Oxime ether derivatives containing a pyrazole group, methods of preparation, uses and bactericides thereof

Abstract

The application belongs to the field of bactericides, and discloses an oxime ether derivative containing a pyrazole group, a preparation method, application and a bactericide, the structure of the derivative is shown as formula (I); the preparation method of the compound disclosed by the application is simple, the compound has the effect of preventing and treating plant pathogenic fungi, and can be applied to plant protection as a bactericide.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of pesticides, in particular to an oxime ether derivative containing a pyrazole group, and also to a method for preparing the derivative, to the use of the derivative for controlling fungal diseases of plants, and to a fungicide comprising the derivative. BACKGROUND

[0002] Pyrazole compounds have attracted more and more attention from medicinal chemists and chemists due to their wide physiological and biochemical activities. In the field of pesticides, the pyrazole ring is an important active group and is often introduced into the molecular structure of pesticides, such as the insecticides tebufenpyrad and tolfenpyrad, the herbicide fluazolate, the fungicides pyraclostrobin, penthiopyrad, pyrazolonamide and pydiflumetofen, etc. Pyrazole compounds are increasingly becoming one of the hotspots of new pesticide creation and development today, due to their high biological activity, strong systemicity, environmental friendliness and other excellent properties.

[0003] Oxime ether structures are widely used in the fields of anticancer, antibacterial, herbicidal, antifungal, antiviral, insecticidal, rodenticidal, anti-inflammatory, anti-spasmodic, etc. In 1974, the first oxime ether fungicide cymoxanil was successfully developed by DuPont Company in the United States, which is mainly used to prevent and treat downy mildew and late blight. Subsequently, oxime ether fungicides have been rapidly developed, such as dimoxystrobin, fluoxastrobin, trifloxystrobin, picarbutrazox, Pyrapropoyne, etc. It can be seen that the oxime ether structure has important reference significance for designing new fungicides.

[0004] In the present application, the substituted pyrazole group is organically combined with the substituted phenone oxime ether structure through an oxygen atom, and screening of fungicidal activity has found that an oxime ether derivative containing a pyrazole group has significant inhibitory activity against plant pathogenic fungi. SUMMARY

[0005] The present application aims to provide an oxime ether derivative containing a pyrazole group, a preparation method thereof, the use of the derivative in the prevention and treatment of fungal diseases of plants, and a fungicide comprising the derivative.

[0006] To achieve the above object, the first aspect of the present application provides a pyrazole group-containing acetophenone oxime ether derivative having a structure represented by the general formula (I) or an agriculturally acceptable salt, hydrate and solvate thereof,

[0007]

[0008] In the formula (I), each of the groups has the following definitions:

[0009] R 1 selected from the group consisting of C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylmethyl, benzyl;

[0010] R 2 selected from the group consisting of H, halogen, C1-C6 alkyl having 0 to 3 halogens, C3-C6 cycloalkyl;

[0011] R 3 selected from the group consisting of 1 to 4 groups of H, halogen, C1-C6 alkyl having 0 to 3 halogens, C1-C6 alkoxy having 0 to 3 halogens, phenyl having 0 to 3 halogens, phenoxy having 0 to 3 halogens;

[0012] R 4 selected from the group consisting of H, C1-C6 alkyl, C3-C6 cycloalkylmethyl, C2-C6 alkenyl, C2-C6 alkynyl, benzyl having 0 to 3 halogens;

[0013] The halogen mentioned in the definition of the above groups is selected from the group consisting of F, Cl, Br, I;

[0014] The configuration of the oxime ether structure is selected from the group consisting of (Z)-form, (E)-form, (Z / E)-form.

[0015] In the formula (I), each of the groups has the following preferred definitions:

[0016] R 1 selected from the group consisting of difluoromethyl, trifluoromethyl;

[0017] R 2 selected from the group consisting of H, halogen, methyl;

[0018] R 3 selected from the group consisting of 1 to 3 groups of H, halogen, methyl having 0 to 3 halogens, C1-C3 alkoxy, phenyl having 0 to 1 halogen, phenoxy having 0 to 3 halogens;

[0019] R 4 selected from the group consisting of H, C1-C4 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylmethyl, benzyl;

[0020] The halogen mentioned in the definition of the above groups is selected from the group consisting of F, Cl, Br, I;

[0021] the configuration of the oxime ether structure is selected from the group consisting of (Z)-formula, (E)-formula, (Z / E)-formula.

[0022] In formula (I), the individual radicals have the further preferred definitions as described below:

[0023] R 1 selected from the group consisting of difluoromethyl, trifluoromethyl;

[0024] R 2 selected from the group consisting of H, F, methyl;

[0025] R 3 selected from the group consisting of 1 to 3 of the following radicals: H, F, CI, methyl, trifluoromethyl, methoxy, phenyl, phenoxy, trifluoromethoxy, chlorophenoxy, nitro;

[0026] R 4 selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, cyclohexyl, cyclopropylmethyl, cyclohexylmethyl, benzyl, allyl, propargyl;

[0027] the configuration of the oxime ether structure is selected from the group consisting of (Z)-formula, (E)-formula, (Z / E)-formula.

[0028] In formula (I), the individual radicals have the further preferred definitions as described below:

[0029] (Z / E)-2-((3-(difluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-phenylethan-l-one-O- methyl oxime (1-1),

[0030] (Z / E)-2-((3-(difluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-(2-fluorophenyl)ethan- 1-one-O-methyl oxime (1-2),

[0031] (Z / E)-2-((3-(difluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-(3-fluorophenyl)ethan- 1-one-O-methyl oxime (1-3),

[0032] (Z / E)-2-((3-(difluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-(4-fluorophenyl)ethan- 1-one-O-methyl oxime (1-4),

[0033] (Z / E)-2-((3-(difluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-(2,4-difluorophenyl)ethan- 1-one-O-methyl oxime (1-5),

[0034] (Z / E)-1-(2-chlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5- yl)oxy)ethan-1-one-O-methyl oxime (1-6),

[0035] (Z / E)-1-(3-chlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5- yl)oxy)ethan-1-one-O-methyl oxime (1-7),

[0036] (Z / E)-1-(4-chlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5- yl)oxy)ethan-1-one-O-methyl oxime (1-8),

[0037] (Z / E)-1-(2,4-chlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5- yl)oxy)ethan-1-one-O-methyl oxime (1-9),

[0038] (Z / E)-1-(3,4-chlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5- yl)oxy)ethan-1-one-O-methyl oxime (1-10),

[0039] (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-(m-tolyl)ethan-1- one-O-methyl oxime (1-11),

[0040] (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-(p-tolyl)ethan-1- one-O-methyl oxime (1-12),

[0041] (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-(4- (trifluoromethyl)phenyl)ethan-1-one-O-methyl oxime (1-13),

[0042] (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-(2- methoxyphenyl)ethan-1-one-O-methyl oxime (1-14),

[0043] (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-(3- methoxyphenyl)ethan-1-one-O-methyl oxime (1-15),

[0044] (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-(4- methoxyphenyl)ethan-1-one-O-methyl oxime (1-16),

[0045] (Z / E)-2-((3-(di£uoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-(3,4- dimethoxyphenyl)ethan-l-one-O-methyloxime (1-17),

[0046] (Z / E)-2-((3-(di£uoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-(3,5- dimethoxyphenyl)ethan-l-one-O-methyloxime (1-18),

[0047] (Z / E)-2-((3-(di£uoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-(3,4,5- trimethoxyphenyl)ethan-l-one-O-methyloxime (1-19),

[0048] (Z / E)-2-((3-(di£uoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-phenylethan-l-one-O- ethyloxime (1-20),

[0049] (Z / E)-2-((3-(di£uoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-phenylethan-l-one-O- allyloxime (1-21),

[0050] (Z / E)-2-((3-(di£uoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-phenylethan-l-one-O- isopropyl oxime (1-22),

[0051] (Z / E)-2-((3-(di£uoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-phenylethan-l-one-O- butyloxime (1-23),

[0052] (Z / E)-2-((3-(di£uoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-phenylethan-l-one-O- benzyl oxime (1-24),

[0053] (Z / E)-l-(2,4-chlorophenyl)-2-((3-(di£uoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)ethan- l-one-O-ethyloxime (1-25),

[0054] (Z / E)-l-(2,4-chlorophenyl)-2-((3-(di£uoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)ethan- l-one-O-allyloxime (1-26),

[0055] (Z / E)-1-(2,4-chlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)ethan-1-one-O-isopropyloxime (I-27),

[0056] (Z / E)-1-(2,4-chlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)ethan-1-one-O-butyl oxime (I-28),

[0057] (Z / E)-1-(2,4-chlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)ethan-1-one-O-benzyl oxime (I-29),

[0058] (Z / E)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)-1-phenylethan-1-one-O-methyloxime (I-30),

[0059] (Z / E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-methyloxime (I-31),

[0060] (Z / E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-ethyl oxime (I-32),

[0061] (Z / E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-allyl oxime (I-33),

[0062] (Z / E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-isopropyloxime (I-34),

[0063] (Z / E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one oxime (I-35),

[0064] (Z)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-propyl oxime (I-36),

[0065] (Z)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one O-butyl oxime (I-37),

[0066] (Z)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1 H-pyrazol-5- yl)oxy)ethan-1 -one-O-cyclohexylmethyl oxime (1-42),

[0067] (E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1 H-pyrazol-5- yl)oxy)ethan-1 -one-O-cyclohexylmethyl oxime (1-43),

[0068] (Z)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1 H-pyrazol-5- yl)oxy)ethan-1 -one-O-cyclohexylmethyl oxime (1-42),

[0069] (Z)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1 H-pyrazol-5- yl)oxy)ethan-1 -one-O-cyclohexylmethyl oxime (1-42),

[0070] (Z)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1 H-pyrazol-5- yl)oxy)ethan-1 -one-O-cyclohexylmethyl oxime (1-42),

[0071] (E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1 H-pyrazol-5- yl)oxy)ethan-1 -one-O-cyclohexylmethyl oxime (1-43),

[0072] (Z)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1 H-pyrazol-5- yl)oxy)ethan-1 -one-O-cyclohexylmethyl oxime (1-42),

[0073] (E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1 H-pyrazol-5- yl)oxy)ethan-1 -one-O-cyclohexylmethyl oxime (1-43),

[0074] (Z)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1 H-pyrazol-5- yl)oxy)ethan-1 -one-O-cyclohexylmethyl oxime (1-42),

[0075] (Z / E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1 H-pyrazol-5- yl)oxy)ethan-1 -one-O-cyclohexylmethyl oxime (1-42),

[0076] (Z / E)-1-(2,4-dichlorophenyl)-2-((1,4-dimethyl-3-(trifluoromethyl)-1 H- pyrazol-5-yl)oxy)ethan-1 -one-O-ethyl oxime (1-48),

[0077] (Z / E)-1-(2,4-dichlorophenyl)-2-((1,4-dimethyl-3-(trifluoromethyl)-1 H- pyrazol-5-yl)oxy)ethan-1 -one-O-ethyl oxime (1-48),

[0078] (Z / E)-1-(2,4-dichlorophenyl)-2-((1,4-dimethyl-3-(trifluoromethyl)-1 H- pyrazol-5-yl)oxy)ethan-1 -one-O-ethyl oxime (1-48),

[0079] (Z)-1-(2,4-dichlorophenyl)-2-((4-fluoro-1-methyl-3-(trifluoromethyl)-1 H- pyrazol-5-yl)oxy)ethan-1 -one-O-methyl oxime (1-51 ),

[0080] (E)-1-(2,4-dichlorophenyl)-2-((4-fluoro-1-methyl-3-(trifluoromethyl)-1 H- pyrazol-5-yl)oxy)ethan-1 -one-O-methyl oxime (1-52),

[0081] (Z)-1-(2,4-dichlorophenyl)-2-((4-fluoro-1-methyl-3-(trifluoromethyl)-1 H- pyrazol-5-yl)oxy)ethan-1 -one-O-ethyl oxime (1-53),

[0082] (E)-1-(2,4-dichlorophenyl)-2-((4-fluoro-1-methyl-3-(trifluoromethyl)-1 H- pyrazol-5-yl)oxy)ethan-1 -one-O-ethyl oxime (1-54),

[0083] (Z)-1-(2,4-dichlorophenyl)-2-((4-fluoro-1-methyl-3-(trifluoromethyl)-1 H- pyrazol-5-yl)oxy)ethan-1 -one-O-ethyl oxime (1-53),

[0084] (E)-1-(2,4-dichlorophenyl)-2-((4-fluoro-1-methyl-3-(trifluoromethyl)-1 H- pyrazol-5-yl)oxy)ethan-1 -one-O-ethyl oxime (1-54),

[0085] (Z)-1-(2,4-dichlorophenyl)-2-((4-fluoro-1-methyl-3-(trifluoromethyl)-1 H- pyrazol-5-yl)oxy)ethan-1 -one-O-ethyl oxime (1-53),

[0086] (E)-1-(2,4-dichlorophenyl)-2-((4-fluoro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-isobutyloxime (I-58),

[0087] (Z / E)1-(3,5-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-ethyl oxime (I-59),

[0088] (Z)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)-1-(2,3,4-trichlorophenyl)ethan-1-one-O-ethyl oxime (I-60),

[0089] (E)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)-1-(2,3,4-trichlorophenyl)ethan-1-one-O-ethyl oxime (I-61),

[0090] (Z)-1-(2,4-dichloro-5-fluorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-ethyl oxime (I-62),

[0091] (E)-1-(2,4-dichloro-5-fluorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-ethyl oxime (I-63),

[0092] (Z)-1-(2,4-dichloro-5-fluorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-propyn-1-yl oxime (I-64),

[0093] (E)-1-(2,4-dichloro-5-fluorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-propyn-1-yl oxime (I-65),

[0094] (Z / E)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)-1-(3,4,5-trifluorophenyl)ethan-1-one-O-ethyl oxime (I-66),

[0095] (Z / E)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)-1-(3-nitrophenyl)ethan-1-one-O-ethyl oxime (I-67),

[0096] (Z / E)-2-((1 -methyl-3-(trifluoromethyl)-1 H-pyrazol-5-yl)oxy)-1 -(3- nitrophenyl)ethan-1 -one-O-propyl oxime (1-68),

[0097] (Z)-2-((1 -methyl-3-(trifluoromethyl)-1 H-pyrazol-5-yl)oxy)-1 -(3-(trifluoromethyl)phenyl)ethan-1 -one-O-ethyl oxime (1-69),

[0098] (Z / E)-2-((1 -methyl-3-(trifluoromethyl)-1 H-pyrazol-5-yl)oxy)-1 -(3-(trifluoromethoxy)phenyl)ethan-1 -one-O-ethyl oxime (1-70),

[0099] (Z / E)-1 -([1,1 '-biphenyl]-4-yl)-2-((1 -methyl-3-(trifluoromethyl)-1 H-pyrazol-5-yl)oxy)ethan-1 -one-O-ethyl oxime (1-71 ),

[0100] (Z / E)-2-((1 -methyl-3-(trifluoromethyl)-1 H-pyrazol-5-yl)oxy)-1 -(4-phenoxyphenyl)ethan-1 -one-O-ethyl oxime (1-72),

[0101] (Z)-1 -(2-chloro-4-(4-chlorophenoxy)phenyl)-2-((1 -methyl-3-(trifluoromethyl)-1 H-pyrazol-5-yl)oxy)ethan-1 -one-O-ethyl oxime (1-73),

[0102] (E)-1 -(2-chloro-4-(4-chlorophenoxy)phenyl)-2-((1 -methyl-3-(trifluoromethyl)-1 H-pyrazol-5-yl)oxy)ethanone-O-ethyl oxime (1-74).

[0103] The second aspect of the present application provides a method for preparing a pyrazole group-containing acetophenone oxime ether derivative (I) as shown in general formula (A). First, pyrazole alcohol (II) and halogenated acetophenone (III) are reacted in the presence of K2CO3, with acetonitrile as solvent, to synthesize 2-pyrazolyloxy-1 -phenyl ethan-1 -one (IV). Then, 2-pyrazolyloxy-1 -phenyl ethan-1 -one (IV) and R 3 ONH2-HCl to form a pyrazole group-containing acetophenone oxime ether derivative (I):

[0104]

[0105] In the above structural formulae:

[0106] R 1 , R 2、R 3 、R 4 All have the same definitions as above;

[0107] X is selected from Cl, Br;

[0108] The third aspect of the present invention provides the use of an acetophenone oxime ether derivative containing a pyrazole group having a structure represented by general formula (I) or its agriculturally acceptable salts, hydrates and solvates as pesticides for controlling plant fungal diseases as described in the first aspect.

[0109] The application described in the third aspect of the present invention refers to the use of an oxime ether derivative containing a pyrazole group having a structure represented by general formula (I) or its agriculturally acceptable salts, hydrates and solvates in pesticides for preventing and controlling plant diseases caused by rice sheath blight, wheat fusarium and tomato gray mold.

[0110] The fourth aspect of the present invention provides the use of an oxime ether derivative containing a pyrazole group having a structure represented by general formula (I) or an agriculturally acceptable salt, hydrate and solvate thereof as an agricultural fungicide according to the first aspect.

[0111] The fifth aspect of the present invention provides a fungicide, characterized in that the fungicide is composed of an active ingredient and an excipient, wherein the active ingredient includes at least one of an oxime ether derivative containing a pyrazole group or an agriculturally acceptable salt, hydrate and solvate thereof according to any one of claims 1 to 4; the excipient is various excipients commonly used in the pesticide field, such as surfactants, solvents, cosolvents, dispersants, antifreeze agents, etc.

[0112] The content of the active ingredient in the fungicide described in the fifth aspect is in the range of 0.1 to 99.9% by weight.

[0113] The fungicide described in the fifth aspect above has a dosage form selected from at least one of mother powder, mother liquid, emulsifiable concentrate, suspension, aqueous solution, aqueous emulsion, microemulsion, dust, wettable powder, granule, oil, smoke agent, and bait.

[0114] Beneficial effects:

[0115] Compared with the prior art, the present application has obvious beneficial effects. From the above technical scheme, it can be known that the present application combines a pyrazole group and a phenone oxime ether structural unit through an oxygen atom, and designs and synthesizes a phenone oxime ether derivative (I) containing a pyrazole group. The molecular structure of the derivative is novel. The derivative is applied to the research on the resistance to plant pathogenic fungi, and it is found for the first time that the compound has significant inhibitory activity on plant pathogenic fungi, which embodies the creativity of the technical scheme. The inhibitory activity of some compounds on tomato botrytis cinerea is higher than that of the control agents fluazinam, penthiopyrad or boscalid, which embodies the practicability of the present application. DETAILED DESCRIPTION

[0116] Example 1: Synthesis of (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-phenylethan-1-one-O-methyloxime (I-1)

[0117]

[0118] In a 50mI round-bottom flask, 0.37g of 3-difluoromethyl-1-methyl-1H-pyrazol-5-ol (II-1), 0.39g of 2-chloro-1-phenylethan-1-one (III-1), 0.41g of potassium carbonate and 30mL of acetonitrile were sequentially added, and the reaction was stirred at room temperature for 8h. Filtration was performed, and the filtrate was distilled under reduced pressure to obtain a deep red liquid. The liquid was poured into ice water to precipitate a yellow solid. The solid was filtered, washed and dried to obtain a light yellow powder, which was compound 2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-phenylethan-1-one (IV-1).

[0119] In a 50mL three-necked flask, 0.53g of compound IV-1, 0.33g of MeONH2-HCl, 1.11g of potassium carbonate and 25mL of ethanol were added, and the reaction was stirred at room temperature for 6h. The solvent ethanol was removed by distillation under reduced pressure, 10mL of water was added for washing, and 10mL of ethyl acetate was used for extraction three times. The organic phases were combined, dried with anhydrous manganese sulfate, filtered and distilled under reduced pressure to obtain a yellow solid. The solid was purified by silica gel column chromatography (ethyl acetate + petroleum ether = 1:2, V / V) to obtain a white solid, which was (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-phenylethan-1-one-O-methyloxime (I-1), with a yield of 86%.

[0120] Example 2: Synthesis of (Z)-2-((l-methyl-3-trifluoromethyl-lH-pyrazol-5-yl)oxy)-l- (2,4-dichloro-5-fluorophenyl)ethan-l-one-O-propargyl oxime (I-64) and (E)-2-((l- methyl-3-trifluoromethyl-lH-pyrazol-5-yl)oxy)-l-(2,4-dichloro-5-fluorophenyl)ethan-l- one-O-propargyl oxime (I-65)

[0121]

[0122] In a 100 mL round bottom flask, 2.00 g of 3-trifluoromethyl-l-methyl-lH-pyrazol-5-ol (II-2), 3.44 g of 2-bromo-l-(2,4-dichlorophenyl)ethan-l-one (III-2), 3.33 g of potassium carbonate and 60 mL of acetonitrile were added, and the reaction was stirred at room temperature. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the solvent was removed by rotary evaporation, 30 mL of water was added, and the mixture was extracted with 10 mL x 3 of ethyl acetate three times. The organic phase was combined, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The product, 2-((l-methyl-3-trifluoromethyl-lH-pyrazol-5-yl)oxy)-l-(2,4-dichloro-5- fluorophenyl)ethan-l-one (IV-2), was obtained as a light yellow solid by silica gel column chromatography (ethyl acetate + petroleum ether = 1:2, V / V).

[0123] In a 50 mL round bottom flask, 1 g of compound (IV-2), 0.43 g of CH≡CCH2ONH2-HCl, 0.74 g of potassium carbonate and 30 mL of anhydrous ethanol were added, and the reaction was heated to reflux for 4 h. The inorganic salt was removed by filtration, and the ethanol was removed by rotary evaporation. The product was obtained as (Z)-2-((l-methyl-3-trifluoromethyl-lH-pyrazol-5-yl)oxy)-l-(2,4-dichloro-5- fluorophenyl)ethan-l-one-O-propargyl oxime (I-64) and (E)-2-((l-methyl-3-trifluoromethyl-lH-pyrazol-5-yl)oxy)-l-(2,4-dichloro-5-fluorophenyl)ethan-l-one-O-propargyl oxime (I-65) by silica gel column chromatography (ethyl acetate + petroleum ether = 2:98, V / V) after extraction with 10 mL x 3 of ethyl acetate three times and removal of the solvent by rotary evaporation. The yields were 71% and 18%, respectively.

[0124] I-1 to I-74 of the phenylacetone oxime ether derivative (I) containing a pyrazole group were sequentially synthesized according to the method of Example 1 or Example 2. The molecular structures of the synthesized compounds were confirmed by nuclear magnetic resonance spectroscopy (H NMR). 1 The names, structural formulas, appearances, and hydrogen spectrum data of compounds I-1 to I-74 are shown below.

[0125] (Z / E)-2-((3-(difluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-phenylethan-l-one-O- methyloxime (1-1)

[0126]

[0127] Yellow liquid; yield 86%; 1 H NMR (400 MHz, CDC13) δ: 7.65 (d, J = 2.0 Hz, 1H, ArH), 7.63 (d, J = 4.2 Hz, 1H, ArH), 7.42 (d, J = 3.7 Hz, 2H, ArH), 7.40 (d, J = 1.6 Hz, 1H, ArH), 6.53 (t, J = 55.1 Hz, 1H, CHF2), 5.87 (s, 1H, CH), 5.28 (s, 2H, CH2), 4.08 (s, 3H, CH3), 3.49 (s, 3H, CH3).

[0128] (Z / E)-2-((3-(difluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-(2-fluorophenyl)ethan-l-one-O- methyloxime (1-2)

[0129]

[0130] Yellow liquid; yield 84%; 1 H NMR (400 MHz, CDC13) δ: 7.39 (dd, J = 7.5, 6.4 Hz, 2H, ArH), 7.17 (d, J = 7.3 Hz, 1H, ArH), 7.15-7.08 (m, 1H, ArH), 6.51 (t, J = 55.1 Hz, 1H, CHF2), 5.80 (s, 1H, CH), 5.27 (s, 2H, CH2), 4.08 (s, 3H, CH3), 3.36 (s, 3H, CH3).

[0131] (Z / E)-2-((3-(difluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-(3-fluorophenyl)ethan-l-one-O- methyloxime (1-3)

[0132]

[0133] White solid; yield 85%; m.p. 59-60 °C; 1H NMR (400 MHz, CDC13) δ: 7.44-7.39 (m, 2H, 2H, ArH), 7.37 (dd, J = 8.0, 2.0 Hz, 1H, ArH), 7.12 (ddd, J = 7.2, 2.5, 1.4 Hz, 1H, ArH), 6.53 (t, J = 55.1 Hz, 1H, CHF2), 5.87 (s, 1H, CH), 5.26 (s, 2H, CH2), 4.09 (s, 3H, CH3), 3.53 (s, 3H, CH3).

[0134] (Z / E)-2-((3-(Difluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-(4- fluorophenyl)ethan-l-one-O-methyl oxime (1-4)

[0135]

[0136] pale yellow solid; yield 88%; m.p. 49-50 °C; 1 H NMR (400 MHz, CDC13) δ: 7.64 (dd, J = 8.9, 5.4 Hz, 2H, ArH), 7.09 (t, J = 8.7 Hz, 2H, ArH), 6.52 (t, J = 55.1 Hz, 1H, CHF2), 5.86 (s, 1H, CH), 5.27 (s, 2H, CH2), 4.07 (s, 3H, CH3), 3.51 (s, 3H, CH3).

[0137] (Z / E)-2-((3-(Difluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-(2,4- difluorophenyl)ethan-l-one-O-methyl oxime (1-5)

[0138]

[0139] pale yellow liquid; yield 88%; 1 H NMR (400 MHz, CDC13) δ: 7.45-7.37 (m, 1H, ArH), 6.92 (dd, J = 8.6, 2.6 Hz, 1H, ArH), 6.89-6.84 (m, 1H, ArH), 6.52 (t, J = 55.1 Hz, 1H, CHF2), 5.79 (s, 1H, CH), 5.24 (d, J = 0.8 Hz, 2H, CH2), 4.07 (s, 3H, CH3), 3.41 (s, 3H, CH3).

[0140] (Z / E)-l-(2-Chlorophenyl)-2-((3-(difluoromethyl)-l-methyl-lH-pyrazol-5- yl)oxy)ethan-l-one-O-methyl oxime (1-6)

[0141]

[0142] Yellow liquid; yield 83%; 1 H NMR (400 MHz, CDC13) δ: 7.45-7.41 (m, 1H, ArH), 7.39-7.33 (m, 1H, ArH), 7.28-7.23 (m, 2H, ArH), 6.50 (t, J = 55.1 Hz, 1H, CHF2), 5.80 (s, 1H, CH), 5.29 (s, 2H, CH2), 4.07 (s, 3H, CH3), 3.29 (s, 3H, CH3).

[0143] (Z / E)-1-(3-chlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)ethan-1-one-O-methyloxime (1-7)

[0144]

[0145] Yellow solid; yield 90%; m.p. 64-65 °C; 1 H NMR (400 MHz, CDC13) δ: 7.45-7.41 (m, 1H, ArH), 7.39-7.33 (m, 1H, ArH), 7.28-7.23 (m, 2H, ArH), 6.50 (t, J = 55.1 Hz, 1H, CHF2), 5.80 (s, 1H, CH), 5.29 (s, 2H, CH2), 4.07 (s, 3H, CH3), 3.29 (s, 3H, CH3).

[0146] (Z / E)-1-(4-chlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)ethan-1-one-O-methyloxime (1-8)

[0147]

[0148] Yellow solid; yield 92%; m.p. 44-45 °C; 1 H NMR (400 MHz, CDC13) δ: 7.45-7.41 (m, 1H, ArH), 7.39-7.33 (m, 1H, ArH), 7.28-7.23 (m, 2H, ArH), 6.50 (t, J = 55.1 Hz, 1H, CHF2), 5.80 (s, 1H, CH), 5.29 (s, 2H, CH2), 4.07 (s, 3H, CH3), 3.29 (s, 3H, CH3).

[0149] (Z / E)-1 -(2,4-chlorophenyl)-2-((3-(difluoromethyl)-1 -methyl-1 H-pyrazol-5- yl)oxy)ethan-1 -one-O-methyloxime (1-9)

[0150]

[0151] Yellowish liquid; yield 90%; m.p. 48-49 °C; 1 H NMR (400 MHz, CDC13) δ: 7.28 (s, 1H, ArH), 7.26 (d, J = 1.1 Hz, 1H, ArH), 7.21 (d, J = 8.2 Hz, 1H, ArH), 6.50 (t, J = 55.1 Hz, 1H, CHF2), 5.79 (s, 1H, CH), 5.26 (s, 2H, CH2), 4.06 (s, 3H, CH3), 3.35 (s, 3H, CH3).

[0152] (Z / E)-1 -(3,4-chlorophenyl)-2-((3-(difluoromethyl)-1 -methyl-1 H-pyrazol-5- yl)oxy)ethan-1 -one-O-methyloxime (1-10)

[0153]

[0154] Yellow solid; yield 89%; m.p. 69-70 °C; 1 H NMR (400 MHz, CDC13) δ: 7.80 (d, J = 1.7 Hz, 1H, ArH), 7.50-7.47 (m, 2H, ArH), 6.52 (t, J = 55.1 Hz, 1H, CHF2), 5.85 (s, 1H, CH), 5.25 (s, 2H, CH2), 4.09 (s, 3H, CH3), 3.55 (s, 3H, CH3).

[0155] (Z / E)-2-((3-(difluoromethyl)-1 -methyl-1 H-pyrazol-5-yl)oxy)-1 -(m-tolyl)ethan-1 - one-O-methyloxime (1-11)

[0156]

[0157] White solid; yield 92%; m.p. 63-64 °C; 1H NMR (400 MHz, CDC13) δ: 7.41 (d, J = 7.7 Hz, 1H, ArH), 7.35-7.30 (m, 1H, ArH), 7.29 (d, J = 2.3 Hz, 1H, ArH), 7.23 (d, J = 7.5 Hz, 1H, ArH), 6.53 (t, J = 55.1 Hz, 1H, CHF2), 5.87 (s, 1H, CH), 5.27 (s, 2H, CH2), 4.08 (s, 3H, CH3), 3.50 (s, 3H, CH3), 2.39 (s, 3H, CH3).

[0158] (Z / E)-2-((3-(Difluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-(p-tolyl)ethan-l-one-O- methyl oxime (1-12)

[0159]

[0160] Yellow solid; yield 93%; m.p. 44-45 °C; 1 H NMR (400 MHz, CDC13) δ: 7.41 (d, J = 7.7 Hz, 1H, ArH), 7.35-7.30 (m, 1H, ArH), 7.29 (d, J = 2.3 Hz, 1H, ArH), 7.23 (d, J = 7.5 Hz, 1H, ArH), 6.53 (t, J = 55.1 Hz, 1H, CHF2), 5.87 (s, 1H, CH), 5.27 (s, 2H, CH2), 4.08 (s, 3H, CH3), 3.50 (s, 3H, CH3), 2.39 (s, 3H, CH3).

[0161] (Z / E)-2-((3-(Difluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-(p-tolyl)ethan-l-one-O- methyl oxime (1-12)

[0162]

[0163] Yellow liquid; yield 91%; 1 H NMR (400 MHz, CDC13) δ: 7.41 (d, J = 7.7 Hz, 1H, ArH), 7.35-7.30 (m, 1H, ArH), 7.29 (d, J = 2.3 Hz, 1H, ArH), 7.23 (d, J = 7.5 Hz, 1H, ArH), 6.53 (t, J = 55.1 Hz, 1H, CHF2), 5.87 (s, 1H, CH), 5.27 (s, 2H, CH2), 4.08 (s, 3H, CH3), 3.50 (s, 3H, CH3), 2.39 (s, 3H, CH3).

[0164] (Z / E)-2-((3-(difluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-(2- methoxyphenyl)ethan-l-one-O-methyloxime (1-14)

[0165]

[0166] White solid; yield 84%; m.p. 73-74 °C; 1 H NMR (400 MHz, CDC13) δ: 7.37 (td, J = 8.2, 1.7 Hz, 1H, ArH), 7.21 (dd, J = 7.5, 1.6 Hz, 1H, ArH), 6.94 (td, J = 7.5, 0.6 Hz, 1H, ArH), 6.89 (d, J = 8.3 Hz, 1H, ArH), 6.50 (t, J = 55.1 Hz, 1H, CHF2), 5.79 (s, 1H, CH), 5.26 (s, 2H, CH2), 4.04 (s, 3H, CH3), 3.78 (s, 3H, CH3), 3.24 (s, 3H, CH3). (Z / E)-2-((3-(difluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-(3- methoxyphenyl)ethan-l-one-O-methyloxime (1-15)

[0167]

[0168] White solid; yield 87%; m.p. 77-78 °C; 1 H NMR (400 MHz, CDC13) δ: 7.32 (t, J = 8.1 Hz, 1H, ArH), 7.20 (d, J = 7.1 Hz, 1H, ArH), 7.19 (d, J = 1.5 Hz, 1H, ArH), 6.99-6.94 (m, 1H, ArH), 6.53 (t, J = 55.1 Hz, 1H, CHF2), 5.87 (s, 1H, CH), 5.26 (s, 2H, CH2), 4.08 (s, 3H, CH3), 3.84 (s, 3H, CH3), 3.51 (s, 3H, CH3).

[0169] (Z / E)-2-((3-(difluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-(4- methoxyphenyl)ethan-l-one-O-methyloxime (1-16)

[0170]

[0171] White solid; yield 84%; m.p. 57-58 °C; 1H NMR (400 MHz, CDC13) δ: 7.93 (d, J = 2.8 Hz, 1H, ArH), 7.90 (d, J = 2.8 Hz, 1H, ArH), 7.65-7.63 (m, 1H, ArH), 7.62-7.60 (m, 1H, ArH), 6.92 (s, 1H, CH), 6.68 (t, J = 55.1 Hz, 1H, CHF2), 5.44 (s, 2H, CH2), 4.04 (s, 3H, CH3), 3.86 (s, 3H, CH3), 3.83 (s, 3H, CH3).

[0172] (Z / E)-2-((3-(DiFluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-(3,4- dimethoxyphenyl)ethan-l-one-O-methyloxime (1-17)

[0173]

[0174] White solid; yield 82%; m.p. 88-89 °C; 1 H NMR (400 MHz, CDC13) δ: 7.25 (d, J = 1.7 Hz, 1H, ArH), 7.17 (dd, J = 8.4, 1.8 Hz, 1H, ArH), 6.87 (d, J = 8.4 Hz, 1H, ArH), 6.53 (t, J = 55.1 Hz, 1H, CHF2), 5.89 (s, 1H, CH), 5.26 (s, 2H, CH2), 4.07 (s, 3H, CH3), 3.93 (s, 6H, 2CH3), 3.53 (s, 3H, CH3).

[0175] (Z / E)-2-((3-(DiFluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-(3,5- dimethoxyphenyl)ethan-l-one-O-methyloxime (1-18)

[0176]

[0177] White solid; yield 87%; m.p. 98-99 °C; 1 H NMR (400 MHz, CDC13) δ: 7.28 (d, J = 2.3 Hz, 3H, ArH), 6.53 (t, J = 55.1 Hz, 1H, CHF2), 5.87 (s, 1H, CH), 5.23 (s, 2H, CH2), 4.08 (s, 3H, CH3), 3.81 (d, J = 6.0 Hz, 6H, 2CH3), 3.54 (s, 3H, CH3).

[0178] (Z / E)-2-((3-(difluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-(3,4,5- trimethoxyphenyl)ethan-l-one-O-methyl oxime (1-19)

[0179]

[0180] Yellow liquid; yield 89%; 1 H NMR (400 MHz, CDC13) δ: 6.84 (s, 2H, ArH), 6.53 (t, J = 55.1 Hz, 1H, CHF2), 5.89 (s, 1H, CH), 5.27 (s, 2H, CH2), 4.08 (s, 3H, CH3), 3.88 (s, 9H, 3CH3), 3.53 (s, 3H, CH3).

[0181] (Z / E)-2-((3-(difluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-phenylethan-l-one-O- ethyloxime (1-20)

[0182]

[0183] White solid; yield 87%; m.p. 42-43 °C; 1 H NMR (400 MHz, CDC13) δ: 7.65 (d, J = 2.1 Hz, 1H, ArH), 7.64 (d, J = 3.8 Hz, 1H, ArH), 7.41 (d, J = 2.3 Hz, 2H, ArH), 7.40 (s, 1H, ArH), 6.53 (t, J = 55.1 Hz, 1H, CHF2), 5.90 (s, 1H, CH), 5.30 (s, 2H, CH2), 4.34 (q, J = 7.1 Hz, 2H, CH2), 3.49 (s, 3H, CH3), 1.38 (t, J = 7.1 Hz, 3H, CH3).

[0184] (Z / E)-2-((3-(difluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-phenylethan-l-one-O- ethyloxime (1-20)

[0185]

[0186] Yellow liquid; yield 89%; 1H NMR (400 MHz, CDC13) δ: 7.65 (d, J = 1.8 Hz, 1H, ArH), 7.63 (d, J = 4.3 Hz, 1H, ArH), 7.41 (d, J = 1.7 Hz, 2H, ArH), 7.40-7.38 (m, 1H, ArH), 6.52 (t, J = 55.1 Hz, 1H, CHF2), 6.14-6.02 (m, 1H, CH), 5.90 (s, 1H, CH), 5.42-5.31 (m, 4H, CH2+CH2), 4.78 (d, J = 5.9 Hz, 2H, CH2), 3.48 (s, 3H, CH3).

[0187] (Z / E)-2-((3-(difluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-phenylethan-l-one-O- isopropyl oxime (1-22)

[0188]

[0189] Dark yellow liquid; yield 81 %; 1 H NMR (400 MHz, CDC13) δ: 7.70-7.66 (m, 1H, ArH), 7.66-7.64 (m, 1H, ArH), 7.40 (d, J = 3.1 Hz, 2H, ArH), 7.39 (s, 1H, ArH), 6.52 (t, J = 55.2 Hz, 1H, CHF2), 5.92 (s, 1H, CH), 5.30 (s, 2H, CH2), 4.56 (dq, J = 12.5, 6.3 Hz, 1H, CH), 3.48 (s, 3H, CH3), 1.37 (d, J = 6.3 Hz, 6H, (CH3)2).

[0190] (Z / E)-2-((3-(difluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-phenylethan-l-one-O- isopropyl oxime (1-22)

[0191]

[0192] Yellow liquid; yield 81 %; 1H NMR (400 MHz, CDC13) δ: 7.65 (d, J = 2.3 Hz, 1H, ArH), 7.63 (d, J = 3.7 Hz, 1H, ArH), 7.41 (dd, J = 6.2, 2.2 Hz, 2H, ArH), 7.39 (d, J = 0.8 Hz, 1H, ArH), 6.52 (t, J = 55.1 Hz, 1H, CHF2), 5.89 (s, 1H, CH), 5.30 (s, 2H, CH2), 4.28 (t, J = 6.7 Hz, 2H, CH2), 3.49 (s, 3H, CH3), 1.76 (dd, J = 14.5, 7.3 Hz, 2H, CH2), 1.46 (dd, J = 15.1, 7.5 Hz, 2H, CH2), 0.99 (t, J = 7.4 Hz, 3H, CH3).

[0193] (Z / E)-2-((3-(Diifluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)-l-phenyl ethan-l-one-O- benzyl oxime (I-24)

[0194]

[0195] Yellow solid; yield 88%; m.p. 59-60 °C; 1 H NMR (400 MHz, CDC13) δ: 7.64 (d, J = 1.9 Hz, 1H, ArH), 7.64-7.61 (m, 1H, ArH), 7.47-7.43 (m, 3H, ArH), 7.42 (s, 1H, ArH), 7.41 (d, J = 1.8 Hz, 2H, ArH), 7.39 (t, J = 2.3 Hz, 2H, ArH), 6.50 (t, J = 55.1 Hz, 1H, CHF2), 5.83 (s, 1H, CH), 5.31 (d, J = 2.4 Hz, 4H, 2CH2), 3.46 (s, 3H, CH3).

[0196] (Z / E)-l-(2,4-Chlorophenyl)-2-((3-(difluoromethyl)-l-methyl-lH-pyrazol-5-yl)oxy)ethan-l- one-O-ethyl oxime (I-25)

[0197]

[0198] Yellow liquid; yield 86%; 1H NMR (400 MHz, CDC13) δ: 7.45 (d, J = 1.8 Hz, 1H, ArH), 7.29-7.20 (m, 2H, ArH), 6.50 (t, J = 55.1 Hz, 1H, CHF2), 5.80 (s, 1H, CH), 5.27 (s, 2H, CH2), 4.30 (q, J = 7.1 Hz, 2H, CH2), 3.35 (s, 3H, CH3), 1.37 (t, J = 7.1 Hz, 3H, CH3).

[0199] (Z / E)-1-(2,4-dichlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)ethan-1-one-O-allyl oxime (1-26)

[0200]

[0201] Yellow liquid; yield 90%; 1 H NMR (400 MHz, CDC13) δ: 7.45 (d, J = 1.8 Hz, 1H, ArH), 7.29-7.20 (m, 2H, ArH), 6.50 (t, J = 55.1 Hz, 1H, CHF2), 6.06 (ddd, J = 23.0, 11.0, 5.8 Hz, 1H, CH=C), 5.80 (s, 1H, CH), 5.43-5.24 (m, 4H, CH2+CH2), 4.75 (d, J = 5.8 Hz, 2H, CH2), 3.35 (s, 3H, CH3).

[0202] (Z / E)-1-(2,4-dichlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)ethan-1-one-O-allyl oxime (1-26)

[0203]

[0204] Dark yellow liquid; yield 84%; 1 H NMR (400 MHz, CDC13) δ: 7.45 (d, J = 1.8 Hz, 1H, ArH), 7.29-7.20 (m, 2H, ArH), 6.50 (t, J = 55.1 Hz, 1H, CHF2), 5.80 (s, 1H, CH), 5.27 (s, 2H, CH2), 4.52 (dq, J = 12.5, 6.2 Hz, 1H, CH), 3.36 (s, 3H, CH3), 1.35 (d, J = 6.3 Hz, 6H, (CH3)2).

[0205] (Z / E)-1-(2,4-chlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)ethan-1-one-O- benzyl oxime (1-29)

[0206]

[0207] dark yellow liquid; yield 87%; m.p. 48-49°C; 1 H NMR (400 MHz, CDC13) δ: 7.45 (d, J = 2.0 Hz, 1H, ArH), 7.30-7.20 (m, 2H, ArH), 6.51 (t, J = 55.1 Hz, 1H, CHF2), 5.80 (s, 1H, CH), 5.27 (s, 2H, CH2), 4.26 (t, J = 6.7 Hz, 2H, CH2), 3.36 (s, 3H, CH3), 1.75 (dt, J = 14.6, 6.8 Hz, 2H, CH2), 1.46 (dd, J = 15.0, 7.4 Hz, 2H, CH2), 1.00 (t, J = 7.4 Hz, 3H, CH3).

[0208] (Z / E)-1-(2,4-chlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)ethan-1-one-O- benzyl oxime (1-29)

[0209]

[0210] dark yellow solid; yield 90%; m.p. 59-60°C; 1 H NMR (400 MHz, CDC13) δ: 7.45 (d, J = 2.0 Hz, 1H, ArH), 7.44 (s, 2H, ArH), 7.43 (s, 2H, ArH), 7.39 (dd, J = 11.2, 5.7 Hz, 1H, ArH), 7.25 (dd, J = 8.2, 2.0 Hz, 1H, ArH), 7.15 (d, J = 8.2 Hz, 1H, ArH), 6.49 (t, J = 55.0 Hz, 1H, CHF2), 5.71 (s, 1H, CH), 5.29 (s, 2H, CH2), 5.28 (s, 2H, CH2), 3.34 (s, 3H, CH3).

[0211] (Z / E)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)-1-phenylethan-1-one-O-methyl oxime (1-30)

[0212]

[0213] white solid; yield 92%; m.p. 42-42°C;1 H NMR (400 MHz, CDC13) δ: 7.64 (d, J = 1.9 Hz, 1H, ArH), 7.64-7.61 (m, 1H, ArH), 7.42 (d, J = 1.8 Hz, 2H, ArH), 7.40 (d, J = 1.7 Hz, 1H, ArH), 5.91 (s, 1H, CH), 5.29 (s, 2H, CH2), 4.08 (s, 3H, CH3), 3.52 (s, 3H, CH3).

[0214] (Z / E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5- yl)oxy)ethan-1-one-O-allyl oxime (1-33)

[0215]

[0216] Yellow liquid; yield 88%; 1H NMR (400 MHz, CDC13) δ: 7.46 (d, J = 1.7 Hz, 1H, ArH), 7.28 (d, J = 5.2 Hz, 2H, ArH), 5.85 (s, 1H, CH), 5.28 (s, 2H, CH2), 4.36-4.25 (m, 2H, CH2), 3.40 (s, 3H, CH3), 1.37 (t, J = 7.1 Hz, CH3). 1 H NMR (400 MHz, CDC13) δ: 7.64 (d, J = 1.9 Hz, 1H, ArH), 7.64-7.61 (m, 1H, ArH), 7.42 (d, J = 1.8 Hz, 2H, ArH), 7.40 (d, J = 1.7 Hz, 1H, ArH), 5.91 (s, 1H, CH), 5.29 (s, 2H, CH2), 4.08 (s, 3H, CH3), 3.52 (s, 3H, CH3).

[0217] (Z / E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5- yl)oxy)ethan-1-one-O-allyl oxime (1-33)

[0218]

[0219] Yellow liquid; yield 88%; 1H NMR (400 MHz, CDC13) δ: 7.46 (d, J = 1.7 Hz, 1H, ArH), 7.28 (d, J = 5.2 Hz, 2H, ArH), 5.85 (s, 1H, CH), 5.28 (s, 2H, CH2), 4.36-4.25 (m, 2H, CH2), 3.40 (s, 3H, CH3), 1.37 (t, J = 7.1 Hz, CH3). 1 H NMR (400 MHz, CDC13) δ: 7.64 (d, J = 1.9 Hz, 1H, ArH), 7.64-7.61 (m, 1H, ArH), 7.42 (d, J = 1.8 Hz, 2H, ArH), 7.40 (d, J = 1.7 Hz, 1H, ArH), 5.91 (s, 1H, CH), 5.29 (s, 2H, CH2), 4.08 (s, 3H, CH3), 3.52 (s, 3H, CH3).

[0220] (Z / E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5- yl)oxy)ethan-1-one-O-allyl oxime (1-33)

[0221]

[0222] Yellow liquid; yield 88%; 1H NMR (400 MHz, CDC13) δ: 7.46 (d, J = 1.7 Hz, 1H, ArH), 7.28 (d, J = 5.2 Hz, 2H, ArH), 5.85 (s, 1H, CH), 5.28 (s, 2H, CH2), 4.36-4.25 (m, 2H, CH2), 3.40 (s, 3H, CH3), 1.37 (t, J = 7.1 Hz, CH3).1 H NMR (400MHz, CDCl3) δ: 7.46 (d, J=2.0Hz, 1H, ArH), 7.30-7.27 (m, 1H, ArH), 7.26 (d, J=2.0Hz, 1H, ArH), 6.12-5.97 (m, 1H, CH), 5.84 (s, 1H, CH), 5.35 (ddd, J=13.9, 11.7, 1.3Hz, 2H, CH2), 5.30 (s, 2H, CH2), 4.75 (d, J=5.9Hz, 2H, CH2), 3.39 (s, 3H, CH3), 2.06 (s, 4H).

[0223] (Z / E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-isopropyloxime (I-34)

[0224]

[0225] Yellow liquid; yield 87%; 1 H NMR (400MHz, CDCl3) δ: 7.46 (d, J=1.8Hz, 1H, ArH), 7.28 (d, J=6.0Hz, 1H, ArH), 7.26 (d, J=1.8Hz, 1H, ArH), 5.85 (s, 1H, CH), 5.27 (s, 2H, CH2), 4.52 (dt, J=12.5, 6.2Hz, 1H, CH), 3.40 (s, 3H, CH3), 1.36 (s, 3H, CH3), 1.34 (s, 3H, CH3).

[0226] (Z / E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one oxime (I-35)

[0227]

[0228] Pale yellow oil; yield 82%; 1H NMR (400 MHz, CDC13) δ 7.46 (d, J = 2.0 Hz, 1H, ArH), 7.28 (dd, J = 8.6, 1.6 Hz, 1H, ArH), 7.20 (d, J = 8.2 Hz, 1H, ArH), 5.84 (s, 1H, CH), 5.28 (s, 2H, CH2), 4.22 (t, J = 6.7 Hz, 2H, CH2), 3.40 (s, 3H, CH3), 1.84 - 1.73 (m, 2H, CH2), 1.02 (t, J = 7.4 Hz, 3H, CH3).

[0229] (Z)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O- propyl oxime (1-36)

[0230]

[0231] pale yellow oil; yield 68%; 1 H NMR (400 MHz, CDC13) δ 7.46 (d, J = 2.0 Hz, 1H, ArH), 7.28 (dd, J = 8.6, 1.6 Hz, 1H, ArH), 7.20 (d, J = 8.2 Hz, 1H, ArH), 5.84 (s, 1H, CH), 5.28 (s, 2H, CH2), 4.22 (t, J = 6.7 Hz, 2H, CH2), 3.40 (s, 3H, CH3), 1.84 - 1.73 (m, 2H, CH2), 1.02 (t, J = 7.4 Hz, 3H, CH3).

[0232] (Z)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O- propyl oxime (1-36)

[0233]

[0234] pale yellow oil; yield 65%; 1H NMR (400 MHz, CDC13) δ 7.44 (d, J = 2.0 Hz, 1H, ArH), 7.24 (d, J = 2.0 Hz, 1H, ArH), 7.18 (d, J = 8.2 Hz, 1H, ArH), 5.82 (s, 1H, CH), 5.25 (s, 2H, CH2), 4.24 (t, J = 6.7 Hz, 2H, CH2), 3.38 (s, 3H, CH3), 1.76-1.68 (m, 2H, CH2), 1.44 (q, J = 7.4 Hz, 4H, (CH2)2), 0.98 (t, J = 7.4 Hz, 3H, CH3).

[0235] (Z)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O- isobutyl oxime (1-38)

[0236]

[0237] pale yellow oil; yield 66%; 1 H NMR (400 MHz, CDC13) δ 7.44 (d, J = 2.0 Hz, 1H, ArH), 7.24 (d, J = 2.0 Hz, 1H, ArH), 7.18 (d, J = 8.2 Hz, 1H, ArH), 5.82 (s, 1H, CH), 5.25 (s, 2H, CH2), 4.24 (t, J = 6.7 Hz, 2H, CH2), 3.38 (s, 3H, CH3), 1.76-1.68 (m, 2H, CH2), 1.44 (q, J = 7.4 Hz, 4H, (CH2)2), 0.98 (t, J = 7.4 Hz, 3H, CH3).

[0238] (E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O- isobutyl oxime (1-39)

[0239]

[0240] pale yellow oil; yield 17%; 1 H NMR (400 MHz, CDC13) δ 7.48 (d, J = 1.8 Hz, 1H, ArH), 7.32-7.27 (m, 1H, ArH), 6.98 (d, J = 8.3 Hz, 1H, ArH), 5.92 (s, 1H, CH), 4.92 (s, 2H), 3.88 (d, J = 6.8 Hz, 2H, CH2), 3.57 (s, 3H, CH3), 1.94 (td, J = 13.5, 6.7 Hz, 1H, CH), 0.85 (d, J = 6.7 Hz, 6H, C(CH3)2).

[0241] (Z)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one 0-cyclohexylmethyl oxime (1-42)

[0242]

[0243] pale yellow oil; yield 67%; 1 H NMR (400 MHz, CDC13) δ 7.44 (d, J = 2.0 Hz, 1H, ArH), 7.28-7.23 (m, 1H, ArH), 7.17 (d, J = 8.2 Hz, 1H, ArH), 5.87 (s, 1H, CH), 5.30 (s, 2H, CH2), 4.06 (d, J = 7.2 Hz, 2H, CH2), 3.38 (s, 3H, CH3), 1.25-1.17 (m, 1H, CH), 0.68-0.52 (m, 2H, CH2), 0.39-0.27 (m, 2H, CH2).

[0244] (Z)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one 0-cyclohexylmethyl oxime (1-42)

[0245]

[0246] pale yellow oil; yield 67%; 1 H NMR (400 MHz, CDC13) δ 7.44 (d, J = 2.0 Hz, 1H, ArH), 7.28-7.23 (m, 1H, ArH), 7.17 (d, J = 8.2 Hz, 1H, ArH), 5.87 (s, 1H, CH), 5.30 (s, 2H, CH2), 4.06 (d, J = 7.2 Hz, 2H, CH2), 3.38 (s, 3H, CH3), 1.25-1.17 (m, 1H, CH), 0.68-0.52 (m, 2H, CH2), 0.39-0.27 (m, 2H, CH2).

[0247] (Z)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one 0-cyclohexylmethyl oxime (1-42)

[0248]

[0249] Pale yellow oil; yield 63%; 1 H NMR (400 MHz, CDC13) δ 7.44 (d, J = 1.9 Hz, 1H, ArH), 7.24 (d, J = 1.9 Hz, 1H, ArH), 7.18 (d, J = 8.2 Hz, 1H, ArH), 5.82 (s, 1H, CH), 5.25 (s, 2H, CH2), 4.05 (d, J = 6.3 Hz, 2H, CH2), 3.38 (s, 3H, CH3), 1.76 (td, J = 10.3, 6.2 Hz, 6H, (CH2)3), 1.32 - 1.18 (m, 5H, CH(CH2)2), 0.88 (t, J = 6.6 Hz, 1H, CH).

[0250] (E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-cyclohexylmethyl oxime (1-43)

[0251]

[0252] Pale yellow oil; yield 67%; 1 H NMR (400 MHz, CDC13) δ 7.44 - 7.34 (m, 6H, ArH), 7.23 (dd, J = 8.2, 2.0 Hz, 1H, ArH), 7.13 (d, J = 8.2 Hz, 1H, ArH), 5.72 (s, 1H, CH), 5.26 (d, J = 3.2 Hz, 4H, CH2), 3.34 (s, 3H, CH3).

[0253] (Z)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-benzyl oxime (1-44)

[0254]

[0255] Pale yellow oil; yield 67%; 1 H NMR (400 MHz, CDC13) δ 7.44 - 7.34 (m, 6H, ArH), 7.23 (dd, J = 8.2, 2.0 Hz, 1H, ArH), 7.13 (d, J = 8.2 Hz, 1H, ArH), 5.72 (s, 1H, CH), 5.26 (d, J = 3.2 Hz, 4H, CH2), 3.34 (s, 3H, CH3).

[0256] (E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O- benzyl oxime (1-45)

[0257]

[0258] pale yellow oil; yield 20%; 1 H NMR (400 MHz, CDC13) δ 7.47 (s, 1H, ArH), 7.35-7.25 (m, 6H, ArH), 6.96 (d, J = 8.2 Hz, 1H, ArH), 5.81 (s, 1H, CH), 5.14 (s, 2H, CH2), 4.90 (s, 2H, CH2), 3.54 (s, 3H, CH3).

[0259] (Z)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O- propargyl oxime (1-46)

[0260]

[0261] pale yellow oil; yield 72%; 1 H NMR (400 MHz, CDC13) δ 7.45 (d, J = 2.0 Hz, 1H, ArH), 7.26 (dd, J = 8.2, 2.0 Hz, 1H, ArH), 7.19 (d, J = 8.2 Hz, 1H, ArH), 5.86 (s, 1H, CH), 5.29 (s, 2H, CH2), 4.84 (d, J = 2.4 Hz, 2H, CH2), 3.37 (s, 3H, CH3), 2.56 (t, J = 2.4 Hz, 1H, CH).

[0262] (Z / E)-1-(2,4-dichlorophenyl)-2-((1,4-dimethyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O- methyl oxime (1-47)

[0263]

[0264] pale yellow oil; yield 90%; 1H NMR (400 MHz, CDC13) δz: 7.47 (d, J = 1.9 Hz, 1H, ArH), 7.33-7.29 (m, 1H, ArH), 7.28 (d, J = 7.8 Hz, 1H, ArH), 5.25 (s, 2H, CH2), 4.02 (s, 3H, NCH3), 3.43 (s, 3H, CH3), 2.05 (d, J = 0.6 Hz, 3H, CH3); E: 7.52 (d, J = 2.0 Hz, 1H, ArH), 7.35 (dd, J = 6.9, 1.8 Hz, 1H, ArH), 7.17 (d, J = 8.3 Hz, 1H, ArH), 4.94 (s, 2H, CH2), 3.94 (s, 3H, CH3), 3.51 (s, 3H, CH3), 2.02 (d, J = 0.6 Hz, 3H, CH3).

[0265] (Z / E)-1-(2,4-dichlorophenyl)-2-((1,4-dimethyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-ethyl oxime (I-48)

[0266]

[0267] White solid; yield 91%; m.p. 39-41 °C; 1 H NMR (400 MHz, CDC13) δz: 7.47 (d, J = 1.9 Hz, 1H, ArH), 7.33-7.29 (m, 1H, ArH), 7.28 (d, J = 7.8 Hz, 1H, ArH), 5.25 (s, 2H, CH2), 4.02 (s, 3H, NCH3), 3.43 (s, 3H, CH3), 2.05 (d, J = 0.6 Hz, 3H, CH3); E: 7.52 (d, J = 2.0 Hz, 1H, ArH), 7.35 (dd, J = 6.9, 1.8 Hz, 1H, ArH), 7.17 (d, J = 8.3 Hz, 1H, ArH), 4.94 (s, 2H, CH2), 3.94 (s, 3H, CH3), 3.51 (s, 3H, CH3), 2.02 (d, J = 0.6 Hz, 3H, CH3).

[0268] (Z / E)-1-(2,4-dichlorophenyl)-2-((1,4-dimethyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-propyl oxime (I-49)

[0269]

[0270] Yellow oil; yield 88%; 1H NMR (400 MHz, CDC13) δZ: 7.46 (d, J = 1.8 Hz, 1H, ArH), 7.32-7.29 (m, 1H, ArH), 7.28 (s, 1H, ArH), 5.27 (s, 2H, CH2), 4.17 (t, J = 6.7 Hz, 2H, CH2), 3.44 (s, 3H, CH3), 2.06 (d, J = 0.7 Hz, 3H, CH3), 1.74 (dt, J = 14.3, 7.2 Hz, 2H, CH2), 0.96 (t, J = 7.4 Hz, 3H, CH3); E: 7.49 (d, J = 2.0 Hz, 1H, ArH), 7.35-7.32 (m, 1H, ArH), 7.13 (d, J = 8.3 Hz, 1H, ArH), 5.27 (s, 2H, CH2), 4.93 (s, 2H, CH2), 4.07 (t, J = 6.7 Hz, 3H, CH3), 3.48 (s, 3H, CH3), 2.00 (d, J = 0.7 Hz, 3H, CH3), 1.64 (td, J = 14.3, 7.4 Hz, 2H, CH2), 0.87 (t, J = 7.4 Hz, 3H, CH3).

[0271] (Z / E)-1-(2,4-dichlorophenyl)-2-((1,4-dimethyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-sec-butyl oxime (1-50)

[0272]

[0273] pale yellow oil; yield 86%; 1H NMR (400 MHz, CDC13) δ 7.46 (d, J = 1.7 Hz, 1H, ArH), 7.29 (dd, J = 4.1, 2.3 Hz, 2H, ArH), 5.26 (s, 2H, OCH2), 4.27 (h, J = 6.3 Hz, 1H, CH), 3.44 (s, 3H, CH3), 2.06 (s, 3H, CH3), 1.80-1.52 (m, 3H, CH3), 1.27 (d, J = 6.3 Hz, 3H, CH3), 0.94 (t, J = 7.5 Hz, 3H, CH3); E: 7.48 (t, J = 2.3 Hz, 1H, ArH), 7.32 (t, J = 1.9 Hz, 1H, ArH), 7.10 (t, J = 7.6 Hz, 1H, ArH), 4.94 (s, 2H, CH2), 4.17 (dt, J = 12.6, 6.3 Hz, 1H, CH), 3.46 (d, J = 8.5 Hz, 3H, CH3), 2.01 (s, 3H, CH3), 1.54-1.36 (m, 2H, CH2), 1.18 (d, J = 6.3 Hz, 3H, CH3), 0.84 (t, J = 7.5 Hz, 3H, CH3).

[0274] (Z)-1-(2,4-dichlorophenyl)-2-((4-fluoro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-methyloxime (I-51)

[0275]

[0276] pale yellow oil; yield 71 %; 1 H NMR (400 MHz, CDC13) δ 7.45 (dd, J = 1.5, 0.6 Hz, 1H, CH), 7.29 (s, 1H, CH), 7.26 (s, 1H, CH), 5.46 (d, J = 1.3 Hz, 2H, CH2), 4.02 (s, 3H, CH3), 3.36 (s, 3H, CH3).

[0277] (E)-1-(2,4-dichlorophenyl)-2-((4-fluoro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-methyloxime (I-52)

[0278]

[0279] pale yellow oil; yield 21 %; 1H NMR (400 MHz, CDC13) δ 7.48 (d, J = 2.0 Hz, 1H, ArH), 7.32 (dd, J = 8.3, 2.0 Hz, 1H, ArH), 7.12 (d, J = 8.3 Hz, 1H, ArH), 5.11 (d, J = 1.0 Hz, 2H, CH2), 3.90 (s, 3H, CH3), 3.53 (s, 3H, CH3).

[0280] (Z)-1-(2,4-dichlorophenyl)-2-((4-fluoro-1-methyl-3-(trifluoromethyl)-1H- pyrazol-5-yl)oxy)ethan-1-one-O-ethyl oxime (1-53)

[0281]

[0282] pale yellow oil; yield 73%; 1 H NMR (400 MHz, CDC13) δ 7.46-7.44 (m, 1H, ArH), 7.28 (d, J = 1.5 Hz, 2H, ArH), 5.47 (d, J = 1.2 Hz, 2H, CH2), 4.27 (q, J = 7.1 Hz, 2H, CH2), 3.37 (s, 3H, CH3), 1.32 (t, J = 7.1 Hz, 3H, CH3).

[0283] (E)-1-(2,4-dichlorophenyl)-2-((4-fluoro-1-methyl-3-(trifluoromethyl)-1H- pyrazol-5-yl)oxy)ethan-1-one-O-ethyl oxime (1-54)

[0284]

[0285] pale yellow oil; yield 19%; 1 H NMR (500 MHz, CDC13) δ 7.48 (d, J = 1.9 Hz, 1H, ArH), 7.33-7.30 (m, 1H, ArH), 7.11 (d, J = 8.3 Hz, 1H, ArH), 5.12 (s, 2H, CH2), 4.15 (q, J = 7.1 Hz, 3H, CH3), 3.52 (s, 2H, CH2), 1.22 (dd, J = 7.3, 6.9 Hz, 3H, CH3).

[0286] (z)-1-(2,4-dichlorophenyl)-2-((4-fluoro-1-methyl-3-(trifluoromethyl)-1H- pyrazol-5-yl)oxy)ethan-1-one-O-propyl oxime (1-55)

[0287]

[0288] Pale yellow oil; yield 67%; 1 H NMR (400 MHz, CDC13) δ 7.45 (s, 1H, ArH), 7.28 (s, 2H, ArH), 5.48 (s, 2H, CH2), 4.17 (t, J = 6.7 Hz, 2H, CH2), 3.36 (s, 3H, CH3), 1.73 (dd, J = 14.3, 7.1 Hz, 2H, CH2), 0.97 (t, J = 7.4 Hz, 3H, CH3).

[0289] (E)-1-(2,4-dichlorophenyl)-2-((4-fluoro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O- isobutyl oxime (1-58)

[0290]

[0291] Pale yellow oil; yield 21%; 1 H NMR (400 MHz, CDC13) δ 7.48 (s, 1H, ArH), 7.34-7.29 (m, 1H, ArH), 7.10 (d, J = 8.2 Hz, 1H, ArH), 5.12 (s, 2H, CH2), 4.05 (t, J = 6.7 Hz, 2H, CH2), 3.52 (s, 3H, CH3), 1.62 (dd, J = 14.2, 7.0 Hz, 2H, CH2), 0.86 (t, J = 7.4 Hz, 3H, CH3).

[0292] (Z)-1-(2,4-dichlorophenyl)-2-((4-fluoro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O- isobutyl oxime (1-57)

[0293]

[0294] Pale yellow oil; yield 69%; 1 H NMR (400 MHz, CDC13) δ 7.46-7.43 (m, 1H, ArH), 7.29-7.26 (m, 2H, ArH), 5.48 (d, J = 1.2 Hz, 2H, CH2), 4.00 (d, J = 6.8 Hz, 2H, CH2), 3.36 (s, 3H, CH3), 2.09-1.98 (m, 1H, CH), 0.96 (d, J = 6.7 Hz, 6H, (CH3)2).

[0295] (E)-1-(2,4-dichlorophenyl)-2-((4-fluoro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O- isobutyl oxime (1-58)

[0296]

[0297] pale yellow oil; yield 22 %; 1 H NMR (400 MHz, CDC13) δ 7.50 (d, J = 2.0 Hz, 1 H, ArH), 7.33 (dd, J = 8.3, 2.0 Hz, 1 H, ArH), 7.12 (d, J = 8.3 Hz, 1 H, ArH), 5.14 (d, J = 1.0 Hz, 2 H, CH2), 3.89 (d, J = 6.8 Hz, 2 H, CH2), 3.55 (s, 3 H, CH3), 1.94 (dt, J = 13.5, 6.8 Hz, 1 H, CH), 0.86 (d, J = 6.7 Hz, 6 H, (CH3)2).

[0298] (Z / E) 1 -(3,5-dichlorophenyl)-2-((1 -methyl-3-(trifluoromethyl)-1 H-pyrazol-5-yl)oxy)ethan-1 -one-O- ethyloxime (1-59)

[0299]

[0300] white powder; yield 90 %; m.p. 85-87 °C; 1 H NMR (400 MHz, CDC13) δ Z: 7.55 (d, J = 1.4 Hz, 2 H, ArH), 7.39 (s, 1 H, ArH), 5.90 (s, 1 H, CH), 5.24 (s, 2 H, CH2), 4.34 (q, J = 7.1 Hz, 2 H, CH2), 3.59 (s, 3 H, CH3), 1.37 (t, J = 7.1 Hz, 3 H, CH3); E: 7.46 (d, J = 1.4 Hz, 2 H, ArH), 7.41 (s, 1 H, ArH), 5.95 (s, 1 H, CH), 4.92 (s, 2 H, CH2), 4.23 (dd, J = 14.1, 7.0 Hz, 2 H, CH2), 3.60 (s, 3 H, CH3), 1.30 (t, J = 7.1 Hz, 3 H, CH3).

[0301] (Z)-2-((1 -methyl-3-(trifluoromethyl)-1 H-pyrazol-5-yl)oxy)-1 -(2,3,4-trichlorophenyl)ethan-1 -one-O- ethyloxime (1-60)

[0302]

[0303] pale yellow oil; 72 %; 1H NMR (400 MHz, CDC13) δ 7.39 (d, J = 8.3 Hz, 1H, ArH), 7.10 (d, J = 8.3 Hz, 1H, ArH), 5.83 (s, 1H, CH), 5.25 (s, 2H, CH2), 4.29 (q, J = 7.1 Hz, CH2), 3.38 (s, 3H, CH3), 1.35 (t, J = 7.1 Hz, 3H, CH3).

[0304] (E)-2-((1 -Methyl-3-(trifluoromethyl)-1 H-pyrazol-5-yl)oxy)-1 -(2,3,4- trichlorophenyl)ethan-1 -one-O-ethyl oxime (1-61 )

[0305]

[0306] Colorless transparent crystals; yield 20%; m.p. 48-50 °C; 1 H NMR (400 MHz, CDC13) δ 7.42 (d, J = 8.3 Hz, 1H, ArH), 6.91 (d, J = 8.3 Hz, 1H, ArH), 5.92 (s, 1H, CH), 4.92 (s, 2H, CH2), 4.17 (q, J = 7.0 Hz, 2H, CH2), 3.57 (s, 3H, CH3), 1.23 (t, J = 7.0 Hz, 3H, CH3).

[0307] (Z)-1 -(2,4-Dichloro-5-fluorophenyl)-2-((1 -methyl-3-(trifluoromethyl)-1 H-pyrazol-5- yl)oxy)ethan-1 -one-O-ethyl oxime (1-62)

[0308]

[0309] Pale yellow oil; yield 72%; 1 H NMR (400 MHz, CDC13) δ 7.48 (d, J = 6.5 Hz, 1H, ArH), 7.13 (d, J = 8.7 Hz, 1H, ArH ), 5.84 (s, 1H, CH2), 5.24 (s, 2H, CH2), 4.30 (q, J = 7.1 Hz, 2H, CH2), 3.44 (s, 3H, CH3), 1.35 (t, J = 7.1 Hz, 3H, CH3).

[0310] (E)-1 -(2,4-Dichloro-5-fluorophenyl)-2-((1 -methyl-3-(trifluoromethyl)-1 H-pyrazol-5- yl)oxy)ethan-1 -one-O-ethyl oxime (1-63)

[0311]

[0312] pale yellow oil; yield 17%; 1 H NMR (400 MHz, CDC13) δ 7.52 (d, J = 6.5 Hz, 1H, ArH), 6.91 (d, J = 8.5 Hz, 1H, ArH), 5.91 (s, 1H, CH), 4.91 (s, 2H, CH2), 4.18 (q, J = 7.0 Hz, 2H, CH2), 3.60 (s, 3H, CH3), 1.24 (t, J = 7.1 Hz, 3H, CH3).

[0313] (Z)-1-(2,4-dichloro-5-fluorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H- pyrazol-5-yl)oxy)ethan-1-one-O-propargyl-hydroxylamine (1-64)

[0314]

[0315] pale yellow oil; yield 71%; 1 H NMR (400 MHz, CDC13) δ 7.49 (d, J = 6.5 Hz, 1H, ArH), 7.14 (d, J = 8.6 Hz, 1H, ArH), 5.86 (s, 1H, CH), 5.28 (s, 2H, CH2), 4.84 (d, J = 2.4 Hz, 2H, CH2), 3.43 (s, 3H, CH3), 2.57 (t, J = 2.4 Hz, 1H, CH).

[0316] (E)-1-(2,4-dichloro-5-fluorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H- pyrazol-5-yl)oxy)ethan-1-one-O-propargyl-hydroxylamine (1-65)

[0317]

[0318] pale yellow oil; yield 18%; 1 H NMR (400 MHz, CDC13) δ 7.53 (d, J = 6.5 Hz, 1H, ArH), 6.91 (d, J = 8.5 Hz, 1H, ArH), 5.99 (s, 1H, CH), 4.96 (s, 2H, CH2), 4.70 (d, J = 2.4 Hz, 2H, CH2), 3.60 (s, 3H, CH3), 2.50 (t, J = 2.4 Hz, 1H, CH).

[0319] (Z / E)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)-1-(3,4,5- trifluorophenyl)ethan-1-one-O-ethyl-hydroxylamine (1-66)

[0320]

[0321] White powder; yield 89%; mp 56-58℃; 1 H NMR (400MHz, CDCl3) δZ: 7.37-7.30 (m, 2H, ArH), 5.91 (s, 1H, CH), 5.23 (s, 2H, CH2), 4.34 (q, J=7.1Hz, 2H, CH2), 3.60 (s, 3H, CH3), 1.37 (t, J=7.1Hz , 3H, CH3); E: 7.37 (d, J=4.8Hz, 3H, ArH), 5.95 (s, 1H, CH), 4.93 (s, 2H, CH2), 4.28-4.22 (m, 2H, CH2), 3.61 (s, 3H, CH3), 1.32 (t, J=7.1Hz, 3H, CH3).

[0322] (Z / E)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)-1-(3-nitrophenyl)ethan-1-one-O-ethyl oxime (I-67)

[0323]

[0324] White solid; yield 86%; mp 74-76°C; 1 H NMR (400MHz, CDCl3) δZ: 8.58 (s, 1H, ArH), 8.26 (d, J=8.3Hz, 1H, ArH), 8.02 (d, J=7.8Hz, 1H, ArH), 7.58 (t, J= 8.1Hz, 1H, ArH), 5.93 (s, 1H, CH), 5.34 (s, 2H, CH2), 4.38 (q, J=7.1Hz, 2H, CH2), 3.57 (s, 3H, CH3), 1.39 (t, J=7 .1Hz, 3H, CH3); E: 8.53 (s, 1H, ArH), 8.29 (s, 1H, ArH), 7.92 (d, J=7.8Hz, 1H, ArH), 7.64 (d, J=8.0Hz, 1H, ArH) , 5.98 (s, 1H, CH), 5.02 (s, 2H, CH2), 4.26 (q, J=7.1Hz, 2H, CH2), 3.59 (s, 3H, CH3), 1.31 (t, J=7.0Hz, 3H, CH3).

[0325] (Z / E)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)-1-(3-nitrophenyl)ethan-1-one-O-propyl oxime (I-68)

[0326]

[0327] pale yellow solid; yield 84%; m.p. 53 °C; 1 H NMR (400 MHz, CDC13) δ Z: 8.57 (s, 1 H, ArH), 8.25 (d, J = 8.4 Hz, 1 H, ArH), 8.01 (d, J = 7.8 Hz, 1 H, ArH), 7.58 (t, J = 8.1 Hz, 1 H, ArH), 5.93 (s, 1 H, CH), 5.35 (s, 2 H, CH2), 4.28 (t, J = 6.7 Hz, 2 H, CH2), 3.57 (s, 3 H, CH3), 1.81 (dt, J = 14.3, 7.1 Hz, 2 H, CH2), 1.01 (t, J = 7.4 Hz, 3 H, CH3); E: 7.88 (s, 1 H, ArH), 7.76 (d, J = 7.7 Hz, 1 H, ArH), 7.70 (d, J = 16.4 Hz, 1 H, ArH), 7.57 (d, J = 7.7 Hz, 1 H, ArH), 5.96 (s, 1 H, CH), 4.99 (s, 2 H, CH2), 4.23 (q, J = 7.1 Hz, 2 H, CH2), 3.54 (s, 3 H, CH3), 1.29 (d, J = 7.7 Hz, 3 H, CH3).

[0328] (Z)-2-((1-Methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)-1-(3- (trifluoromethyl)phenyl)ethan-1-one-O-ethyl oxime (1-69)

[0329]

[0330] colorless transparent crystals; yield 72%; m.p. 62-64 °C; 1 H NMR (400 MHz, CDC13) δ 7.93 (s, 1 H, ArH), 7.83 (d, J = 7.9 Hz, 1 H, ArH), 7.65 (d, J = 7.5 Hz, 1 H, ArH), 7.51 (t, J = 7.9 Hz, 1 H, ArH), 5.92 (s, 1 H, CH), 5.32 (s, 2 H, CH2), 4.35 (q, J = 7.1 Hz, 2 H, CH2), 3.52 (s, 3 H, CH3), 1.38 (t, J = 7.1 Hz, 3 H, CH3).

[0331] (Z / E0-2-((1-Methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)-1-(3- (trifluoromethoxy)phenyl)ethan-1-one-O-ethyl oxime (1-70)

[0332]

[0333] White powder; yield 88%; m.p. 49-51 °C; Z: 1 H NMR (400 MHz, CDC13) δ Z: 7.59 (d, J = 7.8 Hz, 1 H, ArH), 7.53 (s, 1 H, ArH), 7.42 (t, J = 8.1 Hz, 1 H, ArH), 7.24 (s, 1 H, ArH), 5.91 (s, 1 H, CH), 5.28 (s, 2 H, CH2), 4.34 (q, J = 7.1 Hz, 2 H, CH2), 3.53 (s, 3 H, CH3), 1.37 (t, J = 7.1 Hz, 3 H, CH3). E: 7.60 (s, 1 H, ArH), 7.51 (s, 1 H, ArH), 7.47 (d, J = 8.2 Hz, 1 H, ArH), 7.28 (s, 1 H, ArH), 5.95 (s, 1 H, CH), 4.97 (s, 2 H, CH2), 4.23 (q, J = 7.1 Hz, 2 H, CH2), 3.54 (s, 3 H, CH3), 1.30 (t, J = 7.1 Hz, 3 H, CH3).

[0334] (Z / E)-1-([1,1'-biphenyl]-4-yl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O- ethyloxime (1-71)

[0335]

[0336] White powder; yield 85%; m.p. 66-68 °C; 1 H NMR (400 MHz, CDC13) δ Z: 7.72 (d, J = 8.3 Hz, 2 H, ArH), 7.61 (dd, J = 7.7, 4.1 Hz, 4 H, ArH), 7.46 (t, J = 7.5 Hz, 2 H, ArH), 7.38 (d, J = 7.3 Hz, 1 H, ArH), 5.95 (s, 1 H, CH), 5.31 (s, 2 H, CH2), 4.34 (q, J = 7.0 Hz, 2 H, CH2), 3.54 (s, 3 H, CH3), 1.37 (t, J = 7.1 Hz, 3 H, CH3); E: 7.69 (s, 2 H, ArH), 7.66 (s, 2 H, ArH), 7.48 (s, 3 H, ArH), 7.35 (s, 2 H, ArH), 5.98 (s, 1 H, CH), 5.01 (s, 2 H, CH2), 4.24 (q, J = 7.1 Hz, 2 H, CH2), 3.54 (s, 3 H, CH3), 1.33 (t, J = 7.1 Hz, 3 H, CH3).

[0337] (Z / E)-2-((1 -methyl-3-(trifluoromethyl)-1 H-pyrazol-5-yl)oxy)-1 -(4- phenoxyphenyl)ethan-1 -one-O-ethyl oxime (1-72)

[0338]

[0339] White solid; yield 91 %; m.p. 77-79 °C; 1 H NMR (400 MHz, CDC13) δ Z: 7.60 (d, J = 8.8 Hz, 2H, ArH), 7.35 (d, J = 7.6 Hz, 2H, ArH), 7.15 (t, J = 7.4 Hz, 1H, ArH), 7.01 (dd, J = 15.0, 8.3 Hz, 4H, ArH), 5.92 (s, 1H, CH), 5.27 (s, 2H, CH2), 4.30 (q, J = 7.1 Hz, 2H, CH2), 3.54 (s, 3H, CH3), 1.35 (t, J = 7.1 Hz, 3H, CH3); E: 7.66 (d, J = 8.9 Hz, 2H, ArH), 7.39 (d, J = 5.9 Hz, 2H, ArH), 7.18 (d, J = 7.7 Hz, 1H, ArH), 7.06 (d, J = 10.5 Hz, 4H, ArH), 5.96 (s, 1H, CH), 4.97 (s, 2H, CH2), 4.22 (q, J = 7.1 Hz, 2H, CH2), 3.55 (s, 3H, CH3), 1.31 (t, J = 7.1 Hz, 3H, CH3).

[0340] (Z)-1-(2-chloro-4-(4-chlorophenoxy)phenyl)-2-((1-methyl-3-(trifluoromethyl)-1H- pyrazol-5-yl)oxy)ethan-1-one-O-ethyl oxime (1-73)

[0341]

[0342] White solid; yield 70 %; m.p. 66-68 °C; 1 H NMR (400 MHz, CDC13) δ 7.34 (d, J = 8.8 Hz, 2H, ArH), 7.19 (d, J = 8.5 Hz, 1H, ArH), 7.02 (d, J = 2.0 Hz, 1H, ArH), 6.95 (d, J = 8.8 Hz, 2H, ArH), 6.85 (dd, J = 8.5, 1.5 Hz, 1H, ArH), 5.82 (s, 1H, CH), 5.26 (s, 2H, CH2), 4.29 (q, J = 7.1 Hz, 2H, CH2), 3.41 (s, 3H, CH3), 1.35 (t, J = 7.1 Hz, 3H, CH3).

[0343] (E)-1-(2-chloro-4-(4-chlorophenoxy)phenyl)-2-((1-methyl-3-(trifluoromethyl)-1H- pyrazol-5-yl)oxy)ethanone-O-ethyl oxime (I-74)

[0344]

[0345] White oil; yield 21 %; 1 H NMR (400 MHz, CDC13) δ 7.34 (d, J = 8.8 Hz, 2H, ArH), 7.04-6.98 (m, 4H, ArH), 6.89 (dd, J = 8.5, 1.6 Hz, 1H, ArH), 5.90 (s, 1H, CH), 4.93 (s, 2H, CH2), 4.18 (q, J = 7.0 Hz, 2H, CH2), 3.58 (s, 3H, CH3), 1.25 (t, J = 7.0 Hz, 3H, CH3).

[0346] Example 3: Inhibitory activity of oxime ether derivatives containing pyrazole groups (I-1 ~ I-74) against plant pathogenic fungi

[0347] The inhibitory activity of oxime ether derivatives containing pyrazole groups (I-1 ~ I-19) against Rhizoctonia solani, Fusarium graminearum and Botrytis cinerea was determined by mycelial growth rate method. The method was as follows: a certain amount of compound was dissolved in a certain volume of DMSO to obtain a mother liquor of a certain concentration. A certain volume of the mother liquor was added to 45 mL of sterilized potato agar medium, shaken to obtain a medium containing 10 μg / mL of the agent. The above medium was uniformly poured into 3 culture dishes with a diameter of 9 cm, and after solidification, a 5 mm diameter fungus cake was transferred to the center of the medium. The above culture dishes were incubated at 25°C, and when the colony of the blank control (containing the same amount of DMSO) directly grew to 7.0 cm in diameter, the diameter of the colony was measured by cross method, and the average inhibition rate of each agent was calculated. Fluazinam, boscalid, penthiopyrad and hymexazol were used as control agents. The calculation formula of the inhibition rate of each compound against each fungus was as follows:

[0348] Inhibition rate (%) = (blank control colony diameter - test agent colony diameter) ÷ (blank control colony diameter - 5 mm) x 100%

[0349] The results of the determination of the inhibitory activity of compounds I-1 ~ I-19 are shown in Table 1.

[0350] Inhibitory activity (%) of compounds I-1 to I-19 (50 μg / mL) against three plant pathogenic fungi

[0351]

[0352] As can be seen from Table 1, at a concentration of 50 μg / mL, the oxime ether derivatives containing a pyrazole group (I-1 to I-19) all have obvious inhibitory activity against Rhizoctonia solani, Fusarium graminearum and Botrytis cinerea, among which the inhibition rate against Rhizoctonia solani is between 28.0% and 76.8%, and 11 target compounds have an inhibition rate of more than 60% against Rhizoctonia solani; the inhibition rate against Fusarium graminearum is between 15.2% and 64.9%, and more than half of the compounds have an inhibition rate higher than 44.7% of the control drug fluazinam; the inhibition rate against Botrytis cinerea is between 14.0% and 84.7%.

[0353] The same method as that for compounds I-1 to I-19 was used to determine the inhibitory activity of oxime ether derivatives containing a pyrazole group (I-20 to I-34) against Rhizoctonia solani, Fusarium graminearum and Botrytis cinerea at 50 μg / mL, and the determination results are shown in Table 2.

[0354] Inhibitory activity (%) of compounds I-20 to I-34 (50 μg / mL) against three plant pathogenic fungi

[0355]

[0356] As can be seen from Table 2, at a concentration of 50 μg / mL, the oxime ether derivatives containing a pyrazole group (I-20 to I-34) also have obvious inhibitory activity against Rhizoctonia solani, Fusarium graminearum and Botrytis cinerea, among which the inhibition rate against Rhizoctonia solani is between 10.6% and 65.3%; the inhibition rate against Fusarium graminearum is between 14.9% and 66.2%, and 7 compounds have an inhibition rate higher than 44.4% of the control drug fluazinam; the inhibition rate against Botrytis cinerea is between 11.1% and 97.1%, and 7 compounds have an inhibition rate of more than 90% against Botrytis cinerea, which is higher than 85.1% of the control drug fluazinam.

[0357] The inhibitory activities of oxime ether derivatives containing pyrazole group (I-35 to I-74) against Rhizoctonia solani, Fusarium graminearum and Botrytis cinerea at 50 μg / mL were determined by the same method as that of compounds I-1 to I-19, and with aviglycine and boscalid as control agents, and the results are shown in Table 3.

[0358] Table 3 Inhibitory activities of compounds I-20 to I-34 (50 μg / mL) against three plant pathogenic fungi (%)

[0359]

[0360]

[0361] As shown in Table 3, oxime ether derivatives containing pyrazole group (I-35 to I-74) also showed obvious inhibitory activities against Rhizoctonia solani, Fusarium graminearum and Botrytis cinerea at 50 μg / mL, wherein the inhibition rate against Rhizoctonia solani was between 0.00% and 82.3%, and the inhibition rate of compound I-62 was 65.3%, which was higher than that of aviglycine (78.2%); the inhibition rate against Fusarium graminearum was between 3.3% and 75.9%, and the inhibition rate of 5 compounds was higher than that of aviglycine (32.4%) and boscalid (40.4%); the inhibition rate against Botrytis cinerea was between 1.3% and 100.0%, and the inhibition rate of 13 compounds was more than 85%, which was higher than that of aviglycine (85.0%), and the inhibition rate of 7 compounds was more than that of boscalid (92.0%).

[0362] Example Four: Fungicide containing (Z)-1-(2,4-dichloro-5-fluorophenyl)-2-((1-methyl-3- (trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-ethyl oxime (I-62) and its emulsifiable concentrate formulation

[0363] A fungicide containing compound I-62, i.e., 20% I-62 emulsifiable concentrate, was prepared, and the composition thereof comprises effective component I-62 and adjuvant, the content of effective component I-62 is 20%, and the adjuvant comprises 10% 0204 emulsifier and 70% xylene, and all the above are weight ratios.

[0364] Example Five: Fungicide containing (Z)-1-(2,4-dichloro-5-fluorophenyl)-2-((1-methyl-3- (trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-ethyl oxime (I-62) and its aqueous emulsion formulation

[0365] A bactericide containing compound I-62, i.e. 20% I-62 emulsion in water, is prepared, which comprises active ingredient I-62 and adjuvants, the content of active ingredient I-62 is 15%, and the adjuvants comprise 8% of agricultural emulsifier 602, 4% of ethylene glycol, 0.1% of defoaming agent and 72.9% of water, all by weight.

[0366] The above is only a preferred embodiment of the present application, and does not limit the present application in any form. Any simple modification, equivalent change and modification of the above embodiment without departing from the technical solution content of the present application, according to the technical essence of the present application, all belong to the scope of the technical solution of the present application.

Claims

1. An oxime ether derivative containing a pyrazole group having a structure represented by formula (I), in, R 1 Selected from difluoromethyl, trifluoromethyl; R 2 is selected from H, F, and methyl; R 3 is selected from 1 to 3 of the following groups: H, F, Cl, methyl, trifluoromethyl, methoxy, phenyl, phenoxy, trifluoromethoxy, and nitro; R4 is selected from H, methyl, ethyl, isopropyl, n-butyl, isobutyl, sec-butyl, cyclopropylmethyl, allyl, and propargyl; the configuration of the oxime ether structure is selected from (Z)-formula, (E)-formula, and (Z / E)-formula.

2. The oxime ether derivative containing a pyrazole group according to claim 1, characterized in that it is one of the following compounds: (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-phenylethan-1-one-O-methyloxime (I-1), (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-(2-fluorophenyl)ethan-1-one-O-methyloxime (I-2), (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-(3-fluorophenyl)ethan-1-one-O-methyloxime (I-3), (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-(4-fluorophenyl)ethan-1-one-O-methyloxime (I-4), (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-(2,4-difluorophenyl)ethan-1-one-O-methyloxime (I-5), (Z / E)-1-(2-chlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)ethan-1-one-O-methyloxime (I-6), (Z / E)-1-(3-chlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)ethan-1-one-O-methyloxime (I-7), (Z / E)-1-(4-chlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)ethan-1-one-O-methyloxime (I-8), (Z / E)-1-(2,4-chlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)ethan-1-one-O-methyloxime (I-9), (Z / E)-1-(3,4-chlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)ethan-1-one-O-methyloxime (I-10), (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-(m-tolyl)ethan-1-one-O-methyloxime (I-11), (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-(p-tolyl)ethan-1-one-O-methyloxime (I-12), (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-(4-(trifluoromethyl)phenyl)ethan-1-one-O-methyloxime (I-13), (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-(2-methoxyphenyl)ethan-1-one-O-methyloxime (I-14), (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-(3-methoxyphenyl)ethan-1-one-O-methyloxime (I-15), (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-(4-methoxyphenyl)ethan-1-one-O-methyloxime (I-16), (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-(3,4-dimethoxyphenyl)ethan-1-one-O-methyloxime (I-17), (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-(3,5-dimethoxyphenyl)ethan-1-one-O-methyloxime (I-18), (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-(3,4,5-trimethoxyphenyl)ethan-1-one-O-methyloxime (I-19), (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-phenylethan-1-one-O-ethyl oxime (I-20), (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-phenylethan-1-one-O-allyl oxime (I-21), (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-phenylethan-1-one-O-isopropyloxime (I-22), (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-phenylethan-1-one-O-butyl oxime (I-23), (Z / E)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)-1-phenylethan-1-one-O-benzyl oxime (I-24), (Z / E)-1-(2,4-chlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)ethan-1-one-O-ethyl oxime (1-25), (Z / E)-1-(2,4-chlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)ethan-1-one-O-allyl oxime (I-26), (Z / E)-1-(2,4-chlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)ethan-1-one-O-isopropyl oxime (I-27), (Z / E)-1-(2,4-chlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)ethan-1-one-O-butyl oxime (1-28), (Z / E)-1-(2,4-chlorophenyl)-2-((3-(difluoromethyl)-1-methyl-1H-pyrazol-5-yl)oxy)ethan-1-one-O-benzyl oxime (1-29), (Z / E)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)-1-phenylethan-1-one-O-methyloxime (I-30), (Z / E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-methyloxime (I-31), (Z / E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-ethyl oxime (I-32), (Z / E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-allyl oxime (1-33), (Z / E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-isopropyloxime (I-34), (Z / E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one oxime (I-35), (Z)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-propyl oxime (I-36), (Z)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one O-butyl oxime (I-37), (Z)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-isobutyl oxime (I-38), (E)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-isobutyl oxime (I-39), (Z)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-cyclopropylmethyloxime (I-40), (Z)-1-(2,4-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-propyn-1-yl oxime (I-46), (Z / E)-1-(2,4-dichlorophenyl)-2-((1,4-dimethyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-methyloxime (I-47), (Z / E)-1-(2,4-dichlorophenyl)-2-((1,4-dimethyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-ethyl oxime (I-48), (Z / E)-1-(2,4-dichlorophenyl)-2-((1,4-dimethyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-propyl oxime (I-49), (Z / E)-1-(2,4-dichlorophenyl)-2-((1,4-dimethyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-sec-butyl oxime (I-50), (Z)-1-(2,4-dichlorophenyl)-2-((4-fluoro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-methyloxime (I-51), (E)-1-(2,4-dichlorophenyl)-2-((4-fluoro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-methyloxime (I-52), (Z)-1-(2,4-dichlorophenyl)-2-((4-fluoro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-ethyl oxime (I-53), (E)-1-(2,4-dichlorophenyl)-2-((4-fluoro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-ethyl oxime (I-54), (Z)-1-(2,4-dichlorophenyl)-2-((4-fluoro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-isobutyloxime (I-57), (E)-1-(2,4-dichlorophenyl)-2-((4-fluoro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-isobutyloxime (I-58), (Z / E)1-(3,5-dichlorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-ethyl oxime (I-59), (Z)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)-1-(2,3,4-trichlorophenyl)ethan-1-one-O-ethyl oxime (I-60), (E)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)-1-(2,3,4-trichlorophenyl)ethan-1-one-O-ethyl oxime (I-61), (Z)-1-(2,4-dichloro-5-fluorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-ethyl oxime (I-62), (E)-1-(2,4-dichloro-5-fluorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-ethyl oxime (I-63), (Z)-1-(2,4-dichloro-5-fluorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-propyn-1-yl oxime (I-64), (E)-1-(2,4-dichloro-5-fluorophenyl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-propyn-1-yl oxime (1-65), (Z / E)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)-1-(3,4,5-trifluorophenyl)ethan-1-one-O-ethyl oxime (I-66), (Z / E)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)-1-(3-nitrophenyl)ethan-1-one-O-ethyl oxime (I-67), (Z / E)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)-1-(3-nitrophenyl)ethan-1-one-O-propyl oxime (I-68), (Z)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)-1-(3-(trifluoromethyl)phenyl)ethan-1-one-O-ethyl oxime (I-69), (Z / E)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)-1-(3-(trifluoromethoxy)phenyl)ethan-1-one-O-ethyl oxime (I-70), (Z / E)-1-([1,1′-biphenyl]-4-yl)-2-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)ethan-1-one-O-ethyl oxime (I-71), (Z / E)-2-((1-Methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)oxy)-1-(4-phenoxyphenyl)ethan-1-one-O-ethyl oxime (1-72).

3. A method for preparing an oxime ether derivative containing a pyrazole group according to any one of claims 1 to 2, characterized in that Prepared by the method represented by general formula (A), first, in the presence of K2CO3 and acetonitrile as solvent, pyrazolol (II) and halogenated acetophenone (III) react to synthesize 2-pyrazoloxy-1-phenylethan-1-one (IV), then in the presence of K2CO3 and ethanol as solvent, 2-pyrazoloxy-1-phenylethan-1-one (IV) reacts with R4ONH2-HCl to generate an oxime ether derivative containing a pyrazole group (I): Among the above structural formulas: R 1 、R 2 、R 3 , R4, and the configuration of the oxime ether structure all have the meanings as defined in any one of claims 1 to 2; X is selected from Cl and Br.

4. Use of an oxime ether derivative containing a pyrazole group according to any one of claims 1 to 2 in preventing and controlling plant diseases caused by Rhizoctonia solani, Gibberella zeae, and Botrytis cinerea.

5. Use of an oxime ether derivative containing a pyrazole group according to any one of claims 1 to 2 as an agricultural fungicide.

6. A fungicide, characterized in that The fungicide consists of active ingredients and auxiliary materials, wherein the active ingredients include at least one of the oxime ether derivatives containing a pyrazole group according to any one of claims 1 to 2.

7. The bactericide according to claim 6, characterized in that The dosage form is selected from at least one of emulsifiable concentrate, suspension, aqueous solution, aqueous emulsion, microemulsion, wettable powder, granule, oil, smoke agent and bait.

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