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CN1004272B - Pyrazoline insecticides - Google Patents

Pyrazoline insecticides Download PDF

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Publication number
CN1004272B
CN1004272B CN85107882.6A CN85107882A CN1004272B CN 1004272 B CN1004272 B CN 1004272B CN 85107882 A CN85107882 A CN 85107882A CN 1004272 B CN1004272 B CN 1004272B
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Prior art keywords
carboxamide
pyrazoline
hydrogen
halogen
lower alkyl
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CN85107882A (en
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安吉利娜·乔伊·杜根
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FMC Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/06—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

本发明涉及含有化学式的吡唑啉杀虫剂以及用来防治虫害的吡唑啉的使用方法，生产这类吡唑啉杀虫剂的工艺过程和中间体。这类吡唑啉杀虫剂对于防治危害庄稼的各种害虫效果尤为显著。The present invention relates to the chemical formula Pyrazoline insecticides and the use of pyrazolines for controlling pests, processes and intermediates for producing such pyrazoline insecticides. This type of pyrazoline insecticide is particularly effective in controlling various pests that endanger crops.

Description

Pyrazoline insecticide
The present invention relates to the field of compositions of chemicals having biological effects, and more particularly to novel pyrazoline pesticides, processes and intermediates for preparing such pesticides, pyrazoline-containing pesticide mixtures, and methods of using pyrazolines for controlling insect pests.
Pyrazolines are heterocyclic compounds having five atoms in the ring and have the following chemical formula and ring atom position numbering scheme:
Certain derivatives of 1-carbamoyl pyrazoline are known in the art of pesticides and are useful as pesticides. For example, U.S. patent 4,174,393 discloses insecticidal activity of 1-carbamoyl pyrazolines which may also have phenyl substituents in positions 3 and 4 of the pyrazoline ring.
The present invention provides pyrazolines having the structural formula, they exhibit said insecticidal activity, the structural formula:
Figure 85107882_IMG25
Wherein R A has the chemical formula R A' is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, lower alkynyloxy and lower haloalkyl, orWherein X is of the formula
Figure 85107882_IMG28
O-(CR′BAR′BB)a-Oa′
Figure 85107882_IMG29
Wherein a is 1 to 3, a ' is 0 or 1, a+a ' is at least 2 but not more than 3, R ' AA and R ' AB are selected from the group consisting of hydrogen, halogen and lower alkyl, R ' AC is selected from the group consisting of hydrogen, halogen lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl, and R B is of the formula
Wherein R B' is selected from hydrogen, halogen, lower alkyl, lower alkoxy and lower haloalkyl, or
Wherein Y is of the formula
Figure 85107882_IMG32
O-(CR′BAR′BB）b-Ob′Wherein b is 1 to 3, b 'is 0 or 1, b+b' is at least 2 but not more than 3, R 'BA and R' BB are optionally selected from hydrogen, halogen and lower alkyl,
Figure 85107882_IMG34
R' BC is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl;
R C has the chemical formula
Figure 85107882_IMG35
Wherein R D is selected from hydrogen and lower alkyl and R E is selected from hydrogen, lower alkyl, lower alkoxy, lower haloalkoxy, lower haloalkyl, cyano, nitro, -NR FRG (where R F and R G are optionally lower alkyl) and-SO nRH (where R H is lower alkyl and n is 0-3), orWherein Z is of the formula
Figure 85107882_IMG37
O-(CR′CAR′CB)c-Oc′Where c is 1 to 3, c 'is 0 or 1, c+c' is at least 2 but not more than 3, R 'CA and R' CB are optionally selected from hydrogen, halogen and lower alkyl, in certain compounds, when c is 1 and c 'is 1, both R' CA and R 'CB cannot be hydrogen and R' CC is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl;
R N is hydrogen or lower alkyl, and V and W are optionally oxygen or sulfur.
The terms "halo" or "halogen" when used herein refer to fluorine, chlorine or bromine. The term "lower" modifying "alkyl", "alkoxy", "alkynyloxy" and its homologs refers to a straight or side chain hydrocarbon chain of 1 to 6, but preferably 1 to 4 carbon atoms, and the term "halo" attached to another term refers to one or more hydrogen atoms that have been replaced with a halogen.
Among the pyrazolines mentioned above, those in which W is oxygen are relatively suitable for a wide variety of applications, especially when R 'A is a 4-substituent, preferably selected from the group consisting of halogen, e.g., nitrogen or fluorine, or lower haloalkoxy, e.g., difluoromethoxy, those in which R B is a 4-substituent are generally more reactive than the corresponding 5-substituted pyrazolines, and those in which R B is phenyl having the substituent R' B are particularly attractive. From this point of view, it is then desirable that R' B is a 4-substituent, especially halogen, such as chlorine or fluorine.
In terms of R c, the most attractive pesticides are generally derived from certain specific compounds containing 2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl, 2, 3-dihydro-2, 3-tetrafluorobenzofuran-6-yl, 2-difluoro-1, 3-benzodioxol-5-yl, or 2, 2-dimethyl-1, 3-benzodioxol-5-yl groups, or 4-phenoxyphenyl groups. In this latter case, it is most desirable that R D is hydrogen and R is a 4-substituent, especially lower haloalkoxy.
Pyrazolines of the invention having a remarkable insecticidal activity include, for example, 3- (4-difluoromethoxyphenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -4-phenylpyrazolin-1-carboxamide (Carboxamide), 3, 4-bis (4-fluorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazolin-1-carboxamide, N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) -3- (4-difluoromethoxyphenyl) -4-phenylpyrazolin-1-carboxamide, N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) -N-methyl-4-phenylpyrazolin-1-carboxamide, 3, 4-bis (4-chlorophenyl) -N- (2, 2-dimethyl-1, 3-benzodioxol-1-carboxamide, N- (2-difluoro-2, 3-tetrafluorobenzofuran-5-yl) -3- (4-difluoro-1-carboxamide, 2, 3-benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) -N-methyl-4-phenylpyrazolin-1-carboxamide. 3- (4-chlorophenyl) -N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide, 3- (4-difluoromethoxyphenyl) -N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) -N-methyl-4-phenylpyrazolin-1-carboxamide, 3- (4-chlorophenyl) -N- [ 4- (4-difluoromethoxyphenoxy) phenyl ] -4-phenylpyrazolin-1-carboxamide, N- [ 4- (4-difluoromethoxyphenoxy) phenyl ] -3- (4-difluoromethoxyphenyl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide, 3- (4-difluoromethoxyphenyl) -4- (4-fluorophenyl) -N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) pyrazoline-1-carboxamide, 3- (4-difluoromethoxyphenyl) -4- (4-difluoromethoxyphenyl) -N- (2, 3-tetrafluorophenyl) -N- (2, 3-difluoromethoxyphenyl) -N- (2, 3-tetrafluorobenzofuran-5-yl) carboxamide, 3- (4-difluoromethoxyphenyl) -1-carboxamide, 4- (4-chlorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -3-phenylpyrazolin-1-carboxamide, 3- (4-chlorophenyl) -4- (4-fluorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazolin-1-carboxamide, 3- (4-difluoromethoxyphenyl) -4- (4-fluorophenyl) -N- (2, 3-dihydro-2-dimethylbenzofuran-5-yl) pyrazolin-1-carboxamide and 4- (4-chlorophenyl) -3- (4-difluoromethoxyphenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazolin-1-carboxamide.
Likewise, within the intended scope of the invention are pesticidal mixtures which contain an amount (which achieves a pesticidal effect) of at least one of the pyrazolines described above, in turn admixed with an agriculturally acceptable carrier. The invention also includes a method of controlling insect pests comprising applying an amount (to achieve an insecticidal effect) of at least one pyrazoline as described above to a locus where insect pest control is desired.
The pyrazolines of the invention can be manufactured by a process in which the appropriate aromatic isocyanate or isothiocyanate is coupled to the pyrazoline which has been suitably substituted, in other words, a process within the scope of the invention is as follows:
The product can be alkylated by well known methods to produce the corresponding N-alkylated pyrazolines.
The pyrazoline starting materials which are appropriately substituted are generally known substances. The requisite isocyanates and isothiocyanates can be prepared from the corresponding amines. A certain amount of amines are commercially available. Other amines of interest can also be prepared by the methods described in the examples below.
Example 1
3- (4-Chlorophenyl) -N- [ 4- (4-chlorophenoxy) phenyl ] -4-phenylpyrazoline-1-carboxamide
A stirred mixture of 10.9 g (0.077 g) of 4-fluoronitrobenzene, 9.95 g (0.077 g) of 4-chlorophenol and 11.8 g (0.085 g) of potassium carbonate in 175 ml of dimethyl sulfoxide was heated at a temperature of 70℃for two days under a dry nitrogen atmosphere. The reaction mixture was then cooled and filtered. The filtrate was diluted with water until the diluted volume was 1 liter. The mixture was then extracted with three more 200 ml portions of diethyl ether. The mixed ether extract is washed with water and then with an aqueous saturated sodium chloride solution. The washed extract was dried over anhydrous sodium sulfate and filtered. Finally, the filtrate was evaporated under reduced pressure to obtain 13.5 g of 4- (4-chlorophenoxy) nitrobenzene (melting point 67 to 70 ℃).
Hydrogenation of 13.5 g (0.054 molar) of 4- (4-chlorophenoxy) nitrobenzene with a catalytic amount (0.15 molar) of platinum oxide in 250 ml of tetrahydrofuran produced a quantitative yield of 4- (4-chlorophenoxy) aniline.
0.43 Ml (0.0036 mol) of a solution of trichloromethyl chloroformate (in 20 ml of toluene) was added dropwise to a stirred solution of 0.75 g (0.0034 mol) of 4- (4-chlorophenoxy) aniline (in 25 ml of toluene). After complete addition, the mixture was heated at a temperature of 85 ℃ for three hours. The mixture was then cooled to room temperature and the solvent evaporated under reduced pressure leaving a residue. The residue was then dissolved in 25 ml of diethyl ether. The solution was also added drop by drop to a stirred slurry of 1.0g (0.0034 g molecules) of 3- (4-chlorophenyl) -4-phenylpyrazoline in diethyl ether. Three drops of triethylamine were added and the mixture was stirred at room temperature for two days. After evaporation of the solvent from the mixture, 0.92 g of 3- (4-chlorophenyl) -N- [ 4- (4-chlorophenoxy) phenyl ] -4-phenylpyrazoline-1-carboxamide (melting point 158 to 161 ℃ C.) is obtained
Analysis:
calculated C66.92; H4.22
Found C66.06; H4.95
Nuclear magnetic resonance (nmr): 8.06PPm (CDCl 3)
Example 2
3- (4-Chlorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -4-phenylpyrazolin-1-carboxamide
An ice-cold mixture of 43 ml of concentrated nitric acid and 50 ml of concentrated sulfuric acid was added drop-by-drop to 100.0 g (0.67 g molecules) of 2, 3-dihydro-2, 2-dimethylbenzofuran over a period of one hour to maintain the temperature at 5 ℃. After complete addition, the mixture was stirred at 0 ℃ for 2.5 hours. The reaction mixture was then poured into ice water and the whole was extracted with diethyl ether. The extract was dried over anhydrous magnesium chloride and filtered. A black oil was obtained by evaporating the filtrate under reduced pressure. This black oil was purified by column chromatography on silica gel and eluted with toluene and n-hexane in a 9:1 ratio to give 50.0 g of 2, 3-dihydro-2, 2-dimethyl-5-nitrobenzofuran, which was already solid.
20.0 G (0.1 g moles) of 2, 3-dihydro-2, 2-dimethyl-5-nitrobenzofuran were hydrogenated with a catalytic amount (0.2 g) of platinum oxide in 250 ml of methanol, thus obtaining 16.6 g of 5-amino-2, 3-dihydro-2, 2-dimethylbenzofuran.
0.43 Ml (0.0036 mol) of trichloromethyl chloroformate (in 20 ml of toluene) was added dropwise to a stirred solution of 0.56 g (0.0034 mol) of 5-amino-2, 3-dihydro-2, 2-dimethylbenzofuran (in 20 ml of toluene). The mixture was heated at reflux for three hours after complete addition. The mixture was then cooled to room temperature and the solvent evaporated under reduced pressure, leaving a residue. The residue was dissolved in 25 ml of dry diethyl ether and the solution was added drop by drop to a stirred mixture of 1.0g (0.034 g molecules) of 3- (4-chlorophenyl) -4-phenyl-pyrazoline and three drops of triethylamine (in 25 ml of diethyl ether). The reaction mixture was stirred at room temperature for about 18 hours, at which time the solids were filtered from the mixture. The cake was slurried in ethanol and recovered by filtration to give 0.47 g of 3- (4-chlorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -4-phenylpyrazolin-1-carboxamide (melting point 160-162 ℃ C.).
Analysis:
Calculated C70.00; H5.43
Found C69.50; H3.36
Nuclear magnetic resonance (nmr) 9.00ppm (DMSo-d 6)
Other products in the series produced using similar techniques may be represented by the following additional examples. Melting point is expressed in degrees celsius. The nuclear magnetic resonance (nmr) mono (spectrum) line corresponding to the = NH proton, i.e. the properties of these compounds, are also given in some examples. Unless otherwise indicated, the nuclear magnetic resonance (nmr) solvent was CDCl 3. Elemental analysis has been shown in some examples.
Example 3
3, 4-Diphenyl-N- (4-phenoxyphenyl) pyrazoline-1 carboxyl amide with a melting point of 184-188 ℃.9.17ppm (DMSo-d 6)
Example 4
N- [ 4- (4-chlorophenoxy) phenyl ] -3, 4-diphenylpyrazoline-1-carboxamide has a melting point of 146-149 ℃.8.83ppm (DMSo-d 6)
Example 5
3- (4-Chlorophenyl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide has a melting point of 163-166 ℃.8.03ppm
Example 6
N- (4-phenoxyphenyl) -4-phenyl-3- (4-trifluoromethyl phenyl) pyrazoline-1-carboxyl amide, and the melting point is 188-190 ℃.8.10ppm
Example 7
3, 4-Bis (4-chlorophenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide has a melting point of 189-193 ℃.8.20ppm (CDCl 3/DMSo-d6)
Example 8
3- (4-Chlorophenyl) -N- (3-methyl-4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide has a melting point of 151-157 ℃.9.13ppm (DMSo-d 3)
Example 9
3- (-4-Chlorophenyl) -N- [ 4- (2-fluorophenoxy) phenyl ] -4-phenylpyrazoline-1-carboxamide having a melting point of 153 to 155 ℃.8.16ppm
Example 10
3- (4-Chlorophenyl) -N- [ 4- (3-fluorophenoxy) phenyl ] -4-phenylpyrazoline-1-carboxamide has a melting point of 173-175 ℃.9.33ppm (DMSo-d 6)
Example 11
N- [ 4- (3-chlorophenoxy) phenyl ] -3- (4-chlorophenyl) -4-phenylpyrazoline-1-carboxamide has a melting point of 169-175 ℃.9.30ppm (DMSo-d 6)
Example 12
3- (4-Chlorophenyl) -N- [ 4- (4-fluorophenoxy) phenyl ] -4-phenylpyrazoline-1-carboxamide has a melting point of 164-167 ℃.8.13ppm
Example 13
3- (4-Chlorophenyl) -N- [ 4- (4-trifluoromethylphenoxy) -phenyl ] -4-phenylpyrazoline-1-carboxamide has a melting point of 161-164 ℃.8.03ppm
Example 14
N- [ 4- (4-chlorophenoxy) phenyl ] -3- (4-difluoromethoxy phenyl) -4-phenylpyrazoline-1-carboxamide has a melting point of 103-107 ℃.8.00ppm
Example 15
3, 4-Bis (4-chlorophenyl) -N- (3-methyl-4-phenoxyphenyl) -pyrazoline-1-carboxamide has a melting point of 188-190 ℃.9.23ppm (DMSo-d 6)
Example 16
3, 4-Bis (4-chlorophenyl) -N- [ 4- (2-fluorophenoxy) phenyl ] -pyrazoline-1-carboxamide has a melting point of 160-162 ℃.8.10ppm
Example 17
3, 4-Bis (4-chlorophenyl) -N- [ 4- (3-fluorophenoxy) phenyl ] -pyrazoline-1-carboxamide has a melting point of 144-146 ℃.9.20ppm (DMSo-d 6)
Example 18
N- [ 4- (3-chlorophenoxy) phenyl ] -3, 4-bis (4-chlorophenyl) -pyrazoline-1-carboxamide has a melting point of 135-140 ℃.9.30ppm (DMSo-d 6)
Example 19
3, 4-Bis (4-chlorophenyl) -N- [ 4- (4-fluorophenoxy) phenyl ] -pyrazoline-1-carboxamide has a melting point of 168-170 ℃.9.23ppm (DMSo-d 6)
Example 20
N- [ 4- (4-chlorophenoxy) phenyl ] -3, 4-bis (4-chlorophenyl) -pyrazoline-1-carboxamide having a melting point of 154 to 156℃C9.30ppm (DMSo-d 6)
Example 21
3, 4-Bis (4-chlorophenyl) -N- [ 4- (4-trifluoromethylphenoxy) phenyl ] -pyrazoline-1-carboxamide has a melting point of 191-194 ℃.9.30ppm (DMSo-d 6)
Example 22
3- (4-Chlorophenyl) -4-phenyl-N- (4-phenylsulfanyl) pyrazoline-1-carboxamide has a melting point of 157-162 ℃.8.20ppm
Example 23
3, 4-Bis (4-chlorophenyl) -N- (4-phenylsulfanyl) pyrazoline-1-carboxamide has a melting point of 169-171 ℃.8.20ppm
Example 24
3, 5-Bis (4-chlorophenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide has a melting point of 168-170 ℃.8.30ppm (CDCl 3/DMSo-d6)
Example 25
3- (4-Chlorophenyl) -5- (4-trifluoromethylphenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide has a melting point of 164-167 ℃.8.00ppm
Example 26
3, 5-Bis (4-chlorophenyl) -N- [ 4- (2-fluorophenoxy) phenyl ] -pyrazoline-1-carboxamide has a melting point of 174-178 ℃.8.50ppm
Example 27
3, 5-Bis (4-chlorophenyl) -N- [ 4- (3-fluorophenoxy) phenyl ] -pyrazoline-1-carboxamide has a melting point of 164-168. 9.00ppm (DMSo-d 6)
Example 28
3, 5-Bis (4-chlorophenyl) -N- [ 4- (4-fluorophenoxy) phenyl ] -pyrazoline-1-carboxamide has a melting point of 165-167. 9.16ppm (DMSo-d 6)
Example 29
N- [ 4- (4-chlorophenoxy) phenyl ] -3, 5-bis (4-chlorophenyl) -pyrazoline-1-carboxamide having a melting point of 142 to 144℃in 9.20ppm (DMSo-d 6)
Example 30
3, 5-Bis (4-chlorophenyl) -N- [ 4- (4-trifluoromethylphenoxy) phenyl ] -pyrazoline-1-carboxamide has a melting point of 155-158. 8.43ppm (CDCl 3/DMSo-d6)
Example 31
3- (4-Chlorophenyl) -N- [ 4- (4-trifluoromethylphenoxy) -phenyl ] -5- (4-trifluoromethylphenyl) pyrazoline-1-carboxamide has a melting point of 144-146 ℃.8.06ppm
Example 32
N- [ 4- (4-chlorophenoxy) phenyl ] -5- (4-chlorophenyl) -3- (4-difluoromethoxy phenyl) pyrazoline-1-carboxamide has a melting point of 66-70 ℃.8.60ppm (DMSo-d 6)
Example 33
5- (1, 3-Benzodioxol-5-yl) -3- (4-chlorophenyl) -N- (4-phenoxyphenyl) -pyrazoline-1-carboxamide has a melting point of 125-128 ℃.8.36ppm (CDCl 3/DMSo-d6)
Example 34
5- (1, 3-Benzodioxol-5-yl) -N- [ 4- (4-chlorophenoxy) phenyl ] -3- (4-chlorophenyl) pyrazoline-1-carboxamide has a melting point of 174-175 ℃.8.06ppm
Example 35
N- (2, 3-dioxo-2, 2-dimethylbenzofuran-5-yl) -3, 4-diphenylpyrazoline-1-carboxamide has a melting point of 139-143 ℃.7.96ppm
Example 36
3- (4-Difluoromethoxy phenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide has a melting point of 72-82 ℃.7.96ppm
Example 37
(±) -3, 4-Bis (4-chlorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide, having a melting point of 134-137 ℃.7.93ppm
Example 38
3, 5-Bis (4-chlorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide has a melting point of 175-180 ℃.8.86ppm (DMSo-d 6)
Example 39
N- (1, 4-benzodioxan-6-yl) -3- (4-chlorophenyl) -4-phenylpyrazoline-1-carboxamide has a melting point of 112-115 ℃.7.96ppm
Example 40
N- (1, 4-benzodioxan-6-yl) -3, 4-bis (4-chlorophenyl) pyrazoline-1-carboxyl amide has a melting point of 140-145 ℃.7.96ppm
Example 41
3- (4-Chlorophenyl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carbothioamide having a melting point of 105 to 110℃C10.30ppm (DMSo-d 6)
Example 42
3, 4-Bis (4-chlorophenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carbothioamide having a melting point of 151 to 153℃C9.26ppm (DMSo-d 6)
Example 43
N- [ 4- (4-chlorophenoxy) phenyl ] -3, 4-bis (4-chlorophenyl) -pyrazoline-1-carbothioamide with a melting point of 179-183 ℃ C9.10ppm
Example 44
3- (4-Chlorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -4-phenylpyrazolin-1-carbothioamide having a melting point of 92 to 95℃C10.12ppm (DMSo-d 6)
Example 45
3, 4-Bis (4-chlorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carbothioamide, the melting point is 149-154 ℃.9.00ppm (DMSo-d 6)
Example 46
N- (1, 4-benzodioxan-6-yl) 3, 5-bis (4-chlorophenyl) pyrazoline-1-carboxamide has a melting point of 83-85 ℃.9.33ppm (DMSo-d 6)
Example 47
5- (4-Chlorophenyl) -3- (4-trifluoromethylphenyl) -N- [ 4- (4-trifluoromethylphenoxy) phenyl ] pyrazoline-1-carboxamide has a melting point of 183-185 ℃.8.77ppm (CDCl 3/DMSo-d6)
Example 48
N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) -3- (4-difluoromethoxyphenyl) -4-phenylpyrazoline-1-carboxamide
15.0 G (0.086 g) of 2-chloro-4-nitrophenol, 11.9 g (0.086 g) of potassium carbonate, 1.5 g (0.02 g) of propanethiol, 33.7 g (0.13 g) of 1, 2-dibromotetrafluoroethane and 115 ml of N, N-dimethylformamide were placed in a pressure-resistant bottle. The pressure bottle was then sealed and the mixture was stirred at a temperature of 50 ℃ for 48 hours. The pressure bottle was then cooled to room temperature and opened, and the contents of the bottle were poured into a separating funnel. Approximately 200 ml of 2N (equivalent) sodium hydroxide solution was added to the separatory funnel. The resulting mixture was then extracted with four more 300 ml of diethyl ether. These extracts were combined and washed with two 100 ml of 2N (equivalent) sodium hydroxide solution. The washed extract was dried over anhydrous magnesium sulfate and was also filtered. The filtrate was then evaporated again under reduced pressure to leave an oil. The reaction described above was repeated three more times. The remaining oils from the four experiments were combined and purified by column-in-column color separation on silica gel, eluting with 95:5 ratio of n-heptane and toluene to yield 57.6 g of solid 3-chloro-4- (2-bromo-1,1,22-tetrafluoroethoxy) nitrobenzene.
In a pressure-resistant flask were placed 10.0 g (0.028 g) of 3-chloro-4- (2-bromo-1, 2-tetrafluoroethoxy) nitrobenzene, 9.0 g (0.14 g) of copper powder (200 mesh), 0.45 g (0.0028 g) of 2,2' -bipyridine and 40 ml of dimethyl sulfoxide. The pressure-resistant bottle is then sealed and the reaction mixture is stirred at a temperature of 190 to 195 ℃ for two hours. Then, the pressure-resistant bottle was cooled to room temperature, after which the pressure-resistant bottle was opened and the contents were poured into a separating funnel. About 200 ml of a 2N (equivalent) hydrochloric acid solution was added to the separating funnel. The mixture was extracted with three more 150 ml of diethyl ether. The extracts were then combined and subsequently washed successively with 200 ml of 2N (equivalents) hydrochloric acid solution. The washed extract was dried over anhydrous magnesium sulfate and further filtered. After the solution had evaporated under reduced pressure, an oil remained. The above reaction was repeated six more times. The remaining oils from the seven experiments were combined and purified by column chromatography on silica gel eluting with toluene to give a yellow oil. This yellow oil was then dissolved in 125 ml of methylcyclohexane, and the resulting solution was placed in a freezer for approximately 18 hours. Crystals were formed and collected by filtration, thus obtaining 20.7 g of 2, 3-tetrafluoro-5-nitrobenzofuran. The filtrate was subjected to evaporation under reduced pressure to leave an oil. After distillation of the oil under reduced pressure, an additional 3 g of product (boiling point 75 ℃ C./0.2 mmHg) were obtained
2.15 G (0.011 mol) of 2, 3-tetrafluoro-5-nitrobenzene are hydrogenated in 150 ml of methanol with a catalytic amount (0.25 g) of platinum oxide, thus obtaining 2.15 g of 5-amino-2, 3-tetrafluorobenzofuran.
0.75 G (0.0036 g molecules) of a solution of 5-amino-2, 3-tetrafluorobenzofuran dissolved in 109 ml of toluene is added drop by drop to the stirred solution of 8.0 ml of 20% phosgene in toluene. After complete addition, the mixture was heated at reflux for two hours. The mixture is then cooled and the solvent is removed by evaporation under reduced pressure, leaving a residue. The residue was dissolved in 15 ml of diethyl ether and added to a stirred solution of 1.04 g (0.0036 g molecules) of 3- (4-difluoromethoxyphenyl) -4-phenylpyrazoline and three drops of triethylamine (in 100 ml of diethyl ether). After complete addition, the mixture was heated at reflux for one hour, then cooled to room temperature and stirred for about 18 hours. The solvent was removed from the reaction mixture by evaporation under reduced pressure, leaving a solid residue. 0.99 g of N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) -3- (4-difluoromethoxyphenyl) -4-phenylpyrazolin-1-carboxamide (melting point 155 ℃ C. To 159 ℃ C.) is obtained by recrystallisation from ethanol.
Analysis:
Calculated C:58.58; H:3.29
Found C57.81; H3.75
Nuclear magnetic resonance 8.16ppm
Example 49
3, 4-Bis (4-chlorophenyl) -N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) pyrazoline-1-carboxamide.
A solution of 1.18 g (0.0068 g molecules) of 5-amino-2, -difluoro-1, 3-benzodioxole prepared by the method described in the literature and dissolved in 80 ml of tetrahydrofuran is added drop by drop to 24 ml of a cold (5-10 ℃) solution of 20% phosgene (in toluene). After complete addition, the mixture was stirred at a temperature of 2 ℃ for one hour and then heated at reflux for 2 hours to evaporate the solvent under reduced pressure leaving 1.4 g of a liquid residue.
In a clean reaction beaker, 0.68 g of this residue was slowly added to a stirred solution of 0.93 g (0.0032 g molecules) of 3, 4-bis (4-chlorophenyl) pyrazoline and three drops of triethylamine in 20 ml of diethyl ether. After complete addition, the mixture was stirred at room temperature for about 18 hours. A small amount of solids is present in the reaction mixture but can be removed by filtration. The filtrate was evaporated under reduced pressure leaving a residue. The residue was purified by column chromatography on silica gel and eluted with 1:1 ratio of N-heptane and ethyl acetate to give 1.3 g of 3, 4-bis (4-chlorophenyl) -N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) pyrazoline-1-carboxamide having a melting point of 150-155 ℃.
Analysis:
calculated C56.34H 3.08
Found C57.16H 2.89
Nuclear magnetic resonance 8.10ppm
The compound of example 50 can be prepared by a similar method.
Example 50
N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -3- (4-difluoromethoxy phenyl) -4-phenylpyrazoline-1-carboxamide has a melting point of 135-138 ℃.8.10ppm
Example 51
3- (4-Fluorophenyl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide has a melting point of 187-191 ℃.8.10ppm
Example 52
3- (4-Difluoromethoxy phenyl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide has a melting point of 139-144 ℃.8.10ppm
Example 53
3- (4-Chlorophenyl) -N- [ 4- (4-chlorophenoxy) -phenyl ] -4-phenylpyrazoline-1-carboxamide has a melting point of 170-174 ℃.8.10ppm
Example 54
3- (4-Chlorophenyl) -N- [ 4- (4-nitrophenoxy) phenyl ] -4-phenylpyrazoline-1-carboxamide has a melting point of 187-189 ℃.8.30ppm
Example 55
3- (4-Chlorophenyl) -N- [ 4- (4-methoxyphenoxy) -phenyl ] -4-phenylpyrazoline-1-carboxamide has a melting point of 159-160 ℃.8.07ppm
Example 56
3- (4-Chlorophenyl) -N- [ 4- (4-difluoromethoxyphenoxy) phenyl ] -4-phenylpyrazoline-1-carboxamide has a melting point of 181-184 ℃.8.07ppm
Example 57
N- [ 4- (4-chlorophenoxy) phenyl ] -3- (4-trifluoromethoxy phenyl) -4-phenylpyrazoline-1-carboxamide has a melting point of 132-134 ℃.8.16ppm
Example 58
N- [ 4- (4-chlorophenoxy) phenyl ] -4-phenyl-3- [ 4- (2-propynyloxy) phenyl ] pyrazoline-1-carboxamide with a melting point of 160-164 ℃.8.13ppm
Example 59
3- (1, 3-Benzodioxol-5-yl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide has a melting point of 220-223 ℃.8.06ppm
Example 60
4- (4-Chlorophenyl) -N- (4-phenoxyphenyl) -3-phenylpyrazoline-1-carboxamide has a melting point of 153-155 ℃.8.16ppm
Example 61
3, 4-Bis (4-fluorophenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide has a melting point of 194-198 ℃.8.16ppm
Example 62
N- [ 4- (2-chlorophenoxy) phenyl ] -3, 4-bis (4-chlorophenyl) pyrazoline-1-carboxamide has a melting point of 182-186 ℃.8.10ppm
Example 63
3, 4-Bis (4-chlorophenyl) -N- [ 4- (4-methoxyphenoxy) phenyl ] pyrazoline-1-carboxamide. 8.20ppm
Example 64
3- (4-Chlorophenyl) -4- (4-fluorophenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide has a melting point of 178-179 ℃.8.10ppm
Example 65
N- [ 4- (4-chlorophenoxy) phenyl ] -3- (4-chlorophenyl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide has a melting point of 143-145 ℃.8.03ppm
Example 66
3- (4-Chlorophenyl) -4- (4-methylphenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide has a melting point of 165-168 ℃.8.10ppm
Example 67
N- [ 4- (4-chlorophenoxy) phenyl ] -3- (4-chlorophenyl) -4- (4-methoxyphenyl) pyrazoline-1-carboxyl amide, and the melting point is 169-173 ℃.8.07ppm
Example 68
4- (4-Fluorophenyl) -3- (4-methoxyphenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide has a melting point of 184-187 ℃.8.17ppm
Example 69
N- [ 4- (4-difluoromethoxyphenoxy) phenyl ] -3- (4-difluoromethoxyphenyl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide. 8.10ppm
Example 70
N- [ 4- (4-fluorophenoxy) phenyl ] -3- (4-chlorophenyl) -4-phenylpyrazoline-1-thiocarboxamide with a melting point of 179-183 ℃.9.10ppm
Example 71
3- (4-Difluoromethoxy phenyl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-thiocarboxamide with a melting point of 132-136 ℃.9.13ppm
Example 72
4- (4-Chlorophenyl) -N- (4-phenoxyphenyl) -3-phenylpyrazoline-1-thiocarboxamide having a melting point of 131-133 ℃.9.16ppm
Example 73
N- [ 4- (4-chlorophenyl thio) phenyl ] -3, 4-diphenylpyrazoline-1-carboxamide has a melting point of 186-190 ℃.8.20ppm
Example 74
3- (4-Chlorophenyl) -N- [ 4- (4-chlorophenyl thio) phenyl ] -4-phenylpyrazoline-1-carboxamide has a melting point of 178-181 ℃.8.23ppm
Example 75
3- (4-Difluoromethoxy phenyl) -4-phenyl-N- (4-phenylthio-phenyl) pyrazoline-1-carboxamide has a melting point of 135-140 ℃.8.13ppm
Example 76
3, 4-Bis (4-chlorophenyl) -N- [ 4- (4-fluorophenylthio) phenyl ] pyrazoline-1-carboxamide has a melting point of 171-175 ℃.8.20ppm
Example 77
3, 4-Bis (4-chlorophenyl) -N- [ 4- (4-chlorophenyl thio) phenyl ] pyrazoline-1-carboxamide has a melting point of 151-156 ℃.8.13ppm
Example 78
3, 4-Bis (4-chlorophenyl) -N- [ 4- (3-chlorophenoxy) phenyl ] pyrazoline-1-carboxamide has a melting point of 135-140 ℃.9.20ppm (DMSO-d 3)
Example 79
3- (4-Methoxyphenyl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide has a melting point of 188-192 ℃.8.46ppm (CDCl/DMSO-d 6)
Example 80
3- [ 4- (2-Propynyloxy) phenyl ] -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide has a melting point of 121-126 ℃.8.10ppm
Example 81
3- (4-Chlorophenyl) -N- (2, 3-dihydrobenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide has a melting point of 155-158 ℃.7.93ppm
Example 82
3- (4-Difluoromethoxyphenyl) -N- (2, 3-dihydrobenzofuran-5-yl) -4-phenylpyrazolin-1-carboxamide. 7.93ppm
Example 83
3, 4-Bis (4-chlorophenyl) -N- (2, 3-dihydrobenzofuran-5-yl) pyrazoline-1-carboxamide has a melting point of 214-216 ℃.7.93ppm
Example 84
3- (4-Fluorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide has a melting point of 156-160 ℃.7.93ppm
Example 85
3- (4-Methoxyphenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide has a melting point of 164-169 ℃.8.00ppm
Example 86
3- (4-Trifluoromethoxyphenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide has a melting point of 81-83 ℃.7.98ppm
Example 87
N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -4-phenyl-3- [ 4- (2-propynyloxy) phenyl ] pyrazoline-1-carboxamide has a melting point of 175-179 ℃.8.00ppm
Example 88
3- (1, 3-Benzodioxol-5-yl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -4-phenylpyrazolin-1-carboxamide has a melting point of 223 to 227 ℃.8.90ppm (DMSO-d 6)
Example 89
4- (4-Chlorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -3-phenylpyrazolin-1-carboxamide. 8.00ppm
Example 90
3, 4-Bis (4-fluorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide has a melting point of 161-166 ℃.7.93ppm
Example 91
3- (4-Chlorophenyl) -4- (4-fluorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide has a melting point of 169-171 ℃.7.96ppm
Example 92
3- (4-Chlorophenyl) -4- (4-tolyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide has a melting point of 137-139 ℃.7.96ppm
Example 93
3- (4-Chlorophenyl) -4- (4-methoxyphenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide has a melting point of 182-186 ℃.7.93ppm
Example 94
4- (4-Fluorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -3- (4-methoxyphenyl) pyrazoline-1-carboxamide has a melting point of 179-182 ℃.7.93ppm
Example 95
4- (4-Chlorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -3- (4-methoxyphenyl) pyrazoline-1-carboxamide has a melting point of 157-160 ℃.7.96ppm
Example 96
3- (4-Difluoromethoxy phenyl) -4- (4-fluorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide has a melting point of 169-172 ℃.7.93ppm
Example 97
4- (4-Chlorophenyl) -3- (4-difluoromethoxyphenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide has a melting point of 90-95 ℃.7.93ppm
Example 98
3- (4-Difluoromethoxy phenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide has a melting point of 152-157 ℃.8.33ppm
Example 99
3- (4-Difluoromethoxy phenyl) -4- (4-fluorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide has a melting point of 110-114 ℃.8.33ppm
Example 100
3- (4-Difluoromethoxy phenyl) -4- (4-fluorophenyl) -N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) pyrazoline-1-carboxamide has a melting point of 155-159 ℃.8.20ppm
Example 101
3- (4-Chlorophenyl) -N- (2, 2-dimethyl-1, 3-benzodioxol-5-yl) -4-phenylpyrazoline-1-carboxamide has a melting point of 182-186 ℃.7.96ppm
Example 102
3- (4-Difluoromethoxy phenyl) -N- (2, 2-dimethyl-1, 3-benzodioxol-5-yl) -4-phenylpyrazoline-1-carboxamide has a melting point of 148-150 ℃.7.93ppm
Example 103
3, 4-Bis (4-chlorophenyl) -N- (2, 2-dimethyl-1, 3-benzodioxol-5-yl) -pyrazoline-1-carboxamide has a melting point of 168-169 ℃.7.93ppm
Example 104
N- (1, 4-Benzodioxan-5-yl) -3- (4-difluoromethoxyphenyl) -4-phenylpyrazolin-carboxamide, 7.93ppm
Example 105
N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -3- (4-difluoromethoxy phenyl) -N-methyl-4-phenylpyrazoline-1-carboxamide has a melting point of 110-114 ℃.
Example 106
4- (1, 3-Benzodioxol-5-yl) -N- (4-phenoxyphenyl) -3-phenylpyrazoline-1-carboxamide has a melting point of 195-197 ℃.8.03ppm
Example 107
3- (4-Chlorophenyl) -N- {4- [ 4- (1, 1-dimethylethyl) phenoxy ] -phenyl } -4-phenylpyrazoline-1-carboxamide having a melting point of 192.5 to 194 ℃.8.03ppm
Example 108
3- (4-Chlorophenyl) -4- (4-fluorophenyl) -N- [ 4- (4-methylphenoxy) phenyl ] pyrazoline-1-carboxamide has a melting point of 162-164 ℃.8.03ppm
Example 109
3- (4-Chlorophenyl) -4- (4-fluorophenyl) -N- {4- [ 4- (1, 1-dimethylethyl) phenoxy ] phenyl } pyrazoline-1-carboxamide, the melting point is 188-198 ℃.8.03ppm
Example 110
3- (4-Chlorophenyl) -N- {4- [ 4- (1-methylethyl) phenoxy ] phenyl } -4-phenylpyrazoline-1-carboxamide, having a melting point of 181-182.5 ℃.8.06ppm
Example 111
3- (4-Chlorophenyl) -4- (4-fluorophenyl) -N- {4- [ 4- (1-methylethyl) phenoxy ] phenyl } pyrazoline-1-carboxamide, the melting point is 186-187 ℃.8.06ppm (CDCL 3/DMSO-d 6)
Example 112
3- (4-Chlorophenyl) -N- [ 4- (4-methylphenoxy) phenyl ] -4-phenylpyrazoline-1-carboxamide has a melting point of 150-151 ℃.8.06ppm
Example 113
3- (4-Chlorophenyl) -N- {4- [ 4- (1-methylethoxy) phenoxy ] phenyl } -4-phenylpyrazoline-1-carboxamide, having a melting point of 158 to 160.5 ℃.8.06ppm
Example 114
3- (4-Chlorophenyl) -4- (4-fluorophenyl) -N- {4- [ 4- (1-methylethyl) phenoxy ] phenyl } pyrazoline-1-carboxamide, the melting point is 182-186 ℃.8.06ppm (CDCL 3/DMSO-d 6)
Example 115
3, 4-Bis (4-fluorophenyl) -N- {4- [ 4- (1-methylethoxy) phenoxy ] phenyl } pyrazoline-1-carboxamide, the melting point is 134-136 ℃.8.06ppm.
Example 116
3, 4-Bis (4-fluorophenyl) -N- [ 4- (4-chlorophenoxy) phenyl ] pyrazoline-1-carboxamide has a melting point of 197-198.5 ℃.8.70ppm. (CDCL 3/DMSO-d 6)
Example 117
3, 4-Bis (4-fluorophenyl) -N- {4- [ 4- (1, 1-dimethylethyl) phenoxy ] -phenyl } pyrazoline-1-carboxamide, the melting point is 189-192 ℃.8.70ppm (CDCL 3/DMSO-d 6)
Example 118
3, 4-Bis (4-fluorophenyl) -N-N [ 4- (4-cyanophenoxy) phenyl ] pyrazoline-1-carboxamide has a melting point of 198-200 ℃.8.13ppm
Example 119
3, 4-Bis (4-fluorophenyl) -N- {4- [ 4- (N, N-dimethylamino) phenoxy ] -phenyl } pyrazoline-1-carboxamide, the melting point is 148-150 ℃.8.02ppm
Example 120
3- (4-Chlorophenyl) -N- [ 4- (4-cyanophenoxy) phenyl ] -4-phenylpyrazoline-1-carboxamide has a melting point of 170-172 ℃.8.16ppm
Example 121
N- (1, 4-benzodioxan-6-yl) -4- (4-chlorophenyl) -3- (4-difluoromethoxy phenyl) pyrazoline-1-carboxamide has a melting point of 124-128 ℃.7.93ppm.
Example 122
3, 4-Bis (4-chlorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -N-methylpyrazolin-1-carboxamide has a melting point of 150-155 ℃.
Example 123
N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -3, 4-diphenylpyrazoline-1-carboxamide has a melting point of 214-216 ℃.8.83ppm (CDCL 3/DMSO-d 6)
Example 124
N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -3, 4-bis (4-fluorophenyl) pyrazoline-1-carboxamide has a melting point of 178-180 ℃.8.10ppm
Example 125
3- (4-Chlorophenyl) -N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide has a melting point of 147-151 ℃.8.06ppm
Example 126
3- (4-Difluoromethoxyphenyl) -N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) -N-methyl-4-phenylpyrazolin-1-carboxamide.
Example 127
3- (4-Chlorophenyl) -4- (4-difluoromethoxyphenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide has a melting point of 150-159 ℃.7.96ppm
Example 128
3- (4-Difluoromethoxyphenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -N-methyl-4-phenylpyrazolin-1-carboxamide.
Example 129
4- (4-Chlorophenyl) -N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide. 8.06ppm
Example 130
4- (1, 3-Benzodioxol-5-yl) -3- (4-chlorophenyl) -N- [ 4- (4-fluoromethoxyphenoxy) phenyl ] pyrazoline-1-carboxamide.
Example 131
4- (1, 3-Benzodioxol-5-yl) -N- [ 4- (4-chlorophenoxy) phenyl ] 3- (4-chlorophenyl) pyrazoline-1-carboxamide.
Example 132
4- (1, 3-Benzodioxol-5-yl) 3- (4-chlorophenyl) -N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) pyrazoline-1-carboxamide.
Example 133
4- (1, 3-Benzodioxol-5-yl) -3- (4-chlorophenyl) -N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) pyrazoline-1-carboxamide.
Example 134
4- (1, 3-Benzodioxol-5-yl) -3- (4-chlorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.
Example 135
4- (1, 3-Benzodioxol-5-yl) -N- [ 4- (4-difluoromethoxyphenyl) phenyl ] -3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide.
Example 136
4- (1, 3-Benzodioxol-5-yl) -N- [ 4- (4-chlorophenoxy) phenyl ] -3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide.
Example 137
4- (1, 3-Benzodioxol-5-yl) -N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide.
Example 138
4- (1, 3-Benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) - (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) pyrazoline-1-carboxamide.
Example 139
4- (1, 3-Benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.
Example 140
4- (1, 3-Benzodioxol-5-yl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -3-phenylpyrazolin-1-carboxamide.
Example 141
4- (1, 3-Benzodioxol-5-yl) - (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) -3-phenylpyrazolin-1-carboxamide.
Example 142
4- (1, 3-Benzodioxol-5-yl) -N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -3-phenylpyrazolin-1-carboxamide.
Example 143
4- (1, 3-Benzodioxol-5-yl) -N- [ 4- (4-difluoromethoxyphenyl) phenyl ] -3-phenylpyrazoline-1-carboxamide.
Example 144
4- (1, 3-Benzodioxol-5-yl) -N- [ 4- (4-chlorophenoxy) phenyl ] -3-phenylpyrazoline-1-carboxamide.
Example 145
N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) N- [ 4- (4-difluoromethoxyphenyl) phenyl ] -3- (4-chlorophenyl) pyrazoline-1-carboxamide.
Example 146
N- [ 4- (4-chlorophenyl) phenyl ] -4- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -3- (4-chlorophenyl) pyrazoline-1-carboxamide.
Example 147
4, N-bis (2, 2-difluoro-1, 3-benzodioxol-5-yl) -3- (4-fluorophenyl) pyrazoline-1-carboxamide.
Example 148
4- (2, 2-Difluoro-1, 3-benzodioxol-5-yl) -3- (4-fluorophenyl) -N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) pyrazoline-1-carboxamide.
Example 149
4- (2, 2-Difluoro-1, 3-benzodioxol-5-yl) -3- (4-fluorophenyl-N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.
Example 150
4- (2-Difluoro-1, 3-benzodioxol-5-yl) -N- [ 4- (4-difluoromethoxyphenyl) phenyl ] -3-phenylpyrazoline-1-carboxamide.
Example 151
N- [ 4- (4-difluoromethoxyphenyl) phenyl ] -4- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -3-phenylpyrazolin-1-carboxamide.
Example 152
4, N-bis (2, 2-difluoro-1, 3-benzodioxol-5-yl) -3-phenylpyrazolin-1-carboxamide.
Example 153
4- (2, 2-Difluoro-1, 3-benzodioxol-5-yl) -N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) -3-phenylpyrazolin-1-carboxamide.
Example 154
4- (2, 2-Difluoro-1, 3-benzodioxol-5-yl) -N- (2, 3-dihydro-2, 3-dimethylbenzofuran-5-yl) -3-phenylpyrazolin-1-carboxamide.
Example 155
4- (2, 2-Difluoro-1, 3-benzodioxol-5-yl) -N- [ 4- (4-difluoromethoxyphenyl) phenyl ] -3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide.
Example 156
N- [ 4- (4-difluoromethoxyphenyl) phenyl ] -4- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide.
Example 157
4, N-bis (2, 2-difluoro-1, 3-benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide.
Example 158
4- (2, 2-Difluoro-1, 3-benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-yl) pyrazoline-1-carboxamide.
Example 159
4- (2, 2-Difluoro-1, 3-benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.
Example 160
4- (1, 4-Benzodioxan-6-yl) -3- (4-chlorophenyl) -N- [ 4- (4-difluoromethoxyphenoxy) phenyl ] pyrazoline-1-carboxamide.
Example 161
4- (1, 4-Benzodioxan-6-yl) -N- [ 4- (4-difluoromethoxyphenyl) phenyl ] -3- (4-chlorophenyl) pyrazoline-1-carboxamide.
Example 162
4- (1, 4-Benzodioxan-6-yl) -3- (4-chlorophenyl) -N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) pyrazoline-1-carboxamide.
Example 163
4- (1, 4-Benzodioxan-6-yl) -3- (4-chlorophenyl) -N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) pyrazoline-1-carboxamide.
Example 164
4- (1, 4-Benzodioxan-6-yl) -3- (4-chlorophenyl) -N- (2, 3-difluoro-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.
Example 165
4- (1, 4-Benzodioxan-6-yl) N- [ 4- (4-difluoromethoxyphenyl) phenyl ] -3- (4-difluoromethoxyphenoxy) pyrazoline-1-carboxamide.
Example 166
4- (1, 4-Benzodioxan-6-yl) -N- [ 4- (4-chlorophenoxy) phenyl ] -3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide.
Example 167
4- (1, 4-Benzodioxan-6-yl) -N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide.
Example 168
4- (1, 4-Benzodioxan-6-yl) -3- (4-difluoromethoxyphenyl) -N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) pyrazoline-1-carboxamide.
Example 169
4- (1, 4-Benzodioxan-6-yl) -3- (4-difluoromethoxyphenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.
Example 170
4- (1, 4-Benzodioxan-6-yl) -N- [4- (4-difluoromethoxyphenoxy) phenyl ] -3-phenylpyrazolin-1-carboxamide.
Example 171
4- (1, 4-Benzodioxan-6-yl) -N- [ 4- (4-chlorophenyl) phenyl) -3-phenylpyrazoline-1-carboxamide.
Example 172
4- (1, 4-Benzodioxan-6-yl) -N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -3-phenylpyrazolin-1-carboxamide.
Example 173
4- (1, 4-Benzodioxan-6-yl) -N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) -3-phenylpyrazolin-1-carboxamide.
Example 174
4- (1, 4-Benzodioxan-6-yl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -3-phenylpyrazolin-1-carboxamide.
Example 175
3- (1, 3-Benzodioxol-5-yl) -N- [ 4- (4-difluoromethoxyphenyl) phenyl ] -4- (4-chlorophenyl) -N-methylpyrazoline-1-carboxamide.
Example 176
3- (1, 3-Benzodioxol-5-yl) -N- [ 4- (4-chlorophenoxy) phenyl ] -4- (4-fluorophenyl) pyrazoline-1-carboxamide.
Example 177
3- (1, 3-Benzodioxol-5-yl) -N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide.
Example 178
3- (1, 3-Benzodioxol-5-yl) -4- (4-fluorophenyl) -N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) pyrazoline-1-carboxamide.
Example 179
3- (1, 3-Benzodioxol-5-yl) -4- (4-fluorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.
Example 180
3- (2, 2-Difluoro-1, 3-benzodioxol-5-yl) -N- [ 4- (4-difluoromethoxyphenoxy) phenyl ] -4- (4-fluorophenyl) pyrazoline-1-carboxamide.
Example 181
N- [ 4-4 (4-chlorophenoxy) phenyl ] -3- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -4- (4-fluorophenyl) -N-methylpyrazoline-1-carboxamide.
Example 182
3. N-bis (2, 2-difluoro-1, 3-benzodioxol-5-yl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide.
Example 183
3- (2, 2-Difluoro-1, 3-benzodioxol-5-yl) -4- (4-fluorophenyl) -N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) pyrazoline-1-carboxamide.
Example 184
3- (2, 2-Difluoro-1, 3-benzodioxol-5-yl) -4- (4-fluorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.
Example 185
3- (1, 4-Benzodioxan-6-yl) -N- [ 4- (4-difluoromethoxyphenyl) phenyl ] -4-phenyl) -pyrazoline-1-carboxamide.
Example 186
3- (1, 4-Benzodioxan-6-yl) -N- [ 4- (4-chlorophenoxy) phenyl ] -4-phenyl) -pyrazoline-1-carboxamide.
Example 187A
3- (1, 4-Benzodioxan-6-yl) -N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -N-methyl-4-phenyl) pyrazoline-1-carboxamide.
Example 188
3- (1, 4-Benzodioxan-6-yl) -N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) -4-pyrazoline-1-carboxamide.
Example 189
3- (1, 4-Benzodioxan-6-yl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -4-) pyrazoline-1-carboxamide.
Example 190
N- [ 4- (4-difluoromethoxyphenoxy) phenyl ] -3- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -4-phenyl) pyrazoline-1-carboxamide.
Example 191
N- [ 4- (4-chlorophenyl) phenyl ] -3- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -4-phenylpyrazolin-1-carboxamide.
Example 192
N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -3- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -4-phenyl) pyrazoline-1-carboxamide.
Example 193
N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) -3- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -N-methyl-4-phenyl) pyrazoline-1-carboxamide.
Example 194
3, N-bis (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -4-phenyl) pyrazoline-1-carboxamide.
Example 195
N- [ 4- (4-difluoromethoxyphenoxy) phenyl ] -4- (4-fluorophenyl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.
Example 196
N- [4- (4-chlorophenyl) phenyl ] -4- (4-fluorophenyl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.
Example 197
N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -4- (4-fluorophenyl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.
Example 198
4- (4-Fluorophenyl) -N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl-3- (4-methylphenyl) pyrazoline-1-carboxamide.
Example 199
4- (4-Fluorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl-N-methyl-3- (4-tolyl) pyrazoline-1-carboxamide.
Example 200
N- [ 4- (4-difluoromethoxyphenoxy) phenyl ] -4- (3-fluorophenyl) -N-methyl-3- (4-methylphenyl) pyrazoline-1-carboxamide.
Example 201
N- [4- (4-chlorophenoxy) phenyl ] -4- (3-fluorophenyl) -3- (4-tolyl) pyrazoline-1-carboxamide.
Example 202
N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -4- (3-fluorophenyl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.
Example 203
4- (3-Fluorophenyl) -N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.
Example 204
4- (3-Fluorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -3- (4-tolyl) pyrazoline-1-carboxamide.
Example 205
N- [ 4- (4-difluoromethoxyphenoxy) phenyl ] -4- (2-fluorophenyl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.
Example 206
N- [4- (4-chlorophenoxy) phenyl ] -4- (3-fluorophenyl) -N-methyl-3- (4-methylphenyl) pyrazoline-1-carboxamide.
Example 207
N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -4- (2-fluorophenyl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.
Example 208
4- (2-Fluorophenyl) -N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) -3- (4-tolyl) pyrazoline-1-carboxamide.
Example 209
4- (2-Fluorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.
Example 210
N- [ 4- (4-difluoromethoxyphenoxy) phenyl ] -3- (3-fluorophenyl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide.
Example 211
N- [4- (4-fluorophenoxy) phenyl ] -3- (3-fluorophenyl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide.
Example 212
N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -3- (3-fluorophenyl) -4- (4-fluorophenyl) -N-methylpyrazoline-1-carboxamide.
Example 213
3- (3-Fluorophenyl) -4- (4-fluorophenyl) -N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) pyrazoline-1-carboxamide.
Example 214
3- (3-Fluorophenyl) -4- (4-fluorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.
Example 215
N- [ 4- (4-difluoromethoxyphenoxy) phenyl ] -3- (2-fluorophenyl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide.
Example 216
N- [4- (4-chlorophenoxy) phenyl ] -3- (2-fluorophenyl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide.
Example 217
N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) -3- (2-fluorophenyl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide.
Example 218
3- (2-Fluorophenyl) -4- (4-fluorophenyl) N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) -N-methylpyrazoline-1-carboxamide.
Example 219
3- (2-Fluorophenyl) -4- (4-fluorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.
Example 220
3, 4-Bis (4-fluorophenyl) -N- (2, 3-dihydro-2,2,3,3,7-pentafluorofuran-5-yl) pyrazoline-1-carboxamide.
Example 221
4- (4-Chlorophenyl) -N- (2, 3-dihydro-2,2,3,3,7-pentafluorofuran-5-yl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.
Example 222
N- (2, 3-dihydro-2,2,3,3,7-pentafluorofuran-5-yl) -3, 4-diphenylpyrazoline-1-carboxamide.
Example 223
3- (4-Difluoromethoxyphenyl) -N- (2, 3-dihydro-2,2,3,3,7-pentafluorobenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide.
Example 224
3- (4-Chlorophenyl) N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide.
Example 225
3, 4-Bis (4-fluorophenyl) -N- (2, 6-trimethyl-1, 3-benzodioxol-5-yl) pyrazoline-1-carboxamide.
Example 226
4- (4-Chlorophenyl) -N- (2, 6-trimethyl-1, 3-benzodioxol-5-yl) pyrazoline-1-carboxamide.
Example 227
(2, 6-Trimethyl-1, 3-benzodioxol-5-yl) -3, 4-diphenylpyrazoline-1-carboxamide.
Example 228
3- (4-Difluoromethoxyphenyl) -N- (2, 6-trimethyl-1, 3-benzodioxol-5-yl) -4-phenylpyrazoline-1-carboxamide.
Example 229
3- (4-Chlorophenyl) -N- (2, 6-trimethyl-1, 3-benzodioxol-5-yl) -4-phenylpyrazoline-1-carboxamide.
Example 230
3, 4-Bis (4-fluorophenyl) -N- (7-methoxy-2, 2-dimethyl-1, 3-benzodioxol 5-yl) pyrazoline-1-carboxamide.
Example 231
4- (Chlorophenyl) -N- (7-methyl-2, 2-1, 3-benzodioxol-5-yl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.
Example 232
N- (7-methoxy-2, 2-dimethyl-1, 3-benzodioxol-5-yl) -3, 4-diphenylpyrazoline-1-carboxamide.
Example 233
3- (4-Difluoromethoxyphenyl) -N- (7-methoxy-2, 2-dimethyl-1, 3-benzodioxol-5-yl) -4-phenylpyrazoline-1-carboxamide.
Example 234
3- (4-Chlorophenyl) -N- (7-methoxy-2, 2-dimethyl-1, 3-benzodioxol-5-yl) -4-phenylpyrazoline-1-carboxamide.
Example 235
3, 4-Bis (4-fluorophenyl) -N- [ 2, 2-dimethyl-7- (1-methylethyl) -1, 3-benzodioxol-5-yl ] pyrazoline-1-carboxamide.
Example 236
4- (4-Chlorophenyl) -N- [2, 2-dimethyl-7- (1-methylethyl) 1, 3-benzodioxol-5-yl ] -3- (4-tolyl) pyrazoline-1-carboxamide.
Example 237
N- [ 2, 2-dimethyl-7- (1-methylethyl) 1, 3-benzodioxol-5-yl ] -3, 4-diphenylpyrazoline-1-carboxamide.
Example 238
3- (4-Difluoromethoxyphenyl) -N- [2, 2-dimethyl-7- (1-methylethyl) 1, 3-benzodioxol-5-yl ] -4-phenylpyrazolin-1-carboxamide.
Example 239
3- (4-Chlorophenyl) -N- [2, 2-dimethyl-7- (1-methylethyl) 1, 3-benzodioxol-5-yl) -4-phenylpyrazolin-1-carboxamide.
Example 240
3, 4-Bis (4-fluorophenyl) -N- (2, 3-dihydro-7-ethyl-2, 3-tetrafluorobenzofuran-5-yl) pyrazoline-1-carboxamide.
Example 241
4- (4-Chlorophenyl) -N- (2, 3-dihydro-7-ethyl-2, 3-tetrafluorobenzofuran-5-yl) -pyrazoline-1-carboxamide.
Example 242
N- (2, 3-dihydro-7-ethyl-2, 3-tetrafluorobenzofuran-5-yl) -3, 4-diphenylpyrazoline-1-carboxamide.
Example 243
3- (4-Difluoromethoxyphenyl) -N- (2, 3-dihydro-7-ethyl-2, 3-tetrafluorobenzofuran-5-yl) -4-pyrazoline-1-carboxamide.
Example 244
3- (4-Chlorophenyl) -N- (2, 3-dihydro-7-ethyl-2, 3-tetrafluorobenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide.
Example 245
3- (4-Chlorophenyl) -N- [ 4- (4-methylsulfonylphenoxy) phenyl ] -4-phenylpyrazoline-1-carboxamide.
Example 246
3, 4-Bis (4-fluorophenyl) -N- [ 4- (4-methylsulfonylphenoxy) phenyl ] pyrazoline-1-carboxamide.
Example 247
3- (4-Difluoromethoxyphenyl) -N- [ 4- (4-methylsulfonylphenoxy) phenyl ] -4-phenylpyrazoline-1-carboxamide.
Example 248
3- (4-Chlorophenyl) -4- (4-fluorophenyl) -N- [ 4- (4-methylsulfonylphenoxy) phenyl ] pyrazoline-1-carboxamide.
Example 249
N- [ 4- (4-methylsulfonylphenoxy) phenyl ] -3, 4-diphenylpyrazoline-1-carboxamide.
Example 250
3, 4-Bis (4-fluorophenyl) -N- (2, 3-dihydro-7-difluoromethoxy-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.
Example 251
4- (4-Chlorophenyl) -N- (2, 3-dihydro-7-difluoromethoxy-2, 2-dimethylbenzofuran-5-yl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.
Example 252
N- (2, 3-dihydro-7-difluoromethoxy-2, 2-dimethylbenzofuran-5-yl) -3-diphenylpyrazoline-1-carboxamide.
Example 253
3- (4-Difluoromethoxyphenyl) -N- (2, 3-dihydro-7-difluoromethoxy-2, 2-dimethylbenzofuran-5-yl) -4-phenylpyrazolin-1-carboxamide.
Example 254
3- (4-Chlorophenyl) -N- (2, 3-dihydro-7-difluoromethoxy-2, 2-dimethylbenzofuran-5-yl) -4-phenylpyrazolin-1-carboxamide.
Example 255
N- (7-chloromethyl-2, 2-dimethyl-1, 3-benzodioxol-5-yl) 3, 4-bis (4-fluorophenyl) pyrazoline-1-carboxamide.
Example 256
N- (7-chloromethyl-2, 2-dimethyl-1, 3-benzodioxol-5-yl) -4- (4-chlorophenyl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.
Example 257
N- (7-chloromethyl-2, 2-dimethyl-1, 3-benzodioxol-5-yl) -3, 4-diphenylpyrazoline-1-carboxamide.
Example 258
N- (7-chloromethyl-2, 2-dimethyl-1, 3-benzodioxol-5-yl) 3- (4-difluoromethoxyphenyl) -4-phenylpyrazolin-1-carboxamide.
Example 259
N- (7-chloromethyl-2, 2-dimethyl-1, 3-benzodioxol-5-yl) -3- (4-chlorophenyl) -4-phenylpyrazoline-1-carboxamide.
Example 260
N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -3- [ 7- (1-methylethyl) -2, 2-dimethyl-1, 3-benzodioxol-5-yl) -4-phenylpyrazolin-1-carboxamide.
Example 261
N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -3- (7-methoxy-2, 2-dimethyl-1, 3-benzodioxol-5-yl) -4-phenylpyrazolin-1-carboxamide.
Example 262
N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -3- (7-fluoro-2, 2-dimethyl-1, 3-benzodioxol-5-yl) -4-phenylpyrazolin-1-carboxamide.
Example 263
N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -3- (7-difluoromethoxy-2, 2-dimethyl-1, 3-benzodioxol-5-yl) -4-phenylpyrazolin-1-carboxamide.
Example 264
N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) 3- (4-fluorophenyl) -4- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.
Example 265
N- (2, 2-difluoro-1, 3-benzodioxol-5-yl) 3- (4-fluorophenyl) -4-N- (2, 3-dihydro-2, 3-tetrafluorobenzofuran-5-yl) pyrazoline-1-carboxamide.
Example 266
N- [ 3- (4-trifluoromethylphenoxy) phenyl ] 3, 4-bis (4-fluorophenyl) pyrazoline-1-carboxamide.
Example 267
N- [ 3- (4-fluorophenoxy) phenyl ] 3, 4-bis (4-fluorophenyl) pyrazoline-1-carboxamide.
Example 268
N- [ 3- (4-difluoromethoxyphenoxy) phenyl ] -3, 4-bis (4-fluorophenyl) pyrazoline-1-carboxamide.
Example 269
3, 4-Bis (4-fluorophenyl) -N- [ 3- (4-methylphenoxy) phenyl ] pyrazoline-1-carboxamide.
Example 270
3- (7-Chloromethyl-2, 2-dimethyl-1, 3-benzodioxol-5-yl) -4, n-bis (4-fluorophenyl) pyrazoline-1-carboxamide.
Example 271
N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -4- [ 7- (1-methylethyl) -2, 2-dimethyl-1, 3-benzodioxol-5-yl ] -3-phenylpyrazolin-1-carboxamide.
Example 272
N- (2, 3-dihydro-2, -dimethylbenzofuran-5-yl) -4- (-7-methoxy-2, 2-dimethyl-1, 3-benzodioxol-5-yl) -3-phenylpyrazolin-1-carboxamide.
Example 273
N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -4 (7-difluoro-2, 2-dimethyl-1, 3-benzodioxol-5-yl) -3-phenylpyrazolin-1-carboxamide.
Example 274
N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -4- (7-difluoromethoxy-2, 2-dimethyl-1, 3-benzodioxol-5-yl) -3-phenylpyrazolin-1-carboxamide.
Example 275
4- (7-Chloromethyl-2, 2-dimethyl-1, 3-benzodioxol-5-yl) -3, n-bis (4-fluorophenyl) pyrazoline-1-carboxamide.
In general, in the use of the insecticidal pyrazolines of the invention, these pyrazolines are not used in admixture or in diluted form, but are often used in a suitable formulated composition which is suitable for the application and which contains the pyrazolines in amounts which achieve the insecticidal effect. As with most pesticides, the pyrazolines of this invention can be admixed with those agriculturally acceptable surfactants and carriers typically used to facilitate dispersion of the active ingredient, as we see the well-recognized fact that the composition of a pesticide and its manner of use will affect the activity of the material. The pyrazoline of the invention can be applied to places where pest control is desired, for example, in the form of spray, powder or granule, and the manner of use varies depending on the pest and the environment. Thus, the pyrazoline of the invention can be formulated into large granules, powdery powders, wettable powders, emulsifiable concentrates (emulsifiable concentrates) and solutions and the like.
The granules may comprise porous or non-porous particles such as attapulgite (attapulgite) or sand, which may be used, for example, as a carrier for pyrazoline. The granules are relatively large, typically about 400 to 2500 microns in diameter. These particles are either immersed in a solution of pyrazoline or coated with pyrazoline, and in some cases a viscous material is used. The granule usually contains 0.05 to 10% of the active ingredient as an amount effective for killing insects, but preferably 0.5 to 5%.
Powders are mixtures of pyrazoline with finely divided solids such as talc, attapulgite, kieselguhr (kieselguhr), pyrophyllite, talc, diatomaceous earth (diato maccous carth), calcium phosphate, calcium and magnesium carbonates, sulphur, flours, and other organic or inorganic solids that can be used as carriers for pesticides.
These finely divided solids have an average particle size of less than about 50 microns. A typical powder formulation for effective pest control contains one part pyrazoline. For example 3- (4-chlorophenyl) -N- [4- (4-chlorophenoxy) phenyl ] -4-phenylpyrazoline-1-carboxamide and contains 99 parts of talc.
The pyrazolines of the invention can be prepared as liquid concentrates by dissolving or emulsifying in a suitable liquid, or as solid concentrates by blending with talc, clay and other solid carriers known in the pesticide arts. Such concentrates are mixtures containing about 5 to 50% pyrazoline, such as 3- (4-chlorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -4-phenylpyrazolin-1-carboxamide, in an amount effective as an insecticide, and 95 to 50% inert materials, including surface active dispersants, emulsifiers and wetting agents, however, higher concentrations of the active ingredient may also be used experimentally. The concentrate is diluted with water or other liquid that is actually used as a spray or with an additional solid carrier that is used as a powder.
Typical carriers suitable for use in solid concentrates (also known as wettable powders) include acid clay (bleaching clay) (fulier searth) clays, silica and other readily wettable inorganic diluents having high absorption properties. A solid concentrate formulation for effective pest control contains 1.5 parts each of sodium lignin sulfonate and sodium dodecyl sulfate as wetting agents, 25 parts of 3- (4-chlorophenyl) -N- (2, 3-dihydro-2, 2-dimethylbenzofuran-5-yl) -4- (4-chlorophenyl) phenylpyrazoline-1-carboxamide and 72 parts of attapulgite.
The manufacture of the concentrate will facilitate shipping of the low melting point product of the present invention. The concentrate is prepared by melting a low melting point solid product with one percent or more of a solvent to obtain a concentrate that does not solidify upon cooling to the freezing point of the neat product or less.
Useful liquid concentrates include emulsifiable concentrates. They are homogeneous liquids or pasty mixtures that are readily dispersed in water or other liquid carriers. They may consist entirely of pyrazolines with emulsifiers which are liquid or solid or they may also contain liquid carriers, for example xylene, heavy aromatic naphthas, isophorone and other relatively nonvolatile organic solvents. In application, these concentrates are dispersed in water or other liquid carrier, and are typically applied as a spray to the site where remediation is desired.
Typical surface-active wetting, dispersing and emulsifying agents used in pesticide formulations include, for example, alkyl and alkylaryl sulfonates and sulfates and their sodium salts, alkylamide sulfonates including fatty methyl taurates, alkylaryl polyether alcohols, sulfated higher alcohols, polyvinyl alcohols, polyethylene oxides, sulfonated animal and vegetable oils, phosphated petroleum oils, fatty acid esters of polyols and ethylene oxide adducts of such esters, and long chain thiols and ethylene oxide adducts. Many other types of useful surfactants are commercially available. Such surfactants typically contain about 1 to 15% by weight of the insecticide ingredient at the time of use.
Other useful formulations include simple solutions of the active ingredient in solvents in which the active ingredient is fully soluble and thus gives the desired concentration, such solvents being for example acetone or other organic solvents.
In pesticide mixtures (diluted for use), the amount of pyrazoline having pesticidal effect is generally in the range of about 0.001% to 8% by weight. Many variations of spraying and powdering pesticide mixtures known in the art can be utilized by replacing the pyrazoline of the invention with a component known or apparent in the art.
The insecticide formulations of the present invention may be formulated with other active ingredients including other insecticides, nematicides, acaricides, fungicides, plant growth regulators, fertilizers and the like. In the case of using such a mixture for controlling insect pests, it is only necessary to apply the pyrazoline in an amount having an insecticidal effect to a place where control is desired. Such a place may be, for example, the insect itself, a plant consumed by the insect, or the habitat of the insect. When the locus is soil, for example, soil in which crops have been planted or are to be planted, the active compound may be applied to the soil or optionally incorporated into the soil. For most applications, the amount of insecticidal effect is about 75 to 4000 grams, but preferably 150 to 3000 grams per hectare.
The pesticidal activity of pyrazolines whose preparation process has been described above was evaluated as follows:
in foliar application, the compounds were tested in various concentrations in aqueous solutions containing 10% acetone and 0.25% octylphenoxy polyethoxylaldehyde. The legumes were placed in a rotating turret within a hood, and the test solution was sprayed by a sprayer. The test solution was sprayed onto the surfaces of the upper and lower parts of the plant leaves and then dropped. The plant is then allowed to dry and cut at the root of the stem. Each rhizome was inserted into the water through a paper cup. Ten insects of the proper kind were placed in each cup and the cup was covered. For the measurement, southern armyworm (Spodoptera eridania), mexico soybean beetle (EPILACHNA VARIVESTIS), beet armyworm (Spodopteraexigua) and cabbage looper (trichloilusia nia) were used. After four days at 26 ℃ and 50% relative temperature, mortality was read. The results of the test are shown in Table 1, and if the test values are read earlier, the mortality rate of the insects is generally lower.
Several pyrazolines were also effective against larvae of southern corn root (Diabrot undecimpunctata howardi Barber) when applied to soil, and those pyrazolines tested were also effective against beetles of Colorado potato (Leptinotara dece-MLINEATA SAY).
TABLE I
Evaluation of foliar application
Insect consumption rate of compound (killing)
(PPM) M** SAW BAM CL
1 500 100 100
2 500 100 100
3 500 100 100
4 500 100 100
5 250 100 87 100
6 500 70 68 90
7 500 100 50 90
8 500 100 85
9 500 90 70
10 500 100 35
11 500 85 15
12 500 100 100
13 500 93 50
14 500 100 100
15 500 100 90
16 500 100
17 500 100 35
18 500 90 55
19 500 100 100
20 500 80 40
21 500 70 15
22 500 100 100
23 500 40 30
24 250 95
25 500 30 75
26 500 80 65
27 500 75 95
28 500 95 90
29 500 10 90
30 500 5 64
31 500 5 65 70
32 500 100 50
33 500 100 80
34 500 10 75
35 500 100 100
36 8 100 98 45 90
37 32 98 98 97 100
38 500 95 80
39 500 100 25
40 500 100 100
41 128 95 70
42 128 95 100
43 500 100 100
44 500 100 100
45 32 100 100 100 100
46 500 30 40
47 500 5 10
48 8 100 100 100 95
49 500 100 100
50 500 100 100
51 100 40 60
52 500 100 95
53 500 100 10
54 500 100 85
55 500 100 80
56 500 100 100
57 250 100 100
58 500 100 40
59 500 100 100
60 200 100 60
61 32 54 100 55 90
62 500 95 95
63 500 100 95
64 500 100 100
500 100 100
66 500 100 100
67 500 85 95
68 500 100 0
69 8 100 60 5 100
70 500 100 100
71 200 60 10
72 200 100 30
73 500 100 90
74 500 100 80
75 200 100 45
76 200 95 100
77 500 80
200 0 95
78 500 90 55
79 200 95 60
80 500 100 100
81 250 100 100
82 128 100 90
83 250 85 100
84 100 100 90
85 200 100 100
86 16 95 95 40 100
87 500 100 100
88 100 100 25 40 85
89 200 100 100
90 16 100 100 100 90
91 32 100 100 100 100
92 500 100 100
93 500 100 100
94 500 100 100
95 200 100 90
96 32 100 100 85 95
97 8 100 100 85
98 16 100 40 35 80
99 16 100 100 90 85
100 32 100 100 100 100
101 1000 100 100
102 128 100 100
103 16 90 95 15 100
104 16 100 100
105 256 100 70
106 1000 45 0
107 1000 100 75
108 1000 0 0
109 1000 70 0
110 1000 0 0
111 1000 100 90
112 1000 100 10
113 1000 100 30
114 1000 100 15
115 500 100 100
116 500 55 0
117 500 100 100
118 500 100 95
119 500 100 100
120 500 95 100
121 64 100 100
122 64 15 0
123 64 100 100
124 64 100 100
MBB = mexico soybean beetle
SAW = armyworm in south
BAW = beet armyworm
CL = cabbage looper

Claims (6)

1. The pesticide mixture consists of agriculturally acceptable carrier and pesticidal active component, and features that the agriculturally acceptable carrier is in liquid or solid state and its content is 5-99.99% and the pesticidal active component is 0.01-95% in chemical formula
The insecticidal pyrazoline of the formula, R is of the formula
Figure 85107882_IMG3
Wherein R' is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, lower alkynyloxy and lower haloalkyl, or
Figure 85107882_IMG4
X in the radical is a bridge of the formula [ O- (CR ' AAR′AB）a-Oa ' ], where a is 1 to 3, a ' is 0 or 1, a+a ' is at least 2 but not more than 3, R ' AA and R ' AB are optionally selected from hydrogen, halogen and lower alkyl, and R ' AC is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl, R B in the formula is
Figure 85107882_IMG5
Wherein R' is selected from hydrogen, halogen, lower alkyl, lower alkoxy and lower haloalkyl, or
Figure 85107882_IMG6
Wherein Y is a bridge of the formula [ O- (CR 'BAR′BB) b-Ob ], wherein b is 1 to 3, b' is 0 or 1, b+b 'is at least 2 but not more than 3, R' BA and R 'BB are optionally selected from hydrogen, halogen and lower alkyl, and R' BC is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl, R c in the formula of the insecticidal pyrazoline is
Figure 85107882_IMG7
Wherein R D is selected from hydrogen and lower alkyl, R E is selected from halogen lower alkyl, lower alkoxy, lower haloalkoxy, lower haloalkyl, cyano, nitro, -NR FRG (where R F and R G are optionally lower alkyl) and SO nRH (where R H is lower alkyl and n is 0-2), or
Figure 85107882_IMG8
Wherein Z is a bridge of the formula [ O- (CR 'CAR′CB）c-Oc' ], wherein c is 1 to 3, c 'is 0 or 1, c+c' is at least 2 but not greater than 3, R 'CA and R' CB are optionally selected from hydrogen, halogen and lower alkyl, with the proviso that when c is 1 and c 'is 1, R' CA and R 'CB are not both hydrogen and R' cc are selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl, and R N in the formula of the pesticidal pyrazoline is hydrogen or lower alkyl and V and W are optionally oxygen or sulfur.
2. The mixture of claim 1 wherein W is oxygen.
3. The mixture of claim 1, wherein R' A is halogen or lower haloalkoxy.
4. The mixture of claim 1, wherein R B is a 4-substituent.
5. A method for preventing and controlling pests features that the mixture containing the insecticidal effect of the insecticidal pyrazoline is applied to the area where pest control is needed or directly sprayed onto pests by foliage application or soil application
Figure 85107882_IMG9
Wherein R A is represented by the formula
Wherein R' A is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, lower alkynyloxy and lower haloalkyl, or
Figure 85107882_IMG11
Wherein X is a bridge of the formula [ O- (CR ' ABR′AB) a-Oa ' ], wherein a is 1 to 3, a ' is 0 or 1, a+a ' is at least 2 but not more than 3, R ' AA and R ' AB are selected from the group consisting of hydrogen, halogen and lower alkyl, and R ' AC is selected from the group consisting of hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl, and R B in the formula of pyrazoline is
Figure 85107882_IMG12
Wherein R' B is selected from hydrogen, halogen, lower alkyl, lower alkoxy and lower haloalkyl, or is
Figure 85107882_IMG13
Wherein Y is a bridge of the formula [ O- (CR 'BAR′BB) b-Ob' ], wherein b is 1 to 3, b 'is 0 or 1, b+b' is at least 2 but not more than 3, R 'BA and R' BB are optionally selected from hydrogen, halogen and lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl, and R C in the formula is
Wherein R D is selected from hydrogen and lower alkyl, R E is selected from lower alkyl, halogen, lower alkoxy, lower haloalkoxy and lower haloalkyl, cyano, nitro, -NR FRG (where R F and R G are optionally lower alkyl) and-SO nRH (where R H is lower alkyl and n is 0-2), or
Wherein Z is a bridge of the formula [ O- (CR 'CAR′CB）c-Oc' ], where c is 1 to 3, c 'is 0 or 1, c+c' is at least 2 but not greater than 3, R 'CA and R' CB are optionally selected from hydrogen, halogen and lower alkyl, with the proviso that when c is 1 and c 'is 1, both R' CA and R 'CB cannot be hydrogen and R' CC is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl, R N in the formula of the pesticidal pyrazoline is hydrogen or lower alkyl, and V and W are optionally oxygen or sulfur.
6. The mixture of claim 1, wherein the pesticidally active ingredient pyrazoline is prepared by reacting a compound of the formula R c -n=c=w with a compound of the formula
Figure 85107882_IMG16
The compounds of formula (I) are reacted and optionally the product is alkylated to give
Is used for killing the insect pyrazoline of the formula (I), wherein, R A has the chemical formula
Figure 85107882_IMG18
Wherein R' A is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, lower alkynyloxy and lower haloalkyl, or
Wherein X is a bridge of the formula [ O- (CR ' AAR′AB) a-Oa ' ], wherein a is 1 to 3, a ' is 0 or 1, a+a ' is at least 2 but not more than 3, R ' AA and R ' AB are optionally selected from hydrogen, halogen and lower alkyl, and R ' AO is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl, R B in the formula is
Wherein R' B is selected from hydrogen, halogen, lower alkyl, lower alkoxy and lower haloalkyl, or is
Wherein Y is a bridge of the formula [ O- (CR ' BAR′BB) b-Ob ' ], wherein b is 1 to 3, b ' is 0 or 1, b+b ' is at least 2 but not more than 3, R ' BA and R ' BB are any selected from hydrogen, halogen and lower alkyl, and R ' BC is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl, and R c in the formula is
Wherein R D is selected from hydrogen and lower alkyl, R E is selected from lower alkyl, halogen, lower alkoxy, lower haloalkoxy, lower haloalkyl, cyano, nitro, NR FRG (where R F and R G are optionally lower alkyl), and SO nRH (where R H is lower alkyl and n is 0-2), or
Figure 85107882_IMG23
Wherein Z is a bridge of the formula [ O- (CR 'CAR′CA）c-Oc' ], where c is 1 to, c 'is 0 or 1, c+c' is at least 2 but not greater than 3, R 'CA and R' CB are optionally selected from hydrogen, halogen and lower alkyl, with the proviso that when c is 1 and c 'is 1, R' CA and R 'CB are not both hydrogen and R' cc is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl, R N in the formula of the pesticidal pyrazoline is hydrogen or lower alkyl, and V and W are optionally oxygen or sulfur.
CN85107882.6A 1984-10-25 1985-10-24 Pyrazoline insecticides Expired CN1004272B (en)

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JPH02504273A (en) * 1987-07-17 1990-12-06 イー・アイ・デユポン・デ・ニモアス・アンド・カンパニー Insecticide pyrazoline
AU4316189A (en) * 1988-09-22 1990-04-18 E.I. Du Pont De Nemours And Company Substituted indazole arthropodicides
JPH05112556A (en) * 1991-10-18 1993-05-07 Nippon Bayeragrochem Kk Insecticidal pyrazolines
US5684041A (en) * 1996-02-01 1997-11-04 The Procter & Gamble Company Dihydrobenzofuran and related compounds useful as anti-inflammatory agents
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US4174393A (en) * 1975-07-09 1979-11-13 Duphar International Research B.V. 1,3,4-Substituted pyrazoline derivatives
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US4407813A (en) * 1981-02-17 1983-10-04 Nissan Chemical Industries Ltd. Insecticidal pyrazoline derivatives and composition
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