Ηΐ 's)g9 ·9  ' (Ηΐ 's)g9 ·9
Ζ8 Ζ8
' (Ηΐ 's)60 "9 '(Η2 'Ρ)86 "9-98 "9 '(H6's)09 "ΐ ' (Ηΐ 's)60 "9 '(Η2 'Ρ)86 "9-98 "9 '(H6' s )09 "ΐ
(Ηΐ „ ·8- ' (IE '冚) 8£ ·8—  (Ηΐ „ ·8- ' (IE '冚) 8£ ·8—
1 (Η2 'ω) 8ΐ "8-80 "8 ' (Ηΐ '^)09 " -½ ' ' (Ηΐ 's)gO "Ζ  1 (Η2 'ω) 8ΐ "8-80 "8 ' (Ηΐ '^)09 " -1⁄2 ' ' (Ηΐ 's)gO "Ζ
98 (Η2 'Ρ)00 "9-^8 "9 '(HS 's)9g '(H6'S)9S "ΐ :9Ρ- OSMI 29Τ-09Ϊ 98 (Η2 'Ρ)00 "9-^8 "9 '(HS 's)9g '(H6' S )9S "ΐ : 9 Ρ- OSMI 29Τ-09Ϊ
(Ηΐ 's)9T Όΐ  (Ηΐ 's)9T Όΐ
'(Ηΐ 'Ρ)^ S-£ "8 '(Ηΐ 'P)S8 "Ζ-Ϊ8 "Ζ '(Ηΐ 's)T9  '(Ηΐ 'Ρ)^ S-£ "8 '(Ηΐ 'P)S8 "Ζ-Ϊ8 "Ζ '(Ηΐ 's)T9
(Ηΐ 's)l 'I '(Ηΐ 'ω)9ε ' ' (Ηΐ 's)26 "9 ' (Ηΐ 's)86 "9 (Ηΐ 's)l 'I '(Ηΐ 'ω)9ε ' ' (Ηΐ 's)26 "9 ' (Ηΐ 's)86 "9
98 '(Η2 'Ρ)96 "9-28 "9 ' (HS 's)gT '(H6'S)9S "ΐ 98 '(Η2 'Ρ)96 "9-28 "9 ' (HS 's)gT '(H6' S )9S "ΐ
(Ηΐ 's)T ·0ΐ '(Ηΐ 'Ρ) Lf ·8- 9 ·8  (Ηΐ 's)T ·0ΐ '(Ηΐ 'Ρ) Lf ·8- 9 ·8
' (Ηΐ 'ω) Π ·8- Οΐ ·8 ' (Ηΐ 's) 8Ζ ' ' (Η2 89 "Ζ-ΐ9 '  ' (Ηΐ 'ω) Π ·8- Οΐ ·8 ' (Ηΐ 's) 8Ζ ' ' (Η2 89 "Ζ-ΐ9 '
'(Ηΐ 's)g6 ·9  '(Ηΐ 's)g6 ·9
(Ηΐ 's) 0 ·9 ' (Η2 'Ρ) 86 "9-98 "9 ' (Η2 Π - 80 '  (Ηΐ 's) 0 ·9 ' (Η2 'Ρ) 86 "9-98 "9 ' (Η2 Π - 80 '
^8 ^8
(Η2 'P)f6 '£-Z6 '£ '(HS 's)ZZ 'Ζ '(HS '^)92 "ΐ-9ΐ "ΐ :9Ρ- OSMI (Η2 'P)f6 '£-Z6 '£ '(HS 's)ZZ 'Ζ '(HS '^)92 "ΐ-9ΐ "ΐ : 9 Ρ - OSMI
Ol8C.0/llOZN3/X3d co o Ζ OAV '(Ηΐ 's)L ' '(HS 's)U "Z '(Ηΐ 's)½ "9 '(HT 's)8 ·9Ol8C.0/llOZN3/X3d co o Ζ OAV '(Ηΐ 's)L ''(HS's)U"Z'(Ηΐ's)1⁄2"9'(HT's)8 ·9
W, 'P)TS "9-92 "9 W, 'P)S8 "9-Ϊ8 "9 '(Η2 'P)Z9 ^-29 f£Z-Z£Z LOT W, 'P)TS "9-92 "9 W, 'P)S8 "9-Ϊ8 "9 '(Η2 'P)Z9 ^-29 f£Z-Z£Z LOT
(Ηΐ 's)66 "6 '(Ηΐ 'Ρ)ε ·8- '(Ηΐ 'Ρ)28 "Ζ-08 "Ζ (Ηΐ 's)66 "6 '(Ηΐ 'Ρ)ε ·8- '(Ηΐ 'Ρ)28 "Ζ-08"Ζ
'(Ηΐ '^)η 'ί ' (Η2 'ω) 90 "Ζ-86 "9 ' (Η2 'Ρ) S6 "9-08 "9  '(Ηΐ '^)η 'ί ' (Η2 'ω) 90 "Ζ-86 "9 ' (Η2 'Ρ) S6 "9-08 "9
'0κ' )8ε·ε ' (Η2 'ω) go -ε-ε6 τ ' κ ΐ9 Ί- Ί  '0κ' )8ε·ε ' (Η2 'ω) go -ε-ε6 τ ' κ ΐ9 Ί- Ί
'(Ηΐ 8ΐ ·ΐ- ΐ ·ΐ ' (HS 'ω) 96 Ό-26 Ό '(Ηΐ 'ω)0 Ό-99 Ό SLI-LLI 90ΐ '(Ηΐ 8ΐ ·ΐ- ΐ ·ΐ ' (HS 'ω) 96 Ό-26 Ό '(Ηΐ 'ω)0 Ό-99 Ό SLI-LLI 90ΐ
(Ηΐ 's)69 "6 '(Ηΐ 'Ρ) ·8- ·8 '(Ηΐ 'P)S8 "Ζ-ΐ8 "Ζ '(Η2 (Ηΐ 's)69 "6 '(Ηΐ 'Ρ) ·8- ·8 '(Ηΐ 'P)S8 "Ζ-ΐ8 "Ζ '(Η2
<lu)gg "Ζ '(Ηΐ 's)S8 "9 '(Ηΐ 's)62 "9 ' (Η2 'P)f6 "9-ΐ8 "9 < lu )gg "Ζ '(Ηΐ 's)S8 "9 '(Ηΐ 's)62 "9 ' (Η2 'P)f6 "9-ΐ8 "9
'(Η2 'ω)ΐε τ-9ζ τ 'ΟΕ'^ Ή ·ΐ ' (Hd) ε6 ·Ο-06 ·ο ΐΖΐ-ΟΖΐ 90ΐ  '(Η2 'ω)ΐε τ-9ζ τ 'ΟΕ'^ Ή ·ΐ ' (Hd) ε6 ·Ο-06 ·ο ΐΖΐ-ΟΖΐ 90ΐ
(Ηΐ 's)gg Όΐ '(Ηΐ 'Ρ)9 ·8- ·8  (Ηΐ 's)gg Όΐ '(Ηΐ 'Ρ)9 ·8- ·8
'ΟΕ 'Ρ)ΐΐ ·8— Οΐ ·8 '(Ηΐ 's)08 "Ζ '(Ηΐ '^)89 " -½ '  'ΟΕ 'Ρ)ΐΐ ·8— Οΐ ·8 '(Ηΐ 's)08 "Ζ '(Ηΐ '^)89 " -1⁄2 '
'(Ηΐ 's)^ · '(Ηΐ 's)20 "Ζ '(Η2 'Ρ) 86 "9-98 "9  '(Ηΐ 's)^ · '(Ηΐ 's)20 "Ζ '(Η2 'Ρ) 86 "9-98 "9
'(Ηΐ 'ω)26 Τ '(Η9'Ρ)Μ)·ΐ-¾)·ΐ :9Ρ- OSMI 002-Ζ6Ϊ '(Ηΐ 'ω)26 Τ '(Η9'Ρ)Μ)·ΐ-3⁄4)·ΐ : 9 Ρ- OSMI 002-Ζ6Ϊ
(Ηΐ 's)99 '6 '(Ηΐ„·8- ·8 '(Ηΐ 'Ρ)  (Ηΐ 's)99 '6 '(Ηΐ„·8- ·8 '(Ηΐ 'Ρ)
^8 Ί-ZS 'ί W, 'm)L£ " -9ε "Ζ ' (Ηΐ 's)08 "9 ' (Ηΐ 's)92 "9 ^8 Ί-ZS 'ί W, ' m )L£ " -9ε "Ζ ' (Ηΐ 's)08 "9 ' (Ηΐ 's)92 "9
'(Η2 'Ρ)96 "9-28 "9 ' (Η2 '^) ~η '£ ' (HS '^)9ΐ Ί-ΖΙ Ί Ζ8Ϊ-98Ϊ εοτ  '(Η2 'Ρ)96 "9-28 "9 ' (Η2 '^) ~η '£ ' (HS '^)9ΐ Ί-ΖΙ Ί Ζ8Ϊ-98Ϊ εοτ
{WZ 'Ρ)8 ·8- 9 ·8  {WZ 'Ρ)8 ·8- 9 ·8
' (Ηΐ 'Ρ) Ζ\ ·8- Οΐ ·8 ' (Ηΐ 's) 8Ζ "Ζ ' (Ηΐ 89 "Ζ-99 "Ζ  ' (Ηΐ 'Ρ) Ζ\ ·8- Οΐ ·8 ' (Ηΐ 's) 8Ζ "Ζ ' (Ηΐ 89 "Ζ-99 "Ζ
'(Ηΐ 's)9^ Ί '(Ηΐ 's)00 Ί '(Η2 'Ρ)66 "9-98 "9 ' (Ηΐ '^) ΐθ ' '(Ηΐ 's)9^ Ί '(Ηΐ 's)00 Ί '(Η2 'Ρ)66 "9-98 "9 ' (Ηΐ '^) ΐθ '
002-66Ϊ ΐθΐ '(Ηΐ '^)29 Ό-Ϊ9 Ό ' (Η2 '^) 99 Ό ' (Η2 '^) Ό :9Ρ- OSMI 002-66Ϊ ΐθΐ '(Ηΐ '^)29 Ό-Ϊ9 Ό ' (Η2 '^) 99 Ό ' (Η2 '^) Ό : 9 Ρ - OSMI
(Ηΐ 's)02 Όΐ '(Ηΐ 'Ρ)6 ·8- 8 ·8 ' (Ηΐ 'Ρ) 9ΐ ·8- Π ·8  (Ηΐ 's)02 Όΐ '(Ηΐ 'Ρ)6 ·8- 8 ·8 ' (Ηΐ 'Ρ) 9ΐ ·8- Π ·8
'(Ηΐ 's)6Z "Ζ '(Ηΐ 'ω)09 "Ζ-Ζ9 "Ζ ' (Ηΐ 's)9^ Ί  '(Ηΐ 's)6Z "Ζ '(Ηΐ 'ω)09 "Ζ-Ζ9 "Ζ ' (Ηΐ 's)9^ Ί
'(Ηΐ 's)Z6 "9 '(Η2 'Ρ)86 "9-98 "9 ' (HS 's)68 'Ζ ' (HS 's)Z97 ΟΟΐ'(Ηΐ 's)Z6 "9 '(Η2 'Ρ)86 "9-98 "9 ' (HS 's)68 'Ζ ' (HS 's)Z97 ΟΟΐ
(Ηΐ 's)89 "6 '(Ηΐ 'Ρ)8 8- '(Ηΐ 'Ρ)\Ζ "8-0ΐ "8 (Ηΐ 's)89 "6 '(Ηΐ 'Ρ)8 8- '(Ηΐ 'Ρ)\Ζ "8-0ΐ"8
'(Ηΐ 's)T "Ζ '(Ηΐ 'ω)29 "Ζ-99 "Ζ ' (Ηΐ 's)9^ 'ί ' (Ηΐ 's) 06 "9 '(Ηΐ 's)T "Ζ '(Ηΐ 'ω)29 "Ζ-99 "Ζ ' (Ηΐ 's)9^ 'ί ' (Ηΐ 's) 06 "9
'(Η2 'Ρ)86 "9-^8 "9 ' (HS 's)887 ' (HS 's)T9 :9Ρ- OSMI 66 '(Η2 'Ρ)86 "9-^8 "9 ' (HS 's)887 ' (HS 's)T9 : 9 Ρ- OSMI 66
(Ηΐ 's)02 ·0ΐ  (Ηΐ 's)02 ·0ΐ
'(Ηΐ 'Ρ)6 ·8- 8 ·8 '(Ηΐ 'Ρ)9ΐ ·8- ΐ ·8 '(Ηΐ '(Ηΐ 'Ρ)6 ·8- 8 ·8 '(Ηΐ 'Ρ)9ΐ ·8- ΐ ·8 '(Ηΐ
9 "Ζ-Ζ9 "Ζ '(Η2 's)8S "Ζ ' (Η2 '^)Ζ£ 'ί ' (Ηΐ 's)06 "9  9 "Ζ -Ζ9 "Ζ '(Η2 's)8S "Ζ ' (Η2 '^)Ζ£ 'ί ' (Ηΐ 's)06 "9
'(Η2 'Ρ)ΐΟ "9-98 "9 ' (HS 's)087 ' (HS 's)Z9 'Ζ :9Ρ- OSMI 99Τ-99Ϊ 86 '(Η2 'Ρ)ΐΟ "9-98 "9 ' (HS 's)087 ' (HS 's)Z9 'Ζ : 9 Ρ- OSMI 99Τ-99Ϊ 86
(Ηΐ 's)9S Όΐ '(Ηΐ 'P ·8- 9 ·8  (Ηΐ 's)9S Όΐ '(Ηΐ 'P ·8- 9 ·8
' (Ηΐ 's) 82 ·8 ' (Ηΐ 'Ρ) Ζ\ ·8- Οΐ ·8 ' (Ηΐ 's) 6Ζ '  ' (Ηΐ 's) 82 ·8 ' (Ηΐ 'Ρ) Ζ\ ·8- Οΐ ·8 ' (Ηΐ 's) 6Ζ '
'(Ηΐ 'ω) 9 "Ζ-99 "Ζ '(Ηΐ 's)09 "Ζ ' (Ηΐ 's)86 "9  '(Ηΐ 'ω) 9 "Ζ-99 "Ζ '(Ηΐ 's)09 "Ζ ' (Ηΐ 's)86 "9
'(Η2 'Ρ)86 "9-98 "9 ' (HS 'Ρ) Ζ97-997 :9Ρ- OSMI Ζ6 '(Η2 'Ρ)86 "9-98 "9 ' (HS 'Ρ) Ζ97-997 : 9 Ρ- OSMI Ζ6
(Ηΐ 's)OT Όΐ '(Ηΐ 'Ρ)6 8— 9 8  (Ηΐ 's)OT Όΐ '(Ηΐ 'Ρ)6 8— 9 8
' (Η2 'Ρ) Π ·8- ΐ ΐ ·8 ' (Ηΐ 89 "Ζ-99 "Ζ ' (Ηΐ Lf Ί-ff Ί ' (Η2 'Ρ) Π ·8- ΐ ΐ ·8 ' (Ηΐ 89 "Ζ-99 "Ζ ' (Ηΐ Lf Ί-ff Ί
'(Ηΐ 'ω)9ε -L-Z "Ζ '(Ηΐ 's)96 "9 ' (Η2 'Ρ)66 "9-98 "9  '(Ηΐ 'ω)9ε -L-Z "Ζ '(Ηΐ 's)96 "9 ' (Η2 'Ρ)66 "9-98"9
'(HS 'Ρ)697-897 '(HS 's)6T :9Ρ- OSMI 96'(HS 'Ρ) 697-897 '(HS 's)6T : 9 Ρ- OSMI 96
(Ηΐ 's)90 Όΐ '(Ηΐ 'Ρ)8 8— '(Ηΐ 's)8T "8 (Ηΐ 's)90 Όΐ '(Ηΐ 'Ρ)8 8— '(Ηΐ 's)8T "8
'(Ηΐ 'Ρ)Π ·8- Οΐ ·8 '(Ηΐ 's) l Ί ' (Ηΐ 's)T9 '  '(Ηΐ 'Ρ)Π ·8- Οΐ ·8 '(Ηΐ 's) l Ί ' (Ηΐ 's)T9 '
'(Ηΐ 'ω)89 " -½ "Ζ '(Ηΐ 's)S6 "9 ' (Η2 'Ρ)66 "9-98 "9  '(Ηΐ 'ω)89 " -1⁄2 "Ζ '(Ηΐ 's)S6 "9 ' (Η2 'Ρ)66 "9-98 "9
'(HS 'Ρ)Ζ97-99 '(H£'s)n,2 :9Ρ- OSMI 96 '(HS 'Ρ)Ζ97-99 '(H£'s)n, 2 : 9 Ρ- OSMI 96
(Ηΐ 's)T \ '(Ηΐ 's)^8 "8  (Ηΐ 's)T \ '(Ηΐ 's)^8 "8
'(Ηΐ 'Ρ)29 '8-ΐ9 "8 '(Η2 ίΖ "8-6ΐ "8 ' (Ηΐ 'Ρ) S8 "Ζ-ΐ8 "Ζ  '(Ηΐ 'Ρ)29 '8-ΐ9 "8 '(Η2 Ζ "8-6ΐ "8 ' (Ηΐ 'Ρ) S8 "Ζ-ΐ8"Ζ
'(Ηΐ 'ω)99 "Ζ-Ϊ9 'ί '(Ηΐ 'ω)09 "Ζ ' (Ηΐ '^)ΖΖ 'LSI 'ί  '(Ηΐ 'ω)99 "Ζ-Ϊ9 'ί '(Ηΐ 'ω)09 "Ζ ' (Ηΐ '^)ΖΖ 'LSI 'ί
'(Ηΐ 's)2 '9 '(Η2 'Ρ)ΐΟ "9-88 "9 ' (HS 'Ρ) 987-^87 :9Ρ- OSMI f6 '(Ηΐ 's)2 '9 '(Η2 'Ρ)ΐΟ "9-88 "9 ' (HS 'Ρ) 987-^87 : 9 Ρ- OSMI f6
OT8C.0/llOZN3/X3d co o Ζ OAV 7. 82-7. 84 (d, IH) , 8· 44- 8· 45 (d, IH) , 9. 35 (s, IH) OT8C.0/llOZN3/X3d co o Ζ OAV 7. 82-7. 84 (d, IH) , 8· 44- 8· 45 (d, IH) , 9. 35 (s, IH)
108 186-187 1. 28-1. 32 (t, 3H) , 4· 09— 4· 10 (d, 2H) , 4. 21-4. 26 (m, 2H) ,  108 186-187 1. 28-1. 32 (t, 3H) , 4· 09— 4· 10 (d, 2H) , 4. 21-4. 26 (m, 2H) ,
5. 81-5. 96 (d, 2H) , 6. 69 (s, IH) , 6. 87 (s, IH) , 7. 26 (s, IH) , 7. 41-7. 47 (m, 2H) , 7. 82-7. 84 (m, IH) , 8· 41- 8· 42 (d, IH) , 9. 41 (s, IH)  5. 81-5. 96 (d, 2H), 6. 69 (s, IH), 6. 87 (s, IH), 7. 26 (s, IH), 7. 41-7. 47 (m, 2H) , 7. 82-7. 84 (m, IH) , 8· 41- 8· 42 (d, IH) , 9. 41 (s, IH)
109 122-123 1. 38 (s, 6H) , 2. 10 (s, 3H) , 2. 93 (s, 2H) , 5· 80- 5· 94 (d, 2H),  109 122-123 1. 38 (s, 6H) , 2. 10 (s, 3H) , 2. 93 (s, 2H) , 5· 80- 5· 94 (d, 2H),
6. 20 (s, IH) , 6. 84 (s, IH) , 7. 26— 7. 34 (m, 3H) ,  6. 20 (s, IH), 6. 84 (s, IH), 7. 26- 7. 34 (m, 3H),
7. 82-7. 84 (d, IH) , 8· 43- 8· 44 (d, IH) , 9. 68 (s, IH)  7. 82-7. 84 (d, IH) , 8· 43- 8· 44 (d, IH) , 9. 68 (s, IH)
DMS0-d6: 0. 45-0. 48 (m, IH) , 0. 58-0. 65 (m, 3H) , 2. 21 (s, 3H) ,DMS0-d 6 : 0. 45-0. 48 (m, IH) , 0. 58-0. 65 (m, 3H) , 2. 21 (s, 3H) ,
110 148-149 110 148-149
2. 70-2. 71 (m, IH) , 5. 86— 5. 99 (d, 2H) , 6. 97 (s, IH) ,  2. 70-2. 71 (m, IH), 5. 86- 5. 99 (d, 2H), 6. 97 (s, IH),
7. 55-7. 58 (m, IH) , 7. 72 (s, IH) , 7. 84 (s, IH) ,  7. 55-7. 58 (m, IH) , 7. 72 (s, IH) , 7. 84 (s, IH) ,
8. 10-8. 13 (d, IH) , 8. 46-8. 47 (m, 2H)  8. 10-8. 13 (d, IH) , 8. 46-8. 47 (m, 2H)
190-192 DMS0-d6: 1. 17 (d, 3H) , 2. 15 (s, 3H) , 3. 24-3. 27 (d, 3H) ,190-192 DMS0-d 6 : 1. 17 (d, 3H) , 2. 15 (s, 3H) , 3. 24-3. 27 (d, 3H) ,
111 111
3. 88-3. 94 (m, IH) , 5· 85— 5· 98 (d, 2H) , 6. 95 (s, IH) ,  3. 88-3. 94 (m, IH), 5·85—5· 98 (d, 2H), 6. 95 (s, IH),
7. 54-7. 57 (m, 2H) , 7. 73 (s, IH) , 7· 99— 8· 01 (d, IH),  7. 54-7. 57 (m, 2H) , 7. 73 (s, IH) , 7·99—8· 01 (d, IH),
8. 09-8. 11 (d, IH) , 8. 44-8· 46 (d, IH) , 10. 11 (s, IH) 8. 09-8. 11 (d, IH) , 8. 44-8· 46 (d, IH) , 10. 11 (s, IH)
153-155 1. 17-1. 21 (t, 3H) , 2. 15 (s, 3H) , 3. 38-3. 43 (m, 2H) ,153-155 1. 17-1. 21 (t, 3H) , 2. 15 (s, 3H) , 3. 38-3. 43 (m, 2H) ,
112 112
5. 82-5. 96  5. 82-5. 96
(d, 2H) , 6. 20 (s, IH) , 6. 70 (s, IH) , 7. 26— 7. 36 (m, IH) , 7. 58-7. 59 (d, 2H) , 7. 81-7· 83 (d, IH) , 8. 44-8· 46 (d, IH) (d, 2H), 6. 20 (s, IH), 6. 70 (s, IH), 7. 26- 7. 36 (m, IH), 7. 58-7. 59 (d, 2H), 7. 81-7· 83 (d, IH) , 8. 44-8· 46 (d, IH)
230-231 0. 93-0. 97 (t, 3H) , 1. 54-1. 59 (m, 2H) , 2. 15 (s, 3H) ,230-231 0. 93-0. 97 (t, 3H) , 1. 54-1. 59 (m, 2H) , 2. 15 (s, 3H) ,
113 113
3. 30-3. 35 (m, 2H) , 5. 82-5. 96 (d, 2H) , 6. 15 (s, IH) ,  3. 30-3. 35 (m, 2H), 5. 82-5. 96 (d, 2H), 6. 15 (s, IH),
6. 72 (s, IH) , 7. 26-7. 36 (m, IH) , 7· 51— 7· 59 (d, 2H) , 6. 72 (s, IH) , 7. 26-7. 36 (m, IH) , 7· 51— 7· 59 (d, 2H) ,
7. 81-7. 83 (d, IH) , 8· 44- 8· 46 (d, IH) , 10. 07 (s, IH) 7. 81-7. 83 (d, IH) , 8· 44- 8· 46 (d, IH) , 10. 07 (s, IH)
DMS0-d6: 2. 18 (s, 3H) , 2. 50 (s, 3H) , 2. 87-2. 90 (s, 3H) ,DMS0-d 6 : 2. 18 (s, 3H) , 2. 50 (s, 3H) , 2. 87-2. 90 (s, 3H) ,
114 230-231 114 230-231
5. 85-5. 98 (d, 2H) , 6. 91 (s, IH) , 7. 15— 7. 17 (d, IH) , 7. 45- 5. 85-5. 98 (d, 2H) , 6. 91 (s, IH) , 7. 15— 7. 17 (d, IH) , 7. 45-
7. 47 (d, IH) , 7. 56-7. 59 (m, IH) , 8· 13- 8· 15 (d, IH) ,7. 47 (d, IH) , 7. 56-7. 59 (m, IH) , 8· 13- 8· 15 (d, IH),
8. 48-8. 49 (d, IH) , 10. 05 (s, IH) 8. 48-8. 49 (d, IH) , 10. 05 (s, IH)
DMS0-d6: 2. 09 (s, 3H) , 3. 85 (brs, IH) , 3. 97-4. 01 (m, 2H) ,DMS0-d 6 : 2. 09 (s, 3H) , 3. 85 (brs, IH) , 3. 97-4. 01 (m, 2H) ,
116 116
4. 59-4. 61 (m, 2H) , 5. 88-6. 01 (d, 2H) , 6. 48 (s, IH) , 4. 59-4. 61 (m, 2H) , 5. 88-6. 01 (d, 2H) , 6. 48 (s, IH) ,
7. 23-7. 25 7. 23-7. 25
(m, IH) , 7. 57 (s, IH) , 7· 90- 7· 92 (d, IH) , 8. 12-8. 13 (m, IH) , (m, IH) , 7. 57 (s, IH) , 7· 90- 7· 92 (d, IH) , 8. 12-8. 13 (m, IH) ,
8. 22 (s, IH) 8. 22 (s, IH)
4. 36-4. 37 (d, 2H), 5. 85-5· 98 (d, 2H), 6. 62 (s, IH), 6. 99 (brs, 4. 36-4. 37 (d, 2H), 5. 85-5. 98 (d, 2H), 6. 62 (s, IH), 6. 99 (brs,
117 117
IH), 7. 09 (m, 4H), 7. 91-7· 93 (d, IH), 8. 47-8· 53 (m, 2H) IH), 7. 09 (m, 4H), 7. 91-7· 93 (d, IH), 8. 47-8· 53 (m, 2H)
201-203 2. 95-2. 96 (d, 3H), 5. 82-5· 95 (d, 2H), 6. 34 (brs, IH), 7. 19-7·201-203 2. 95-2. 96 (d, 3H), 5. 82-5· 95 (d, 2H), 6. 34 (brs, IH), 7. 19-7·
118 118
37 (m, 3H), 7. 86 (s, IH), 8. 44-8· 45 (d, IH)  37 (m, 3H), 7. 86 (s, IH), 8. 44-8· 45 (d, IH)
142-146 1. 17-1. 20 (t, 3H) , 3. 36-3. 43 (m, 2H) , 5. 81-5. 94 (d, 2H) , 142-146 1. 17-1. 20 (t, 3H) , 3. 36-3. 43 (m, 2H) , 5. 81-5. 94 (d, 2H) ,
119 119
6. 36 (brs, IH), 6. 66 (s, IH), 7. 15-7· 36 (m, 3H), 7. 83-7· 84 (d, 1H) , 8. 43-8. 44 (d, IH)  6. 36 (brs, IH), 6. 66 (s, IH), 7. 15-7· 36 (m, 3H), 7. 83-7· 84 (d, 1H) , 8. 43-8. 44 (d, IH)
132-135 0. 95-0. 99 (t, 3H) , 1. 56-1. 60 (m, 2H) , 3. 33 (m, 2H) , 132-135 0. 95-0. 99 (t, 3H) , 1. 56-1. 60 (m, 2H) , 3. 33 (m, 2H) ,
120 120
5. 83-5. 96 (d, 2H), 6. 25 (brs, IH), 6. 63 (s, IH) ,  5. 83-5. 96 (d, 2H), 6. 25 (brs, IH), 6. 63 (s, IH),
7. 13-7. 46 (m, 3H) , 7. 84-7· 86 (d, IH) , 8. 45-8· 46 (d, IH) 7. 13-7. 46 (m, 3H) , 7. 84-7· 86 (d, IH) , 8. 45-8· 46 (d, IH)
162-165 1. 22-1. 24 (d, 6H), 4. 16—4· 21 (m, IH), 5. 82—5· 95 (d, 2H) ,162-165 1. 22-1. 24 (d, 6H), 4. 16—4· 21 (m, IH), 5. 82—5· 95 (d, 2H),
121 121
6. 00-6. 02 (d, IH) , 6. 64 (s, IH) , 7. 13-7. 47 (m, 2H) , 6. 00-6. 02 (d, IH) , 6. 64 (s, IH) , 7. 13-7. 47 (m, 2H) ,
7. 84-7. 86 (d, IH) , 8. 45-8. 46 (d, IH) , 186-189 0. 94-0. 96 (t, 3H) , 1. 35-1. 80 (m, 4H) , 3. 37-3. 42 (m, 2H) ,7. 84-7. 86 (d, IH) , 8. 45-8. 46 (d, IH), 186-189 0. 94-0. 96 (t, 3H) , 1. 35-1. 80 (m, 4H) , 3. 37-3. 42 (m, 2H) ,
122 122
5. 83-5. 96 (d, 2H), 6. 22 (brs, IH), 6. 63 (s, IH), 7. 21-7· 38 (m, 5. 83-5. 96 (d, 2H), 6. 22 (brs, IH), 6. 63 (s, IH), 7. 21-7· 38 (m,
3H) , 7. 85-7. 86 (d, IH) , 8. 46-8· 47 (d, IH) 3H) , 7. 85-7. 86 (d, IH) , 8. 46-8· 47 (d, IH)
239-242 1. 42 (s, 9H), 5. 83-5. 96 (d, 2H), 5. 91 (s, IH), 6. 67 (s, IH), 7. 1 239-242 1. 42 (s, 9H), 5. 83-5. 96 (d, 2H), 5. 91 (s, IH), 6. 67 (s, IH), 7. 1
123 123
6-7. 38 (m, 3H) , 7. 84-7· 86 (d, IH) , 8. 47-8· 48 (d, IH)  6-7. 38 (m, 3H) , 7. 84-7· 86 (d, IH) , 8. 47-8· 48 (d, IH)
150-154 0. 58-0. 62 (m, 2H), 0. 86-0. 91 (m, 2H), 5. 82-5. 96 (d, 2H), 6. 54 150-154 0. 58-0. 62 (m, 2H), 0. 86-0. 91 (m, 2H), 5. 82-5. 96 (d, 2H), 6. 54
124 124
(s, IH), 6. 64 (s, IH), 7. 19-7· 47 (m, 3H), 7. 84-7· 86 (d, IH), 8. 46-8. 47 (d, IH) , 9. 96 (s, IH)  (s, IH), 6. 64 (s, IH), 7. 19-7· 47 (m, 3H), 7. 84-7· 86 (d, IH), 8. 46-8. 47 (d , IH) , 9. 96 (s, IH)
218-220 2. 83 (s, 3H), 3. 07 (s, 3H), 5. 83-5. 96 (d, 2H), 6. 90-7. 38 (m, 4H 218-220 2. 83 (s, 3H), 3. 07 (s, 3H), 5. 83-5. 96 (d, 2H), 6. 90-7. 38 (m, 4H
125 125
) , 7. 84-7. 86 (d, IH) , 8. 46-8. 47 (d, IH) , 9. 90 (s, IH)  ) , 7. 84-7. 86 (d, IH) , 8. 46-8. 47 (d, IH) , 9. 90 (s, IH)
170-173 0. 90-0. 96 (dd, 3H) , 1. 11-1. 79 (m, 9H) , 5. 82-5. 96 (d, 2H) , 6. 6 170-173 0. 90-0. 96 (dd, 3H) , 1. 11-1. 79 (m, 9H) , 5. 82-5. 96 (d, 2H) , 6. 6
127 127
0 (s, IH), 7. 21-7. 37 (m, 3H), 7. 83-7. 85 (d, IH), 8. 46-8. 47 (d, 0 (s, IH), 7. 21-7. 37 (m, 3H), 7. 83-7. 85 (d, IH), 8. 46-8. 47 (d,
IH) IH)
223-227 1. 15-1. 97 (m, 10H), 3. 86-3. 88 (m, IH), 5. 82-5. 95 (d, 2H), 6. 0 223-227 1. 15-1. 97 (m, 10H), 3. 86-3. 88 (m, IH), 5. 82-5. 95 (d, 2H), 6. 0
128 128
3-6. 05 (d, IH), 6. 64 (s, IH), 7. 18—7. 37 (m, 3H), 7. 83—7. 85 (d, IH) , 8. 45-8. 46 (d, IH) , 10. 00 (s, IH)  3-6. 05 (d, IH), 6. 64 (s, IH), 7. 18—7. 37 (m, 3H), 7. 83—7. 85 (d, IH) , 8. 45- 8. 46 (d, IH) , 10. 00 (s, IH)
152-155 4. 21-4. 22 (d, 2H) , 5. 81-5· 94 (d, 2H) , 6. 62 (s, IH) , 7. 27-7· 38 152-155 4. 21-4. 22 (d, 2H) , 5. 81-5· 94 (d, 2H) , 6. 62 (s, IH) , 7. 27-7· 38
129 129
(m, 3H) , 7. 86-7. 88 (d, IH) , 8. 43-8· 44 (d, IH) ,  (m, 3H) , 7. 86-7. 88 (d, IH) , 8. 43-8· 44 (d, IH) ,
128-131 2. 2. 86 (s, 3H), 5. 83-5. 96 (d, 2H), 6. 44 (s, IH), 6. 88 (s, IH), 7 128-131 2. 2. 86 (s, 3H), 5. 83-5. 96 (d, 2H), 6. 44 (s, IH), 6. 88 (s, IH), 7
130 130
• 28-7. 88 (m, 4H) , 8. 45-8· 46 (d, IH)  • 28-7. 88 (m, 4H) , 8. 45-8· 46 (d, IH)
175-178 1. 04-1. 07 (t, 3H), 3. 29-3. 36 (m, 2H), 5. 82-5. 95 (d, 2H), 6. 40 175-178 1. 04-1. 07 (t, 3H), 3. 29-3. 36 (m, 2H), 5. 82-5. 95 (d, 2H), 6. 40
131 131
(s, IH) , 6. 96-7. 85 (m, 5H), 8. 42—8· 43 (d, IH), 9. 73 (s, IH) (s, IH) , 6. 96-7. 85 (m, 5H), 8. 42—8· 43 (d, IH), 9. 73 (s, IH)
179-181 0. 84-0. 85 (m, 3H), 3. 23-3. 28 (m, 2H), 5. 79-5· 93 (d, 2H), 6. 45179-181 0. 84-0. 85 (m, 3H), 3. 23-3. 28 (m, 2H), 5. 79-5. 93 (d, 2H), 6. 45
132 132
(brs, IH), 7. 27-7. 85 (m, 4H), 8. 42-8· 43 (d, IH), 9. 74 (s, IH) (brs, IH), 7. 27-7. 85 (m, 4H), 8. 42-8· 43 (d, IH), 9. 74 (s, IH)
215-219 1. 06-1. 07 (d, 6H), 4. 05-4. 10 (m, IH), 5. 82-5. 95 (d, 2H), 6. 25215-219 1. 06-1. 07 (d, 6H), 4. 05-4. 10 (m, IH), 5. 82-5. 95 (d, 2H), 6. 25
133 133
-6. 27 (d, IH) , 6. 98 (s, IH) , 7. 34-7. 85 (m, 5H) , 8. 42-8· 43 (d, 1 -6. 27 (d, IH) , 6. 98 (s, IH) , 7. 34-7. 85 (m, 5H) , 8. 42-8· 43 (d, 1
H) H)
207-210 0. 85-0. 88 (m, 3H) , 1. 19-1. 43 (m, 4H) , 3. 26-3. 31 (m, 2H) , 5. 82 207-210 0. 85-0. 88 (m, 3H) , 1. 19-1. 43 (m, 4H) , 3. 26-3. 31 (m, 2H) , 5. 82
134 134
-5. 92  -5. 92
(d, 2H) , 6. 40 (brs, IH) , 6. 94 (s, IH) , 7. 33-7· 86 (m, 4H) , 8. 41- 8. 43 (d, IH)  (d, 2H) , 6. 40 (brs, IH) , 6. 94 (s, IH) , 7. 33-7· 86 (m, 4H) , 8. 41- 8. 43 (d, IH)
124-126 1. 26 (s, 9H), 5. 78-5. 92 (d, 2H), 6. 25-6. 27 (d, IH), 7. 13-7. 60 124-126 1. 26 (s, 9H), 5. 78-5. 92 (d, 2H), 6. 25-6. 27 (d, IH), 7. 13-7. 60
135 135
(m, 4H) , 7. 81-7. 82 (d, IH) , 8. 40-8· 41 (d, IH) ,  (m, 4H) , 7. 81-7. 82 (d, IH) , 8. 40-8· 41 (d, IH) ,
0. 94-0. 97 (t, 3H) , 1. 54-1. 56 (m, 2H) , 2. 21 (s, 3H) , 0. 94-0. 97 (t, 3H) , 1. 54-1. 56 (m, 2H) , 2. 21 (s, 3H) ,
136 136
3. 32-3. 37  3. 32-3. 37
(m, 2H) , 5. 83-5. 96 (d, 2H) , 6. 14-6. 15 (m, IH) , 6. 64 (s, IH) , 7. 12-7. 16 (m, IH) , 7. 23-7· 29 (m, IH) , 7. 32-7· 35 (m, 2H) , 7. 81-7. 83 (d, IH) , 8. 44-8. 46 (d, IH) ,  (m, 2H) , 5. 83-5. 96 (d, 2H) , 6. 14-6. 15 (m, IH) , 6. 64 (s, IH) , 7. 12-7. 16 (m , IH) , 7. 23-7· 29 (m, IH) , 7. 32-7· 35 (m, 2H) , 7. 81-7. 83 (d, IH) , 8. 44-8. 46 (d, IH),
2. 12 (s, 3H) , 2. 81 (s, 3H) , 3. 07 (s, 3H) , 5. 82— 5. 95 (d, 2H) , 2. 12 (s, 3H) , 2. 81 (s, 3H) , 3. 07 (s, 3H) , 5. 82— 5. 95 (d, 2H) ,
137 137
6. 74 (s, IH) , 7. 02-7. 04 (m, IH) , 7. 12-7. 13 (m, 2H) , 6. 74 (s, IH) , 7. 02-7. 04 (m, IH) , 7. 12-7. 13 (m, 2H) ,
7. 32-7. 35 (m, IH) , 7· 81- 7· 83 (d, IH) , 8· 44- 8· 46 (d, IH) , 9. 34 (s, IH) 7. 32-7. 35 (m, IH) , 7· 81- 7· 83 (d, IH) , 8· 44- 8· 46 (d, IH) , 9. 34 (s, IH)
3. 30-3. 71 (m, 8H), 5. 71-5· 84 (d, 2H), 6. 89-6· 94 (m, 3H), 7. 37 3. 30-3. 71 (m, 8H), 5. 71-5· 84 (d, 2H), 6. 89-6· 94 (m, 3H), 7. 37
142 216-218 142 216-218
-7. 40 (m, IH) , 7. 85-7. 87 (d, IH) , 8. 46-8. 47 (dlH)  -7. 40 (m, IH) , 7. 85-7. 87 (d, IH) , 8. 46-8. 47 (dlH)
1. 37-1. 60 (m, 6H), 3. 19-3. 65 (m, 4H), 5. 78-5. 91 (d, 2H), 6. 85 1. 37-1. 60 (m, 6H), 3. 19-3. 65 (m, 4H), 5. 78-5. 91 (d, 2H), 6. 85
143 208-210 143 208-210
-7. 37 (m, 4H), 7. 83-7· 85 (d, IH), 8. 44-8· 45 (d, IH) 1. 31-1. 32 (m, 3H), 4. 14—4. 16 (d, 2H), 4. 17—4. 28 (m, 4H), 5. 83-7. 37 (m, 4H), 7. 83-7. 85 (d, IH), 8. 44-8· 45 (d, IH) 1. 31-1. 32 (m, 3H), 4. 14-4. 16 (d, 2H), 4. 17-4. 28 (m, 4H), 5. 83
145 158-161 145 158-161
-5. 96  -5. 96
(d, 2H), 6. 59 (s, IH), 6. 74 (brs, IH), 7. 13-7· 34 (m, 3H), 7. 85- 7. 87 (d, 1H) , 8. 44-8. 45 (d, IH)  (d, 2H), 6. 59 (s, IH), 6. 74 (brs, IH), 7. 13-7· 34 (m, 3H), 7. 85- 7. 87 (d, 1H), 8. 44-8. 45 (d, IH)
193-195 4. 56-4. 57 (d, 2H), 5. 83-5. 96 (d, 2H), 6. 30-6. 59 (m, 4H) , 7. 21 193-195 4. 56-4. 57 (d, 2H), 5. 83-5. 96 (d, 2H), 6. 30-6. 59 (m, 4H) , 7. 21
146 146
-7. 38 (m, 3H) , 7. 83-7. 85 (d, IH) , 8. 44-8. 45 (d, IH) , 9. 36 (s, 1 -7. 38 (m, 3H) , 7. 83-7. 85 (d, IH) , 8. 44-8. 45 (d, IH) , 9. 36 (s, 1
H) H)
169-173 0. 93-1. 66 (m, 8H), 3. 07——3. 51 (m, 4H), 5. 80—5. 93 (d, 2H), 6. 8 169-173 0. 93-1. 66 (m, 8H), 3. 07——3. 51 (m, 4H), 5. 80—5. 93 (d, 2H), 6. 8
147 147
5-7. 36 (m, 4H) , 7. 82-7· 84 (d, IH) , 8. 44-8· 45 (d, IH)  5-7. 36 (m, 4H) , 7. 82-7· 84 (d, IH) , 8. 44-8· 45 (d, IH)
130-134 0. 91-1. 66 (m, 10H), 2. 98-3. 50 (m, 2H), 5. 80-5. 94 (d, 2H), 6. 8 130-134 0. 91-1. 66 (m, 10H), 2. 98-3. 50 (m, 2H), 5. 80-5. 94 (d, 2H), 6. 8
148 148
7-7. 36 (m, 4H) , 7. 82-7· 84 (d, IH) , 8. 44-8· 45 (d, IH)  7-7. 36 (m, 4H) , 7. 82-7· 84 (d, IH) , 8. 44-8· 45 (d, IH)
195-196 0. 97-1. 00 (m, 3H) , 1. 42-1. 66 (m, 6H) , 3. 43-3. 48 (m, 2H) , 5. 90 195-196 0. 97-1. 00 (m, 3H) , 1. 42-1. 66 (m, 6H) , 3. 43-3. 48 (m, 2H) , 5. 90
149 149
-6. 03  -6. 03
(d, 2H), 6. 24 (brs, IH), 6. 69 (s, IH), 7. 28-7. 43 (m, 3H), 7. 91- 7. 93 (d, IH) , 8. 52-8. 54 (d, IH) , 10. 05 (brs, IH)  (d, 2H), 6. 24 (brs, IH), 6. 69 (s, IH), 7. 28-7. 43 (m, 3H), 7. 91- 7. 93 (d, IH) , 8. 52-8. 54 (d, IH) , 10. 05 (brs, IH)
251-255 1. 00-1. 80 (m, 10H), 5. 79-5· 96 (d, 2H), 6. 86 (s, IH), 7. 35-7. 8 251-255 1. 00-1. 80 (m, 10H), 5. 79-5. 96 (d, 2H), 6. 86 (s, IH), 7. 35-7. 8
154 154
7 (m, 4H) , 8. 42-8. 43 (d, IH)  7 (m, 4H) , 8. 42-8. 43 (d, IH)
196-199 4. 45-4. 16 (d, 2H), 5. 82-5. 95 (d, 2H), 6. 72 (s, IH), 7. 19-7. 92 196-199 4. 45-4. 16 (d, 2H), 5. 82-5. 95 (d, 2H), 6. 72 (s, IH), 7. 19-7. 92
155 155
(m, 5H) , 8. 42-8. 43 (d, 2H) , 8. 94 (s, IH)  (m, 5H) , 8. 42-8. 43 (d, 2H) , 8. 94 (s, IH)
2. 98-3. 00 (s, 3H), 5. 87-6. 00 (d, 2H), 6. 37 (s, IH), 6. 67 (s, IH 2. 98-3. 00 (s, 3H), 5. 87-6. 00 (d, 2H), 6. 37 (s, IH), 6. 67 (s, IH
161 161
) , 7. 23- 7. 40 (m, 4H) , 7. 88-7· 90 (d, IH) , 8. 49- 8. 50 (d, IH) , 10. 19 (s, IH)  ), 7. 23- 7. 40 (m, 4H) , 7. 88-7· 90 (d, IH) , 8. 49- 8. 50 (d, IH) , 10. 19 (s, IH)
1. 47 (s, 9H) , 5. 88-6. 01 (d, 2H) , 6. 01 (s, IH) , 6. 68 (s, IH) , 1. 47 (s, 9H) , 5. 88-6. 01 (d, 2H) , 6. 01 (s, IH) , 6. 68 (s, IH) ,
163 163
7. 20-7. 38 (m, 4H), 7. 88-7· 89 (d, IH), 8. 51-8· 52 (d, IH) , 10. 07 (s, IH)  7. 20-7. 38 (m, 4H), 7. 88-7· 89 (d, IH), 8. 51-8· 52 (d, IH) , 10. 07 (s, IH)
3. 32 (s, 3H), 3. 49 (s, 3H), 5. 84—5. 97 (d, 2H), 6. 74 (s, IH), 7. 3 3. 32 (s, 3H), 3. 49 (s, 3H), 5. 84—5. 97 (d, 2H), 6. 74 (s, IH), 7. 3
180 180
1-7. 46  1-7. 46
( m, 3H) , 7. 86-7. 88 (d, IH) , 8. 48-8. 49 (d, IH) 8. 95 (brs, IH) ( m, 3H) , 7. 86-7. 88 (d, IH) , 8. 48-8. 49 (d, IH) 8. 95 (brs, IH)
129-132 2. 96-2. 97 (s, 3H), 5. 86-6· 00 (d, 2H), 6. 20 (brs, IH), 7. 02 (s,129-132 2. 96-2. 97 (s, 3H), 5. 86-6· 00 (d, 2H), 6. 20 (brs, IH), 7. 02 (s,
182 182
IH) , 7. 23-7. 39 (m, 3H) , 7. 86-7· 88 (d, IH) , 8. 48-8· 49 (d, IH) IH) , 7. 23-7. 39 (m, 3H) , 7. 86-7· 88 (d, IH) , 8. 48-8· 49 (d, IH)
130-135 1. 19-1. 23 (t, 3H) , 3. 44-3· 49 (m, 2H) , 5. 90-6· 03 (d, 2H) , 6. 21130-135 1. 19-1. 23 (t, 3H) , 3. 44-3· 49 (m, 2H) , 5. 90-6· 03 (d, 2H) , 6. 21
183 183
(brs,  (brs,
IH), 7. 00 (s, IH), 7. 29-7. 43 (m, 3H), 7. 90-7· 92 (d, IH), 8. 52- 8. 53 (d, IH) , 9. 73 (brs, IH)  IH), 7. 00 (s, IH), 7. 29-7. 43 (m, 3H), 7. 90-7· 92 (d, IH), 8. 52- 8. 53 (d, IH) , 9. 73 (brs, IH)
218-220 0. 90-0. 94 (m, 3H), 1. 49—1· 51 (m, 2H), 3. 30—3· 35 (m, 2H), 5. 83 218-220 0. 90-0. 94 (m, 3H), 1. 49—1· 51 (m, 2H), 3. 30—3· 35 (m, 2H), 5. 83
184 184
-5. 96  -5. 96
(d, 2H), 6. 16 (brs, IH), 6. 99 (s, IH), 7. 19-7· 35 (m, 3H), 7. 82- 7. 84 (d, IH) , 8. 43-8. 45 (d, IH) , 9. 82 (brs, IH)  (d, 2H), 6. 16 (brs, IH), 6. 99 (s, IH), 7. 19-7· 35 (m, 3H), 7. 82- 7. 84 (d, IH) , 8. 43-8. 45 (d, IH) , 9. 82 (brs, IH)
123-126 1. 13-1. 15 (d, 6H) , 4. 15—4. 21 (m, IH) , 5. 82—5. 95 (d, 2H) , 6. 94 123-126 1. 13-1. 15 (d, 6H) , 4. 15—4. 21 (m, IH), 5. 82—5. 95 (d, 2H), 6. 94
185 185
-6. 96  -6. 96
( d, IH) , 7. 20-7. 36 (m, 3H) , 7. 83-7· 85 (d, IH) , 8. 43-8· 44 (d, ( d, IH) , 7. 20-7. 36 (m, 3H) , 7. 83-7· 85 (d, IH) , 8. 43-8· 44 (d,
IH) IH)
110-113 0. 86-0. 92 (m, 3H), 1. 27-1. 47 (m, 4H), 3. 34-3. 39 (m, 2H), 5. 83 110-113 0. 86-0. 92 (m, 3H), 1. 27-1. 47 (m, 4H), 3. 34-3. 39 (m, 2H), 5. 83
186 186
-5. 96  -5. 96
(d, 2H), 6. 18 (brs, IH), 6. 98 (s, IH), 7. 20-7. 36 (m, 3H), 7. 83- 7. 85 (d, 1H) , 8. 44-8. 45 (d, IH) 239-243 1. 42 (s, 9H), 5. 80-5. 94 (d, 2H), 5. 97 (brs, IH), 7. 04-7· 33 (m,(d, 2H), 6. 18 (brs, IH), 6. 98 (s, IH), 7. 20-7. 36 (m, 3H), 7. 83- 7. 85 (d, 1H), 8. 44-8. 45 (d, IH) 239-243 1. 42 (s, 9H), 5. 80-5. 94 (d, 2H), 5. 97 (brs, IH), 7. 04-7· 33 (m,
187 187
4H) , 7. 80-7. 82 (d, IH) , 8· 41— 8· 42 (d, IH)  4H) , 7. 80-7. 82 (d, IH) , 8· 41— 8· 42 (d, IH)
137-139 0. 54-0. 84 (m, 4H) , 2. 81-2· 83 (m, IH) , 5. 82-5· 96 (d, 2H) , 6. 31 137-139 0. 54-0. 84 (m, 4H) , 2. 81-2· 83 (m, IH) , 5. 82-5· 96 (d, 2H) , 6. 31
188 188
(s, IH), 6. 99-7. 36 (m, 3H), 7. 83-7· 85 (d, IH), 8. 45-8· 47 (d, 1 H) , 9. 68 (brs, IH)  (s, IH), 6. 99-7. 36 (m, 3H), 7. 83-7· 85 (d, IH), 8. 45-8· 47 (d, 1 H) , 9. 68 ( Brs, IH)
220-221 0. 86-0. 90 (m, 3H), 1. 30-1. 50 (m, 6H), 3. 32-3. 37 (m, 2H), 5. 82 220-221 0. 86-0. 90 (m, 3H), 1. 30-1. 50 (m, 6H), 3. 32-3. 37 (m, 2H), 5. 82
189 189
-5. 96  -5. 96
(d, 2H), 6. 18 (brs, IH), 6. 94-7· 35 (m, 4H), 7. 82-7· 84 (d, IH) , 8. 44- 8. 45 (d, 1H) , 9. 72 (brs, IH)  (d, 2H), 6. 18 (brs, IH), 6. 94-7· 35 (m, 4H), 7. 82-7· 84 (d, IH) , 8. 44- 8. 45 (d , 1H) , 9. 72 (brs, IH)
0. 82-0. 84 (m, 3H) , 0. 91—1· 61 ( (m, 9H) , 3. 54—4· 20 (m, IH) , 5. 8 0. 82-0. 84 (m, 3H) , 0. 91—1· 61 ( (m, 9H) , 3. 54—4· 20 (m, IH) , 5. 8
190 190
2-5. 95 (d, 2H), 7. 02-7. 34 (m, 4H), 7. 80-7. 82 (d, IH), 8. 42-8. 43 (d, IH) , 10. 00 (brs, IH)  2-5. 95 (d, 2H), 7. 02-7. 34 (m, 4H), 7. 80-7. 82 (d, IH), 8. 42-8. 43 (d, IH) , 10. 00 (brs, IH)
226-228 1. 07-1. 86 (m, 10H), 3. 83-3. 85 (m, IH), 5. 82-5. 96 (d, 2H), 7. 0 226-228 1. 07-1. 86 (m, 10H), 3. 83-3. 85 (m, IH), 5. 82-5. 96 (d, 2H), 7. 0
200 200
3-7. 34 (m, 4H) , 7. 81-7· 83 (d, IH) , 8. 42-8· 43 (d, IH)  3-7. 34 (m, 4H) , 7. 81-7· 83 (d, IH) , 8. 42-8· 43 (d, IH)
166-169 0. 92-1. 28 (m, 8H), 2. 85-3. 52 (m, 4H), 5. 82-5. 95 (d, 2H), 6. 99 166-169 0. 92-1. 28 (m, 8H), 2. 85-3. 52 (m, 4H), 5. 82-5. 95 (d, 2H), 6. 99
201 201
-7. 33 (m, 4H) , 7. 81-7· 82 (d, IH) , 8. 42-8· 43 (d, IH)  -7. 33 (m, 4H) , 7. 81-7· 82 (d, IH) , 8. 42-8· 43 (d, IH)
109-113 0. 91-1. 63 (m, 10H) , 2. 86-3· 73 (m, 4H) , 5. 81-5· 94 (d, 2H) , 7. 0 109-113 0. 91-1. 63 (m, 10H) , 2. 86-3· 73 (m, 4H) , 5. 81-5· 94 (d, 2H) , 7. 0
202 202
1-7. 33 (m, 4H) , 7. 81-7· 83 (d, IH) , 8. 41-8· 42 (d, IH)  1-7. 33 (m, 4H) , 7. 81-7· 83 (d, IH) , 8. 41-8· 42 (d, IH)
121-124 2. 71 (s, 3H), 3. 09 (s, 3H), 5. 82-5. 95 (d, 2H), 6. 98-7. 35 (m, 4H 121-124 2. 71 (s, 3H), 3. 09 (s, 3H), 5. 82-5. 95 (d, 2H), 6. 98-7. 35 (m, 4H
203 203
) , 7. 83-7. 84 (d, IH) , 8. 44-8· 45 (d, IH)  ), 7. 83-7. 84 (d, IH) , 8. 44-8· 45 (d, IH)
219-221 1. 13-1. 72 (m, 6H), 2. 96-3. 05 (m, 2H), 3. 68-3. 70 (m, 2H), 5. 80 219-221 1. 13-1. 72 (m, 6H), 2. 96-3. 05 (m, 2H), 3. 68-3. 70 (m, 2H), 5. 80
204 204
-5. 93  -5. 93
(d, 2H) , 6. 98-7. 32 (m, 4H) , 7. 80-7· 82 (d, IH) , 8. 41-8· 42 (d, 1 (d, 2H) , 6. 98-7. 32 (m, 4H) , 7. 80-7· 82 (d, IH) , 8. 41-8· 42 (d, 1
H) H)
171-174 0. 92-1. 28 (m, 8H), 2. 79-3. 39 (m, 4H), 5. 80-5. 93 (d, 2H), 6. 92 171-174 0. 92-1. 28 (m, 8H), 2. 79-3. 39 (m, 4H), 5. 80-5. 93 (d, 2H), 6. 92
205 205
-7. 27 (m, 4H) , 7. 81-7· 82 (d, IH) , 8. 43-8· 44 (d, IH)  -7. 27 (m, 4H) , 7. 81-7· 82 (d, IH) , 8. 43-8· 44 (d, IH)
225-227 1. 10-1. 90 (m, 10H), 3. 83-3. 85 (m, IH), 5. 81-5. 95 (d, 2H), 6. 9 225-227 1. 10-1. 90 (m, 10H), 3. 83-3. 85 (m, IH), 5. 81-5. 95 (d, 2H), 6. 9
206 206
0-7. 36 (m, 4H) , 7. 82-7· 84 (d, IH) , 8. 44-8· 45 (d, IH)  0-7. 36 (m, 4H) , 7. 82-7· 84 (d, IH) , 8. 44-8· 45 (d, IH)
223-225 0. 82-0. 84 (m, 3H), 0. 96-1. 54 ( (m, 9H), 3. 55-4. 15 (m, IH), 5. 8 223-225 0. 82-0. 84 (m, 3H), 0. 96-1. 54 ( (m, 9H), 3. 55-4. 15 (m, IH), 5. 8
207 207
1-5. 94 (d, 2H) , 6. 98-7. 34 (m, 4H) , 7. 81—7. 82 (d, IH) , 8. 43—8. 1-5. 94 (d, 2H), 6. 98-7. 34 (m, 4H), 7. 81-7. 82 (d, IH), 8. 43-8.
44 (d, IH) 44 (d, IH)
214-216 0. 87-0. 90 (m, 3H), 1. 30-1· 51 (m, 6H), 3. 29-3· 34 (m, 2H) , 5. 81 214-216 0. 87-0. 90 (m, 3H), 1. 30-1· 51 (m, 6H), 3. 29-3· 34 (m, 2H) , 5. 81
208 208
-5. 95  -5. 95
(d, 2H), 6. 25 (brs, IH), 6. 91-7· 34 (m, 4H), 7. 82—7· 84 (d, IH) , 8. 44- 8. 45 (d, IH)  (d, 2H), 6. 25 (brs, IH), 6. 91-7· 34 (m, 4H), 7. 82—7· 84 (d, IH) , 8. 44- 8. 45 (d , IH)
228-229 0. 48-0. 82 (m, 4H), 2. 75-2. 76 (m, IH), 5. 82-5. 95 (d, 2H), 6. 41 228-229 0. 48-0. 82 (m, 4H), 2. 75-2. 76 (m, IH), 5. 82-5. 95 (d, 2H), 6. 41
209 209
(s, IH), 6. 94-7. 36 (m, 3H), 7. 83-7· 85 (d, IH), 8. 45-8· 47 (d, 1 H) , 10. 01 (brs, IH)  (s, IH), 6. 94-7. 36 (m, 3H), 7. 83-7· 85 (d, IH), 8. 45-8· 47 (d, 1 H) , 10. 01 ( Brs, IH)
215-219 1. 33 (s, 9H), 5. 82-5. 95 (d, 2H), 6. 04 (brs, IH), 7. 03-7· 35 (m, 215-219 1. 33 (s, 9H), 5. 82-5. 95 (d, 2H), 6. 04 (brs, IH), 7. 03-7· 35 (m,
210 210
4H) , 7. 82-7. 84 (d, IH) , 8. 44-8· 45 (d, IH)  4H) , 7. 82-7. 84 (d, IH) , 8. 44-8· 45 (d, IH)
180-183 0. 90-0. 94 (m, 3H), 1. 27-1. 48 (m, 4H), 3. 30-3. 35 (m, 2H), 5. 82 180-183 0. 90-0. 94 (m, 3H), 1. 27-1. 48 (m, 4H), 3. 30-3. 35 (m, 2H), 5. 82
211 211
-5. 95  -5. 95
(d, 2H), 6. 27 (brs, IH), 6. 91 (s, IH), 7. 18—7· 32 (m, 3H), 7. 83- 7. 85 (d, 1H) , 8. 45-8. 46 (d, IH)  (d, 2H), 6. 27 (brs, IH), 6. 91 (s, IH), 7. 18—7· 32 (m, 3H), 7. 83- 7. 85 (d, 1H), 8. 45-8. 46 (d, IH)
211-214 1. 13-1. 15 (d, 6H) , 4. 15—4. 21 (m, IH) , 5. 82—5. 95 (d, 2H) , 6. 94 211-214 1. 13-1. 15 (d, 6H) , 4. 15—4. 21 (m, IH), 5. 82—5. 95 (d, 2H), 6. 94
212 212
-6. 96 ( d, 1H) , 7. 20-7. 36 (m, 3H) , 7. 83-7· 85 (d, 1H) , 8. 43-8· 44 (d, -6. 96 ( d, 1H) , 7. 20-7. 36 (m, 3H) , 7. 83-7· 85 (d, 1H) , 8. 43-8· 44 (d,
1H)  1H)
129-132 1. 14-1. 16 (d, 6H) , 4. 13-4. 18 (m, 1H) , 5. 82-5. 95 (d, 2H) , 6. 04 129-132 1. 14-1. 16 (d, 6H) , 4. 13-4. 18 (m, 1H) , 5. 82-5. 95 (d, 2H) , 6. 04
213 213
(brs,  (brs,
1H), 6. 97 (s, 1H), 7. 14-7. 36 (m, 3H), 7. 83-7. 85 (d, 1H), 8. 45- 8. 46 (d, 1H)  1H), 6. 97 (s, 1H), 7. 14-7. 36 (m, 3H), 7. 83-7. 85 (d, 1H), 8. 45- 8. 46 (d, 1H)
168-170 2. 67 (s, 3H), 5. 86-5. 99 (d, 2H), 6. 99 (s, 1H), 7. 43-7. 56 (m, 3H 168-170 2. 67 (s, 3H), 5. 86-5. 99 (d, 2H), 6. 99 (s, 1H), 7. 43-7. 56 (m, 3H
214 214
) , 8. 10-8. 12 (d, 1H) , 8. 46—8· 47 (d, 1H)  ) , 8. 10-8. 12 (d, 1H) , 8. 46—8· 47 (d, 1H)
190-193 1. 19-1. 23 (t, 3H) , 3. 42-3. 48 (m, 2H) , 5. 89-6. 02 (d, 2H) , 6. 27 190-193 1. 19-1. 23 (t, 3H) , 3. 42-3. 48 (m, 2H) , 5. 89-6. 02 (d, 2H) , 6. 27
215 215
(brs,  (brs,
1H), 6. 96 (s, 1H), 7. 26-7. 39 (m, 3H), 7. 90-7. 92 (d, 1H), 8. 52- 8. 53 (d, 1H) , 10. 13 (brs, 1H)  1H), 6. 96 (s, 1H), 7. 26-7. 39 (m, 3H), 7. 90-7. 92 (d, 1H), 8. 52- 8. 53 (d, 1H) , 10. 13 (brs, 1H)
211-214 1. 13-1. 15 (d, 6H) , 4. 15—4. 21 (m, 1H) , 5. 82—5. 95 (d, 2H) , 6. 94 211-214 1. 13-1. 15 (d, 6H) , 4. 15—4. 21 (m, 1H), 5. 82—5. 95 (d, 2H), 6. 94
216 216
-6. 96  -6. 96
( d, 1H) , 7. 20-7. 36 (m, 3H) , 7. 83-7· 85 (d, 1H) , 8. 43-8· 44 (d, ( d, 1H) , 7. 20-7. 36 (m, 3H) , 7. 83-7· 85 (d, 1H) , 8. 43-8· 44 (d,
1H) 1H)
218-220 0. 90-0. 94 (m, 3H), 1. 49—1· 51 (m, 2H), 3. 30—3· 35 (m, 2H), 5. 83 218-220 0. 90-0. 94 (m, 3H), 1. 49—1· 51 (m, 2H), 3. 30—3· 35 (m, 2H), 5. 83
217 217
-5. 96  -5. 96
(d, 2H), 6. 16 (brs, 1H), 6. 99 (s, 1H), 7. 19-7· 35 (m, 3H), 7. 82- 7. 84 (d, 1H) , 8. 43-8. 45 (d, 1H) , 9. 82 (brs, 1H) 索引表 1和索引表 2中列举的本发明所述的结构式(I)表示的化合物均可根据本专利 说明书中所描述的合成方法及合成实施例 1-3所述的制备方法进行合成。  (d, 2H), 6. 16 (brs, 1H), 6. 99 (s, 1H), 7. 19-7· 35 (m, 3H), 7. 82- 7. 84 (d, 1H), 8. 43-8. 45 (d, 1H), 9. 82 (brs, 1H) The compounds represented by the structural formula (I) of the present invention listed in the index table 1 and the index table 2 can be used according to the present patent specification. The synthesis methods described and the preparation methods described in Synthesis Examples 1-3 were synthesized.
本发明还提供结构式 ( I ) 表示的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类化合物或 其农业上适用的盐的用途、 一种防治有害生物的农药制剂和一种防治有害生物的方法。  The present invention also provides the use of a monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I) or an agriculturally applicable salt thereof, a pesticide preparation for controlling pests, and a control The method of pests.
含有本发明所述结构式 ( I ) 表示的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类化合物 或其农业上适用的盐的有害生物防治剂可用于农作物上的害虫防治, 例如作为在农业园艺领 域中成为问题的各种有害生物的防治剂、 即农业园艺有害生物防治剂, 或寄生于动物的有害 生物防治剂、 即动物寄生生物防治剂特别有用。  A pest control agent containing a fluoromethoxypyrazole-containing orthoformylbenzamide compound represented by the structural formula (I) of the present invention or an agriculturally applicable salt thereof can be used for pest control on agricultural crops, for example It is particularly useful as a control agent for various pests that is a problem in the field of agriculture and horticulture, that is, an agricultural and horticultural pest control agent, or a pest control agent that is parasitic on animals, that is, an animal parasite control agent.
作为农业园艺用有害生物防治剂, 例如作为杀虫、 杀螨剂, 是有用的, 具体地说, 对于 防治二斑叶螨、 红叶螨、 柑桔全爪螨、 苹果全爪螨等植物寄生性螨类; 小菜蛾、 甘蓝夜蛾、 斜纹夜蛾、 棉铃虫、 烟夜蛾、 烟毒蛾、 稻纵卷叶野螟、 稻褐带卷蛾、 苹果小卷蛾、 桃小实心 蛾、 梨小食心虫、 小地老虎、 马铃薯叶甲、 黄守瓜、 蚜虫类、 粉虱类、 蓟马类、 蝗虫类、 斑 潜蝇类等农业害虫类。 其中, 含有本发明化合物的农业园艺用有害生物防治剂, 对于农业害 虫类等特别有效。 另外, 含有本发明所述结构式 ( I ) 表示的含一氟甲氧基吡唑的邻甲酰氨 基苯甲酰胺类化合物或其农业上适用的盐的农业园艺用有害生物防治剂, 对于防治对有机磷 剂、 氨基甲酸酯剂、 合成除虫菊酯剂等的药剂的各种抗性害虫有效。 进而, 本发明所述结构 式 ( I ) 表示的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类化合物或其农业上适用的盐因为 具有优异的渗透转移性, 所以通过使用含有本发明所述结构式 (I)表示的化合物的农业园艺 用有害生物防治剂来处理土壤, 在防治土壤有害昆虫类、 螨类等类的同时也可防治茎叶部的 害虫。 It is useful as a pest control agent for agricultural and horticultural purposes, for example, as a pesticidal or acaricide, in particular, for controlling plant parasitism such as two-spotted spider mites, red leafhopper, citrus scorpion, and whole claw scorpion. Anthraquinones, Plutella xylostella, Brassica chinensis, Spodoptera litura, Helicoverpa armigera, Helicoverpa armigera, Tobacco moth, Rice leaf roller, Wild rice moth, Apple small moth, Peach small moth, Pear , agricultural tiger pests such as small tigers, potato leaf beetles, yellow squash, locusts, whiteflies, thrips, locusts, and larvae. Among them, the agricultural and horticultural pest control agent containing the compound of the present invention is particularly effective for agricultural pests and the like. Further, the agricultural or horticultural pest control agent containing the fluoromethoxypyrazole-containing orthoformylaminobenzamide compound represented by the structural formula (I) of the present invention or an agriculturally applicable salt thereof Various resistant pests of an agent such as an organophosphorus agent, a carbamate agent, or a pyrethroid agent are effective. Further, the monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole represented by the structural formula (I) of the present invention or an agriculturally applicable salt thereof It has excellent osmotic transferability, so the soil can be treated by using an agricultural and horticultural pest control agent containing the compound represented by the structural formula (I) of the present invention, and can also be controlled while controlling soil harmful insects, mites and the like. Pests in the stems and leaves.
作为含有本发明所述结构式 ( I ) 表示的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类化 合物或其农业上适用的盐的有害生物防治剂的其他的优选形态, 可列举出综合防治上述植物 寄生性螨类、 农业害虫类、 土壤害虫类等的农业园艺用有害生物防治剂。  Other preferred embodiments of the pest control agent containing the monofluoroamidobenzamide compound containing the monofluoromethoxypyrazole represented by the structural formula (I) of the present invention or an agriculturally applicable salt thereof may be mentioned. A pest control agent for agricultural and horticultural pest control, such as plant parasitic mites, agricultural pests, and soil pests.
含有本发明所述结构式 ( I ) 表示的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类化合物 或其农业上适用的盐的农业园艺用有害生物防治剂, 通常混合该化合物与各种农药上的辅助 剂即载体, 形成粉剂、 颗粒剂、 颗粒可湿性粉剂、 可湿性粉剂、 水性悬浮剂、 油性悬浮剂、 水溶剂、 乳剂、 糊剂、 气雾剂、 微量散布剂等的各种形态的制剂来使用, 但只要适合本发明 的目的, 则可以制成通常在该领域中使用的所有制剂形态。 作为制剂中使用的辅助剂, 可以 列举出硅藻土、 消石灰、 碳酸钙、 滑石、 白炭墨、 高岭土、 膨润土、 高岭石和绢云母的混合 物、 粘土、 碳酸钠、 小苏打、 芒硝、 沸石、 淀粉等的固体载体; 水、 甲苯、 二甲苯、 溶剂石 脑油、 二噁烷、 丙酮、 异佛尔酮、 甲基异丁基酮、 氯苯、 环己烷、 二甲亚砜、 N,N-二甲基甲 酰胺、 二甲基乙酰胺、 N-甲基 -2-吡咯烷酮、 醇等的溶剂; 脂肪酸盐、 苯甲酸盐、 烷基磺基琥 珀酸盐、 二烷基磺基琥珀酸盐、 聚羧酸盐、 烷基硫酸酯盐、 烷基硫酸盐、 烷基芳基硫酸盐、 烷基二甘醇醚硫酸盐、 醇硫酸酯盐、 烷基磺酸盐、 烷基芳基磺酸盐、 芳基磺酸盐、 木质磺酸 盐、 烷基二苯基醚二磺酸盐、 聚苯乙烯磺酸盐、 烷基磷酸酯盐、 烷基芳基磷酸盐、 芳基磷酸 盐、 苯乙烯基芳基磷酸盐、 聚氧乙烯烷基醚磷酸盐、 聚氧乙烯烷基芳基磷酸酯盐、 萘磺酸甲 醛縮合物的盐这样的阴离子类的表面活性剂或展开剂; 脱水山梨糖醇脂肪酸酯、 甘油脂肪酸 酯、 脂肪酸聚甘油酯、 脂肪酸醇聚二醇醚、 乙块二醇、 块属醇、 氧化烯嵌段聚合物、 聚氧乙 烯烷基醚、 聚氧乙烯烷基芳基醚、 聚氧乙烯苯乙烯基芳基醚、 聚氧乙烯二醇烷基醚、 聚乙二 醇、 聚氧乙烯脂肪酸酯、 聚氧乙烯脱水山梨糖醇脂肪酸酯、 聚氧乙烯甘油脂肪酸酯、 聚氧乙 烯硬化蓖麻油、 聚氧丙烯脂肪酸酯这样的非离子类的表面活性剂、 展开剂; 橄榄油、 瓜哇木 棉油、 蓖麻油、 棕榈油、 山茶油、 椰子油、 芝麻油、 玉米油、 米糠油、 落花生油、 棉籽油、 大豆油、 菜籽油、 亚麻子油、 桐油、 液体石蜡等的植物油或矿物油等。 这些辅助剂的各种成 分, 只要不脱离本发明的目的, 可以适当选择 1种或 2种以上来使用。 另外, 也可以在上述 的辅助剂之外从该领域公知的物质中适当选择使用。 也可以使用例如增量剂、 增稠剂、 防尘 降剂、 防冻剂、 分散稳定剂、 药害减轻剂、 防霉剂等通常使用的各种辅助剂。  An agricultural and horticultural pest control agent containing the fluoromethoxypyrazole-containing orthoformylaminobenzamide compound represented by the structural formula (I) of the present invention or an agriculturally applicable salt thereof, usually mixed with the compound and Auxiliary agent for various pesticides, forming a powder, granules, granule wettable powder, wettable powder, aqueous suspension, oily suspension, aqueous solvent, emulsion, paste, aerosol, microdispersion, etc. Various forms of preparation are used, but as long as it is suitable for the purpose of the present invention, it can be made into all preparation forms which are generally used in the field. Examples of the adjuvant used in the preparation include diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, kaolinite and sericite mixture, clay, sodium carbonate, baking soda, thenardite, zeolite, starch. Solid support; water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl sulfoxide, N, N a solvent such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, or the like; a fatty acid salt, a benzoate, an alkyl sulfosuccinate, a dialkyl sulfo amber Acid salt, polycarboxylate, alkyl sulfate salt, alkyl sulfate, alkyl aryl sulfate, alkyl diglycol ether sulfate, alcohol sulfate salt, alkyl sulfonate, alkyl aryl Sulfonic acid salt, aryl sulfonate, lignosulfonate, alkyl diphenyl ether disulfonate, polystyrene sulfonate, alkyl phosphate salt, alkyl aryl phosphate, aryl phosphate Styrene aryl phosphate, polyoxyethylene alkyl ether phosphorus An anionic surfactant or developer such as a salt of a salt, a polyoxyethylene alkyl aryl phosphate or a naphthalene sulfonic acid formaldehyde condensate; a sorbitan fatty acid ester, a glycerin fatty acid ester, a fatty acid polyglyceride , fatty acid alcohol polyglycol ether, block diol, block alcohol, alkylene oxide block polymer, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl aryl ether, Polyoxyethylene glycol alkyl ether, polyethylene glycol, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene hardened castor oil, polyoxypropylene Nonionic surfactants and developing agents such as fatty acid esters; olive oil, guava, castor oil, palm oil, camellia oil, coconut oil, sesame oil, corn oil, rice bran oil, groundnut oil, cottonseed oil, Vegetable oil or mineral oil such as soybean oil, rapeseed oil, linseed oil, tung oil, liquid paraffin, and the like. The various components of the above-mentioned auxiliary agents can be used singly or in combination of two or more kinds as long as they do not deviate from the object of the present invention. Further, it may be appropriately selected from those known in the art in addition to the above-mentioned auxiliary agents. Various adjuvants commonly used, such as extenders, thickeners, dustproofing agents, antifreeze agents, dispersion stabilizers, phytotoxicity reducing agents, and antifungal agents, can also be used.
本发明所述结构式 ( I ) 表示化合物和各种辅助剂即载体的重量配合比例, 通常为 0. 1: 99. 9〜90: 10。 在实际使用这些制剂时, 可以直接使用, 或用稀释剂稀释至规定浓度后, 根 据需要添加各种展开剂 (表面活性剂、 植物油、 矿物油等) 使用。 The composition of the formula (I) represents a weight ratio of the compound and the various adjuvants, that is, the carrier, usually 0. 1: 99. 9~90: 10. When these preparations are actually used, they can be used directly or diluted with a diluent to a prescribed concentration. Use various developing agents (surfactants, vegetable oils, mineral oils, etc.) as needed.
含有本发明所述结构式 ( I ) 表示化合物的农业园艺用有害生物防治剂的施用, 根据气 象条件、 制剂形态、 施用时期、 施用场所、 病害虫的种类或发生状况等的不同而不同, 不能 一概而定, 但是一般以 0. 05〜800ppm, 优选为 0. 5〜500ppm的有效成分浓度来进行施用, 其 每单位的施用量是每 1公顷本发明化合物为 l〜5000g, 优选为 10〜1000g。 另外, 作为含有 本发明的有害生物防治剂的其他的优选形态的农业园艺用有害生物防治剂的施用, 可根据上 述有害生物防治剂的施用进行。 本发明也包含利用这样的施用方法的有害生物的防治方法, 特别是植物寄生性螨类、 农业害虫类的防治方法。  The application of the agricultural and horticultural pest control agent containing the compound represented by the structural formula (I) of the present invention varies depending on the meteorological conditions, the form of the preparation, the application period, the application site, the type of the pest or the occurrence state, and the like, and cannot be generalized. The application is generally carried out at a concentration of the active ingredient of 0.05 to 800 ppm, preferably 0.5 to 500 ppm, and the application amount per unit is 1 to 5000 g, preferably 10 to 1000 g per 1 hectare of the compound of the invention. Further, the application of the agricultural and horticultural pest control agent containing the other preferred embodiment of the pest control agent of the present invention can be carried out according to the application of the above-mentioned pest control agent. The present invention also encompasses a method for controlling pests using such an application method, particularly a method for controlling plant parasitic mites and agricultural pests.
含有本发明所述结构式 ( I ) 表示化合物的农业园艺用有害生物防治剂的各种制剂、 或 其稀释物的施用, 通常可以利用一般进行的施用方法例如散布、 喷射、 喷雾 (misting)、 雾 化 (atomizing)、 撒粒、 水面施用法、 土壤施用 (混入、 灌注等)、 表面施用 (涂布、 粉衣、 被覆等)、 浸渍毒饵等来进行。 另外, 将上述有效成分混合至伺料中给予家畜, 也可以阻碍在 其排泄物中的害虫、 特别是有害昆虫的发生及生育, 另外可以利用所谓的超高浓度少量散步 法 (ultra low volume ) 施用, 在该方法中, 可以含有 100%的活性成分。 The application of various preparations, or dilutions thereof, of the agricultural and horticultural pest control agent containing the compound of the formula (I) of the present invention can be generally carried out by a usual application method such as spreading, spraying, misting, misting. A tomizi ng , granulation, surface application, soil application (mixing, infusion, etc.), surface application (coating, coating, coating, etc.), impregnation of baits, and the like. In addition, by mixing the above-mentioned active ingredients into the feed to the livestock, it is also possible to hinder the occurrence and growth of pests, particularly harmful insects, in the excrement, and it is also possible to use the so-called ultra low volume. Administration, in this method, may contain 100% of the active ingredient.
另外, 含有本发明所述结构式 ( I ) 表示化合物可与现有杀虫、 杀菌或除草的农药品种 的一种或二种或两种以上进行组合进行使用, 显示更有益的效果、 作用性。 特别是混用或合 用了本发明所述结构式 ( I ) 表示化合物和其他的农药有效成分化合物的 1种或 2种以上的 混合有害生物防治组合物, 可以将适用范围、 药剂处理的时期、 防治活性等向好的方向改良。 另外, 本发明化合物和其他的农药的有效成分化合物, 可以将分别制成的制剂在散布时混合 使用, 也可以将两者一起制成制剂使用, 本发明也包含这样的混合有害生物防治组合物。  Further, the structural formula (I) according to the present invention can be used in combination with one or two or more kinds of conventional insecticidal, bactericidal or herbicidal pesticides, and exhibits more advantageous effects and functions. In particular, one or more mixed pest control compositions of the compound of the formula (I) and the other active ingredients of the pesticidal compound of the present invention may be used in combination or in combination, and the scope of application, the period of treatment of the drug, and the control activity may be applied. Wait for a good direction to improve. Further, the compound of the present invention and other active ingredient compounds of the agricultural chemical may be used by mixing the separately prepared preparations at the time of dispersion, or may be used together as a preparation, and the present invention also encompasses such a mixed pest control composition. .
本发明的所述结构式 ( I ) 表示化合物及其制剂, 具有以下优点:  The structural formula (I) of the present invention represents a compound and a preparation thereof, and has the following advantages:
( 1 ) 本发明首次在吡唑环引入一氟甲氧基, 化合物结构具有新颖性;  (1) The present invention introduces a monofluoromethoxy group for the first time in a pyrazole ring, and the structure of the compound is novel;
( 2 )本发明的化合物及其制剂具有广谱的杀虫活性: 对鳞翅目害虫(小菜蛾、 草地贪夜 蛾和棉铃虫)、 半翅目害虫 (桃蚜和苜蓿蚜)、 同翅目害虫 (水稻褐飞虱)、 双翅目害虫 (三叶 斑潜蝇) 以及叶甲类害虫 (辣根猿叶甲) 都表现出非常良好的活性;  (2) The compound of the present invention and its preparation have a broad spectrum of insecticidal activity: against lepidopteran pests (Plutella xylostella, Spodoptera frugiperda and Helicoverpa armigera), Hemipteran pests (Peach and aphid), and the same wing The target pests (rice planthopper), the dipteran pests (Lepidoptera: Trifolium), and the leaf-like pests (Horse genus) have shown very good activity;
( 3 ) 本发明的化合物及其制剂具有超高的杀虫活性: 在 0. 16mg/L剂量下对小菜蛾、 草 地贪夜蛾和棉铃虫都表现出很好的效果; 在 4mg/L剂量下对蚜虫、 三叶斑潜蝇和辣根猿叶甲 也都表现出很好的效果; 在 20mg/L剂量下对水稻褐飞虱表现出很好的效果;  (3) The compound of the present invention and its preparation have an extremely high insecticidal activity: at a dose of 0.16 mg/L, it has a good effect on Plutella xylostella, Spodoptera frugiperda and Helicoverpa armigera; at a dose of 4 mg/L The lower aphids, trifolium and horseradish have also showed good results; at 20mg/L, the rice brown planthopper showed good effect;
( 4)本发明的化合物及其制剂具有很好的安全性, 对部分作物如小麦、 大豆、 棉花、 水 稻等安全性好, 并且对环境具有性;  (4) The compound of the present invention and its preparation have good safety, and are safe to some crops such as wheat, soybean, cotton, rice, etc., and are environmentally friendly;
( 5 )本发明的化合物及其制剂具有合理的毒性、 生态毒性和环境相容性, 属低毒环境友 好型农药。 下面记载本发明的实施例, 但是本发明不限定于此, 首先记载本发明化合物的合成例。 具体实施方式 (5) The compound of the present invention and its preparation have reasonable toxicity, ecotoxicity and environmental compatibility, and are low-toxic environmental friends. Good pesticides. The examples of the present invention are described below, but the present invention is not limited thereto, and a synthesis example of the compound of the present invention will be described first. detailed description
实施例 1 N-[2- (叔丁基氨基甲酰基) -4-氯 -6-甲基-苯基] -1- (3-氯 -2-吡啶基 )-3-— 氟甲氧基 -1H-吡唑 -5-甲酰胺的合成 (化合物 8)  Example 1 N-[2-(tert-butylcarbamoyl)-4-chloro-6-methyl-phenyl]-1-(3-chloro-2-pyridyl)-3-fluoromethyloxy Synthesis of -1H-pyrazole-5-carboxamide (Compound 8)
第一步: 3-—氟甲氧基 -1-(3_氯 -2-吡啶基) -1H-吡唑 -5-甲酸的合成  First step: Synthesis of 3-fluoromethoxy-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxylic acid
在 500ml 三口圆底烧瓶中, 依次加入 1-(3-氯 -2-吡啶基 )-3-羟基 -1H-吡唑 -5-甲酸乙酯 (13.35g, 0.05mol), 300ml 乙腈, 固体碳酸钾 (8.28g, 0.06mol), 一氟一溴甲烷 (8.48g, 0.075mol), 然后加热回流, 反应至原料完全消失, 冷却至室温, 过滤, 滤饼用乙腈 2*50ml 淋洗, 滤液浓縮后加 200ml 甲醇使之溶解, 然后在室温慢慢向其中滴加含氢氧化钠 (2.4g, 0.06mol)的 50ml水溶液, 室温搅拌约 30min后, 反应完全, 蒸除溶剂, 加水, 用乙醚 2*50ml 萃取, 水相加稀盐酸调 PH值显酸性, 体系有大量的白色固体生成, 过滤, 红外灯干燥, 得 3-—氟甲氧基 -1- (3-氯 -2-吡啶基) -1H-吡唑 -5-甲酸 11.05g,熔点 149-151°C,收率为 81.6%; ¾NMR (400MHz, DMSO— d6) δ5.84—5· 98 (d, 2H) , 6.74 (s, 1H) , 7.62—7· 65 (m, 1H) , 8. 19—8· 21 (d, 1H) , 8.53-8.54 (d, 1H), 13.65 (br, 1H); M(%) : 270(100)。 In a 500 ml three-neck round bottom flask, 1-(3-chloro-2-pyridyl)-3-hydroxy-1H-pyrazole-5-carboxylic acid ethyl ester (13.35 g, 0.05 mol) was added sequentially, 300 ml of acetonitrile, solid carbonic acid Potassium (8.28 g, 0.06 mol), fluoro-bromomethane (8.48 g, 0.075 mol), then heated to reflux, the reaction was taken to complete disappearance, cooled to room temperature, filtered, and the filter cake was rinsed with acetonitrile 2*50 ml. Then, 200 ml of methanol was added to dissolve it, and then a 50 ml aqueous solution containing sodium hydroxide (2.4 g, 0.06 mol) was slowly added thereto at room temperature, and stirred at room temperature for about 30 minutes, the reaction was completed, the solvent was distilled off, water was added, and diethyl ether was used. *50ml extraction, the aqueous phase is diluted with hydrochloric acid to adjust the pH value, the system has a large amount of white solids formed, filtered, and dried by infrared light to give 3-fluoromethoxy-1-(3-chloro-2-pyridyl) -1H-pyrazole-5-carboxylic acid 11.05 g, melting point 149-151 ° C, yield 81.6%; 3⁄4 NMR (400 MHz, DMSO - d 6 ) δ 5.84 - 5 · 98 (d, 2H) , 6.74 (s , 1H) , 7.62—7· 65 (m, 1H) , 8. 19—8· 21 (d, 1H) , 8.53-8.54 (d, 1H), 13.65 (br, 1H); M(%) : 270 (100).
第二步: 6-氯 -2-[3_—氟甲氧基 -l-(3-氯 -2-B比啶基) - 1H-5-吡唑基 ]-8-甲基 -4H-[d] [1, 3]苯并噁嗪 -4-酮的合成  Second step: 6-chloro-2-[3_-fluoromethoxy-l-(3-chloro-2-Bpyridyl)-1H-5-pyrazolyl]-8-methyl-4H-[ Synthesis of d] [1, 3] benzoxazine-4-one
在 250ml 三口圆底烧瓶中, 3-—氟甲氧 -1-(3_氯 -2-吡啶基) -1H-吡唑 -5-甲酸 (3g, O. Ollmol) (实施例 1-合成第一步产物) , 2-氨基- 5-氯- 3-甲基苯甲酸 (2.04g, O. Ollmol), 乙腈 150ml,吡啶 7ml,搅拌使固体全部溶解,将体系冷却,在 _5°〜- 10°滴加甲基磺酰氯(2ml, 2.96g, 0.026mol) /乙腈 20ml溶液, 滴加完毕后, 保持在 _5°〜- 10°反应 lh, 然后自然升至 室温反应 3h,反应完全后,加水 30ml,搅拌 30min,过滤,滤饼先后用 2: 1乙腈 /水 (2*40ml)、 乙腈 (2*20ml) 及乙醚 (2*20ml) 淋洗, 得第一批固体; 滤液蒸除溶剂后, 加水, 用乙酸乙 酯 (3*40ml) 萃取, 有机相用无水硫酸钠干燥、 过滤、 浓縮后, 用乙醇进行重结晶, 得第二 批固体, 两批固体合并, 得 6-氯 -2-[3_—氟甲氧基 -1-(3_氯 -2-吡啶基) - 1H-5-吡唑基 ]-8- 甲基- 4H- [d] [1, 3]苯并噁嗪 -4-酮 4. 17g,熔点 206.0-207.5°C,收率为 84.22%; ¾NMR ( 400ΜΗζ , CDC13) ^1.81(s,3H),5.83-5.97(d,2H), 6.85(s,lH), 7.46-7.49(m,2H), 7.84-7.99(m,2H), 8.54-8.56(d, 1H); M(%) : 421.0(100)。 In a 250 ml three-neck round bottom flask, 3-fluoromethoxy-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxylic acid (3 g, O. Ollmol) (Example 1 - Synthesis One step product), 2-amino-5-chloro-3-methylbenzoic acid (2.04g, O. Ollmol), acetonitrile 150ml, pyridine 7ml, stir to dissolve all solids, and cool the system at _5°~- 10 ° dropwise addition of methylsulfonyl chloride (2ml, 2.96g, 0.026mol) / acetonitrile 20ml solution, after the completion of the addition, kept at _5 ° ~ -10 ° reaction lh, then naturally rise to room temperature for 3h, after the reaction is complete Add 30 ml of water, stir for 30 min, filter, and filter the cake with 2: 1 acetonitrile / water (2 * 40 ml), acetonitrile (2 * 20 ml) and diethyl ether (2 * 20 ml) to obtain the first solid; After the solvent, water was added, and the mixture was extracted with ethyl acetate (3*40 ml). The organic phase was dried over anhydrous sodium sulfate, filtered and concentrated, and then recrystallized from ethanol to obtain a second solid. -Chloro-2-[3_-fluoromethoxy-1-(3-chloro-2-pyridyl)-1H-5-pyrazolyl]-8-methyl- 4H- [d] [1, 3] Benzoxazine-4-one 4.17g, melting point 206.0-207.5 ° C, yield 84.22%; 3⁄4 NMR (400ΜΗζ, CDC 1 3 ) ^1.81(s,3H),5.83-5.97(d,2H), 6.85(s,lH), 7.46-7.49(m,2H), 7.84-7.99(m,2H), 8.54-8.56(d , 1H); M(%): 421.0(100).
第三步: 2- (3-氯 -2-吡啶基 )-5-—氟甲氧基 -2H-吡唑- (2-叔丁氨基甲酰基 -4-氯 -6-甲基 -苯基) 3-甲酰胺的合成 Step 3: 2-(3-Chloro-2-pyridinyl)-5--fluoromethoxy-2H-pyrazole-(2-tert-butylcarbamoyl-4-chloro-6-methyl Synthesis of -phenyl) 3-carboxamide
在 50ml 单口圆底烧瓶中, 向 6-氯 -2- [3-—氟甲氧基 -1- (3-氯 -2-吡啶基) - 1H_5_吡唑 基] -8-甲基 _4H- [d] [1, 3]苯并噁嗪 -4-酮 (lg, 0. 00238mol ) (实施例 1_合成第二步产物) 的 四氢呋喃溶液中慢慢滴加叔丁胺 (0. 21g, 0. 00286mol ), 室温搅拌过夜后, 反应完全, 减 压蒸除四氢呋喃, 残余物中加少许乙醇, 搅拌数分钟后, 过滤, 得白色固体 1. 02 g, 即 为 2- (3-氯 -2-吡啶基 ) -5-—氟甲氧基 -2H-吡唑- (2-叔丁氨基甲酰基 -4-氯 -6-甲基-苯基) 3_ 甲 酰胺 , 熔 点 227.0-228.0°C , 收率 为 87· 6% ; ¾NMR ( 400MHz , DMS0_d6 ) ^ 1.26(s,9H),2.16(s,3H),5.84-5.98(d,2H), 6.93(s,lH), 7.26-7.58(m,4H), 8.10-8.13(m,lH), 8.45-8.46(d, 1H),10.10(S,1H); M (%): 492. 5 (100)。 In a 50 ml single-mouth round bottom flask, 6-chloro-2-[3--fluoromethoxy-1-(3-chloro-2-pyridyl)-1H-5-pyrazolyl]-8-methyl-4H - [d] [1, 3] benzoxazin-4-one (lg, 0. 00238 mol) (Example 1 - synthesis of the second step product) in tetrahydrofuran solution was slowly added dropwise t-butylamine (0. 21g, 0 00286摩尔), After stirring at room temperature overnight, the reaction was completed, the residue was evaporated under reduced pressure, and the residue was evaporated to dryness. -pyridyl)-5-fluoromethyloxy-2H-pyrazole-(2-tert-butylcarbamoyl-4-chloro-6-methyl-phenyl) 3-carboxamide, m.p. 227.0-228.0 ° C, The yield was 87·6%; 3⁄4 NMR (400 MHz, DMS0_d 6 ) ^ 1.26 (s, 9H), 2.16 (s, 3H), 5.84-5.98 (d, 2H), 6.93 (s, lH), 7.26-7.58 ( m, 4H), 8.10-8.13 (m, lH), 8.45-8.46 (d, 1H), 10.10 (S, 1H) ; M (%): 492. 5 (100).
实施例 2 N- [2- (甲氨基甲酰基) -4-氯- 6-甲基-苯基] -1- (3-氯- 2-吡啶基 ) -3-—氟甲 氧基 -1H-吡唑 -5-甲酰胺的合成 (化合物 3) 在 50ml 单口圆底烧瓶中, 向 6-氯 -2- [3-—氟甲氧基 -1- (3-氯 -2-吡啶基) - 1H_5_吡唑 基] -8-甲基 _4H- [d] [1, 3]苯并噁嗪 -4-酮 (lg, 0. 00238mol ) (实施例 1_合成第二步产物) 的 四氢呋喃溶液中加入甲胺盐酸盐(0. 19g, 0. 00286mol )及无水醋酸钠(0. 24g, 0. 00286mol ), 室温搅拌过夜后, 反应完全, 减压蒸除四氢呋喃, 残余物中加水, 用乙酸乙酯萃取, 有机 相用无水硫酸钠干燥, 过滤, 浓縮得粗品, 用乙醇进行重结晶得白色固体 0. 87 g, 即为 N- [2- (甲氨基甲酰基) -4-氯 -6-甲基-苯基] -1- (3_氯 -2-吡啶基 ) -3-—氟甲氧基 -1H-吡唑 -5- 甲酰胺,熔点 236.0-237.4°C,收率为 82. 7%; ¾NMR ( 400MHz , DMSO- d6) δ 2.18(s,3H), 2.93-2.94(d, 2H ), 5.83-5.96(d, 2H),6.16-6.17(d,lH), 6.70(s,lH), 7.20-7.36(m,4H), 7.82-7.84(d,lH), 8.44-8.45(d. 1H),9.96(S,1H); M (%): 450. 0 (100)。 Example 2 N-[2-(Methylcarbamoyl)-4-chloro-6-methyl-phenyl]-1-(3-chloro-2-pyridyl)-3-fluoromethoxy-1H - Synthesis of pyrazole-5-carboxamide (Compound 3) In a 50 ml single-neck round bottom flask to 6-chloro-2-[3-fluoromethoxy-1-(3-chloro-2-pyridinyl) - 1H_5_pyrazolyl]-8-methyl-4H-[d][1,3]benzoxazine-4-one (lg, 0.0000 238 mol) (Example 1 - synthesis of the second step product) Methylamine hydrochloride (0. 19g, 0.0000286 mol) and anhydrous sodium acetate (0. 24g, 0.0000286 mol) were added to the tetrahydrofuran solution. After stirring at room temperature overnight, the reaction was completed, and tetrahydrofuran was evaporated under reduced pressure. After adding water, the mixture was extracted with EtOAc. EtOAc (EtOAc m. 4-chloro-6-methyl-phenyl]-1-(3-chloro-2-pyridyl)-3-fluoromethyl-1H-pyrazole-5-carboxamide, m.p. 236.0-237.4 C, yield 82. 7%; ¾NMR (400MHz, DMSO- d 6) δ 2.18 (s, 3H), 2.93-2.94 (d, 2H), 5.83-5.96 (d, 2H), 6.16-6.17 (d ,lH), 6.70(s,lH), 7.20-7.36( m, 4H), 7.82-7.84 (d, lH), 8.44-8.45 (d. 1H), 9.96 (S, 1H); M (%): 450. 0 (100).
实施例 3 N- [2- (乙氨基甲酰基) -4-氰基 -6-甲基-苯基] -1- (3-氯 -2-吡啶基 ) -3-—氟 甲氧基 -1H-吡唑 -5-甲酰胺的合成 (化合物 33) 第一步: 6-氰基 -2- [3_—氟甲氧基 -1- (3_氯 -2-吡啶基) - 1H-5-吡唑基 ] -8-甲基 -4H- [d] [1, 3]苯并噁嗪 -4-酮的合成 Example 3 N-[2-(ethylcarbamoyl)-4-cyano-6-methyl-phenyl]-1-(3-chloro-2-pyridyl)-3-fluoromethyl- Synthesis of 1H-pyrazole-5-carboxamide (Compound 33) Step 1: 6-Cyano-2-[3_-fluoromethoxy-1-(3-chloro-2-pyridyl)-1H-5 Synthesis of pyrazolyl]-8-methyl-4H-[d] [1,3]benzoxazin-4-one
在 250ml三口圆底烧瓶中, 3-—氟甲氧基 -1- (3-氯 -2-吡啶基) -1H-吡唑 _5_甲酸 (5g, 0. 0185mol ) (实施例 1_合成第一步产物), 2-氨基 _5_氰基 _3_甲基苯甲酸(3. 24g, 0. 0185mol ), 乙腈 150ml,吡啶 15ml,搅拌使固体全部溶解,将体系冷却,在 _5°〜- 10°滴加甲基磺酰氯(4ml, 5.98g, 0.052mol) /乙腈 20ml溶液, 滴加完毕后, 保持在 _5°〜- 10°反应 lh, 然后自然升至 室温反应 3h,反应完全后,加水 30ml,搅拌 30min,过滤,滤饼先后用 2: 1乙腈 /水 (2*40ml)、 乙腈 (2*30ml) 及乙醚 (2*30ml) 淋洗, 得第一批固体; 滤液蒸除溶剂后, 加水, 用乙酸乙 酯 (3*40ml) 萃取, 有机相用无水硫酸钠干燥、 过滤、 浓縮后, 用乙醇进行重结晶, 得第二 批固体, 两批固体合并, 得淡黄色固体 4.17g, 即为 6-氰基 -2-[3_—氟甲氧基 -1-(3_氯 -2- 吡啶基) - 1H-5-吡唑基 ]-8-甲基 _4H-[d] [1,3]苯并噁嗪 -4-酮, 熔点 208.5-211.0°C, 收率为 54.87%; ¾NMR (400MHz, CDC13) δ 1.86(s,3H), 5.84-5.97(d,2H), 6.90(s,lH), 7.27-7.98(m,3H), 8.32(s,lH), 8.55-8.56(d,lH); M (%): 411.1(100)。 In a 250 ml three-neck round bottom flask, 3-fluoromethoxy-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxylic acid (5 g, 0. 0185 mol) (Example 1 - Synthesis The first step product), 2-amino-5-cyano-3-methylbenzoic acid (3. 24g, 0. 0185mol), acetonitrile 150ml, pyridine 15ml, stirring to dissolve all the solids, cooling the system, at _5 °~- 10° dropwise addition of methylsulfonyl chloride (4ml, 5.98g, 0.052mol) / acetonitrile 20ml solution, after the addition is completed, keep the reaction at _5 ° ~ - 10 ° lh, then naturally rise to room temperature for 3h, after the reaction is complete, add water 30ml, stir for 30min, filter, filter cake The first batch of solids was obtained by rinsing with 2:1 acetonitrile/water (2*40 ml), acetonitrile (2*30 ml) and diethyl ether (2*30 ml). After the solvent was distilled off, water was added and ethyl acetate was used. *40ml), the organic phase is dried over anhydrous sodium sulfate, filtered and concentrated, then recrystallized from ethanol to give a second crop of solids, which are combined to give a pale yellow solid, 4.17g, which is 6-cyano -2-[3_-fluoromethoxy-1-(3-chloro-2-pyridyl)-1H-5-pyrazolyl]-8-methyl-4H-[d][1,3]benzo Oxazine-4-one, melting point 208.5-211.0 ° C, yield 54.87%; 3⁄4 NMR (400MHz, CDC1 3 ) δ 1.86 (s, 3H), 5.84-5.97 (d, 2H), 6.90 (s, lH) , 7.27-7.98 (m, 3H), 8.32 (s, lH), 8.55-8.56 (d, lH); M (%): 411.1 (100).
第二步: N-[2- (乙氨基甲酰基) -4-氰基 -6-甲基-苯基] -1- (3-氯 -2-吡啶基 )-3-—氟甲 氧基 -1H-吡唑 -5-甲酰胺的合成  Second step: N-[2-(ethylcarbamoyl)-4-cyano-6-methyl-phenyl]-1-(3-chloro-2-pyridyl)-3-fluoromethyloxy Synthesis of -1H-pyrazole-5-carboxamide
在 50ml单口圆底烧瓶中, 向 6-氰基 -2- [3-—氟甲氧基 -1- (3-氯 _2_吡啶基) - 1H_5_吡唑 基] -8-甲基 _4H-[d] [1,3]苯并噁嗪 -4-酮 (0.4g, 0.00097mol) (实施例 3_合成第一步产物) 的四氢呋喃溶液中慢慢滴加乙胺 (65-70%, 0.083g, 0.0012mol), 室温搅拌过夜后, 反应完 全,减压蒸除四氢呋喃,残余物中加少许乙醇,搅拌数分钟后,过滤,得浅灰色固体 0.35g, 即为 N-[2- (乙氨基甲酰基) -4-氰基 -6-甲基-苯基] -1-(3_氯 -2-吡啶基 )-3-—氟甲氧基 -1H- 吡唑 -5-甲酰胺, 熔点 151.0-152.5°C, 收率为 78.6%; ¾NMR ( 400MHz , DMSO- d6 ) ^i.23-1.27(m,3H),2.26(s,3H),3.45-3.48(m,2H), In a 50 ml single-neck round bottom flask, to 6-cyano-2-[3--fluoromethoxy-1-(3-chloro-2-pyridyl)-1H-5-pyrazolyl]-8-methyl_ 4H-[d] [1,3] benzoxazine-4-one (0.4 g, 0.00097 mol) (Example 3 - synthesis of the first step product) in tetrahydrofuran solution was slowly added dropwise with ethylamine (65-70) %, 0.083g, 0.0012mol), after stirring at room temperature overnight, the reaction was completed, the tetrahydrofuran was evaporated under reduced pressure, and a little ethanol was added to the residue. After stirring for several minutes, it was filtered to give a light gray solid, 0.35 g, which was N-[2 - (ethylcarbamoyl)-4-cyano-6-methyl-phenyl]-1-(3-chloro-2-pyridyl)-3-fluoromethyl-1H-pyrazole-5- Formamide, melting point 151.0-152.5 ° C, yield 78.6%; 3⁄4 NMR (400MHz, DMSO-d 6 ) ^i.23-1.27 (m, 3H), 2.26 (s, 3H), 3.45-3.48 (m, 2H),
5.84-5.98(d,2H),6.23(s,lH),6.64(s,lH),7.36-8.48(m,5H),10.52(s,lH); M (%): 457.1(100)。 以下实施例 4至实施例 6给出以本发明的化合物 ( I ) 作为活性物质组份, 加工配制几 种杀虫剂剂型的实际例子, 需要指出的是本发明并不仅仅局限在下述实例的范围内。 在这些 配方例子中, 所有的 "%"均指重量百分比。 实施例 4可湿性粉剂配方  5.84-5.98 (d, 2H), 6.23 (s, lH), 6.64 (s, lH), 7.36-8.48 (m, 5H), 10.52 (s, lH); M (%): 457.1 (100). The following Examples 4 to 6 give practical examples in which the compound (I) of the present invention is used as an active material component to prepare and prepare several insecticide dosage forms, and it should be noted that the present invention is not limited only to the following examples. Within the scope. In these formulation examples, all "%" refer to weight percentage. Example 4 Wettable Powder Formulation
将 15%的化合物(8) (索引表 1)、3%的木质素磺酸钠盐 (MQ)、2%的月桂醇聚氧乙烯醚 (JFC)、 40%的硅藻土和 40%的轻质碳酸钙充分地混合, 经超细粉碎机粉碎, 即得到 15%可湿性粉剂产15% of compound (8) (index table 1), 3% sodium lignosulfonate (M Q ), 2% lauryl polyoxyethylene ether (JFC), 40% diatomaceous earth and 40% The light calcium carbonate is thoroughly mixed and pulverized by an ultrafine pulverizer to obtain 15% wettable powder.
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实施例 5乳油配方  Example 5 Emulsion Formulation
将 10%的化合物 (8) (索引表 1)、 5%的农乳 500号 (钙盐)、 5%的农乳 602号、 5%的 N- 甲基 -2-吡咯烷酮和 75%的二甲苯加热搅拌均匀, 即得 10%的乳油产品。 实施例 6水分散粒剂配方 10% of compound (8) (index table 1), 5% of agricultural milk 500 (calcium salt), 5% of agricultural milk 602, 5% of N-methyl-2-pyrrolidone and 75% of two The toluene is heated and stirred evenly to obtain a 10% cream product. Example 6 Water Dispersible Granule Formulation
将 60%的化合物(8 ) (索引表 1 )、 2%的聚乙烯吡咯烷酮、 12%的萘磺酸钠甲醛縮合物、 8% 的 N-甲基 -N-油酰基 -牛磺酸钠、 2%的羧甲基纤维素、 和 16%的高岭土均匀地混合, 粉碎, 再 加水捏合后, 加入 10— 100目筛网的造粒机中进行造粒, 然后再经干燥、 筛分 (筛网范围)。 即得 60%的水分散粒剂产品。 以下实施例 7至实施例 14给出下面给出使用本发明的化合物进行生物活性测定的实例, 需要指出的是本发明并不仅仅局限在下述实例的范围内。  60% of compound (8) (index table 1), 2% polyvinylpyrrolidone, 12% sodium naphthalene sulfonate formaldehyde condensate, 8% N-methyl-N-oleoyl-taurate sodium, 2% carboxymethyl cellulose, and 16% kaolin are uniformly mixed, pulverized, kneaded by water, and then granulated by adding a 10-100 mesh sieve granulator, followed by drying and sieving (screening) Net range). That is, 60% of water-dispersible granule products are obtained. The following Examples 7 to 14 give examples of the biological activity assays using the compounds of the present invention, and it should be noted that the present invention is not limited only to the scope of the following examples.
杀虫活性评价试验根据下列方法进行:  The insecticidal activity evaluation test was carried out according to the following methods:
待测化合物用丙酮 /甲醇 (1 : 1 ) 的混合溶剂溶解后, 用含有 0. 1%吐温 80的蒸馏水稀释 至所需的浓度。  After the test compound was dissolved in a mixed solvent of acetone/methanol (1:1), it was diluted to the desired concentration with distilled water containing 0.1% Tween 80.
试验靶标为小菜蛾 Plutella xylostella , 草地贪夜蛾 Spodoptem f rug i per da), 棉铃虫 iHeliothis armigera )、 苜精虫牙 ( Aphis medicaginis ^ 桃虫牙 {Myzus persicae ^ 水稻褐飞虱(
Figure imgf000037_0001
ta lugens)、三叶斑潜蝇( r /o )和辣根猿叶甲( Phaedon cochleariae 。
The test targets were Plutella xylostella, Spodopterem f rug i per da), Helicoverpa armigera, Aphis medicaginis ^Myzus persicae ^
Figure imgf000037_0001
Ta lugens), Liriomyza trifolii (r /o ) and horseradish (Phaedon cochleariae).
以下 "mg/L" 均指每毫克活性物 /升。  The following "mg/L" refers to each mg of active substance per liter.
试验统计: 统计各个处理的死虫数和活虫数, 计算死亡率。  Test Statistics: The number of dead insects and live insects in each treatment was counted, and the mortality was calculated.
死亡率 (%) =试虫数 活虫数 χ Κ)0 Mortality ( % ) = number of live insects 试 Κ)0
试虫数 注: 生物活性测定实施例所述的编号与索引表 1和索引表 2所述的化合物编号相对应。 实施例 7对于小菜蛾 Plutella xylostella) 的效果试验  Number of test insects Note: The numbers described in the biological activity measurement examples correspond to the compound numbers described in the index table 1 and the index table 2. Example 7 Effect test on Plutella xylostella)
将甘蓝片剪下, 打孔成圆片, 然后浸于药液中 20s, 放于 09cm塑料培养皿内 (5片 /皿), 接小菜蛾 2龄幼虫 15头 /皿, 放一张滤纸, 加盖。 置于 26°C室内培养, 72h后检查结果。 试 验重复 4次。 以尖头镊子轻触虫体, 无反应视为死虫。根据上述死亡率计算公式计算死亡率。 异常虫也看作死亡。 索引表 1中化合物 1-27、 33-63、 85-86、 89、 93、 99-106、 110- 112在 4mg/L时得到了 100 %的死亡率。 另外化合物 1、 3、 4、 8、 33、 49-51、 57-58、 59、 83、 89、 101、 103、 106在 0. 16mg/L时得到了至少 80 %的死亡率。 实施例 8对于草地贪夜蛾 i Spodoptera frugiperda) 的效果试验 将盆栽棉花 (2-3张叶龄) 进行药剂喷雾处理, 晾干。 放入培养室继续正常培养。 在 5、 12、 19d后用剪刀将叶片剪下, 放于 09cm塑料培养皿内, 接草地贪夜蛾幼虫, 放一张滤纸, 加盖。 置于观察室内, 6d后检查结果。 根据上述死亡率计算公式计算死亡率。 异常虫也看作 死亡。 索引表 1中化合物 3、 8、 10、 33、 49、 50、 51在 4mg/L时得到了 100 %的死亡率。 化 合物 3、 8、 33、 51在 0. 8mg/L时得到了至少 90 %的死亡率。 化合物 8、 33、 51在 0. 16mg/L 时得到了至少 80 %的死亡率。 实施例 9对于棉铃虫 Heliothis armigera ) 的效果试验 Cut the cabbage slices, punch them into discs, then immerse them in the liquid for 20s, place them in a 09cm plastic dish (5 pieces/dish), and pick up the second instar larvae of the diamondback moth 15 pieces/dish, put a piece of filter paper, cover . The cells were cultured at 26 ° C, and the results were checked after 72 hours. The test was repeated 4 times. The tip of the scorpion touches the worm, and no response is considered to be dead. Mortality was calculated according to the above mortality calculation formula. Abnormal worms are also seen as death. Compounds 1-27, 33-63, 85-86, 89, 93, 99-106, 110-112 in Table 1 gave 100% mortality at 4 mg/L. Further, compounds 1, 3, 4, 8, 33, 49-51, 57-58, 59, 83, 89, 101, 103, 106 gave a mortality rate of at least 80% at 0.16 mg/L. Example 8 Effect test on Spodoptera frugiperda) Potted cotton (2-3 leaf ages) was sprayed with the drug and allowed to dry. Put in the culture room and continue normal culture. After 5, 12, 19d, the leaves were cut with scissors, placed in a 09 cm plastic petri dish, and the larvae of Spodoptera litura were placed, and a filter paper was placed and capped. Place in the observation room and check the results after 6 days. Mortality was calculated according to the above mortality calculation formula. Abnormal worms are also seen as death. Compounds 3, 8, 10, 33, 49, 50, 51 in Table 1 gave 100% mortality at 4 mg/L. Compounds 3, 8, 33, 51 gave at least 90% mortality at 0.8 mg/L. Compounds 8, 33, 51 gave at least 80% mortality at 0.16 mg/L. Example 9 Effect Test on Helicoverpa armigera Heliconia
将盆栽棉花 (2-3张叶龄) 进行药剂喷雾处理, 晾干。 放入培养室继续正常培养。 在 5、 12、 19d 后用剪刀将叶片剪下, 放于 09cm塑料培养皿内, 接棉铃虫幼虫, 放一张滤纸, 加 盖。 置于观察室内, 6d后检查结果。 根据上述死亡率计算公式计算死亡率。 异常虫也看作死 亡。 索引表 1中化合物 3 、 8、 10、 33、 36、 49、 51在 20mg/L时得到了 100 %的死亡率。 化 合物 8、 10、 33、 51在 4mg/L时得到了 100 %的死亡率。  Potted cotton (2-3 leaf ages) was sprayed with the drug and allowed to dry. Put in the culture room and continue normal culture. After 5, 12, 19d, cut the leaves with scissors, place them in a 09cm plastic petri dish, connect the cotton bollworm larvae, put a piece of filter paper, and cover. Place in the observation room and check the results after 6 days. Mortality was calculated according to the above mortality calculation formula. Abnormal worms are also seen as dead. Compounds 3, 8, 10, 33, 36, 49, 51 in Table 1 gave 100% mortality at 20 mg/L. Compounds 8, 10, 33, and 51 gave 100% mortality at 4 mg/L.
化合物 8在 0. 16mg/L时得到了 100 %的死亡率。 实施例 10对于苜蓿蚜 phis medicaginis) 的效果试验 Compound 8 gave 100% mortality at 0.16 mg/L. Example 10 Effect Test on 苜蓿蚜 phis medicaginis)
将蚕豆叶片剪去两端, 背面朝上放在小块棉花上, 置于培养皿内, 加少量水, 接苜蓿蚜 成蚜以产若蚜。 24h后去除成蚜, 继续培养 2d后将叶片在药液中浸润 5s后置于棉花上, 凉 干。 24h 后检查结果。 根据上述死亡率计算公式计算死亡率。 异常虫也看作死亡。 索引表 1 中化合物 3、 8、 10、 33-37、 39、 27、 47、 51、 83、 85、 89、 95、 101在 20mg/L时得到了至 少 90 %的死亡率。 化合物 3、 8、 33、 34、 35、 36、 51、 83、 101在 4mg/L时得到了至少 80 %的死亡率。 实施例 11 对于桃蚜 MyzUs persicae) 的效果试验 Cut the leaves of broad bean into the ends, place the back side up on a small piece of cotton, place it in a petri dish, add a small amount of water, and connect it into a pot. After 24 hours, the mites were removed. After 2 days of culture, the leaves were infiltrated in the liquid for 5 s and then placed on cotton and dried. Check the results after 24h. Mortality was calculated according to the above mortality calculation formula. Abnormal worms are also seen as death. Compounds 3, 8, 10, 33-37, 39, 27, 47, 51, 83, 85, 89, 95, 101 in Table 1 gave at least 90% mortality at 20 mg/L. Compounds 3, 8, 33, 34, 35, 36, 51, 83, 101 gave at least 80% mortality at 4 mg/L. Example 11 Effect Test for Myzus Myz U s persicae) embodiment
将盆栽甘蓝 (3-4张叶龄) 进行药剂喷雾处理, 晾干。 放入培养室继续正常培养。 在 5、 12、 19d 后用分别接入桃蚜若虫。 置于观察室内, 7-10d 后检查结果。 根据上述死亡率计算 公式计算死亡率。 异常虫也看作死亡。 索引表 1中化合物 3、 8、 10、 33、 51在 20mg/L时得 到了 100 %的死亡率。 化合物 3、 8、 33、 51在 4mg/L时得到了至少 90 %的死亡率。 实施例 12对于水稻褐飞虱 Nilaparvata lugens) 的效果试验  Potted cabbage (3-4 leaf ages) was sprayed with the drug and allowed to dry. Put in the culture room and continue normal culture. After 5, 12, 19d, use the nymphs respectively. Place in the observation room and check the results after 7-10d. Mortality is calculated according to the above mortality calculation formula. Abnormal worms are also seen as death. Compounds 3, 8, 10, 33, 51 in Index Table 1 achieved 100% mortality at 20 mg/L. Compounds 3, 8, 33, 51 gave at least 90% mortality at 4 mg/L. Example 12 Effect test on rice brown planthopper Nilaparvata lugens)
将水稻苗用白石英沙固定于培养皿内, 接用 C02麻醉 3龄中期若虫, 置于 POTTER喷雾塔 下喷雾。 喷雾后用透明塑料杯罩住, 标记后放于观察室内。 72h后检查结果。 试验重复 4次。 以尖头镊子轻触虫体, 无反应视为死虫。 根据上述死亡率计算公式计算死亡率。 异常虫也看 作死亡。 索引表 1中化合物 8、 33、 36、 51-53、 57、 58在 100mg/L时得到了至少 90 %的死 亡率。 化合物 8、 33、 51在 20mg/L时得到了至少 80 %的死亡率。 实施例 13 对于三叶斑潜蝇 iriomyza TrifoliD 的效果试验 The rice seedlings were fixed in a petri dish with white quartz sand, and the 3rd instar nymph was anesthetized with C0 2 and placed in the POTTER spray tower. Spray down. Cover with a clear plastic cup after spraying, mark and place in the observation room. The results were checked after 72 hours. The test was repeated 4 times. The tip of the scorpion touches the worm, and no response is considered to be dead. Mortality was calculated according to the above mortality calculation formula. Abnormal worms are also seen as death. Compounds 8, 33, 36, 51-53, 57, 58 in Table 1 gave at least 90% mortality at 100 mg /L. Compounds 8, 33, 51 gave at least 80% mortality at 20 mg/L. Example 13 Effect test on Iriomza trifoliD
将盆栽蚕豆 (3-4张叶龄) 进行药剂喷雾处理, 晾干。 放入培养室继续正常培养。 在 5、 12、 19d后用分别接入三叶斑潜蝇幼虫。 置于观察室内, 7d后检查结果。 根据上述死亡率计算 公式计算死亡率。 异常虫也看作死亡。 索引表 1中化合物 8、 9、 10、 33、 36、 49、 51在 20mg/L 时得到了 100 %的死亡率。 化合物 8、 10、 49、 51在 4mg/L时得到了 100%的死亡率。 实施例 14 对于辣根猿叶甲 Phaedon cochleariae) 的效果试验  Potted broad beans (3-4 leaf ages) were sprayed with chemicals and allowed to dry. Put in the culture room and continue normal culture. After 5, 12, 19d, the larvae of Liriomyza sativa were separately used. Place in the observation room and check the results after 7 days. Mortality is calculated according to the above mortality calculation formula. Abnormal worms are also seen as death. Compounds 8, 9, 10, 33, 36, 49, 51 in Table 1 gave 100% mortality at 20 mg/L. Compounds 8, 10, 49, 51 gave 100% mortality at 4 mg/L. Example 14 Effect test on horseradish Phaedon cochleariae)
将盆栽甘蓝 (3-4张叶龄) 进行药剂喷雾处理, 晾干。 放入培养室继续正常培养。 在 5、 12、 19d 后用剪刀将叶片剪下, 放于 09cm塑料培养皿内, 接辣根猿叶甲或小菜蛾 2龄幼虫, 放一张滤纸, 加盖。 置于观察室内, 6_7d后检查结果。 根据上述死亡率计算公式计算死亡率。 异常虫也看作死亡。 索引表 1中化合物 3、 8、 10、 33、 36、 49、 51在 20mg/L时得到了 100 %的死亡率。化合物 3、 8、 33、 51在 4mg/L时得到了至少 90%的死亡率。化合物 8在 0. 8mg/L 时得到了至少 90%的死亡率。 按照以上方法, 选取化合物 8和已知化合物氯虫酰胺进行了杀小菜蛾、 苜蓿蚜和水稻褐 飞 果见表 3。  Potted cabbage (3-4 leaf ages) was sprayed with the drug and allowed to dry. Put in the culture room and continue normal culture. After 5, 12, 19d, cut the leaves with scissors, place them in a 09cm plastic petri dish, and connect the 2nd instar larvae of horseradish or Plutella xylostella, put a piece of filter paper, and cover. Place in the observation room and check the results after 6-7 days. Mortality was calculated according to the above mortality calculation formula. Abnormal worms are also seen as death. Compounds 3, 8, 10, 33, 36, 49, 51 in Table 1 gave 100% mortality at 20 mg/L. Compounds 3, 8, 33, 51 gave at least 90% mortality at 4 mg/L. Compound 8 gave at least 90% mortality at 0.8 mg/L. According to the above method, compound 8 and the known compound chlorantraniliprole were selected for killing the diamondback moth, cockroach and rice brown fly fruit as shown in Table 3.
Figure imgf000039_0001
Figure imgf000039_0001
氯虫酰胺 化合物 8和已知化合物氯虫酰胺的活性平行比较(死亡率, %) 浓度 浓度  Parallel comparison of chlorfenapyr compound 8 and known compound chlorantraniliprole (mortality, %) concentration concentration
化合物编号 小菜蛾 浓度 (mg/L) 苜蓿蚜 水稻褐飞虱  Compound number Plutella xylostella concentration (mg/L) 苜蓿蚜 rice brown planthopper
(mg/L) (mg/L)  (mg/L) (mg/L)
0.8 100 20 100 100 100 0.8 100 20 100 100 100
8 (实施例 1 ) 0.16 100 4 90 20 80 8 (Example 1) 0.16 100 4 90 20 80
0.032 80 0.8 30 4 0 氯虫酰胺 0.8 100 20 70 100 80  0.032 80 0.8 30 4 0 Chlorantamide 0.8 100 20 70 100 80
0.16 80 4 0 20 10 0.032 20 0.8 0 4 0 结论: 分别在 0. 16mg/L剂量下对鳞翅目害虫小菜蛾, 在 4mg/L剂量下对半翅目害虫苜蓿 蚜, 在 20mg/L剂量下对同翅目害虫水稻褐飞虱; 本发明化合物 8 (实施例 1 ) 的杀虫活性明 显优于已知化合物氯虫酰胺。 0.16 80 4 0 20 10 0.032 20 0.8 0 4 0 Conclusion: For Lepidoptera pests, P. xylostella, at a dose of 0.16 mg/L, for Hemiptera pests at a dose of 4 mg/L, for Homoptera pests at a dose of 20 mg/L Rice brown planthopper; the insecticidal activity of the present compound 8 (Example 1) is significantly better than the known compound chlorantraniliprole.

Claims

权利要求书 Claim
1、 一种结构式 (I ) 表示的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类化合物或其农业 上适用的盐, 1. An o-formylaminobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I) or an agriculturally applicable salt thereof,
Figure imgf000041_0001
Figure imgf000041_0001
其巾:  Its towel:
A为 N或 CH;  A is N or CH;
R1为氢、 卤素、 氰基、 硝基、 烷基、 卤代烷基、 氰基烷基、 链烯基、 卤代链烯基、 块基、 卤代块基、 烷氧基、 氰基烷氧基、 ^代烷氧基、 烷硫基、 ^代烷硫基、 烷基磺酰基、 烷基羰 基、 ^代烷基羰基、 烷氧基羰基、 ^代烷氧基羰基或氨基烷基; R 1 is hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, cyanoalkyl, alkenyl, haloalkenyl, block, halo block, alkoxy, cyanoalkoxy , alkoxy, alkylthio, alkylthio, alkylsulfonyl, alkylcarbonyl, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonyl or aminoalkyl;
R2为氢、 卤素、 烷基、 卤代烷基、 烷氧基、 卤代烷氧基或氰基; R 2 is hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or cyano;
R3为氢、 烷基或烷氧基; R 3 is hydrogen, alkyl or alkoxy;
R4为氢、 氰基、 烷基、 烷氧基、 烷氨基、 ^代烷基、 ^代烷氧基、 ^代烷氨基、 氰基烷 基、 环烷基、 ^代环烷基、 羟烷基、 烷氧羰基甲基、 烷氧基酰胺基、 烷基酰胺基、 ^代烷基 酰胺基、 氰基取代的烷基酰胺基或芳杂环甲基; R 4 is hydrogen, cyano, alkyl, alkoxy, alkylamino, alkyl, alkoxy, alkylamino, cyanoalkyl, cycloalkyl, cycloalkyl, hydroxy An alkyl group, an alkoxycarbonylmethyl group, an alkoxyamide group, an alkylamido group, an alkylalkylamide group, a cyano substituted alkylamido group or an arylheterocyclic methyl group;
或者 R3和 R4与所连接的 N—起形成三元、 四元、 五元或六元环; Or R 3 and R 4 form a ternary, quaternary, five- or six-membered ring with the N-linked group;
m为 0〜4的整数;  m is an integer from 0 to 4;
n为 0〜4的整数。  n is an integer of 0 to 4.
2、按照权利要求 1所述的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类化合物, 其特征在 于所述结构式 (I ) 中:  The orthoformylaminobenzamide compound containing a monofluoromethoxypyrazole according to claim 1, which is characterized by the structural formula (I):
R1为氢、 卤素、 氰基、 硝基、 d-Ce浣基、 d-Ce卤代烷基、 氰基 d-Ce烷基、 C2_C6链烯基、R 1 is hydrogen, halogen, cyano, nitro, d-Ce fluorenyl, d-Ce haloalkyl, cyano d-Ce alkyl, C 2 _C 6 alkenyl,
C2_C6卤代链烯基、 C2-C6块基、 卤代 C3-C6块基、 ( -(:6烷氧基、 d-C6氰基烷氧基、 d-C6卤代烷 氧基、 d-Ce烷硫基、 d-Ce卤代烷硫基、 d-Ce烷基磺酰基、 CfCe烷基羰基、 卤代 CfCe烷基羰 基、 ( Ce烷氧基羰基、 ^代 d-C6烷氧基羰基或氨基 d-C6烷基; C 2 -C 6 haloalkenyl, C 2 -C 6 block, halo C 3 -C 6 block, (-(: 6 alkoxy, dC 6 cyanoalkoxy, dC 6 haloalkoxy) , d-Ce alkylthio, d-Ce haloalkylthio, d-Ce alkylsulfonyl, CfCe alkylcarbonyl, halogenated CfCe alkylcarbonyl, (ce alkoxycarbonyl, ^dC 6 alkoxycarbonyl) Or an amino dC 6 alkyl group;
R2为氢、 卤素、 d-Ce烷基、 卤代 d-Ce烷基、 d-Ce烷氧基、 卤代 CfCe烷氧基或氰基;R 2 is hydrogen, halogen, d-Ce alkyl, halogenated d-Ce alkyl, d-Ce alkoxy, halogenated CfCe alkoxy or cyano;
R3为氢或 烷基; R 3 is hydrogen or an alkyl group;
R4为氢、 氰基、 d-Ce烷基、 d-Ce烷氧基、 d-Ce烷氨基、 卤代 CfCe烷基、 卤代 CfCe烷氧 基、 卤代 d-c6烷氨基、 氰基 d-c6烷基、 c3-c6环烷基、 卤代 c3-c6环烷基、 羟 -(:6烷基、 d-c6 烷氧羰基甲基、 (;-(:6烷氧基酰胺基、 d-c6烷基酰胺基、 ^代 d-c6烷基酰胺基、 氰基取代的 d-c6烷基酰胺基或芳杂环甲基; R 4 is hydrogen, cyano, d-Ce alkyl, d-Ce alkoxy, d-Ce alkylamino, halogenated CfCe alkyl, halogenated CfCe alkoxy , halo dc 6 alkylamino, cyano dc 6 alkyl, c 3 -c 6 cycloalkyl, halo c 3 -c 6 cycloalkyl, hydroxy-(: 6 alkyl, dc 6 alkoxycarbonyl a group, (;-(: 6 alkoxyamido group, dc 6 alkyl amide group, ^ dc 6 alkyl amide group, cyano substituted dc 6 alkyl amide group or aryl heterocyclic methyl group;
m为 2;  m is 2;
n为 1。  n is 1.
3、按照权利要求 2所述的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类化合物, 其特征在 于所述结构式 (I ) 中:  The orthoformylaminobenzamide compound containing a monofluoromethoxypyrazole according to claim 2, which is characterized by the structural formula (I):
A为 N;  A is N;
R1为氢、 卤素、 氰基、 d-C6烷基、 d-C6卤代烷基或 d-C6烷基羰基; R 1 is hydrogen, halogen, cyano, dC 6 alkyl, dC 6 haloalkyl or dC 6 alkylcarbonyl;
R2为卤素、 氰基、 CfCe烷基或卤代 d-C3烷基。 R 2 is halogen, cyano, CfCe alkyl or halogenated dC 3 alkyl.
4、按照权利要求 3所述的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类化合物, 其特征在 于所述结构式 (I ) 中:  The orthoformylaminobenzamide compound containing a monofluoromethoxypyrazole according to claim 3, which is characterized in that the structural formula (I):
R1为氢、 卤素、 氰基、 甲基或三氟甲基; R 1 is hydrogen, halogen, cyano, methyl or trifluoromethyl;
R2为卤素或氰基。 R 2 is a halogen or a cyano group.
5、按照权利要求 4所述的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类化合物, 其特征在 于所述的 I ) 化合物为:  The orthoformylaminobenzamide compound containing a monofluoromethoxypyrazole according to claim 4, wherein the compound I) is:
Figure imgf000042_0001
Figure imgf000042_0001
6、一种制备按照权利要求 1至 5之一所述的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类 化合物的中间体, 其特征在于具有如下结构式 (Π ):
Figure imgf000043_0001
An intermediate for the preparation of a monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole according to any one of claims 1 to 5, which has the following structural formula (Π):
Figure imgf000043_0001
其巾:  Its towel:
A为 N或 CH;  A is N or CH;
R1为氢、 卤素、 氰基、 硝基、 烷基、 卤代烷基、 氰基烷基、 链烯基、 卤代链烯基、 块基、 卤代块基、 烷氧基、 氰基烷氧基、 ^代烷氧基、 烷硫基、 ^代烷硫基、 烷基磺酰基、 烷基羰 基、 ^代烷基羰基、 烷氧基羰基、 ^代烷氧基羰基或氨基烷基; R 1 is hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, cyanoalkyl, alkenyl, haloalkenyl, block, halo block, alkoxy, cyanoalkoxy , alkoxy, alkylthio, alkylthio, alkylsulfonyl, alkylcarbonyl, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonyl or aminoalkyl;
R2为氢、 卤素、 烷基、 卤代烷基、 烷氧基、 卤代烷氧基或氰基; R 2 is hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or cyano;
m为 0〜4的整数;  m is an integer from 0 to 4;
n为 0〜4的整数。  n is an integer of 0 to 4.
7、按照权利要求 6所述的制备按照权利要求 1至 5之一所述的含一氟甲氧基吡唑的邻甲 酰氨基苯甲酰胺类化合物的中间体, 其特征在于结构式 (Π ) 中:  The intermediate for preparing a fluoromethoxypyrazole-containing orthoformylbenzamide compound according to any one of claims 1 to 5, which is characterized in that the structural formula (Π) Medium:
A为 N;  A is N;
R1为氢、 卤素、 氰基、 硝基、 -Ce烷基、 d-C6卤代烷基、 氰基 d-C6烷基、 (:2-(:6链烯基、 C2_C6卤代链烯基、 C2-C6块基、 卤代 C3-C6块基、 d-C6烷氧基、 d-C6氰基烷氧基、 d-C6卤代烷 氧基、 (;-(:6烷硫基、 d-C6卤代烷硫基、 d-C6烷基磺酰基、 d-C6烷基羰基、 卤代 d-C6烷基羰 基、 d-C6烷氧基羰基、 ^代 d-C6烷氧基羰基或氨基 d-C6烷基; R 1 is hydrogen, halogen, cyano, nitro, -Ce alkyl, dC 6 haloalkyl, cyano dC 6 alkyl, (: 2 -(: 6 alkenyl, C 2 -C 6 haloalkenyl) , C 2 -C 6 block, halo C 3 -C 6 block, dC 6 alkoxy, dC 6 cyanoalkoxy, dC 6 haloalkoxy, (;-(: 6 alkylthio, dC 6 haloalkylthio, dC 6 alkylsulfonyl, dC 6 alkylcarbonyl, halo dC 6 alkylcarbonyl, dC 6 alkoxycarbonyl, ^d 6 6 alkoxycarbonyl or amino dC 6 alkyl;
R2为氢、 卤素、 CfCe烷基、 卤代 d-C6烷基、 ( -(:6烷氧基、 卤代 ( -(:6烷氧基或氰基; m为 2; R 2 is hydrogen, halogen, CfCe alkyl, halogenated dC 6 alkyl, (-(: 6 alkoxy, halo (-(: 6 alkoxy or cyano; m is 2;
n为 1。  n is 1.
8、按照权利要求 7所述的制备按照权利要求 1至 5之一所述的含一氟甲氧基吡唑的邻甲 酰氨基苯甲酰胺类化合物的中间体, 其特征在于结构式 (Π ) 中:  The intermediate for preparing a fluoromethoxypyrazole-containing orthoformylbenzamide compound according to any one of claims 1 to 5, which is characterized in that the structural formula (Π) Medium:
R1为氢、 卤素、 氰基、 d-C6烷基、 d-C6卤代烷基或 d-C6烷基羰基; R 1 is hydrogen, halogen, cyano, dC 6 alkyl, dC 6 haloalkyl or dC 6 alkylcarbonyl;
R2为卤素、 氰基、 CfCe烷基或卤代 d-C3烷基。 R 2 is halogen, cyano, CfCe alkyl or halogenated dC 3 alkyl.
9、按照权利要求 8所述的制备按照权利要求 1至 5之一所述的含一氟甲氧基吡唑的邻甲酰氨 基苯甲酰胺类化合物的中间体, 其特征在于结构式 (Π ) 中: The intermediate for preparing a fluoromethoxypyrazole-containing orthoylaminobenzamide compound according to any one of claims 1 to 5, which is characterized in that the structural formula (Π) Medium:
R1为氢、 卤素、 氰基、 甲基或三氟甲基; R 1 is hydrogen, halogen, cyano, methyl or trifluoromethyl;
R2为卤素或氰基。 R 2 is a halogen or a cyano group.
10、 一种按照权利要求 1所述的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类化合物合成 方法, 其特征在于按照如下步骤: 10. Synthesis of an o-formylaminobenzamide compound containing a monofluoromethoxypyrazole according to claim The method is characterized by the following steps:
(1) 在非质子性溶剂中, 结构式 (VI) 表示的化合物与一氟一溴甲烷在缚酸剂作用下, 反应得到结构式 (W) 表示化合物;  (1) In an aprotic solvent, a compound represented by the formula (VI) and a monofluoro-bromomethane are reacted under the action of an acid binding agent to give a structural formula (W) to represent a compound;
(2) 在质子性溶剂中, 结构式 (W) 表示化合物在碱作用下水解得到结构式 (III) 表 示的含一氟甲氧基吡唑羧酸;  (2) In a protic solvent, the structural formula (W) indicates that the compound is hydrolyzed under a base to give a monofluoromethoxypyrazolecarboxylic acid represented by the formula (III);
(3) 在非质子性溶剂中, 加入碱和烷基磺酰氯, 结构式 (III) 表示的含一氟甲氧基吡 唑羧酸和结构式 (V) 表示的取代邻氨基苯甲酸反应得结构式 (Π) 表示的含一氟甲氧基吡 唑的 4H-苯并 [1, 3]噁嗪 -4-酮类化合物;  (3) In a non-protic solvent, a base and an alkylsulfonyl chloride are added, and the monofluoro-aminopyrazolecarboxylic acid represented by the formula (III) and the substituted anthranilic acid represented by the formula (V) are reacted to obtain a structural formula ( 4) a 4H-benzo[1,3]oxazin-4-one compound containing a monofluoromethoxypyrazole;
(4) 在非质子性溶剂中, 结构式 (Π)表示的含一氟甲氧基吡唑的 4H-苯并 [1,3]噁嗪 -4-酮类化合物和结构式 (IV)表示的化合物反应得结构式 (I)表示的含一氟甲氧基吡唑的 邻甲酰氨基苯甲酰胺类化合物;  (4) A tetrafluoromethoxypyrazole-containing 4H-benzo[1,3]oxazin-4-one compound represented by the formula (Π) in an aprotic solvent and a compound represented by the formula (IV) Reacting the o-formylaminobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I);
其中结构式 (Π)、 (111)、 (IV)、 (V)、 (VI) 和 (YD) 表示的化合物如下:  The compounds represented by the structural formulas (Π), (111), (IV), (V), (VI) and (YD) are as follows:
Figure imgf000044_0001
Figure imgf000044_0001
A、 R R2、 R3、 R4和 R5基团以及 m和 n的定义如权利要求 1。 The definitions of A, RR 2 , R 3 , R 4 and R 5 and m and n are as defined in claim 1.
11、 按照权利要求 10 所述的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类化合物合成方 法, 其特征在于:  A method for synthesizing a monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole according to claim 10, which is characterized in that:
步骤(1) 中所述结构式(VI)表示的化合物与一氟一溴甲烷和缚酸剂的投料物质的量比 为 1: 1.1〜2: 1.1〜2, 所述非质子性溶剂选自四氢呋喃、 乙腈、 1, 4-二氧六环或丙酮中 的一种或两种以上组合, 反应温度为 10〜90°C;  The ratio of the compound represented by the structural formula (VI) to the material of the monofluoromethane bromide and the acid binding agent in the step (1) is 1: 1.1 to 2: 1.1 to 2, and the aprotic solvent is selected from tetrahydrofuran. One or a combination of two or more of acetonitrile, 1,4-dioxane or acetone, the reaction temperature is 10 to 90 ° C;
步骤 (2) 中所述结构式 (W) 表示化合物与碱的投料物质的量比为 1: 1〜1.5, 所述质 子性溶剂为甲醇和 /或乙醇, 反应温度为 10〜90°C;  The structural formula (W) in the step (2) represents that the ratio of the compound to the base is 1: 1 to 1.5, the protic solvent is methanol and/or ethanol, and the reaction temperature is 10 to 90 ° C;
步骤(3) 中所述结构式 (III)表示的含一氟甲氧基吡唑羧酸和结构式 (V)表示的取代 邻氨基苯甲酸及烷基磺酰氯的投料物质的量比为 1: 1〜1. 5: 2〜3, 所述烷基磺酰氯为甲基 磺酰氯, 所述非质子性溶剂选自四氢呋喃、 乙腈、 1, 4-二氧六环、 乙醚或甲苯中的一种 或两种以上组合, 所述碱为有机碱, 反应温度为 -30〜80°C ; The monofluoropyrazole-containing carboxylic acid represented by the structural formula (III) represented by the formula (III) and the substitution represented by the structural formula (V) The ratio of the amount of the anthranilic acid and the alkylsulfonyl chloride to be charged is 1:1 to 1. 5: 2 to 3, the alkylsulfonyl chloride is methylsulfonyl chloride, and the aprotic solvent is selected from tetrahydrofuran. One or a combination of two or more of acetonitrile, 1,4-dioxane, diethyl ether or toluene, the base is an organic base, and the reaction temperature is -30 to 80 ° C;
步骤 (4) 中所述结构式 (Π ) 表示的含一氟甲氧基吡唑的 4H-苯并 [1, 3]噁嗪 -4-酮类化 合物和结构式(IV)表示的化合物的投料物质的量比为 1: 1〜5, 所述非质子性溶剂选自四 氢呋喃、 乙腈、 1, 4-二氧六环、 乙醚、 甲苯、 二氯甲烷或氯仿中的一种或两种以上组合。  a material of the compound represented by the structural formula (IV) and a compound represented by the formula (IV) represented by the structural formula (Π) represented by the formula (4): 4H-benzo[1,3]oxazin-4-one compound represented by the formula (IV) The amount ratio is 1:1 to 5, and the aprotic solvent is selected from one or a combination of two or more of tetrahydrofuran, acetonitrile, 1,4-dioxane, diethyl ether, toluene, dichloromethane or chloroform.
12、按照权利要求 11所述的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类化合物合成方法, 其特征在于:  A method for synthesizing a monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole according to claim 11, wherein:
步骤 (1 ) 中所述结构式 (VI) 表示的化合物与一氟一溴甲烷和缚酸剂的投料物质的量比 为 1: 1. 1〜1. 5: 1. 1〜1. 5, 反应温度为 20〜80°C;  The reaction temperature of the compound of the formula (VI) and the amount of the material of the fluoromonobromomethane and the acid-binding agent in the step (1) is 1: 1. 1~1. 5: 1. 1~1. For 20~80 °C;
步骤 (2) 中所述结构式 (VD) 表示化合物与碱的投料物质的量比为 1: 1〜1. 2, 反应温 度为 20〜80°C;  The reaction formula (VD) in the step (2) represents a ratio of the compound to the base material: 1: 1~1. 2, the reaction temperature is 20 to 80 ° C;
步骤(3) 中所述结构式 (III)表示的含一氟甲氧基吡唑羧酸和结构式 (V )表示的取代 邻氨基苯甲酸及烷基磺酰氯的投料物质的量比为 1: 1〜1. 2: 2〜2. 5, 所述有机碱选自三乙 胺、 吡啶或 3-甲基吡啶中的一种或两种以上组合, 反应温度为 -15〜30°C ;  The ratio of the content of the substituted fluoroaminopyrazolecarboxylic acid represented by the structural formula (III) and the substituted anthranilic acid represented by the structural formula (V) and the alkylsulfonyl chloride represented by the formula (III) in the step (3) is 1:1. 〜2. 2〜2. 5, the organic base is selected from one or a combination of two or more of triethylamine, pyridine or 3-methylpyridine, the reaction temperature is -15~30 ° C;
步骤 (4) 中所述结构式 (Π ) 表示的含一氟甲氧基吡唑的 4H-苯并 [1, 3]噁嗪 -4-酮类化 合物和结构式 (IV) 表示的化合物的投料物质的量比为 1: 1〜2。  a material of the compound represented by the structural formula (IV) and a compound represented by the structural formula (IV) represented by the structural formula (Π) represented by the formula (4): 4H-benzo[1,3]oxazin-4-one compound represented by the formula (IV) The ratio is 1:1~2.
13、 一种如权利要求 1至 12之一所述的结构式( I )表示的含一氟甲氧基吡唑的邻甲酰 氨基苯甲酰胺类化合物或其农业上适用的盐的用途, 其特征在于结构(I )化合物用于农作物 上的害虫防治。  13. Use of a monofluoroamidobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I) according to any one of claims 1 to 12, or an agriculturally applicable salt thereof, It is characterized in that the compound of structure (I) is used for pest control on crops.
14、一种防治有害生物的农药制剂,其特征在于:含有按照权利要求 1所述的结构式( I ) 表示的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类化合物或其盐作为活性成分和农业、林业、 卫生上可接受的载体, 其中活性成分与载体的重量配比为 0. 1: 99. 9〜90: 10。  A pesticidal preparation for controlling pests, comprising: a fluoromethoxypyrazole-containing orthoformylaminobenzamide compound represented by the formula (I) according to Claim 1 or a salt thereof至9. 9〜90: 10。 The weight ratio of the active ingredient to the carrier is 0. 1: 99. 9~90: 10.
15、 一种防治有害生物的方法, 其特征在于: 将权利要求 14所述的农药制剂施于需要控 制的有害生物或其生长的介质上, 其中活性成分的有效量为每公顷 10克到 1000克。  A method for controlling pests, characterized in that: the pesticide preparation according to claim 14 is applied to a pest to be controlled or a medium for growth thereof, wherein the effective amount of the active ingredient is from 10 g to 1000 per hectare Gram.
16、 一种防治有害生物的方法, 其特在于: 含有按照权利要求 1所述的结构式 ( I ) 表 示的含一氟甲氧基吡唑的邻甲酰氨基苯甲酰胺类化合物与现有杀虫、 杀菌或除草的农药品种 的一种或二种或两种以上进行组合使用。  A method for controlling pests, comprising: an o-formylaminobenzamide compound containing a monofluoromethoxypyrazole represented by the formula (I) according to claim 1 and an existing killing agent One or two or more kinds of pesticides for worm, sterilizing or weeding are used in combination.
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