HU199808B - Process for producing pyrazoline derivatives and insecticides comprising pyrazoline derivatives as active ingredient - Google Patents

Description

The present invention relates to novel pyrazoline derivatives and to insecticidal compositions containing pyrazoline derivatives.

Pyrazolines are 5-membered heterocyclic ring compounds. They are represented by Formula (1) where the numbering system of the ring atoms is also indicated.

It is known in the literature on insecticides that certain 1-carbamoylpyrazoline derivatives have insecticidal properties. For example, U.S. Patent 4,174, 393 discloses

It discloses the insecticidal activity of 1-carbamoylpyrazoline derivatives which also contain a phenyl substituent at the 3- and 4- positions of the pyrazoline ring.

According to the present invention there is provided an insecticidal pyrazoline derivative of general formula (I) in which

Ra is 1,3-benzodioxol-5-yl or a group of formula (a) wherein

R'a is hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C3-C6 alkynyloxy, C1-C4 haloalkyl,

R b is a 1,3-benzodioxol-5-yl group or a 4-or 5-substituent of formula (c) wherein

R'b is hydrogen, halogen, C 1-4 alkyl, C 1-4 alkoxy, difluoromethoxy or

Is a C 1-4 haloalkyl group,

Re is a radical of formula (b) or (d)

V represents an oxygen or sulfur atom

Rd is hydrogen or C1-C4 alkyl.

Re is hydrogen, halo, C 1-6 alkyl, C 1-6 alkoxy, C 1-4 haloalkyl, C 1-4 haloalkoxy, cyano, nitro, -NR f R g

Rf and Rg are independently C1-C4 alkyl, or -SOn'RH, wherein

Rh is C 1 -C 4 alkyl and n 'is 2; obsession

Rca is hydrogen, halo or C 1-4 alkyl;

Rcb is hydrogen or halogen,

Rcc is hydrogen, halo, (C1-C4) alkyl or (C1-C4) haloalkoxy, n and m are 0 or 1, with the proviso that when n is 1 and m is 0, the presence of Rca is other than hydrogen,

R n is hydrogen or (C 1 -C 4) -alkyl;

W is oxygen or sulfur.

By "halogen" is meant fluorine, chlorine or bromine. Alkyl, alkoxy, alkynyloxy and the like may be straight or branched hydrocarbon chains; the term "halogen" attached to another group means that one or more hydrogen atoms in that group are substituted by halogen.

For most of the above pyrazoline derivatives, compounds in which W is oxygen are most preferred, especially when

R'a is a 4-position substituent, preferably a halogen atom such as ldor or iodine, or a C 1-4 alkoxy group such as difluoromethoxy. Pyrazoline derivatives in which Rb is substituted at the 4-position are generally more active than the corresponding 5-substituted pyrazolines, and compounds in which Rb is a phenyl group bearing R'b are particularly significant. In this regard, it is preferred that R'b be a 4-substituent, especially a halogen such as chlorine or fluorine.

As for the Re substituent, the most significant insecticidal compositions contain compounds in which 2,3-dihydro-2,2-dimethylbenzofuran-5-yl, 2,3-dihydro-2,2,3,3-tetrafluoro benzofuran-5-yl, 2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-6-yl,

2,2-difluoro-1,3-benzodioxol-5-yl or 2,2-dimethyl-1,3-benzodioxol-5-yl or 4-phenoxyphenyl. In the latter case, it is preferred that Rd is hydrogen and that Re is a substituent at the 4-position, especially C 1-4 haloalkoxy.

The pyrazoline derivatives of the present invention having significant insecticidal activity include, for example, a

3- [4- (difluoromethoxy) phenyl] -N- [2,3-dihydro-2,2-dimethylbenzofuran-5-yl] -4-phenylpyrazoline-1-carboxamide;

3,4-bis (4-fluorophenyl) -N- (2,3-dihydro-2,2,3,330-tetrafluorobenzofuran-5-yl) pyrazoline-1-carboxamide;

3.4-bis (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide;

N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -3- [4- (difluoromethoxy) phenyl] -4-phenylpyrazoline-1335-carboxamide;

N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- [4- (difluoromethoxy) phenyl] -N-methyl-4-phenylpyrazoline-1-carboxamide;

3,4-bis (4-chlorophenyl) -N- (2,2-dimethyl-1,340 benzodioxol-5-yl) pyrazoline-1-carboxamide;

N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3,4-bis (4-fluorophenyl) pyrazoline-1-carboxamide;

3- (4-Chloro-phenyl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) -4- (4-fluoro-phenyl) -pyrazoline-1-carboxamide;

3- [4- (Difluoroethoxy) phenyl] -N- [2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -N-methyl-4-phenylpyrazoline- 1-carboxamide;

3- (4-Chloro-phenyl) -N- (4- [4- (difluoromethoxy) -phenoxy] -phenyl} -4-phenyl-pyrazoline-1-carboxamide;

N- {4- [4- (difluoromethoxy) phenoxy] phenyl} -3- [4- (difluoromethoxy) phenyl] -4- (4-fluorophenyl) pyrazoline-1-carboxamide;

3- [4- (Difluoromethoxy) phenyl] -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrahydro-benzofuran-5-yl) pyrazoline-l-carboxamide;

3- [4- (Difluoromethoxy) phenyl] 4- (4-fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-6-yl) -pyrazoline -1-carboxamide;

4- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethyl60-benzofuran-5-yl) -3-phenylpyrazoline-1-carboxamide;

3- (4-Chloro-phenyl) -4- (4-fluoro-phenyl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -pyrazoline-1-carboxamide;

3- [4- (Difluoromethoxy) phenyl] 4- (fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-165-carboxamide, and

HU 199808 Β

4- (4-Chloro-phenyl) -3- [4- (difluoromethoxy) -phenyl] -N- (23-dihydro-2,2-dimethyl-benzofuran-5-yl) -pyrazoline-1-carboxamide.

The present invention also includes insecticidal compositions comprising an effective amount of at least one of the above pyrazoline derivatives in admixture with an agriculturally acceptable carrier.

According to the invention, the pyrazoline derivatives are prepared by the process according to the invention

In Scheme 1, a suitable aromatic isocyanate or isothiocyanate is coupled with an appropriately substituted pyrazoline.

The product can be alkylated in a manner known per se to give the corresponding N-alkylated pyrazolines.

Suitable substituted pyrazoline starting materials are generally known compounds. The required isocyanates or isothiocyanates can be prepared from the corresponding amines. Many amines are commercially available. Other amines may be prepared by the procedures described in the following examples.

Example 1

3- (4-Chloro-phenyl) -N- [4- (4-chloro-phenoxy) -phenyl] -4-phenyl-pyrazoline-1-carboxamide

Under a dry nitrogen atmosphere, 10.9 g (0.077 mol) of 4-fluoronitrobenzene, 9.95 g (0.077 mol) of 4-chlorophenol, 11.8 g (0.085 mol) of potassium carbonate and 175 ml of dimethylsulfoxide the mixture was heated at 70 ° C for 2 days with stirring. The reaction mixture was cooled and filtered. The filtrate was diluted to 1 liter with water. The mixture was extracted with diethyl ether (3 x 200 mL). The combined ethereal extracts were washed with water followed by saturated aqueous sodium chloride. The washed extract was dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to give 13.5 g of 4- (4-dichlorophenoxy) -nitrobenzene (m.p. 67-70 ° C).

13.5 g (0.054 mol) of 4- (4-chlorophenoxy) -nitrobenzene are hydrogenated in 250 ml of tetrahydrofuran with a catalytic amount (0.15 g) of platinum oxide to give 4- (4-chlorophenoxy) aniline in quantitative yield. .

To a solution of 0.75 g (3.4 mmol) of 4- (4-chlorophenoxy) aniline in 25 mL of toluene was added dropwise a solution of 0.43 mL (3.6 mmol) of trichloromethyl chlorine in 20 mL of toluene. formate was added and the mixture heated at 85 ° C for 3 hours. The mixture was cooled to room temperature and the solvent was evaporated under reduced pressure. The residue was dissolved in 25 ml of diethyl ether. The solution was stirred with 1.0 g (3.4 mmol)

It is added to a suspension of 3- (4-chlorophenyl) -4-phenylpyrazoline and diethyl ether. Triethylamine (3 drops) was added to the mixture and stirred at room temperature for 2 days. The solvent was evaporated to give 0.92 g of 3- (4-chlorophenyl) -N- [4- (4-chlorophenoxy) phenyl] -4-phenylpyrazoline-1-carboxamide (m.p. 158-161 ° C). .

Analysis:

C H

Calculated 66.92 4.22

Found 66.06 4.95

Nuclear Magnetic Resonance Spectrum (CDCl 3): 8.06 ppm.

Example 2

Ice-cold mixture of 3- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide in ml of concentrated nitric acid and 50 ml of concentrated sulfuric acid Add dropwise over 1 hour to 100.0 g (0.67 mol) of 2,3-dihydro-2,2-dimethylbenzofuran while maintaining the temperature at 5 ° C. The mixture was stirred at 0 ° C for 2.5 hours, then poured into ice water and extracted with diethyl ether. The extract was dried over anhydrous magnesium chloride and filtered. The filtrate was concentrated under reduced pressure to give a black oil. The oil was purified by silica gel column chromatography using toluene-n-hexane (9: 1) as eluent. 50 g of solid 2,3-dihydro-2,2-dimethyl-5-nitrobenzofuran are obtained.

20.0 g (0.1 mol) of 2,3-dihydro-2,2-dimethyl-5-nitrobenzofuran hydrogenated with a catalytic amount (0.2 g) of platinum oxide in 250 ml of methanol 16.6 g

5-amino-2,3-dihydro-2,2-dimethylbenzofuran is obtained.

trichloromethyl chloroformate (0.43 mL, 3.6 mmol) in toluene (0.56 g, 3.4 mmol) was added dropwise with stirring to 5-amino-2,3-dihydro-2,2-dimethylbenzofuran. 20 ml of a solution of toluene. The mixture was then refluxed for 3 hours, cooled to room temperature and the solvent evaporated under reduced pressure. The residue was dissolved in 25 ml of anhydrous diethyl ether and the solution was added dropwise to 1.0 g (3.4 mmol) of 3- (4-chlorophenyl) -4-phenylpyrazoline and 3 drops of triethylamine in 25 ml of diethyl ether. solution. The reaction mixture was stirred at room temperature for about 18 hours and then the precipitate was filtered off. The filter paste was suspended in ethanol and, after filtration, 0.47 g of 3- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxam time (melting point 160-162 ° C) is obtained.

Analysis:

C H

Calculated, 70.00 5.43

Found 69.50 3.36

NMR (DMSO-d6): 9.00 ppm.

Other members of the series produced by similar procedures are described in the examples below. Melting points are given in degrees Celsius. The NMR singlet corresponding to the compounds = NH protons is also given in some cases. Unless otherwise stated, the NMR spectrum was prepared using CDQ3. In some cases, elementary analysis will be provided.

Example 3

3,4-Diphenyl-N- (4-phenoxyphenyl) pyrazoline-1-carboxamide, m.p. 184-188. 9.17 ppm (DMSO-dodo)

Example 4

N- [4- (4-Chloro-phenoxy) -phenyl] -3,4-diphenyl-pyrazoline-1-carboxamide, m.p. 146-149. 8.83 ppm (DMSO-dodo)

Example 5

3- (4-Chloro-phenyl) -N- (4-phenoxy-phenyl) -4-phenyl-pyrazoline-1-carboxamide, m.p. 163-166. 8.03 PPm

Example 6

N- (4-Phenoxyphenyl) -4-phenyl-3- [4- (trifluoromethyl) phenyl] pyrazoline-1-carboxamide, m.p. 188-190.

8.10 ppm

HU 199808 Β

Example 7

3.4-bis (4-chlorophenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide, m.p. 189-193. 8.20 ppm [CDCl3 / DMSO-dodo]

Example 8

3- (4-Chloro-phenyl) -N- (3-methyl-4-phenoxy-phenyl) -4-phenyl-pyrazoline-1-carboxamide, m.p. 151-157.

9.13 ppm (DMSO dose)

Example 9

3- (4-Chloro-phenyl) -N- [4- (2-fluoro-phenoxy) -phenyl] -4-phenyl-pyrazoline-1-carboxamide, m.p. 153-155.

8.16 ppm

Example 10

3- (4-Chloro-phenyl) -N- [4- (3-fluoro-phenoxy) -phenyl] -4-phenyl-pyrazoline-1-carboxamide, m.p. 173-175.

9.33 ppm (DMSO-dodo)

Example 11

N- [4- (3-Chloro-phenoxy) -phenyl] -3- (4-chloro-phenyl) -4-phenyl-pyrazoline-1-carboxamide, m.p. 169-174.

9.30 ppm (DMSO-dodo)

Example 12

3- (4-Chloro-phenyl) -N- [4- (4-fluoro-phenoxy) -phenyl] -4-phenyl-pyrazoline-1-carboxamide, m.p. 164-167.

8.13 ppm

Example 13

3- {4-Chloro-phenyl-N- {4- [4- (trifluoromethyl) -phenoxy] -phenyl) -4-phenyl-pyrazoline-1-carboxamide, m.p. 161-164. 8.03 ppm

Example 14

N- [4- (4-Chlorophenoxy) phenyl] -3- [4- (difluoromethoxy) phenyl] -4-phenylpyrazoline-1-carboxamide, m.p. 103-107. 8.00 ppm

Example 15

3.4-bis (4-chlorophenyl) -N- (3-methyl-4-phenoxyphenyl) pyrazoline-1-carboxamide, m.p. 188-190. 0.23 ppm (DMSO-dodo)

Example 16

3.4-bis (4-chlorophenyl) -N- [4- (2-fluorophenoxy) phenyl] pyrazoline-1-carboxamide, m.p. 160-162. 8.10 PPm

Example 17

3.4-bis (4-chlorophenyl) -N- [4- (3-fluorophenoxy) phenyl] pyrazoline-1-carboxamide, m.p. 144-146. 9.20 ppm (DMSO-dodo)

Example 18

N- [4- (3-Chloro-phenoxy) -phenyl] -3,4-bis (4-chloro-phenyl) -pyrazoline-1-carboxamide, m.p. 135-140. 9.30 ppm (DMSO-dodo)

Example 79

3.4-bis (4-chlorophenyl) -N- [4- (4-fluorophenoxy) phenyl] pyrazoline-1-carboxamide, m.p. 168-170. 9.23 (DMSO-dto)

Example 20

N- [4- (4-Chloro-phenoxy) -phenyl] -3,4-bis (4-chloro-phenyl) -pyrazoline-1-carboxamide, m.p. 154-156. 9.30 ppm (DMSO-dodo)

Example 27

3.4-bis (4-chlorophenyl) -N- {4- [4- (trifluoromethyl) phenoxy] phenyl} pyrazoline-1-carboxamide, m.p. 191-194. 9.30 ppm (DMSO tax)

Example 22

2- (4-Chloro-phenyl) -4-phenyl-N- [4- (phenylthio) -phenyl] -pyrazoline-1-carboxamide, m.p. 157-162. 8.20 PPm

Example 23

3.4-bis (4-chlorophenyl) -N- [4- (phenylthio) phenyl] pyrazoline-1-carboxamide, m.p. 169-171. 8.20 PPm

Example 24

3.5-bis (4-chlorophenyl) -N- (phenoxyphenyl) pyrazoline-1-carboxamide, m.p. 168-170. 8.30 ppm (CDCl 3 -DMSO-dodo)

Example 25

3- (4-Chloro-phenyl) -5- [4- (trifluoromethyl) -phenyl] -N- (4-phenoxy-phenyl) -pyrazoline-1-carboxamide, m.p. 164-167. 8.00 ppm

Example 26

3.5-bis (4-chlorophenyl) -N- [4- (2-fluorophenoxy) phenyl] pyrazoline-1-carboxamide, m.p. 174-178. 8.50 PPm

Example 27

3.5-bis (4-chlorophenyl) -N- [4- (3-fluorophenoxy) phenyl] pyrazoline-1-carboxamide, m.p. 164-168. 9.00 ppm (DMSO dose)

Example 28

3.5-bis (4-chlorophenyl) -N- [4- (4-fluorophenoxy) phenyl] pyrazoline-1-carboxamide, m.p. 165-167. 9.16 ppm (DMSO-dodo)

Example 29

N- [4- (4-Chloro-phenoxy) -phenyl] -3,5-bis (4-chloro-phenyl) -pyrazoline-1-carboxamide, m.p. 142-144. 9.20 ppm (DMSO-dodo)

Example 30

3.5-bis (4-chlorophenyl) -N- {4- [4- (trifluoromethyl) phenoxy] phenyl] pyrazoline-1-carboxamide, m.p. 155-158. 8.43 ppm (CDCl 3 -DMSO-dodo)

Example 31

3- (4-Chloro-phenyl) -N- {4- [4- (trifluoromethyl) -phenoxy] -phenyl) -5- [4- (trifluoromethyl) -phenyl] -pyrazoline-1-carboxamide, 144-146. 8.06 ppm

Example 32

N- [4- (4-Chloro-phenoxy) -phenyl] -5- (4-chloro-phenyl) -3- [4- (difluoromethoxy) -phenyl] -pyrazoline-1-carboxamide, m.p. 66-70 . 8.60 ppm (DMSO-d6)

HU 199808 Β

Example 33

5- (1,3-Benzodioxol-5-yl) -3- (4-chlorophenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide, m.p.

125-128. 8.36 ppm (CDCL3-DMSO)

Example 34

5- (1,3-Benzodioxol-5-yl) -N- [4- (4-chlorophenoxy) phenyl] -3- (4-chlorophenyl) pyrazoline-1-carboxamide, m.p. 174-175 . 8.06

Example 35

N- (2,3-Dihydro-2,2-dimethylbenzofuran-5-yl) -3,4-diphenylpyrazoline-1-carboxamide, m.p. 139-

143. 7.69 ppm

Example 36

3- [4- (Difluoromethoxy) phenyl] -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide, m.p. 75-82 . 7.96 ppm

EXAMPLE 37 (ae) -3,4-Bis (4-Chloro-phenyl) -N- (2,3-dihydro-2,2-dimethyl-benzopyran-5-yl) -pyrazoline-1-carboxamide; 134-137, 7.93 ppm

Example 38

3,5-bis (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide, m.p. 175-180. 8.86 (DMSO tax)

Example 39

N- (1,4-Benzodioxan-6-yl) -3- (4-chlorophenyl) -4-phenylpyrazoline-1-carboxamide, m.p. 112-1125. 7.96 ppm

Example 40

N- (1,4-Benzodioxan-6-yl) -3,4-bis (4-chlorophenyl) pyrazoline-1-carboxamide, m.p. 140-145. 7.96 PPm

Example 41

3- (4-Chloro-phenyl) -N- (4-phenoxy-phenyl) -4-phenyl-pyrazoline-1-carbothioamide, m.p. 105-110.

10.30 ppm (DMSO-dodo)

Example 42

3.4-bis (4-chlorophenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carbothioamide, m.p. 151-153.9.26 ppm (DMSO dto)

Example 43

N- [4- (4-Chloro-phenoxy) -phenyl] -3,4-bis (4-chloro-phenyl) -pyrazoline-1-carbothioamide, m.p. 179-183. 9.10 ppm

Example 44

3- (4-Chloro-phenyl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -4-phenyl-pyrazoline-1-carbothioamide, m.p. 92-95. 10.12 ppm (DMSO-dodo)

Example 45

3.4-bis (4-Chloro-phenyl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -pyrazoline-carbothioamide, m.p.

149-154. 9.00 ppm (DMSO tax)

Example 46

N- (1,4-Benzodioxan-6-yl) -3,5-bis (4-chlorophenyl) pyrazoline-1-carboxamide, m.p. 83-85. 9.33 ppm (DMSO tax)

Example 47

5- (4-Chloro-phenyl) -3- [4- (trifluoromethyl) -phenyl] -N- {4- [4- (trifluoromethyl) -phenoxy] -pyrazoline-1-quinoxamide, m.p. 185th 8.77 ppm (CDCl 3 -DMSO dodo)

Example 48

N- (25-Dihydro-22d2-tetrofluorobenzofuran-5-yl) -3- [4- (difluoromethoxy) phenyl] -4-phenylpyrazoline-1-carboxamide

15.0 g (0.086 mol) of 2-ldoro-4-nitrophenol, 11.9 g (0.086 mol) of potassium carbonate, 1.5 g (0.02 mol) of propanethiol, 33.7 g of ethyl acetate are weighed in a pressure bottle. 0.13 mol) 1,2-dibromo-tetrafluoroethane and 115 ml of Ν, dimethylformamide. The bottle was sealed and the mixture was stirred at 50 ° C for 48 hours. The bottle is cooled to room temperature, opened and the contents are poured into a separatory funnel. About 200 ml of 2N sodium hydroxide solution are added. The mixture was extracted with diethyl ether (4 x 300 mL). The extracts were combined and washed with 2x100 2N sodium hydroxide solution. The washed extracts were dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to give an oil. The above reaction was repeated three more times. The oil residue from the four experiments was combined and purified by silica gel column chromatography using n-heptane-toluene (95: 5) as eluent. 57.6 g of 3-chloro-4- (2-bromo-1,1,2,2-tetrafluoroethoxy) -nitrobenzene are obtained in the form of an oil.

10.0 g (0.028 mol) of 3-chloro-4- (2-bromo-1,2,2,2-tetrafluoroethoxy) -nitrobenzene, 9.0 g (0.14 mol) of copper powder were charged into a pressure-resistant bottle. 0.074 mm mesh), 0.45 g (2.8 mmol) of 2,2'-bipyridyl and 40 ml of dimethylsulfoxide. The flask was hermetically sealed and the reaction mixture was stirred at 190-195 ° C for 2 hours. The flask was cooled to room temperature, opened and poured into a separatory funnel. About 200 ml of 2N hydrochloric acid are added. The mixture was extracted with diethyl ether (3 x 150 mL). The extracts were combined and washed successively with 2N hydrochloric acid (200 mL), brine (200 mL) and 2N sodium hydroxide (200 mL). The washed extract was dried over anhydrous magnesium sulfate and filtered. The solvent is evaporated under reduced pressure to leave an oil. The above reaction is repeated six times. The oil residue from the seven experiments was combined, chromatographed on a silica gel column, eluted with toluene. A yellow oil was obtained which was dissolved in 125 ml of methylcyclohexane and allowed to stand in the refrigerator for about 18 hours. The precipitated crystals were collected by filtration

20.7 g of 2,2,3,3-tetrafluoro-5-nitrobenzofirrane are obtained. The filtrate was concentrated under reduced pressure to leave an oil. Distillation of the oil under reduced pressure gave an additional 3.0 g of product (b.p. 75 ° C / 26.66 Pa). 2,2,3,3-tetrafluoro-5-nitrobenzene (2.15 g, 0.011 mole) in 150 ml of methanol was catalytic (0.25 g).

g) Hydrogenation with platinum oxide gives 2.15 g of 5-amino-2,2,3,3-tetrafluorobenzofuran.

0.75 g (5.6 mmol) of 5-amino-2,2,3,3-tetrafluoro5

Dissolve benzophorane (199808) in 109 ml of toluene and add dropwise with stirring 8.0 ml of 20% (w / w) solution of phosphene in toluene and reflux for 2 hours. The mixture was cooled and the solvent was evaporated under reduced pressure. The residue was dissolved in diethyl ether (15 mL) and added with stirring, 3- [4- (difluoromethoxy) phenyl] -4-phenylpyrazoline (1.4 g, 3.6 mmol) and triethylamine (3 drops). To a solution of 100 ml diethyl ether. The mixture was then refluxed for 1 hour, cooled to room temperature and stirred for about 18 hours. The solvent was evaporated under reduced pressure to give a solid residue. Recrystallization from ethanol gave 0.99 g of N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -3- [4- (difluoromethoxy) phenyl] -4-phenylpyrazoline-1-one. of carboxamide (m.p. 155-159 ° C).

Analysis:

C H

Calculated: 58.58 3.29

Found 57.81 3.75

NMR: 8.16 ppm

Example 49

3,4-Bis (4-chlorophenyl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) pyrazoline-1-carboxamide

1.18 g (6.8 mmol) of 5-amino-2,2-difluoro-1,3-benzodioxole (prepared by literature procedures) are dissolved in 80 ml of tetrahydrofuran and 24 ml of 20% w / w toluene cold (5 ml) are added dropwise. -10 ° C) for phosgene solution. It is then stirred at 2 ° C for 1 hour and then at reflux for 2 hours. The solvent was evaporated under reduced pressure to give 1.4 g of a liquid residue. 0.68 g of this residue is added with stirring to 0.93 g (3.2 mmol) in a clear flask.

Of 3,4-bis (4-chlorophenyl) pyrazoline and 3 drops of triethylamine in 20 ml of diethyl ether. It is then stirred at room temperature for about 18 hours. A small amount of solid in the reaction mixture was removed by filtration. The filtrate was evaporated under reduced pressure to give a residue, which was purified by column chromatography on silica gel using n-heptane-ethyl acetate (1: 1) as eluent. 1.3 g of 3,4bis (4-chlorophenyl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) pyrazoline-1-carboxamide are obtained (m.p.

150-155 'C).

Analysis:

C H

Calculated: 56.34 3.08

Found 57.16 2.89

NMR: 8.10 ppm

Example 50 was prepared in a similar manner.

Example 50

N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3- [4- (difluoromethoxy) phenyl] -4-phenylpyrazoline-1-carboxamide, m.p. 135-138. 8.10 ppm

Example 51

3- (4-Fluorophenyl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide, m.p. 187-191. 8.10 ppm .52. example

3- [4- (difluoromethoxy) phenyl] -N- (4-phenoxyphenyl) -46

-phenylpyrazoline-1-carboxamide, m.p. 139-144.

8.10 ppm

Example 53

3- (4-Chloro-phenyl) -N- [4- (4-chloro-phenoxy) -phenyl] -N-phenyl-pyrazoline-1-carboxamide, m.p. 170-174.

8.10 ppm

Example 54

3- (4-Chloro-phenyl) -N- [4- (4-nitro-phenoxy) -phenyl] -4-phenyl-pyrazoline-1-carboxamide, m.p. 187-189.

8.30 ppm

Example 55

3- (4-Chloro-phenyl) -N- [4- (4-methoxy-phenoxy) -phenyl] -4-phenyl-pyrazoline-1-carboxamide, m.p. 159-160. 807 ppm

Example 56

3- (4-Chloro-phenyl) -N- {4- [4- (difluoromethoxy) -phenoxy] -phenyl] -4-phenyl-pyrazoline-1-carboxamide, m.p. 181-184. 8.07 ppm

Example 57

N- [4- (4-Chloro-phenoxy) -phenyl] -3- [4- (trifluoromethoxy) -phenyl] -4-phenyl-pyrazoline-1-carboxamide, m.p. 132-134. 8.16 ppm

Example 58

N- [4- (4-Chloro-phenoxy) -phenyl] -4-phenyl-3- [4- (2-propynyloxy) -phenyl] -pyrazoline-1-carboxamide, m.p. 160-164. 8.13 ppm

Example 59

3- (1,3-Benzodioxol-5-yl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide, m.p. 220-223. 8.06 ppm

Example 60

4- (4-Chloro-phenyl) -N- (4-phenoxy-phenyl) -3-phenyl-pyrazoline-1-carboxamide, m.p. 153-155. 8.16 ppm

Example 61

3.4-bis (4-fluorophenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide, m.p. 194-198. 8.16 ppm

Example 62

N- [4- (2-Chloro-phenoxy) -phenyl] -3,4-bis (4-chloro-phenyl) -pyrazoline-1-carboxamide, m.p. 182-186. 8.10 ppm

Example 63

3.4-Bis (4-Chloro-phenyl) -N- [4- (4-methoxy-phenoxy) -phenyl] -pyrazoline-1-carboxamide. 8.20 ppm

Example 64

3- (4-Chloro-phenyl) -4- (4-fluoro-phenyl) -N- (4-phenoxy-phenyl) -pyrazoline-1-carboxamide, m.p. 178-179.

8.10 ppm

Example 65

N- [4- (4-Chloro-phenoxy) -phenyl] -3- (4-chloro-phenyl) -4- (4-fluoro-phenyl) -pyrazoline-1-carboxamide, m.p.

143-145. 8.03 ppm

HU 199808 Β

Example 66

3- (4-Chloro-phenyl) -4- (4-methyl-phenyl) -N- (4-phenoxy-phenyl) -pyrazoline-1-carboxamide, m.p. 165-168.

8.10 ppm

Example 67

N- [4- (4-Chloro-phenoxy) -phenyl] -3- (4-chloro-phenyl) -4- (4-methoxy-phenyl) -pyrazoline-1-carboxamide, m.p. 169-173. 8.07 ppm

Example 68

4- (4-Fluorophenyl) -3- (4-methoxyphenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide, m.p. 184-187.

8.17 ppm

Example 69

N- {4- (4- (Difluoromethoxy) phenoxy) phenyl] -3- [4- (difluoromethoxy) phenyl] -4- (4-fluorophenyl) pyrazoline-1-carboxamide. 8.10 ppm

Example 70

N- [4- (4-Chloro-phenoxy) -phenyl] -3- (4-chloro-phenyl) -4-phenyl-pyrazoline-1-thiocarboxamide, m.p. 179183. 9.10 ppm

Example 71

3- [4- (Difluoromethoxy) phenyl] -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-thiocarboxamide, m.p. 132136. 9.13 ppm

Example 72

4- (4-Chloro-phenyl) -N- (4-phenoxy-phenyl) -3-phenyl-pyrazoline-1-thiocarboxamide, m.p. 131-133.

9.16 ppm

Example 73

N- [4- (4-Chloro-phenylthio) -phenyl] -3,4-diphenyl-pyrazoline-1-carboxamide, m.p. 186-190. 8.20 ppm

Example 74

3- (4-Chloro-phenyl) -N- [4- (4-chloro-phenyl-thio) -phenyl] -4-phenyl-pyrazoline-1-carboxamide, m.p. 178-181.

8.23 ppm

Example 75

3- [4- (Difluoromethoxy) phenyl] -4-phenyl-N- [4- (phenylthio) phenyl] pyrazoline-1-carboxamide, m.p. 135-

140. 8.13 ppm

Example 76

3.4-bis (4-chlorophenyl) -N- [4- (4-fluorophenylthio) phenyl] pyrazoline-1-carboxamide, m.p. 171-175.

8.20 ppm

Example 77

3.4-bis (4-Chloro-phenyl-N- [4- (4-chloro-phenyl-thio) -phenyl] -pyrazoline-1-carboxamide, m.p. 151-156. 8.13 ppm

Example 78

3.4-bis (4-chlorophenyl) -N- [4- (3-chlorophenoxy) phenyl] pyrazoline-1-carboxamide, m.p. 135-140. 9.20 PPm

Example 79

3- (4-Methoxyphenyl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide, m.p. 188-192. 8.46 ppm (CDCl 3 -DMSO-dodo)

Example 80

3- [4- (2-Propynyloxy) phenyl] -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide, m.p. 121-126.

8.10 ppm

Example 81

3- (4-Chloro-phenyl) -N- (2,3-dihydro-benzofuran-5-yl) -4-phenyl-pyrazoline-1-carboxamide, m.p. 155-158.

7.93 ppm

Example 82

3- [4- (Difluoromethoxy) phenyl] -N- (2,3-dihydrobenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide. 7.93 PPm

Example 83

3.4-bis (4-chlorophenyl) -N- (2,3-dihydrobenzofuran-5-yl) pyrazoline-1-carboxamide, m.p. 214-216.

7.93 ppm

Example 84

3- (4-Fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide, m.p. 156-160. 7.93 ppm

Example 85

3- (4-Methoxyphenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide, m.p. 164-169. 8.00 ppm

Example 86

3- [4- (Trifluoromethoxy) phenyl] -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide, m.p. 81-83 . 7.98 ppm

Example 87

N- (2,3-Dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenyl-3- [4- (2-propynyloxy) phenyl] pyrazoline-1-carboxamide, m.p. 175 -179. 8.00 ppm

Example 88

3- (1,3-Benzodioxol-5-yl) -N- (2,3-dihydro-2,2-dimethylbenzophthalan-5-yl) -4-phenylpyrazoline-1-carboxamide, m.p. 223-227 . 8.90 ppm (DMSO-dodo)

Example 89

4- (4-Chloro-phenyl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -3-phenyl-pyrazoline-1-carboxamide, 8.00 PPm

Example 90

3.4-bis (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide, m.p. 161-166. 7.93 ppm

Example 91

3- (4-Chloro-phenyl) -4- (4-fluoro-phenyl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -pyrazoline-1-carboxamide, m.p. 169 -171. 7.96 ppm

HU 199808 Β

Example 92

3- (4-Chloro-phenyl) -4- (4-methyl-phenyl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -pyrazoline-1-carboxamide, m.p. -139. 7.96 ppm

Example 93

3- (4-Chloro-phenyl) -4- (4-methoxy-phenyl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -pyrazoline-1-carboxamide, m.p. 182 -186. 7.93 ppm

Example 94

4- (4-Fluoro-phenyl-N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -3- (4-methoxy-phenyl) -pyrazoline-1-carboxamide, m.p. 182. 7.93 ppm

Example 95

4- (4-Chloro-phenyl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -3- (4-methoxy-phenyl) -pyrazoline-1-carboxamide, m.p. -160. 7.96 ppm

Example 96

3- [4- (Difluoromethoxy) phenyl] -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -pyrazolin-1- carboxamide, m.p. 169-172, 7.93 ppm

Example 97

4- (4-Chloro-phenyl) -3- [4- (difluoromethoxy) -phenyl] -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -pyrazolin-1- carboxamide, m.p. 90-95. 7.92 ppm

Example 98

3- [4- (difluoromethoxy) phenyl] -N- (2,3-dihydro-2,2,3,3-benzofuran-6-yl) -4-phenyl-pyrazoline-l-carboxamide, 152-157. 8.33 ppm

Example 99

3- [4- (difluoromethoxy) phenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2,3,3-benzofuran-6-yl) - pyrazoline-1-carboxamide, m.p. 110-114. 8.33 ppm

Example 100

3- [4- (difluoromethoxy) phenyl] -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2,3,3-benzofuran-5-yl) - pyrazoline-1-carboxamide, m.p. 155-159. 8.20 ppm

Example 101

3- (4-Chloro-phenyl) -N- (2,2-dimethyl-1,3-benzodioxol-5-yl) -4-phenyl-pyrazoline-1-carboxamide, m.p. 182-186. 7.96 ppm

Example 102

3- [4- (Difluoromethoxy) phenyl] -N- (2,2-dimethyl-1,3-benzodioxol-5-yl) -4-phenylpyrazoline-1-carboxamide, m.p. 148-150. 7.93 ppm

Example 103

3,4-Bis (4-chlorophenyl-N- (2,2-dimethyl-1,3-benzodioxol-5-yl) pyrazoline-1-carboxamide, m.p. 168-169. 7.93 ppm

Example 104

N- (1,4-Benzodioxan-5-yl) -3- (4-difluoromethoxyphenyl) -4-phenylpyrazoline-1-carboxamide. 7.93 ppm δ

Example 705

N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3- [4- (difluoromethoxy) phenyl] -N-methyl-4-phenylpyrazoline-1-carboxamide, m.p. 110 -114.

Example 106

4- (1,3-benzodioxol-5-yl) -N- (4-phenoxyphenyl) -3-phenylpyrazoline-1-carboxamide, m.p. 195-197. 8.03 ppm

Example 107

3- (4-Chloro-phenyl) -N- {4- [4- (1,1-dimethylethyl) -phenoxy] -phenyl} -4-phenyl-pyrazoline-1-carboxamide, m.p.

192.5 to 194. 8.03 ppm

Example 108

3- (4-Chloro-phenyl) -4- (4-fluoro-phenyl) -N- [4- (4-methyl-phenoxy) -phenyl] -pyrazoline-1-carboxamide, m.p. 162-164. 8.03 ppm.

Example 709

3- (4-Chloro-phenyl) -4- (4-fluoro-phenyl) -N- (4- (4- (1,1-dimethylethyl) -phenoxy] -phenyl) -pyrazoline-1-carboxamide, mp 188-198 8.03 ppm

Example 770

3- (4-Chloro-phenyl) -N- (4- [4- (1-methylethyl) -phenoxy] -phenyl-4-phenyl-pyrazoline-1-carboxamide, m.p.

181-182.5. 8.06 ppm

Example 777

3- (4-Chloro-phenyl) -4- (4-fluoro-phenyl) -N- (4- (4- (1-methylethyl) -phenoxy] -phenyl} -pyrazoline-1-carboxamide, m.p. 186 -187 8.60 ppm (CDCl3-DMSO dto)

Example 772

3- (4-Chloro-phenyl) -N- [4- (4-methyl-phenoxy) -phenyl] -4-phenyl-pyrazoline-1-carboxamide, m.p. 150-151. 8.06 ppm

Example 113

3- (4-Chloro-phenyl) -N- {4- (4- (1-methyl-ethoxy) -phenoxy] -phenyl} -4-phenyl-pyrazoline-1-carboxamide, m.p. 158-160.5. , 06 ppm

Example 114

3- (4-Chloro-phenyl) -4- (4-fluoro-phenyl) -N- (4- (4- (1-methyl-ethoxy) -phenoxy) -phenyl] -pyrazoline-1-carboxamide, m.p. 216. 8.66 ppm (CDCl 3 -DMSO-dodo)

Example 775

3.4-bis (4-fluorophenyl) -N- {4- [4- (1-methylethoxy) phenoxy] phenyl} pyrazoline-1-carboxamide, m.p. 134-136. 8.06 ppm

Example 776

3.4-bis (4-fluorophenyl) -N- [4- (4-chlorophenoxy) phenyl] pyrazolone-1-carboxamide, m.p. 197-198.5.

8.70 ppm (CDCl3 / DMSO)

Example 777

3.4-bis (4-fluorophenyl) -N- (4- (4- (1,1-dimethylethyl) phenoxy] phenyl} pyrazoline-1-carboxamide, m.p. 189-192. 8.70 ppm (CDCl₃-DMSO-d)

HU 199808 Β

Example 118

3.4-bis (4-fluorophenyl) -N- [4- (4-cyanophenoxy) phenyl] pyrazoline-1-carboxamide, m.p. 198-200.

8.13 ppm

Example 119

3.4-bis (4-fluorophenyl) -N- {4- [4- (N, N-dimethylamino) phenoxy] phenyl} pyrazoline-1-carboxamide, m.p. 148-150. 8.02 ppm

Example 120

3- (4-Chloro-phenyl) -N- [4- (4-cyano-phenoxy) -phenyl] -4-phenyl-pyrazoline-1-carboxamide, m.p. 170-172.

8.16 ppm

Example 121

N- (1,4-Benzodioxan-6-yl) -4- (4-chlorophenyl) -3- [4- (difluoromethoxy) phenyl] pyrazoline-1-carboxamide, m.p. 124-128,7. 93 ppm

Example 122

3.4-bis (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -N-methylpyrazoline-1-carboxamide, m.p. 150-155.

Example 123

N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3,4-diphenylpyrazoline-1-carboxamide, m.p. 214-216. 8.83 ppm (CDCl 3 -DMSO-dodo)

Example 124

N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3,4-bis (4-fluorophenyl) pyrazoline-1-carboxamide, m.p. 178-180. 8.10 ppm

Example 125

3- (4-Chloro-phenyl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) -4- (4-fluoro-phenyl) -pyrazoline-1-carboxamide, m.p. 147-151 . 8.06 ppm

Example 126

3- [4- (difluoromethoxy) phenyl] -N- (2,3-dihydro-2,2,3,3-benzofuran-5-yl) -N-methyl-4-phenyl-pyrazoline 1-Carboxamide

Example 127

3- (4-Chloro-phenyl) -4- [4- (difluoromethoxy) -phenyl] -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -pyrazolin-1- m.p. 155-159; 7.96 ppm

Example 128

3- [4- (Difluoromethoxy) phenyl] -N- (2,3-dihydro-2,2-difluorobenzofuran-5-yl) -N-methyl-4-phenylpyrazoline-1-carboxamide.

Example 729

4- (4-Chloro-phenyl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- [4- (difluoromethoxy) -phenyl] -pyrazoline-1-carboxamide. 8.06 ppm

Example 130

4- (l, 3-benzodioxol-5-yl) -3- (4-chloro-phenyl) -N- {4- [4- (fluoro) phenoxy] phenyl} pyrazoline-l-carboxamide.

Example 737

4- (1,3-Benzodioxol-5-yl) -N- [4- (4-chlorophenoxy) phenyl] -3- (4-chlorophenyl) pyrazoline-1-carboxamide.

Example 732

4- (1,3-Benzodioxol-5-yl) -3- (4-chlorophenyl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) -pyrazoline-1-carboxamide.

Example 733

4- (l, 3-benzodioxol-5-yl) -3- (4-chlorophenyl) -N- (2,3-dihydro-2,2,3,3-benzofuran-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) -pyrazolin-1-yl; carboxamide.

Example 735

4- (1,3-Benzodioxol-5-yl) -N- {4- [4- (difluoromethoxy) phenoxy] phenyl} -3- (4-difluoromethoxy-phenyl) -pyrazoline-1-carboxamide .

Example 736

4- (l, 3-benzodioxol-5-yl) -N- [4- (4-chlorophenoxy) phenyl] -3- [4- (difluoromethoxy) phenyl] pyrazoline-l-carboxamide.

Example 737

4- (1,3-Benzodioxol-5-yl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- [4- (difluoromethoxy) phenyl] pyrazoline- 1-Carboxamide.

Example 138

4- (1,3-Benzodioxol-5-yl) -3- [4- (difluoromethoxy) phenyl] -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5) -yl) -pyrazoline-1-carboxamide.

Example 739

4- (1,3-Benzodioxol-5-yl) -3- [4- (difluoromethoxy) phenyl] -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-dimethylbenzophyran-5-yl) -3-phenylpyrazoline-1-carboxamide.

Example 141

4- (1,3-Benzodioxol-5-yl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -3-phenylpyrazoline-1-carboxamide

Example 142

4- (1,3-Benzodioxol-5-yl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3-phenylpyrazoline-1-carboxamide.

Example 143

4- (1,3-Benzodioxol-5-yl) -N- [4- (4- (difluoromethoxy) phenoxy) phenyl] -3-phenylpyrazoline-1-carboxamide.

Example 144

4- (1,3-Benzodioxol-5-yl) -N- [4- (4-chlorophenoxy) phenyl] -3-phenylpyrazoline-1-carboxamide.

HU 199808 Β

Example 175

3- (1,3-Benzodioxol-5-yl) -N- {4- [4- (difluoromethoxy) phenoxy] phenyl} -4- (4-fluorophenyl) -N-methylpyrazolin-1 -carboxamide.

Example 176

3- (l, 3-benzodioxol-5-yl) -N- [4- (4-chlorophenoxy) phenyl] -4- (4-fluorophenyl) pyrazoline-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- (fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -pyrazoline- 1-Carboxamide.

Example 179

3- (1,3-Benzodioxol-5-yl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2,2-dimethylbenzofuran-5-yl) -pyrazolin-1 -carboxamide.

Example 195

N- {4- [4- (Difluoromethoxy) -phenoxy] -phenyl) -4- (4-fluoro-phenyl) -3- (4-methyl-phenyl) -pyrazoline-1-carboxamide.

Example 196

N- [4- (Chlorophenoxy) 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-k-carboxamide.

Example 198

4- [4-Fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -3- (4-methylphenyl) pyrazoline-1- carboxamide.

Example 199

4- [4-Fluoro-phenyl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -N-methyl-3- (4-methylphenyl) pyrazolin-1 carboxamide.

Example 200

N- {4- [4- (Difluoromethoxy) -phenoxy] -phenyl} -4- (3-fluoro-phenyl) -N-methyl-3- (4-methyl-phenyl) -pyrazoline-1-carboxamide.

Example 201

N- [4- (4-Chloro-phenoxy) -phenyl] -4- (3-fluoro-phenyl) -3- (4-methoxy-phenyl) -pyrazoline-1-carboxamide.

Example 202

N- (2,2-difluoro-1,3-benzodioxol-5-yl) -4- (3-fluorophenyl) -3- (4-methylphenyl) pyrazolin-1-carboxamide.

Example 203

4- (3-Fluoro-phenyl) -N- (2,3-dihydro-2,2,3,3-benzofuran-5-yl) -3- (4-methylphenyl) pyrazolin-l- carboxamide.

Example 204

4- (3-Fluoro-phenyl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -3- (4-methyl-phenyl) -pyrazoline-1-carboxamide.

Example 205

N- (4- [4- (Difluoromethoxy) phenoxy] phenyl} -4- (2-fluorophenyl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.

Example 206

N- [4- (4-Chloro-phenoxy) -phenyl] -4- (3-fluoro-phenyl) -N-methyl-3- (4-methyl-phenyl) -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-2,2,3,3-tetrafluorobenzofuran-5-yl) -3- (4-methylphenyl) pyrazoline-1- carboxamide.

Example 209

4- (2-Fluoro-phenyl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -3- (4-methyl-phenyl) -pyrazoline-1-carboxamide.

Example 210

N- {4- [4- (Difluoro-methoxy) -phenoxy] -phenyl} -3- (3-fluoro-phenyl) -4- (4-fluoro-phenyl) -pyrazoline-1-carboxamide.

Example 211

N- [4- (4-Chloro-phenoxy) -phenyl] -3- (3-fluoro-phenyl) -4- (4-fluoro-phenyl) -N-methyl-pyrazoline-1-carboxamide.

2/2. example

N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (3-fluorophenyl) -4- (4-fluorophenyl) -N-methyl-pyrazoline-l-carboxamide.

Example 213

3- (3-Fluoro-phenyl) -4- (4-fluoro-phenyl) -N- (2,3-dihydro-62,2,3,3-tetrafluorobenzoftran-5-yl) -pyrazoline-1-carboxamide.

Example 214

3- (3-Fluoro-phenyl) -4- (4-fluoro-phenyl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -pyrazoline-1-carboxamide.

2/5. example

N- {4- [4- (Difluoromethoxy) -phenoxy] -phenyl) -3- (2-fluoro-phenyl) -4- (4-fluoro-phenyl) -pyrazoline-1-carboxamide.

Example 216

N- [4- (4-Chloro-phenoxy) -phenyl] -3- (2-fluoro-phenyl) -4- (4-fluoro-phenyl) -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-Fluoro-phenyl) -4- (4-fluoro-phenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluoro-benzofuran-5-yl) -N-methyl- pyrazoline-1-carboxamide.

-101

HU 199808 Β

Example 279

3- (2-Fluoro-phenyl) -4- (4-fluoro-phenyl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -pyrazoline-1-carboxamide.

Example 225

3.4-Bis (4-Fluorophenyl) -N- (2,2,6-trimethyl-1,3-benzodioxol-5-yl) pyrazoline-1-carboxamide.

Example 226

4- (4-Chloro-phenyl) -N- (2,2,6-trimethyl-1,3-benzodioxol-5-yl) -3- (4-methyl-phenyl) -pyrazoline-1-carboxamide.

Example 227

N- (2,2,6-Trimethyl-1,3-benzodioxol-5-yl) -3,4-diphenylpyrazoline-1-carboxamide.

Example 228

3- [4- (Difluoromethoxy) phenyl] -N- (2,2,6-trimethyl-1,3-benzodioxol-5-yl) -4-phenylpyrazoline-1-carboxamide.

Example 229

3- (4-Chloro-phenyl) -N- (2,2,6-trimethyl-1,3-benzodioxol-5-yl) -4-phenyl-pyrazoline-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-Chloro-phenyl) -N- [2,2-dimethyl-7- (1-methylethyl) -1,3-benzodioxol-5-yl] -3- (4-methyl-phenyl) -pyrazoline-carboxamide .

Example 237

N- [2,2-Dimethyl-7- (1-methylethyl) -1,3-benzodioxol-5-yl] -3,4-diphenylpyrazoline-1-carboxamide.

Example 238

3- [4- (Difluoromethoxy) phenyl] -N- [2,2-dimethyl-7- (1-methylethyl) -1,3-benzodioxol-5-yl] -4-phenylpyrazoline-1-carboxamide .

Example 239

3- (4-Chloro-phenyl) -N- [2,2-dimethyl-7- (1-methylethyl) -1,3-benzodioxol-5-yl] -4-phenyl-pyrazoline-1-carboxamide.

Example 240

3.4-Bis (4-Fluorophenyl) -N- (2,3-dihydro-7-ethyl-2,2,3,3-tetrafluorobenzofuran-5-yl) -pyrazoline-1-carboxamide.

Example 241

4- (4-Chloro-phenyl) -N- (2,3-dihydro-7-ethyl-2,2,3,3-tetrafluorobenzofuran-5-yl) -3- (4-methyl-phenyl) -pyrazoline-1 -carboxamide.

Example 242

N- (2,3-Dihydro-7-ethyl-2,2,3,3-tetrafluorobenzofuran-5-yl) -3,4-diphenylpyrazoline-1-carboxamide.

Example 243

3- [4- (difluoromethoxy) phenyl] -N- (2,3-dihydro-7-etil2,2,33-tetrafluoro-benzofuran-5-yl) -4-phenyl-pyrazolin-carboxamide.

Example 244

3- (4-Chloro-phenyl) -N- (2,3-dihydro-7-ethyl-2,2,3,3-benzofuran-5-yl) -4-phenyl-pyrazoline-l-carboxamide.

Example 245

3- (4-Chloro-phenyl) -N- {4- [4- (methylsulfonyl) -phenoxy] -phenyl] -4-phenyl-pyrazoline-1-carboxamide.

Example 246

3.4-Bis (4-Fluorophenyl) -N- {4- [4- (methylsulfonyl) phenoxy] phenyl} pyrazoline-1-carboxamide.

Example 247

3- [4- (Difluoromethoxy) phenyl] -N- {4- [4- (methylsulfonyl) phenoxy] phenyl} -4-phenylpyrazoline-1-carboxamide.

Example 248

3- (4-Chloro-phenyl) -4- (4-fluoro-phenyl) -N- {4- [4- (methylsulfonyl) -phenoxy] -phenyl] -pyrazoline-1-carboxamide.

Example 249

N- {4- [4- (Methylsulfonyl) phenoxy] phenyl} -3,4-diphenylpyrazoline-1-carboxamide.

Example 250

3.4-Bis (4-Fluorophenyl) -N- [2,3-dihydro-7- (difluoromethoxy) -2,2-dimethylbenzophthalan-5-yl] -pyrazoline-1-carboxamide.

Example 251

4- (4-Chloro-phenyl) -N- [2,3-dihydro-7- (difluoromethoxy) -2,2-dimethyl-benzofuran-5-yl] -3- (4-methyl-phenyl) - pyrazoline-l-carboxamide.

Example 252

N- [2,3-Dihydro-7- (difluoromethoxy) -2,2-dimethylbenzofuran-5-yl] -3,4-diphenylpyrazoline-1-carboxamide.

Example 253

3- [4- (Difluoromethoxy) phenyl] -N- [2,3-dihydro-7- (difluoromethoxy) -2,2-dimethylbenzofuran-5-yl] -4-phenylpyrazoline- 1-Carboxamide.

Example 254

3- (4-Chloro-phenyl) -N- [2,3-dihydro-7- (difluoromethoxy) -2,2-dimethyl-benzofuran-5-yl] -4-phenyl-pyrazoline-1-carboxamide.

Example 266

N- {3- [4- (Trifluoromethyl) phenoxy] phenyl} -3,4-bis (4-fluorophenyl) pyrazoline-1-carboxamide.

Example 267

N- [3- (4-Fluoro-phenoxy) -phenyl] -3,4-bis (4-fluoro-phenyl) -pyrazoline-1-carboxamide.

Example 268

N- {4- [4- (Difluoromethoxy) phenoxy] phenyl-3,4-bis (4-fluorophenyl) pyrazoline-1-carboxamide.

Example 276

3.4-bis (4-fluorophenyl-N- (4-phenoxyphenyl) pyrazoline-1-carbothioamide, m.p. 166-168 ° C; 9.05 ppm).

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HU 199808 Β

Example 277

3.4-bis (4-fluorophenyl) -N- [4- (4-methylphenoxy) phenyl] pyrazoline-1-carboxamide; 8.0 ppm.

Example 278

3.4-bis (4-fluorophenyl) -N- {4- [4- (1-methylethyl) phenoxy] phenyl} pyrazoline-1-carboxamide, m.p. 183-185 ° C; 8.0 ppm.

Example 280

3- (4-Chloro-phenyl) -N- [4- (4-cyano-phenoxy) -phenyl] -4- (4-fluoro-phenyl) -pyrazoline-1-carboxamide, m.p. 141-143 ° C ; 8.13 ppm.

Example 281

N- [4- (4-Chloro-phenoxy) -phenyl] -3- (4-fluoro-phenyl) -4-phenyl-pyrazoline-1-carboxamide, m.p. 158-161 ° C; 8.56 ppm; (CDCl3 / DMSO).

Example 282

N- [4- (4-Bromo-phenoxy) -phenyl] -3- (4-chloro-phenyl) -4-phenyl-pyrazoline-1-carboxamide, m.p. 164-166 ° C; 8.06 ppm.

Example 283

N- [4- (4-Bromophenoxy) phenyl] -3,4-bis (4-fluorophenyl) pyrazoline-1-carboxamide, m.p. 186-188 ° C; 8.03 ppm.

Example 284

N- [4- (4-Bromo-phenoxy) -phenyl] -3- (4-chloro-phenyl) -4- (4-fluoro-phenyl) -pyrazoline-1-carboxamide, m.p. 158-160 ° C. ;

8.33 ppm; (CDCl3 / DMSO-d).

Example 285

3.4-bis (4-fluorophenyl) -N- [4- (4-nitrophenoxy) phenyl] pyrazoline-1-carboxamide, m.p. 158-160 ° C; 8.26 ppm.

Example 286

3- (4-Chloro-phenyl) -4- (4-fluoro-phenyl) -N- [4- (4-nitro-phenoxy) -phenyl] -pyrazoline-1-carboxamide, 8.26 ppm.

Example 287

3- (4-Chloro-phenyl) -4- (4-fluoro-phenyl) -N- {4- [4- (N, N-dimethylamino) -phenoxy] -phenyl} -pyrazoline-1-carboxamide, 157-158 ° C; 8.04 ppm.

Example 291

3- (4-Chloro-phenyl) -N- [4- (4-hexoxy-phenoxy) -phenyl] -4-phenyl-pyrazoline-1-carboxamide, m.p. 105-107 ° C; 8.1 ppm.

Example 292

3- (4-Chloro-phenyl) -4- (4-fluoro-phenyl) -N- [4- (4-hexoxy-phenoxy) -phenyl] -pyrazoline-1-carboxamide, m.p. 108-110 ° C ; 8.1 ppm.

Example 297

3- (4-Chloro-phenyl) -N- {4- [4- (difluoromethoxy) -phenoxy] -phenyl} -4- (4-fluoro-phenyl) -pyrazoline-1-carboxamide, m.p. 141 -143 ° C; 8.43 ppm.

Example 306

3.4-bis (4-fluorophenyl) -N- (chroman-6-yl) pyrazoline-1-carboxamide, m.p. 182-185 ° C; 7.96 ppm.

Example 308

3- (4-Chloro-phenyl) -4- (4-fluoro-phenyl) -N- (2,2-dimethyl-chroman-6-yl) -pyrazoline-1-carboxamide, m.p. 187-188,5 'C; 7.93 ppm.

Example 309

3- [4- (Difluoromethoxy) phenyl] -N- (2,2-dimethylchroman-6-yl) -4-phenylpyrazoline-1-carboxamide, m.p. 200-201.5 ° C. ; 7.9 ppm.

Example 310

3,4-bis (4-chlorophenyl) -N- (2,2-dimethylchroman-6-yl) pyrazoline-1-carboxamide, m.p. 160-163 ° C; 7.9 ppm.

Example 312

4- (4-Chlorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -3-phenylpyrazoline-1-carboxamide, m.p. -163 ° C; 8.25 ppm.

Example 313

N- (2,3-Dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -3- (4-fluorophenyl) -4-phenylpyrazoline-1-carboxamide, m.p. -147 ° C; 8.03 ppm.

Example 314

N- (2,3-Dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -4- (4-fluorophenyl) -3-phenylpyrazoline-1-carboxamide, m.p. 169 -173 C; 8.26 ppm.

Example 315

4- (4-Chloro-phenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -3- (4-fluoro-phenyl) -pyrazoline-1- carboxamide, m.p. 153-158 ° C; 8.23 ppm.

Example 316

N- (2,3-Dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -3,4-bis (4-fluorophenyl) pyrazoline-1-carboxamide, m.p. 156- 160 ° C; 8.23 ppm.

Example 317

N- (2,3-Dihydro-7-chloro-2,2,3,3-tetrafluorobenzofuran-5-yl) -3,4-bis (4-fluorophenyl) pyrazoline-1-carboxamide, m.p. 185-189 ° C; 8.66 ppm.

Example 318

4- (4-Chloro-phenyl) -N- (2,3-dihydro-2,2,3,3-benzofuran-5-yl) -3- [4- (difluoromethoxy) phenyl] - pyrazoline-1-carboxamide, m.p. 89-93 ° C; 8.20 ppm.

Example 319

N- (2,3-Dihydro-2,2,3,3-benzofuran-5-yl) -3- [4- (difluoromethoxy) phenyl] -4-phenyl-pyrazoline-l-carboxamide.

Example 320

N- (2,3-Dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -3- [4- (difluoromethoxy) phenyl] -N-propyl-4-phenylpyrazoline- 1-Carboxamide.

Example 321

3- (4-Chloro-phenyl) -N- (2,2-diethyl-1,3-benzodioxol-5-yl) -4- (4-fluoro-phenyl) -pyrazoline-1-carboxamide, m.p. 169 -171C; 7.93 ppm.

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Example 322

N- (2,2-Diethyl-1,3-benzodioxol-5-yl) -3,4-bis (4-fluorophenyl) pyrazoline-1-carboxamide, m.p. 160-163 ° C;

7.93 ppm.

Example 323

4- (4-Chloro-phenyl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3-phenyl-pyrazoline-1-carboxamide, m.p. 139-144 ° C;

8.1 ppm.

Example 324

4- (4-Chloro-phenyl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4-fluoro-phenyl) -pyrazoline-1-carboxamide, m.p. 113 ° C; 7.93 ppm.

Example 325

N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3- (4-fluorophenyl) -4-phenylpyrazoline-1-carboxamide, m.p. 214-218 ° C; 8.96 ppm (CDCl3 / DMSO-dodo).

Example 326

N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -4- (4-fluorophenyl) -3-phenylpyrazoline-1-carboxamide, m.p. 201-204 C; 8.63 ppm (CDCl3 / DMSO).

Example 327

3,4-bis (4-chlorophenyl) -N- (2,2,3-trifluoro-1,4-benzodioxan-6-yl) pyrazoline-1-carboxamide, m.p. 8.03 ppm.

Example 328

3- (4-Chloro-phenyl) -N- (2,2,3-trifluoro-1,4-benzodioxan-6-yl) -4-phenylpyrazoline-1-carboxamide, m.p. 177-180 ° C. ; 9.3 ppm (CDCl 3 / DMSO).

Example 329

N- (2,2,3-Trifluoro-1,4-benzodioxan-6-yl) -3- [4- (difluoromethoxy) phenyl] -4-phenylpyrazoline-1-carboxamide, m.p. -70 ° C; 8.06 ppm.

Example 330

N- (2,2,3-Trifluoro-1,4-benzodioxan-6-yl) -3,4-bis (4-fluorophenyl) pyrazoline-1-carboxamide, m.p. 211214 C; 8.06 ppm.

Example 331

N- (3-Chloro-2,2,3-trifluoro-1,4-benzodioxan-6-yl) -3,4-bis (4-fluorophenyl) pyrazoline-1-carboxamide, m.p. C; 8.16 ppm.

Example 332

N- (3-Chloro-2,2,3-trifluoro-1,4-benzodioxan-6-yl) -3- [4- (difluoromethoxy) phenyl] -4-phenylpyrazoline-1-carboxamide, m.p. 68-71 ° C; 8.13 ppm.

Example 333

N- (3-Chloro-2,2,3-trifluoro-1,4-benzodioxan-6-yl) -3,4-bis (4-chlorophenyl) pyrazoline-1-carboxamide, m.p. 158 ° C; 8.1 ppm.

Example 334

N- (3-Chloro-2,2,3-trifluoro-1,4-benzodioxan-6-yl) -3- (4-chlorophenyl) -4-phenylpyrazoline-1-carboxamide, m.p. -113 ° C; 8.17 ppm.

Example 335

N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -4- (2-fluorophenyl) -3-phenylpyrazoline-1-carboxamide, m.p. 175-177 ° C; 9.30 ppm (DMSO).

The pyrazoline derivatives of the present invention are used in the form of formulations containing suitably formulated excipients and a diluent, which contain an effective amount of the insecticide of the pyrazoline derivative. These pyrazoline derivatives, like most pesticides, can be mixed with conventional agriculturally acceptable surfactants and carriers to facilitate dispersion of the active ingredient, taking into account the accepted fact that the insecticide formulation and mode of application may affect the activity of the substance. The pyrazoline derivatives of the present invention may be used, for example, in the form of sprays, powders or granules in the pest control area, and the type of application will naturally vary with the pest and the environment. can be processed.

The particles may contain porous and non-porous particles such as attapulgite material, sand, or the like, which may serve, for example, as carriers for pyrazoline derivatives. The particle particles are relatively large, typically about 4002500 microns in diameter. The particles are either impregnated with a solution of pyrazoline or coated with pyrazoline, sometimes using an adhesive. The particles generally contain from 0.05 to 10%, preferably from 0.5 to 5%, by weight of the active ingredient in an effective amount of an insecticide.

Powders contain pyrazoline derivatives with finely divided solids such as talc, attapulgite clay, diatomaceous earth, pyrophyllite, chalk, diatomaceous earth, calcium phosphates, calcium and magnesium carbonates, sulfur, flour, and other organic and inorganic compounds, they act as carriers for insecticides. These finely divided solids have an average particle size of less than about 50 micrometers. Typical powders for controlling pests 1 part by weight of a pyrazoline derivative such as 3- (4-chlorophenyl) -N- [4- (4-chlorophenoxy) phenyl] -4-phenylpyrazoline-1-carboxamide and 99 parts by weight contain talkurn.

The pyrazoline derivatives of the present invention may be formulated in liquid concentrates by dissolving or emulsifying the pyrazolines in suitable liquids. To form solid concentrates, the pyrazoline derivatives are mixed with talc clays or other solid carriers known in the art for pesticides. The concentrates contain an effective insecticidal amount of about 5-50% by weight of a pyrazoline derivative such as 3- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzophyran-5-yl) -4-phenylpyrazoline. In combination with -1-carboxamide and 95-50% by weight of inert material as surfactant dispersing, emulsifying and wetting agents, but higher active compound concentrations may also be used. Concentrates with water

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EN 199808 Β diluted with other liquids for use as sprays or as an additional solid support for use as powders.

Typical vehicles for preparing solid concentrates (i.e. wettable powders) are fuller earth, clays, silica and other well absorbable, readily wettable inorganic diluents. Solid concentrates for pest control 1.5-1.5 parts by weight of sodium lignosulphonate and sodium lauryl sulphate and 25 parts by weight of 3- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethyl) as wetting agent benzofuran-5-yl) -4- (4-chlorophenyl) pyrazoline-1-carboxamide and 72 parts by weight of attapulgite clay.

The preparation of concentrates is advantageous for shipboard transport of the low melting product of the invention. Such concentrates are prepared by melting low melting solid compounds with 5 wt% or more of a solvent to give a concentrate which does not solidify upon cooling to a freezing point or below the pure product.

Suitable liquid concentrates are, for example, emulsifiable concentrates which are readily dispersible in water or other liquid carrier in a homogeneous liquid or paste formulation. They may consist of pyrazoline derivatives and liquid or solid emulsifiers, or they may also contain liquid carriers such as xylene, heavy aromatic naphtha, isophorone and other relatively non-volatile organic solvents. For use, these concentrates are dispersed in water or other liquid vehicle and are usually sprayed on the areas to be treated.

Typical surfactant wetting, dispersing and emulsifying agents used in pesticidal formulations include, for example, alkyl and alkylaryl sulfonates and sulfates and their sodium salts; alkyl amides sulfonates, including fatty acid methyl taurates; alkylaryl polyether alcohols, sulfated higher alcohols, polyvinyl alcohols; poly (ethylene oxide) s; sulphonated animal and vegetable oils; sulphonated mineral oils; fatty acid esters of alcohols containing more than two hydroxyl groups and ethylene oxide adducts of such esters; and addition products of long-chain mercaptans and ethylene oxide. Many other types of surfactants are commercially available. The surfactant, when used, typically comprises from 1 to 15% by weight of the insecticidal composition.

Other useful formulations include simple solutions of the active ingredient in a solvent in which the active ingredient is completely dissolved at the desired concentration; such solvents include acetone or other organic solvents.

The effective amount of the pyrazoline derivative in a diluted insecticidal composition for use is generally in the range of about 0.001 to about 8% by weight. Many variations of known permeation and dusting compositions can be used in the process of the present invention using pyrazoline derivatives in the known formulations.

The insecticidal compositions of the present invention may be formulated with other active ingredients including other insecticides, nematodes, mites, fungicides, plant growth regulators, fertilizers 14 and the like. When using the compositions to control pest columns, it is only necessary to apply an effective amount of the insecticide of the pyrazoline derivative at the site to be treated. For example, the site may be the insect itself, the plant on which the insect feeds, or the "residence" of the insect. Where the area to be treated is the soil, for example, where agricultural produce is or will be planted, the active ingredient may be applied to or incorporated into the soil. In most applications, the effective insecticide application rate is 7-4000 g / ha, preferably 150-3000 g / ha.

Preparation Examples T% Powder Quantity (g)

Active ingredient ¹ 1.0

Finely divided silica 99.0

Total: 100.0% oily suspension

Quantity (g)

Active ingredient ² 25.0

Polyoxyethylene sorbitol hexaoleate 5.0 Aliphatic Hydrocarbon Oil 70.0

Altogether; 100.0

50% w / w emulsifiable concentrate

agent

Mixture of alkylnaphthalenesulfonate and polyoxyethylene ethers Epoxidized soybean oil Xylene

Altogether:

t% powder

Active substance ⁴

Sodium dibutylnaphthalenesulfonate

Sodium lignosulfonate

Kaolin

Total concentrate t%

Active ingredient ⁰

Synthetic fine silica Sodium lignosulphonate

Sodium alkyl naphthalene sulphonate

50.0

6.0

1.0

43.0

100.0

90.0

0.5

3.5

6.0

100.0

95.0

2.0

2.5

0.5

Compound 100.0 ': Compound of Example 36, Compound ² : Compound of Example 45, Compound ³ : Compound of Example 48, Compound ⁴ : Compound of Example 69, Compound ⁵ ; Example 97 Compound.

The insecticidal activity of the pyrazoline derivatives prepared as described above is evaluated as follows:

The compounds are tested on the leaves in various concentrations in aqueous solutions containing 10% by weight acetone and 0.25% by weight octylphenoxypolyethoxyethanol. The kidney bean seedlings are placed on a rotating table in the booth and the solutions to be examined are sprayed. The test solutions are applied to the upper and lower surfaces of the leaves of the plant until completely wetted. The plants are then allowed to dry and cut at the lower end of the stem. Place each stem in water using a paper cone. The right species of insect is 10 specimens

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HU 199808 Β put in each funnel and cover the funnel. Sting beetle (Spodoptera eridania), Common vetch (Epilachna varivestis), Southern weed (Spodoptera exigua) and goldenrod (Trichoplusia ni) are used for evaluation. After 4 days, mortality can be determined at 26 'C and 50% relative humidity. The results of this test are shown in Table 1. Insect mortality is generally lower if the assays are evaluated much earlier

Many pyrazoline derivatives, when applied on soil, were also effective against larvae of the 11-point Peruvian oil beetle (Diabrotica undecimpunctata howardi Barber) and were also very potent against the potato beetle (Leptinotara decemlineata Say).

Table 1

Evaluation by letter

Compound Quantity (Ppm) GB Insects (% mortality) HB DGY VA 1 500 100 100 2 500 100 100 3 500 100 100 4 500 100 100 5 250 100 87 100 6 500 70 65 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 90 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 95 100 25 500 30 75 26 500 80 65 27 500 75 95 28 500 95 90 29 500 10 90 30 500 5 64 60 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

Compound Quantity (Ppm) GB Insects (% mortality) HB DGY VA 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 45 100 55 90 62 500 95 95 63 500 100 95 64 500 100 100 65 500 100 100 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 10 85 89 200 100 100 90 16 100 100 100 90

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HU 199808 Β

Quantity

Compound (ppm) Insects (% death)

GB HB DGY VA

Compound Quantity (Ppm) GB Insects (% mortality) HB DGY VA 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 15 100 105 16 100 100 106 256 100 70 107 1000 45 0 108 1000 100 75 109 1000 0 0 110 1000 70 0 111 1000 0 0 112 1000 100 90 113 1000 100 10 114 1000 100 30 115 1000 100 15 116 500 100 100 117 500 55 0 118 500 100 100 119 500 100 95 120 500 100 100 121 500 95 100 122 64 100 100 123 64 15 0 124 64 100 100 125 64 100 100 240 128 65 246 128 100 250 128 75 276 500 100 100 277 128 100 90 278 128 100 5 280 64 100 100 281 32 100 80 282 500 100 100 283 500 100 100 284 64 100 55 285 64 100 95 286 500 100 100 287 750 100 100 297 500 100 100 306 250 100 85 308 500 100 60 309 500 100 80 310 500 100 100 312 8 95 100 100 100

313 16 100 95 314 64 100 100 315 8 100 100 316 4 100 100 317 64 25 318 64 100 100 319 8 95 85 320 16 100 75 321 64 5 20 322 64 75 40 323 8 100 100 324 8 100 100 325 1000 20 40 326 64 30 100 328 500 100 100 329 500 100 100 330 8 100 100 331 500 100 100 332 16 100 95 333 500 100 100 334 500 100 100 335 128 55 336 128 70

100

100 100 100 100

95

15

100 100 100 100

95

95

GB = Pine beech weed (Epilachna varivestis)

HB = Gordian Owl (Spodoptera eridania)

DGY = Southern weed owl (Spodoptera exigua)

VA = Golden Owl (V) (Trichoplusia ni)

Claims (30)

A process for the preparation of an insecticidal pyrazoline derivative of the Formula I wherein Ra is 1,3-benzodioxol-5-yl or a group of Formula a wherein 45 R'VA hydrogen, halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkoxy, C 3-6 alkynyloxy or C 1-4 haloalkyl means; Rb is 1,3-benzodioxol-5-yl or (c) A 4- or 5-substituent having the general formula (50) wherein R'b is hydrogen, halo, C 1-4 alkyl, C 1-4 alkoxy or C 1-4 haloalkyl, or difluoromethoxy 55 represents; Re is a radical of formula (b) or (d) V represents oxygen or sulfur, R d is hydrogen or C 1-4 alkyl 60; Re is C 1-6 alkyl, hydrogen, halo, C 1-6 alkoxy, C 1-4 haloalkoxy, C 1-4 haloalkyl, cyano, nitro or -NR f R g 65, wherein -161 HU 199808 Β R p and R g are independently C 1-4 alkyl -SOn'RH where Rh is C1-C4 alkyl and n 'is 2, Rca is hydrogen, halogen or C1-C4 alkyl, Rcb is idrogen or halogen, Rcc is hydrogen, halogen, C1 -C4 alkyl or C1 -C4 haloalkoxy, n and m are 0 or 1, provided that their sum is 1 or 2 and provided that when n is 1 and m is 0, then Rca is other than hydrogen, R n is hydrogen or C 1-4 alkyl, and W is oxygen or sulfur, characterized in that a compound of the formula R _C -N = C = W is reacted with a compound of the formula (-) in which Ra and Rb are as defined above, to obtain the compounds of the formula: which Ra, Rb, Rc. Rn and W are given in the scope. (Priority: September 24, 1985) 2. A process according to claim 1, wherein the starting material is Rc-N = C = W wherein: W is oxygen and Rc is as defined in claim 1. (Priority: September 24, 1985). 3. A process according to claim 1, wherein the starting material of formula (II) is wherein the substituent Ra represents a group of formula (a) wherein: R'a is halogen or C 1-4 haloalkoxy and Rb is as defined in claim 1. (Priority: September 24, 1985) 4. A process according to claim 1 wherein the starting material of formula II wherein The substituent Rb is in the 4-position and, together with the substituent Ra, is as defined in claim 1 (Priority: September 24, 1985). 5. A process according to claim 1 wherein the starting material of formula II is wherein Rb is a group of formula (c) in which R'b is as defined in claim 1 and Ra is as defined in claim 1. (Priority: September 24, 1985) 6. A process according to claim 5 wherein the starting material of formula II is wherein Rb is a group of formula c wherein R'b is halogen and Ra is as defined in claim 1. (Priority: September 24, 1985) 7. A process according to claim 1 wherein the starting material is Rc-N = C = W, wherein Rc is a group of formula (d) in which Rd and Re are as defined in claim 1, or Rc is 2,3-dihydro-2,2-dimethylbenzofuran-5-yl, 2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl, 2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-6-yl or 1,3-Benzodioxol-5-i, (Priority: 09/29/85) 8. A process according to claim 1 wherein the starting material is Rc-N = C = W, wherein Rc is a group of formula (h) in which Re is as defined in claim 1 and W is as defined in claim 1 (Priority: 09/29/1985) 9. A process according to claim 8 wherein the starting material is Rc-N = C = W, wherein Rc is a group of formula (h) in which Re is C 1-4 haloalkoxy, and W is as defined in claim 1. (Priority: 24/09/1985) 10. An insecticidal composition comprising as active ingredient from 0.001 to 95% by weight of a pyrazoline derivative of formula (I) Ra is 1,3-benzodioxol-5-yl or a group of formula (a) wherein R'a is hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C3-C6 alkynyloxy, C1-C4 haloalkoxy, R b is 1,3-benzodioxol-5-yl or a 4- or 5-substituent of formula (c) in which R'b is selected from the group consisting of hydrogen, halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 haloalkyl, and difluoromethoxy, Rc is a radical of formula (b) or (d) V represents oxygen or sulfur, Rd is hydrogen or (C1-C4) -alkyl; Re is C 1-6 alkyl, hydrogen, C 1 -C 6 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, cyano, nitro or NRfRg where Rf and Rg are independently C1 -C4 alkyl, or - SOn'RH is a group of the general formula wherein Rh is C 1-4 alkyl and n 'is 2, Rca is hydrogen, halogen or C1-C4 alkyl, Rcb is hydrogen or halogen, Rcc is hydrogen, halo, (C 1 -C 4) alkyl or (C 1 -C 4) -haloalkoxy, n and m are 0 or 1, provided that their sum is 1 or 2 and provided that when n is 1 and m is 0, then Rca is other than hydrogen, R n is hydrogen or C 1-4 alkyl, and -171 HU 199808 Β W is oxygen or sulfur, mixed with one or more agriculturally acceptable solid or liquid carriers and optionally with additives, preferably surfactants. (Priority: September 24, 1985) The insecticidal composition according to claim 10, characterized in that it contains an active ingredient of the formula (I) W is O and Ra, Rb, Rc, Rn are as defined in claim 10. (Priority: 9/24/1985) 12. An insecticidal composition according to claim 10, characterized in that it is an active ingredient of the formula (I) Ra is a group of formula (a) wherein R'a is halogen or C1-C4 haloalkoxy, and Rb, Rc, Rn and W are as defined in claim 10. (Priority: September 24, 1985) The insecticidal composition according to claim 10, characterized in that it contains an active ingredient of the formula (I) Rb is a 4-position substituent and represents - Ra, Rc. Together with Rn and W - as defined in claim 10. (Priority: September 24, 1985) 14. The insecticidal composition according to claim 10, wherein the active ingredient is 3- [4- (difluoromethoxy) phenyl] -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl). ) Containing 4-phenylpyrazoline-1-carboxamide. (Priority: September 24, 1985) 15. The insecticidal composition according to claim 10, wherein the active ingredient is 3,4-bis (fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-ol). il) contains pyrazoline-1-carboxamide. (Priority: September 24, 1985) 16. An insecticidal composition according to claim 10, wherein the active ingredient is 3,4-bis (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazolin-1-one. contains carboxamide. (Priority: September 24, 1985) An insecticidal composition according to claim 10, wherein the active ingredient is N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -3- [4- (difluoromethoxy) ) -phenyl] -4-phenylpyrazoline-1-carboxamide. (Priority: 08/08/1985) 18. The insecticidal composition of claim 10, wherein the active ingredient is N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- [4- (difluoromethoxy) phenyl] -N-. Contains methyl 4-phenylpyrazoline-1-carboxamide. (Priority: 9/24/1985) The insecticidal composition according to claim 10, wherein the active ingredient is 3,4-bis (4-chlorophenyl) -N- (2,2-dimethyl-1,3-benzodioxol-5-yl) pyrazolin-1-one. contains carboxamide. (Priority: September 24, 1985) 20. The insecticidal composition according to claim 10, wherein the active ingredient is N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3,4-bis (4-fluorophenyl) pyrazolin-1-one. contains carboxamide. (Priority: September 24, 1985) The insecticidal composition according to claim 10, wherein the active ingredient is 3- (4-chlorophenyl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) -4- (4- Fluorophenyl) -pyrazoline-1-carboxamide. (Priority: September 24, 1985) 22. The insecticidal composition according to claim 10, wherein the active ingredient is 3- [4- (difluoromethoxy) phenyl] -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5). il) Contains N-methyl-4-phenylpyrazoline-1-carboxamide. (Priority: September 24, 1985) An insecticidal composition according to claim 10, wherein the active ingredient is 3- (4-chlorophenyl) -N- {4- [4- (difluoromethoxy) phenoxy] phenyl} -4-phenylpyrazoline Contains -1-carboxamide. (Priority: 9/24/1985) The insecticidal composition according to claim 10, wherein the active ingredient is N- (4- [4- (difluoromethoxy) phenoxy] phenyl} -3- [4- (difluoromethoxy) phenyl] -4-. Contains (4-fluorophenyl) pyrazoline-1-carboxamide. (Priority: September 24, 1985) 25. The insecticidal composition according to claim 10, wherein the active ingredient is 3- [4- (difluoromethoxy) phenyl] -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2,3.3). Contains tetrafluorobenzofuran-5-yl) pyrazoline carboxamide. (Priority: September 24, 1985) 26. The insecticidal composition according to claim 10, wherein the active ingredient is 3- [4- (difluoromethoxy) phenyl] -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2.3). Contains 3-tetrafluorobenzofuran-6-yl) pyrazoline-1-carboxamide. (Priority: September 24, 1985) 27. The insecticidal composition according to claim 10, wherein the active ingredient is 4- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -3-phenylpyrazoline. Contains -1-carboxamide. (Priority: September 24, 1985) 28. The insecticidal composition according to claim 10, wherein the active ingredient is 3- (4-chlorophenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran). Contains 5-yl) -pyrazoline-1-carboxamide. (Priority: September 24, 1985) 29. The insecticidal composition according to claim 10, wherein the active ingredient is 3- [4- (difluoromethoxy) phenyl] -4- (4-fluorophenyl) -N- (2,3-dihydro-2, 2- dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide. (Priority: September 24, 1985) 30. The insecticidal composition according to claim 10, wherein the active ingredient is 4- (4-chlorophenyl) -3- [4- (difluoromethoxy) phenyl] -N- (2,3-dihydro-2,2- dimethylbenzofuran-5-yl) pyrazoline carboxamide.