CH666029A5 - PYRAZOLINE INSECTICIDES. - Google Patents

Description

DESCRIPTION The present invention relates to the field of biologically active chemical substances; in particular, it relates to new pyrazoline insecticides, process 35 and intermediates therefor, insecticidal preparations containing the pyrazolines, and to the use of the pyrazolines for the control of insects.

Pyrazolines are 5-membered heterocyclic ring compounds of the following formula with the following number 40 rank of the ring atoms:

v ~ W

45

H

It is known to those skilled in the art of insecticides that certain 1-carbamoylpyrazoline derivatives are insecticides. For example, U.S. Patent No. 4,174,393 discloses the insecticidal activity of l-carbamoylpyrazolines which also carry phenyl substituents in the 3 and 4 positions of the pyrazoline ring.

The present invention relates to pyrazolines of the formula:

where RD is selected from hydrogen and lower alkyl and Re from lower alkyl, halogen, lower alkoxy, halogeno lower alkoxy, halogeno lower alkyl, cyano, nitro, groups of the formula -NRfRg, where Rf and RG, which are the same or different, each represent lower alkyl, and Groups of the formula -SOnRH, in which RH is lower alkyl and n is 0 to 2, are selected, or for a group of the formula:

55

60

\ s /

«Jr V

w in which Ra for a group of the formula:

65

7

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where R'A is selected from hydrogen, halogen, lower alkyl, lower alkoxy, halogen-lower alkoxy, lower alkynyloxy and halogen-lower alkyl, or for a group of the formula :.

where X stands for a bridge of the formula:

[0- (CR'AAR'AB) a-0a-l, in which a is 1 to 3, a 'is 0 or 1, a + a' is at least 2 but not greater than 3, R'AA and R'AB, which are the same or different, are each selected from hydrogen, halogen and lower alkyl and R'AC is selected from hydrogen, halogen, lower alkyl, lower alkoxy, halogeno lower alkoxy and halogeno lower alkyl, RB for a 4- or 5-substituent of the formula :

R B

where R'B is selected from hydrogen, halogen, lower alkyl, lower alkoxy and halogeno lower alkyl, or for a 4- or 5-substituent of the formula:

where Y is a bridge of the formula:

[0- (CR'BAR'BB) b-0b-]

where b is 1 to 3, b 'is 0 or 1, b + b' is at least 2 but not greater than 3, R'BA and R'bb, which are the same or different, each from hydrogen, Halogen and lower alkyl are selected and R'BC is selected from hydrogen, halogen, lower alkyl, lower alkoxy, halogen lower alkoxy and halogen lower alkyl, Rc for a group of the formula:

where RD is selected from hydrogen and lower alkyl and Re from lower alkyl, halogen, lower alkoxy, halogeno lower alkoxy, halogeno lower alkyl, cyano, nitro, groups of the formula -NRfRg, wherein RF and Rg, which are the same or different, each represent lower alkyl, and Groups of the formula -SOnRH, in which RH is lower alkyl and n is 0 to 2, are selected, or for a group of the formula:

where Z stands for a bridge of the formula:

[0- (CR'caR'cb) c-oc.]

5 is where c is 1 to 3, c 'is 0 or 1, c + e' is at least 2 but not greater than 3, R'CA and R'CB, which are the same or different, each from hydrogen , Halogen and lower alkyl are selected, with the condition that R'ca and R'CB are not both hydrogen if c is 1 and 10 'and c' is 1, and R'Cc is hydrogen, halogen, lower alkyl, lower alkoxy, Halogen lower alkoxy and halogen 'lower alkyl is chosen, RN stands for hydrogen or lower alkyl and V and W, which are the same or different, each stand for oxygen or sulfur, which have a pronounced in-15 secticidal activity.

The term "halogen" used here means fluorine, chlorine or bromine. The term "lower", which modifies the terms "alkyl", "alkoxy", "alkynyloxy" and the like, means an unbranched or branched hydrocarbon chain with 1 to 6, preferably 1 to 4, carbon atoms; if the word «halogen» is coupled with another expression, it means that one or more hydrogen atoms have been replaced by halogen.

25 Of the pyrazolines defined above will become those for most applications. Compounds preferred in which W represents oxygen, in particular if R'A represents a 4-substituent, preferably halogen, for example chlorine or fluorine, or halogen-lower alkoxy, for example difluoromethoxy. Those pyrazolines in which RB is a 4-substituent are generally more active than the corresponding 5-substituted pyrazolines, and the compounds in which RB is phenyl which carries a substituent R'B are particularly interesting. In this context it is preferred that R'B is for a 4-substituent, especially halogen, e.g. Chlorine or fluorine.

The most interesting insecticides are usually derived from those compounds in which Rc is either 40 for 2,3-dihydro-2,2-dimethylbenzofuran-5-yl-, 2,3-di-hydro-2,2,3,3- tetrafluorobenzofuran-5-yl-, 2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-6-yl-, 2,2-difluoro-1,3-benzodi-oxol-5-yl- or 2,2 -Dimethyl-l, 3-benzodioxol-5-yl group or a 4-phenoxyphenyl group. In the latter case, it is preferred that RD stands for hydrogen and that Re stands for a 4-substituent, in particular for halogeno lower alkoxy.

The pyrazolines according to the invention with remarkable insecticidal activity include e.g. 3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -

4-phenylpyrazolin-1-carboxamide, 3,4-bis (4-fluorophenyl) -N-2,3-dihydro-2,2,3,3-tetrafhiorbenzofuran-5-yl) -pyrazo-lin-l-carboxamide , 3,4-bis (4-fluorophenyl) -N- (2,3-dihy-

55 dro-2,2-dimethylbenzofuran-5-yl) pyrazolin-1-carboxamide, N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -3- (4-di -fluoromethoxyphenyl) - 4-phenylpyrazoline-1-carboxamide, N- (2,2-digluoro-l, 3-benzodioxol-5-yl) - 3- (4-difluoromethoxy-phenyl) - N-methyl-4-phenylpyrazoline- 1-carboxamide, 60 3,4-bis- (4-chlorophenyl) -N- (2,2-dimethyl-l, 3-benzodioxol-5-yl) -pyrazoline-l-carboxamide, N- (2,2- Difluoro-l, 3-benzodi-oxol-5-yl) - 3,4-bis- (4-fluorophenyl) - pyrazolin-1-carboxamide, 3- (4-chlorophenyl) -N- (2,2-difluoro- 1,3-benzodioxol-5-yl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide, 3- (4-difluorometh-65 oxyphenyl) - N- (2,3-dihydro-2,2,3 , 3-tetrafluorobenzofuran

5-yl) -N-methyl-4-phenylpyrazoline-1-carboxamide, 3- (4-chlorophenyl) - N- [4- (4-difluoromethoxyphenoxy) - phenyl] -4-phenylpyrazoline-1-carboxamide, N- [ 4-difluoromethoxyphene

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oxy) - phenyl] -3- (4-difluoromethoxyphenyl) - 4- (4-fluorophenyl) pyrazoline-1-carboxamide, 3- (4-difluoromethoxyphenyl) - 4- (4-fluorophenyl) -N- (2,3 -dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -pyrazolin-1-carboxamide, 3- (4-difluoromethoxyphenyl) -4- (4-fluorophenyl) - N- (2,3-dihydro-2 , 2,3,3-tetrafluorobenzofuran-6-yl) pyrazolin-1-carboxamide, 4- (4-chlorophenyl) - N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) - 3- phe-nylpyrazoline-1-carboxamide, 3- (4-chlorophenyl) - 4- (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -pyrazoline- 1-carboxamide, 3- (4-difluoromethoxyphenyl) - 4- (4-fluorophenyl) - N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) - pyrazoline-1-carboxamide and 4- (4-chlorophenyl) -3- (4-difluoro-methoxyphenyl) - N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -pyrazoline-1-carboxamide.

The invention also relates to insecticidal preparations which contain an insecticidally effective amount of at least one of the pyrazolines defined above in a mixture with an agriculturally acceptable carrier. The invention also relates to a method for controlling insects, which is characterized in that an insecticidally effective amount of at least one of the pyrazolines defined above is applied to the place where the control is desired.

The pyrazolines according to the invention can be prepared by coupling an appropriate aromatic isocyanate or isothiocyanate with a correspondingly substituted pyrazoline; this method according to the invention can be represented by the following formulas:

H

+ R_ K = C = W

carbonate in 175 ml of dimethyl sulfoxide heated to 70 ° C with stirring for 2 days. The reaction mixture was cooled and filtered. The filtrate was diluted with water until a volume of one liter was obtained. This mixture was extracted with three portions of 200 ml of diethyl ether each. The combined ether extracts were washed with water and then with an aqueous saturated sodium chloride solution. The washed extract was dried over anhydrous sodium sulfate and filtered. Evaporation of the filtrate under reduced pressure gave 13.5 g of 4- (4-chlorophenoxy) nitrobenzene (melting point 67 to 70 ° C.)

A quantitative yield of 4- (4-chlorophenoxy) was obtained by hydrogenating 13.5 g (0.054 mol) of 4- (4-chlorophenoxy) nitrobenzene with a catalytic amount (0.15 g of 15 platinum oxide in 250 ml of tetrahydrofuran). get aniline.

To a solution of 0.75 g (0.0034 mol) of 4- (4-chlorophenoxy) aniline in 25 ml of toluene was added dropwise a solution of 0.43 ml (0.0036 mol) of trichloro-20 methylchlorononate added in 20 ml of toluene. After the addition was complete, the mixture was heated to 85 ° C for 3 hours. This mixture was cooled to room temperature and the solvent was evaporated under reduced pressure, leaving a residue. The residue 25 was dissolved in 25 ml of diethyl ether. This solution was added dropwise to a slurry of 1.0 g (0.0034 mol) of 3- (4-chlorophenyl) -4-phenylpyrazoline in diethyl ether with stirring. Three drops of triethylamine were added and the mixture was stirred at room temperature for 2 days. The solvent was evaporated 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.) were obtained.

30th

35 Analysis: NMR:

Calculated: Found: 8.06 ppm

C 66.92; C 66.06; (CDClj)

H 4.22 H 4.95

4 ^

(> '■

l ^ -H

Y N

^ Rc

The product can be alkylated by well known procedures to produce the corresponding N-alkylated pyrazolines.

The correspondingly substituted pyrazoline starting materials are generally known substances. The required isocyanates and isothiocyanates can be prepared from the corresponding amines. A number of the amines are commercially available. Other amines of interest can be prepared by the methods described in the following examples.

example 1

3- (4-chlorophenyl) -N- [4- (4-chlorophenoxy) phenylJ-4-plynylpyrazoline-1-carboxamide

A mixture of 10.9 g (0.077 ml) of 4-fluoronitrobenzene, 9.95 g (0.077 mol) of 4-chlorophenol and 11.8 g (0.085 mol) of potassium was evaporated under a dry nitrogen atmosphere.

Example 2

40 3- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide

Over a period of one hour, an ice-cold mixture of 43 ml of concentrated nitric acid and 50 ml of concentrated sulfuric acid was added dropwise to 100.0 g (0.67 mol) of 45 2,3-dihydro-2,2-dimethylbenzofuran while the temperature was reduced to 5 C was held. After the addition was complete, the mixture was stirred at 0 ° C. for 2.5 hours. The reaction mixture was poured into ice water and the whole extracted with diethyl ether. The extract was dried over anhydrous magnesium chloride and filtered. Evaporation of the filtrate under reduced pressure gave a black oil. Purification of this oil by column chromatography on silica gel eluting with a mixture of toluene and n-hexane (9: 1) 55 gave 50.0 g of 2,3-dihydro-2,2-dimethyl-5-nitrobenzofuran as a solid.

By hydrogenating 20.0 g (0.1 mol) of 2,3-dihydro-2,2-dimethyl-5-nitrobenzofuran with a catalytic amount of 60 (0.2 g) platinum oxide in 250 ml of methanol, 16.6 g of 5 -Ami-no-2,3-dihydro-2,2-dimethylbenzofuran.

A solution of 0.43 ml (0.0036 mol) of trichloromethyl chloroformate in 20 ml of toluene was added dropwise to a solution of 0.56 g (0.0034 mol) of 5-amino-2,3-65 dihydro-2 , 2-dimethylbenzofuran in 20 ml of toluene added. After the addition was complete, the mixture was heated to reflux for 3 hours. The mixture was cooled to room temperature and the solvent was removed under

evaporated under reduced pressure, leaving a residue. The residue was dissolved in 25 ml of dry diethyl ether and the solution was added dropwise with stirring to a mixture of 1.0 g (0.0034 mol) of 3- (4-chlorophenyl) -4-phenylpyrazoline and three drops of triethylamine in 25 ml of diethyl ether. The reaction mixture was stirred at room temperature for about 18 hours; a solid substance was then filtered off from the mixture. The filter cake was slurried in ethanol and collected by filtration, 0.47 g of 3- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazo-lin- 1-carboxamide (melting point 160 to 162 ° C) were obtained.

Analysis: Calc .: C 70.00; H 5.43 Found: C 69.50; H 3.36 NMR: 9.00 ppm (DMSO-d6)

Other links in the series of connections made by similar methods are shown in the following additional examples. The melting points are given in degrees Celsius. The NMR singlet, which corresponds to the = NH proton, which is characteristic of these compounds, is also given in some cases. Unless otherwise stated, the NMR solvent is CDC13. In some cases elemental analyzes are given.

Example 3

3,4-diphenyl-N- (4-phenoxyphenyl) pyrazoline-1-carboxamide, mp. 184-188. 9.17 ppm (DMSO-d6)

Example 4

N- [4- (4-chlorophenoxy) phenyl] -3,4-diphenylpyrazoline-1-carboxamide, mp 146-149. 8.83 ppm (DMSO-d6)

Example 5

3- (4-chlorophenyl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide, m.p. 163-166. 8.03 ppm

Example 6

N- (4-phenoxyphenyl) -4-phenyl-3- (4-trifluoromethylphenyl) pyrazoline-1-carboxamide, m.p. 188-190. 8.10 ppm

Example 7

3,4-bis (4-chlorophenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide, m.p. 189-193. 8.20 ppm (CDCl3 / DMSO-d6)

Example 8

3- (4-chlorophenyl) -N- (3-methyl-4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide, m.p. 151-157. 9.13 ppm (DMSO-d6)

Example 9

3- (4-chlorophenyl) -N- [4- (2-fluorophenoxy) phenyl] -4-phenylpyrazoline-1-carboxamide, m.p. 153-155. 8.16 ppm

Example 10

3- (4-chlorophenyl) -N- [4- (3-fluorophenoxy) phenyl] -4-phenylpyrazoline-1-carboxamide, m.p. 173-175. 9.33 ppm (DMSO-dfi)

Example 11

N- [4- (3-chlorophenoxy) phenyl] -3- 64-chlorophenyl) -4-phenylpyrazoline-1-carboxamide, m.p. 169-174. 9.30 ppm (DMSO-d6)

Example 12

3- (4-chlorophenyl) -N- [4- (4-fluorophenoxy) phenyl] -4-phenylpyrazoline-1-carboxamide, mp 164-167. 8.13 ppm

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Example 13

3- (4-chlorophenyl) -N- [4- (4-trifluoromethylphenoxy) - phenyl] -4-phenylpyrazoline-1-carboxamide, m.p. 161-164. 8.03 ppm

Example 14

N- [4- (4-chlorophenoxy) phenyl] -3- (4-difluoromethoxyphenyl) -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. 9.23 ppm (DMSO-d6)

Example 16

3,4-bis (4-chlorophenyl) -N- [4- (2-fluorophenoxy) phenyl) pyrazohn-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-d6)

Example 18

N- [4- (3-chlorophenoxy) phenyl] - 3,4-bis (4-chlorophenyl) pyrazoline-l-carboxamide, m.p. 135-140. 9.30 ppm (DMSO-dg)

Example 19

3,4-bis (4-chlorophenyl) -N- [4- (4-fluorophenoxy) phenyl] pyrazoline-1-carboxamide, m.p. 168-170. 9.23 ppm (DMSO-d6)

Example 20

N- [4- (4-chlorophenoxy) phenyl] -3,4-bis (4-chlorophenyl) pyrazoline-1-carboxamide, m.p. 154-156. 9.30 ppm (DMSO-d6)

Example 21

3,4-bis (4-chlorophenyl) -N- [4- (4-trifluoromethylphenoxy) phenyl] pyrazoline-1-carboxamide, m.p. 191-194. 9.30 ppm (DMSO-d6)

Example 22

3- (4-chlorophenyl) -4-phenyl-N- (4-phenylthiophenyl) -py-razoline-1-carboxamide, m.p. 157-162. 8.20 ppm

Example 23

3.4-bis- (4-chlorophenyl) -N- (4-phenylthiophenyl) pyrazo-lin-1-carboxamide, mp 169-171. 8.20 ppm

Example 24

3.5-bis (4-chlorophenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide, m.p. 168-170. 8.30 ppm (CDCl3 / DMSG-d6)

Example 25

3- (4-chlorophenyl) -5- (4-trifluoromethylphenyl) -N- (4-phenoxyphenyl) 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, mp 174-178. 8.50 ppm

Example 27

3,5-bis- (4-chlorophenyl) -N- [4- (3-fluorophenoxy> phenyl] pyrazoline-1-carboxamide, mp. 164-168. 9.00 ppm (DMSO-d6)

9

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

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10th

Example 28

3,5-bis (4-chlorophenyl) -N- [4- (4-fluorophenoxy) phenyl] pyrazoline-1-carboxamide, m.p. 165-167. 9.16 ppm (DMSO-d6)

Example 29

N- [4- (4-chlorophenoxy) phenyl] -3,5-bis (4-chlorophenyl) pyrazoline-1-carboxamide, m.p. 142-144. 9.20 ppm (DMSO-d6)

Example 30

3,5-bis (4-chlorophenyl) -N- [4- (4-trifluoromethylphenoxy) phenyl] pyrazoline-1-carboxamide, m.p. 155-158. 8.43 ppm (CDCl3 / DMSO-d6)

Example 31

3- (4-chlorophenyl) -N- [4- (4-trifluoromethylphenoxy) - phenyl] -5- (4-trifluoromethylphenyl) pyrazoline-l-carboxamide, m.p. 144-146. 8.06 ppm

Example 32

N- [4- (4-chlorophenoxy) phenyl] -5- (4-chlorophenyl) -3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide, m.p. 66-70. 8.60 ppm (DMSO-d6)

Example 33

5- (1,3-Benzodioxol-5-yl) -3- (4-chlorophenyl) - N- (4-phen-oxyphenyl) pyrazoline-1-carboxamide, m.p. 125-128. 8.36 ppm (CDCl3 / DMSO-d6)

Example 34

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

Example 35

N- (2,3-Dihydro-2,2-dimethylbenzofuran-5-yl) -3,4-diphenylpyrazoline-1-carboxamide, mp 139-143. 7.96 ppm

Example 36

3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide, m.p. 75-82. 7.96 ppm

Example 37

(±) -3,4-bis (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) pyrazoline-1-carboxamide, mp 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 ppm (DMSO-d6)

Example 39

N- (1,4-Benzodioxan-6-yl) -3- (4-chlorophenyl) -4-phenylpyrazoline-1-carboxamide, m.p. 112-115. 7.96 ppm

Example 40

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

Example 41

3- (4-chlorophenyl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carbothioamide, m.p. 105-110. 10.30 ppm (DMSO-d6)

Example 42

3,4-bis (4-chlorophenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carbothioamide, m.p. 151-153. 9.26 ppm (DMSO-d6) -

10th

15

Example 43

N- [4- (4-chlorophenoxy) phenyl] -3,4-bis (4-chlorophenyl> pyrazoline carbothioamide, m.p. 179-183. 9.10 ppm

Example 44

3- (4-chlorophenyl-N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carbothioamide, mp 92-95. 10.12 ppm (DMSO- d6)

Example 45

3,4-bis (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carbothioamide, m.p. 149-154. 9.00 ppm (DMSO-d6)

Example 46

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

Example 47

2 ° 5- (4-chlorophenyl) -3- (4-trifluoromethylphenyl) -N- [4- (4-trifluoromethylphenoxy) phenyl] pyrazoline-l-carboxamide, mp. 183-185, 8.77 ppm (CDCl3 / DMSO-d6)

Example 48

25 N- (2,3-Dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -3- (4-di-ßuormethoxyphenyl) -4-phenylpyrazoline-1-carboxamide

15.0 g (0.086 mol) of 2-chloro-4-nitrophenol, 11.9 g (0.086 mol) of potassium carbonate, 1.5 g (0.02 mol) of propanethiol, 33.7 g (0.13 Mol) 1,2-Dibromtetra-30 fluoroethane and 115 ml of N, N-dimethylformamide filled. The pressure bottle was sealed and the mixture was stirred at 50 ° C for 48 hours. The pressure bottle was cooled to room temperature and opened and the contents were poured into a separatory funnel. Approximately 35 200 ml of a 2 normal sodium hydroxide solution was placed in the separatory funnel. The resulting mixture was extracted with four 300 ml portions of diethyl ether. The extracts were combined and washed with two 100 ml portions of a 2 normal sodium hydroxide solution. The washed extract was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure leaving an oil. The reaction described above was repeated three more times. The oil residues from the four experiments were combined and purified by column chromatography on silica gel, eluting with a mixture of n-heptane and toluene (95: 5) and 57.6 g of 3-chloro-4- (2-bromo -l, l, 2,2-tetrafluoroethoxy) - nitrobenzene as an oil. 10.0 g (0.028 mol) of 3-chloro-50 4- (2-bromo-l, l, 2,2-tetrafluoroethoxy) nitrobenzene, 9.0 g (0.14 mol) of copper powder (0.075 mm mesh size), 0.45 g (0.0028 mol) of 2,2'-bipyridyl and 40 ml of dimethyl sulfoxide. The pressure bottle was sealed and the reaction mixture was stirred at 190 to 195 ° C for 2 hours. The pressure bottle was cooled to room temperature and opened and the contents were poured into a separatory funnel. Approximately 200 ml of a 2 normal hydrochloric acid solution was added to the separatory funnel. The mixture was extracted with three 150 ml portions of 60 diethyl ether. The extracts were combined and washed successively with 200 ml of a 2 normal hydrochloric acid solution, 200 ml of a saturated aqueous sodium chloride solution and 200 ml of a 2 normal sodium hydroxide solution. The washed extract was dried over anhydrous magnesium sulfate and filtered. The solvent was evaporated under reduced pressure leaving an oil. The reaction described above was repeated six more times. The oil residues from the seven

11

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Experiments were combined and subjected to column chromatography on silica gel while eluting with toluene to give a yellow oil. This oil was dissolved in 125 ml of methylcyclohexane and the solution was kept in a freezer for approximately 18 hours. Crystals had formed and were collected by filtration to give 20.7 g of 2,2,3,3-tetrafluoro-5-nitro-benzofuran. The filtrate was evaporated under reduced pressure leaving an oil. Distillation of this oil under reduced pressure gave an additional 3.0 g of product (boiling point 75 ° C / 0.2 mm column of mercury). Hydrogenation of 2, 15 g (0.011 mol) of 2,2,3,3-tetrafluoro-5-nitrobenzene with a catalytic amount (0.25 g) of platinum oxide in 150 ml of methanol gave 2.15 g of 5-amino-2 , 2,3,3-tetrafluorobenzofuran.

A solution of 0.75 g (0.0036 mol) of 5-amino-2,2,3,3-tetrafhiorbenzofuran in 109 ml of toluene was added dropwise with stirring to a solution of 8.0 ml of 20% phosgene in toluene. After the addition was complete, the mixture was heated to reflux for 2 hours. The mixture was cooled and the solvent was removed by evaporation under reduced pressure, leaving a residue. This residue was dissolved in 15 ml of diethyl ether and added with stirring to a solution of 1.04 g (0.0036 mol) of 3- (4-difluoromethoxyphenyl) -4-phenylpyrazoline and three drops of triethylamine in 100 ml of diethyl ether. After the addition was complete, the mixture was heated to 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. Recrystallization from ethanol gave 0.99 g of N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -3- (4-difluoromethoxyphenyl) -4-phenylpyrazoline-1-carb- oxamide (melting point 155 to 159 'C).

Analysis: Calc .: C 58.58; H 3.29 Found: C 57.81; H 3.75 NMR: 8.16 ppm

Example 49

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

A solution of 1.18 g (0.0068 mol) of 5-ammo-2,2-difluoro-1,3-benzodioxole, which had been prepared by the method described in the literature, in 80 ml of tetrahydrofuran was made added dropwise to a cold (5 to 10 ° C) solution of 24 ml of 20% phosgene in toluene. After the addition was complete, the mixture was stirred at 2 ° C for 1 hour and then under reflux for 2 hours. The solvent was evaporated under reduced pressure, leaving 1.4 g of a liquid residue. In a clean reaction flask, 0.68 g of this residue was slowly added with stirring to a solution of 0.93 g (0.0032 mol) of 3,4-bis (4-chlorophenyl) pyrazoline and three drops of triethylamine in 20 ml of diethyl ether . After the addition was complete, the mixture was stirred at room temperature for approximately 18 hours. A small amount of solid was present in the reaction mixture and was removed by filtration. The filtrate was evaporated under reduced pressure, leaving a residue. Purification of this residue by column chromatography on silica gel eluting with a mixture of n-heptane and ethyl acetate (1: 1) gave 1.3 g of 3,4-bis (4-chlorophenyl) -N- (2,2-difluoro- 1,3-benzodioxol-5-yl) -pyrazoline-1-carboxamide (melting point 150 to 155 ° C).

Analysis: Calculated: C56.34; H 3.08 Found: C 57.16; H 2.89 NMR: 8.10 ppm

The compound of Example 50 was made in a similar manner. .

Example 50

N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) -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

Example 52

3- (4-difluoromethoxyphenyl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide, m.p. 139-144. 8.10 ppm

Example 53

3- (4-chlorophenyl) -N- [4- (4-chlorophenoxy) phenyl] - 4-phenylpyrazoline carboxamide, m.p. 170Î-174. 8.10 ppm

Example 54

3- (4-chlorophenyl) -N- [4- (4-nitrophenoxy) phenyl] -4-phenylpyrazoline-1-carboxamide, m.p. 187-189. 8.30 ppm

Example 55

3- (4-chlorophenyl) -N- [4- (4-methoxyphenoxy) phenyl] -4-phenylpyrazoline-1-carboxamide, m.p. 159-160. 8.07 ppm

Example 56

3- (4-chlorophenyl) -N- [4- (4-difluoromethoxyphenoxy) phenyl] -4-phenylpyrazoline-1-carboxamide, m.p. 181-184. 8.07 ppm

Example 57

N- [4- (4-chlorophenoxy) phenyl] -3- (4-trifluoromethoxyphenyl) -4-phenylpyrazoline-1-carboxamide, m.p. 132-134. 8.16 ppm

Example 58

N- [4- (4-chlorophenoxy) 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-chlorophenyl) -N- (4-phenoxyphenyl) -3-phenylpyrazoline-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-chlorophenoxy) phenyl] -3,4-bis (4-chlorophenyl) pyrazoline-1-carboxamide, m.p. 182-186. 8.10 ppm

Example 63

3,4-bis (4-chlorophenyl) -N- [4- (4-methoxyphenoxy) phe-nylj-pyrazoline-1-carboxamide. 8.20 ppm

Example 64

3- (4-chlorophenyl) -4- (4-fluorophenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide, m.p. 178-179. 8.10 ppm

5

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666 029 12

Example 65

N- [4- (4-chlorophenoxy) phenyl] -3- (4-chlorophenyl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide, m.p. 143-145. 8.03 ppm

Example 66

3- (4-chlorophenyl) -4- (4-methylphenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide, m.p. 165-168. 8.10 ppm

Example 67

N- [4- (4-chlorophenoxy) phenyl] -3- (4-chlorophenyl) -4- (4-methoxyphenyl) 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-difluoromethoxyphenoxy) phenyl] - 3- (4-difluoro-methoxyphenyl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide. 8.10 ppm

Example 70

N- [4- (4-chlorophenoxy) phenyl] -3- (4-chlorophenyl) -4-phenylpyrazoline-1-thiocarboxamide, m.p. 179-183. 9.10 ppm

Example 71

3- (4-difluoromethoxyphenyl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-thiocarboxamide, m.p. 132-136. 9.13 ppm

Example 72

4- (4-chlorophenyl) -N- (4-phenoxyphenyl) -3-phenylpyrazoline-1-thiocarboxamide, m.p. 131-133. 9.16 ppm

Example 73

N- [4- (4-chlorophenylthio) phenyl] -3,4-diphenylpyrazo-lin-1-carboxamide, m.p. 186-190. 8.20 ppm

Example 74

3- (4-chlorophenyl) -N- [4- (4-chlorophenylthio) phenyl] -4-phenylpyrazoline-1-carboxamide, m.p. 178-181. 8.23 ppm

Example 75

3- (4-difluoromethoxyphenyl) -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-chlorophenyl) -N- [4- (4-chlorophenylthio) 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 (DMSO-dft)

Example 79

3- (4-methoxyphenyl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide, m.p. 188-192. 8.46 ppm (CDCI3, DMSO-dfi)

Example 80

3- [4- (2-propynyloxy) phenyl] -N- (4-phenoxyphenyl) -4-phenylpyrazoline-l-carboxamide, m.p. 121-126. 8.10 ppm

Example 81

3- (4-chlorophenyl) -N- (2,3-dihydrobenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide, m.p. 155-158. 7.93 ppm

5 Example 82

3- (4-difluoromethoxyphenyl) -N- (2,3-dihydrobenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide. 7.93 ppm

Example 83

10 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-dimethylbenzofu-15 ran-5-yl) -4-phenylpyrazoline-1-carboxamide, m.p. 156-160. 7.93 ppm

Example 85

3- (4-methoxyphenyl) -N- (2,3-dihydro-2,2-dimethylben-20 zofuran-5-yl) -4-phenylpyrazoline-1-carboxamide, mp 164-169. 8.00 ppm

Example 86

3- (4-Trifluoromethoxyphenyl) -N- (2,3-dihydro-2,2-dime-25thylbenzofuran-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-30 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-dimethyl-35 benzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide, m.p.

223-227. 8.90 ppm (DMSO-d6)

Example 89

4- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofu-40ran-5-yl) -3-phenylpyrazoline-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 45 ppm

Example 91

3- (4-chlorophenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide, m.p. 169-171. 7.96 ppm

Example 92

3- (4-chlorophenyl) -4- (4-methylphenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazolin-1-carboxamide, 55 mp 137-139. 7.96 ppm

Example 93

3- (4-chlorophenyl) -4- (4-methoxyphenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) - pyrazolin-1-carboxamide,

60 mp 182-186. 7.93 ppm

Example 94

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

65 mp 179-182. 7.93 ppm

Example 95

4- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofu-

13

666 029

ran-5-yl) -3- (4-methoxyphenyl) pyrazolin-1-carboxamide, m.p. 157-160. 7.96 ppm

Example 96

3- (4-difluoromethoxyphenyl) -4- (4-fluorophenyl) - N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide, m.p. 169-172. 7.93 ppm

Example 97

4- (4-chlorophenyl) -3- (4-difluoromethoxyphenyl) - N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) - pyrazolin-1-carboxamide, m.p. 90-95. 7.93 ppm

Example 98

3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-6-yl) -4-phenylpyrazolin-1-carboxamide, m.p. 152-157. 8.33 ppm

Example 99

3- (4-difluoromethoxyphenyl) -4- (4-fluorophenyl) - N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-6-yl) - pyrazolin-1-carboxamide, m.p. 110- 114. 8.33 ppm

Example 100

3- (4-difluoromethoxyphenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -pyrazoline-1-carboxamide, mp. 155- 159. 8.20 ppm

Example 101

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

Example 102

3- (4-difluoromethoxyphenyl) -N- (2,2-dimethyl-1,3-ben-zodioxol-5-yl) -4-phenylpyrazolin-1-carboxamide, m.p. 148-150. 7.93 ppm

Example 103

3,4-bis (4-chlorophenyl) -N- (2,2-dimethyl-1,3-benzodi-oxol-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

Example 105

N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) -N-methyl-4-phenylpyrazoline-1-carboxamide, m.p. 110-114.

Example 106

4- (1,3-Benzodioxol-5-yl) -N- (4-phenoxyphenyl) -3-phe-nylpyrazoline-1-carboxamide, m.p. 195-197. 8.03 ppm

Example 107

3- (4-chlorophenyl) -N- {4- [4- (l, l-dimethylethyl) phen-oxy] phenyl | - 4-phenylpyrazoline-1-carboxamide, m.p. 192.5-194. 8.03 ppm

Example 108

3- (4-chlorophenyl) -4- (4-fluorophenyl) -N- [4- (4-methylphenoxy) phenyl] pyrazoline-1-carboxamide, m.p. 162-164. 8.03 ppm

Example 109

3- (4-chlorophenyl) -4- (4-fluorophenyl) -N- (4- [4- (1,1-dimethylethyl) phenoxy] phenyl} pyrazoline-1-carboxamide, m.p. 188- 198. 8.03 ppm

10th

15

20th

Example 110

3- (4-chlorophenyl) -N- (4- [4- (l-methylethyl) phenoxy] phenyl j-4-phenylpyrazoline-1-carboxamide, m.p.

181-182.5. 8.06 ppm

Example 111

3- (4-chlorophenyl) -4- (4-fluorophenyl) -N- j4- [4- (l-methyl-ethyl) phenoxy] phenyl) pyrazoline-1-carboxamide, m.p. 186-187. 8.60 ppm (CDCl3 / DMSO-d6)

Example 112

3- (4-chlorophenyl) -N - [4- (4-methylphenoxy) phenyl] -4-phenylpyrazoline-1-carboxamide, m.p. 150-151. 8.06 ppm

Example 113

3- (4-chlorophenyl) -N-14- [4- (1-methylethoxy) phenoxy] phenyl-4-phenylpyrazoline-1-carboxamide, m.p.

158-160.5. 8.06 ppm

Example 114

3- (4-chlorophenyl) -4- (4-fluorophenyl) -N- {4- [4- (l-methylethoxy) phenoxy] phenyl) pyrazoline-1-carboxamide, m.p. 213-216. 8.66 ppm (CDCl3 / DMSO-d6)

25 Example 115

3,4-bis (4-fluorophenyl) -N- {4- [4- (1- methylethoxy) phenoxy] phenyl} pyrazoline-1-carboxamide, mp 134-136. 8.06 ppm

Example 116

30 3,4-bis (4-fluorophenyl) -N- [4- (4-chlorophenoxy) phenyl] pyrazoline-1-carboxamide, m.p. 197-198.5. 8.70 ppm (CDC13 / DMSO-dfj)

Example 117

3,4-bis (4-fluorophenyl) -N- (4- [4- (l, 1-dimethylethyl) -35 phenoxy] phenyl) pyrazoline-1-carboxamide, m.p. 189-192. 8.70 ppm (CDCl3 / DMSO-d6)

Example 118

3,4-bis (4-fluorophenyl) -N- [4- (4-cyanophenoxy) phenyl] -40 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, mp 148-150. 45 8.02 ppm

Example 120

3- (4-chlorophenyl) -N- [4- (4-cyanophenoxy) phenyl] -4-phenylpyrazoline-1-carboxamide, m.p. 170-172. 8.16 ppm

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Example 121

N- (1,4-Benzodioxan-6-yl) -4- (4-chlorophenyl) -3- (4-difluoromethoxyphenyl) 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 (CDC13 / DMSO-d6)

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

666 029

14

Example 125

3- (4-chlorophenyl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide, mp 147-151. 8.06 ppm

Example 126

3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2,3,3-te-trafluorobenzofuran-5-yl) - N-methyl-4-phenylpyrazoline-1-carboxamide.

Example 127

3- (4-Chlorophenyl) -4- (4-difluoromethoxyphenyl) - N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide, m.p. 155-159. 7.96 ppm

Example 128

3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2-difluoro-benzofuran-5-yl) -N-methyl-4-phenylpyrazoline-1-carboxamide.

Example 129

4- (4-chlorophenyl) -N- (2,2-difluoro-1,3-benzodioxoI-5-yl) -3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide. 8.06 ppm

Example 130

4- (1,3-Benzodioxol-5-yl) -3- (4-chlorophenyl) - N- [4- (4-fluoro-ormethoxyphenoxy) phenyl] pyrazolin-1-carboxamide.

Example 131

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

10th

Example 132

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

Example 133

4- (1,3-benzodioxol-5-yl) -3- (4-chlorophenyl) - N- (2,3-di-hydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -pyrazolin- 1-carboxamide.

Example 134

4- (1,3-benzodioxol-5-yl) -3- (4-chlorophenyl) - N- (2,3-di-hydro-2,2-dimethylbenzofuran-5-yl) -pyrazolin-1-carbox- amid.

Example 135

4- (1,3-Benzodioxol-5-yl) -N- [4- (4-difluoromethoxyphenoxy) - 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-6-yl) -N- (2,2-difluoro-1,3-benzodi-oxol-5-yl) -3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide.

Example 138

4- (1,3-benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) - N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) - pyrazolin-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-dimethyl-benzofuran-5-yl) -3-phenylpyrazoIin- 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-benzodi-oxol-5-yl) -3-phenylpyrazolin-1-carboxamide.

Example 143

4- (1,3-Benzodioxol-5-yl) -N- [4- (4-difluoromethoxyphen-15 oxy) phenyl] -3-phenylpyrazolin-1-carboxamide.

Example 144

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

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.- 35

40

Example 145

4- (2,2-difluoro-1,3-benzodioxol-5-yl) -N- [4- (4-difluoro-methoxyphenoxy) phenyl] -3- (4-fluorophenyl) pyrazolin-1-carboxamide.

Example 146

N- [4- (4-chlorophenoxy) phenyl] -4- (2,2-difluoro-1,3-ben-zodioxol-5-yl) -3- (4-fluorophenyl) pyrazoline-1-carboxamide.

Example 147

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

Example 148

4- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4-fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl ) -pyrazo-lin-1-carboxamide.

Example 149

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

45

Example 150

4- (2,2-difluoro-1,3-benzodioxol-5-yl) -N- [4- (4-difluoro-methoxyphenoxy) phenyl] -3-phenylpyrazoline-1-carboxamide.

Example 151

N- [4- (4-chlorophenoxy) phenyl] -4- (2,2-difluoro-1,3-ben-50 zodioxol-5-yl) -3-phenylpyrazoline-1-carboxamide.

Example 152

4, N-bis (2,2-difluoro-1,3-benzodioxol-5-yl) -3-phenylpyrazolin-1-carboxamide.

55

60

65

Example 153

4- (2,2-difluoro-l, 3-benzodioxol-5-yl) - N- (2,3-dihydro-2,2,3,3-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-phenylpyrazohn-1-carboxamide.

Example 155

4- (2,2-difluoro-1,3-benzodioxol-5-yl) -N- [4- (4-difluoromethoxyphenoxy) phenyl] -3- (4-difluoromethoxyphenyl) pyrazoline-1 carboxamide .

Example 156

N- [4- (4-chlorophenoxy) phenyl] -4- (2,2-difluoro-1,3-ben-zodioxol-5-yl) -3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide.

Example 157

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

Example 158

4- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5 -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-di-fluoromethoxyphenoxy) phenylJ-pyrazoline-l-carboxamide.

Example 161

4- (1,4-Benzodioxan-6-yl) -N- [4- (4-chlorophenoxy) phenyl] -3- (4-chlorophenyl) pyrazolin-1-carboxamide.

Example 162

4- (l, 4-Benzodioxan-6-yl) -3- (4-chlorophenyl) - N- (2,2-di-fluoro-l, 3-benzodioxol-5-yl) - pyrazolin-l-carboxamide.

Example 163

4- (1,4-benzodioxan-6-yl) -3- (4-chlorophenyl) -N- (2,3-di-hydro-2,2,3,3-tetrafluorobenzofuran-5-yl) pyrazoline- 1-carboxamide.

Example 164

4- (1,4-Benzodioxan-6-yl) -3- (4-chlorophenyl) - N- (2,3-di-hydro-2,2-dimethylbenzofuran-5-yl) pyrazoline. 1-carboxamide .

Example 165

4- (1,4-Benzodioxan-6-yl) -N- [4- (4-difluoromethoxyphenoxy) phenyl] -3- (4-difluoromethoxyphenyl) pyrazoline-l-carboxamide.

Example 166

4- (1,4-Benzodioxan-6-yl) -N- [4- (4-chlorophenoxy) phenyl] -3- (4-difluoromethoxyphenyl) pyrazolin-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-2,2,3,3-tetrafluoro benzofuran-5-yl) pyrazo-lin - 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-phenylpyrazoline-1-carboxamide.

Example 171

4- (1,4-Benzodioxan-6-yl) -N- [4- (4-chlorophenoxy) phenyl] -3-phenylpyrazoline-1-carboxamide.

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Example 172

4- (1,4-Benzodioxan-6-yl) -N- (2,2-difluoro-1,3-benzodi-oxol-5-yl) phenylpyrazoline-1-carboxamide.

Example 173

4- (1,4-Benzodioxan-6-yl) -N- (2,3-dihydro-2,2,3,3-tetra-fluorobenzofuran-5-ylj-3-phenylpyrazoline-1-carboxamide.

Example 174

4- (1,4-Benzodioxan-6-yl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -3-phenylpyrazoline-1-carboxamide.

Example 175

3- (1,3-Benzodioxol-5-yl) -N- [4- (4-difluoromethoxyphenoxy) phenyl] - 4- (4-fluorophenyl) -N-methylpyrazoline-1-carboxamide.

Example 176

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

Example 177

3- (1,3-Benzodioxol-5-yl) -N- (2,2-difluoro-1,3-benzodi-oxol-5-yl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide.

Example 178

3- (1,3-Benzodioxol-5-yl) -4- (4-fluorophenyl) - N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -pyrazoline- l-carbox amide.

Example 179

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

Example 180

3- (2,2-difluoro-1,3-benzodioxol-5-yl) - N- [4- (4-difluoro-methoxyphenoxy) phenyl] - 4- (4-fluorophenyl) pyrazoline-1-carboxamide.

Example 181

N- [4- (4-chlorophenoxy) phenyl] -3- (2,2-difluoro-l, 3-benzo-dioxol-5-yl) - 4- (4-fluorophenyl) -N-methylpyrazolin-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-2,2,3,3-tetrafluorobenzofuran-5-yl ) -pyrazo-lin-1-carboxamide.

Example 184

3- (2,2-difluoro-l, 3-benzodioxol-5-yl) - 4- (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -pyrazolin- l-carboxamide.

Example 185

3- (1,4-Benzodioxan-6-yl) -N- [4- (4-difluoromethoxyphenoxy) phenyl] -4-phenylpyrazoline-1-carboxamide.

Example 186

3- (1,4-Benzodioxan-6-yl) -N- [4- (4-chlorophenoxy) phenyl] -4-phenylpyrazoline-1-carboxamide.

Example 187

3- (1,4-Benzodioxan-6-yl) -N- (2,2-difluoro-1,3-benzodi-oxol-5-yl) - N-methyl-4-phenylpyrazoline-1-carboxamide.

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Example 188

3- (1,4-Benzodioxan-6-yl) -N- (2,3-dihydro-2,2,3,3-tetra-fluorobenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide.

Example 189

3- (1,4-Benzodioxan-6-yl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide.

Example 190

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

Example 191

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

Example 192

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

Example 193

N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -3- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -N-methyl-4- phenylpyrazoline-1-carboxamide.

Example 194

3, N-bis (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide.

Example 195

N- [4- (4-difluoromethoxyphenoxy) phenyl] - 4- (4-fluorophenyl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.

Example 196

N- [4- (4-chlorophenoxy) phenyl] - 4- (4-fluorophenyl) -3- (4-methylpheny 1) pyrazoline-1-carboxamide.

Example 197

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

10th

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-2,2,3,3-tetrafluorobenz-15 zofuran-5-yl) -3- (4-methylphenylpyrazoline-1-carboxamide.

Example 209

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

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Example 210

N- [4- (4-difluoromethoxyphenoxy) phenyl] - 3- (3-fluorophenyl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide.

Example 211

N- [4- (4-chlorophenoxy) 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-35 2,2,3,3-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. 40 Example 215

N- [4- (4-difluoromethoxyphenoxy) phenyl] - 3- (2-fluorophenyl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide.

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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) -5 ° 4- (4-fluorophenyl) pyrazoline-1-carboxamide.

Example 218

3- (2-fluorophenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -N-methylpyrazoline-55 1-carboxamide.

Example 219

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

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Example 220

3,4-bis (4-fluorophenyl) -N- (2,3-dihydro-2,2,3,3,7-penta-fluorobenzofuran-5-yl) pyrazoline-1-carboxamide.

Example 221

4- (4-chlorophenyl) -N- (2,3-dihydro-2,2,3,3,7-pentafluorobenzofuran-5-yl) -3- (4-methylphenylpyrazoline-1-carboxamide) .

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Example 222

N- (2,3-Dihydro-2,2,3,3,7-pentafluorobenzofuran-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-2,2,3,3,7-pentafluorobenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide.

Example 225

3,4-bis (4-fluorophenyl) -N- (2,2,6-trimethyl-1,3-benzodi-oxol-5-yl) pyrazohn-1-carboxamide.

Example 226

4- (4-chlorophenyl) -N- (2,2,6-trimethyl-1,3-benzodioxol-5-yl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.

Example 227

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

Example 228

3- (4-difluoromethoxyphenyl) -N- (2,2,6-trimethyl-1,3-ben-zodioxol-5-yl) -4-phenylpyrazoline-1-carboxamide.

Example 229

3- (4-chlorophenyl) -N- (2,2,6-trimethyl-1,3-benzodioxol-5-yl) -4-phenylpyrazoline-l-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-methoxy-2,2-dimethyl-1,3-benzo-dioxol-5-yl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.

Example 232

N- (7-methoxy-2,2-dimethyl-1,3-benzodioxol-5-yl) -3,4-di-phenylpyrazoline-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-ben-zodioxol-5-yl) -4-phenylpyrazolin-1-carboxamide.

Example 235

3,4-bis (4-fluorophenyl) -N- [2,2-dimethyl-7- (l-methyl-ethyl) -l, 3-benzodioxol-5-yl] -pyrazoline-l-carboxamide.

Example 236

4- (4-chlorophenyl) -N- [2,2-dimethyl-7- (1-methylethyl) -1, 3-benzodioxol-5-yl)] - 3- (4-methylphenyl) 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-difluoromethoxyphenyl) -N- [2,2-dimethyl- 7- (l-methylethyl) -l, 3-benzodioxol-5-yl] -4-phenylpyrazoline-1-carboxamide.

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Example 239

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

Example 240

3,4-bis (4-fluorophenyl) -N- (2,3-dihydro-7-ethyl-2,2,3,3-tetrafluorobenzofuran-5-yl) pyrazolin-1-carboxamide.

Example 241

4- (4-chlorophenyl) -N- (2,3-dihydro-7-ethyl-2,2,3,3-tetra-fluorobenzofuran-5-yl) -3- (4-methylphenyl) pyrazoline-1- carboxamide.

Example 242

N- (2,3-Dihydro-7-ethyl-2,2,3,3-tetrafluorobenzofuran-5-15 yl) -3,4-diphenylpyrazoline-1-carboxamide.

Example 243

3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-7-ethyl-2,2,3,3-tetrafluorobenzofuran-5-yl) -4-phenylpyrazoline-1-20 carboxamide.

Example 244

3- (4-chlorophenyl) -N- (2,3-dihydro-7-ethyl-2,2,3,3-tetra-fluorobenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide.

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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-methylsulfonyl-35 phenoxy) phenyl] -4-phenylpyrazoline-1-carboxamide.

Example 248

3- (4-Chlorophenyl) -4- (4-fluorophenyl) -N- [4- (4-methylsulfonylphenoxy) phenyl] pyrazoline-1-carboxamide.

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Example 249

M- [4- (4-Methylsulfonylphenoxy) phenyl] -3,4-diphenylpyrazoline-1-carboxamide.

45 Example 250

3,4-bis (4-fluorophenyl) -N- (2,3-dihydro-7-difluoromethoxy-2,2-dimethylbenzofuran-5-yl) pyrazoline-l-carboxamide. Example 251

4- (4-chlorophenyl) -N- (2,3-dihydro-7-difluoromethoxy-2,2-50 dimethylbenzofuran-5-yl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.

Example 252

N- (2,3-Dihydro-7-difluoromethoxy-2,2-dimethylbenzofu-55 ran-5-yl) -3,4-diphenylpyrazoline-1-carboxamide.

Example 253

3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-7-difluoro-methoxy-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-60 1-carboxamide.

Example 254

3- (4-chlorophenyl) -N- (2,3-dihydro-7-difluoromethoxy-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide.

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Example 255

N- (7-chloromethyl-2,2-dimethyl-1,3-benzodioxol-5-yl) -3,4-bis (4-fluorophenyl) pyrazoline-1-carboxamide.

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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- (Chloronethyl-2,2-dimethyl-1,3-benzodioxol-5-yl) -3,4-diphenylpyrazolin-1-carboxamide.

Example 258

N- (7-Chloromethyl-2,2-dimethyl-1,3-benzodioxol-5-yl) -3- (4-dif] uormethoxyphenyl) -4-phenylpyrazoline-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- (l-methylethyl) -2,2-dimethyl-1,3-benzodioxol-5-yl] -4- phenyl-pyrazoline-I-carboxamide.

Example 261

N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -3- (7-methoxy-2,2-dimethyl-1,3-benzodioxol-5-yl) -4-phenylpyrazoline- 1-carboxamide.

Example 262

N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -3- (7-flu-or-2,2-dimethyl-1,3-benzodioxol-5-yl) -4-phenylpyrazoline- 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-phenylpy- razolin-1-carboxamide.

Example 264

N- (2,2-difluoro-1,3-benzodioxoI-5-yl) -3- (4-fluorophenyI) -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- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl ) - pyrazoline-1-carboxamide.

Example 266

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

Example 267

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

Example 268

N- [3- (4-Dif! Uoromethoxyphenoxy) phenyl] - 3,4-bis (4-fluoro-orphenyl) 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- (l-methylethyl) -2,2-dimethyl-1,3-benzodioxol-5-yl] -3- phenyl-pyrazoline-1-carboxamide.

Example 272

N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4- (7-methoxy-2,2-dimethyl-1,3-benzodioxol-5-yl) -3-phenylpyrazoline-1 - carboxamide.

Example 273

N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4- (7-flu-or-2,2-dimethyl-1,3-benzodioxol-5-yl) -3-phenylpyrazoline- 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-phenylpyrazoline 1-carboxamide.

Example 275

4- (7-chloromethyl-2,2-dimethyl-1,3-benzodioxol-5-yl) -3, N-bis (4-fluorophenyl) pyrazoline-1-carboxamide

In the normal use of the insecticidal pyrazolines according to the invention, the pyrazolines are usually not used without admixture or dilution, but are normally used in a suitable formulated preparation which is compatible with the method of use and contains an insecticidally effective amount of pyrazoline. The pyrazolines of the present invention, like most pesticides, can be mixed with agriculturally acceptable surfactants and carriers which are normally used to facilitate the dispersion of the active ingredients, taking into account the recognized fact that the formulation and the manner in which an insecticide is applied affect the activity of the Can influence substance. The present pyrazolines can e.g. be applied as sprays, dusts or granules to the place where pest control is desired, the type of application of course varying according to the pest and the environment. The pyrazolines according to the invention can thus be formulated as granules having a large particle size, as powdered dusts, as wettable powders, as emulsifiable concentrates, as solutions and the like.

Granules can contain porous or non-porous particles, such as attapulgite clay or sand, which serve as carriers for the pyrazolines. The granulate particles are relatively large, a diameter of approximately 400 to 2500 mji being typical. The particles are either impregnated from solution with the pyrazoline or coated with the pyrazoline, sometimes using adhesives. Granules generally contain 0.05 to 10%, preferably 0.5 to 5%, of active ingredient as an insecticidally effective amount.

Dusts are mixtures of pyrazolines with finely divided solid substances such as talc, attapulgite clay, kieselguhr, pyrophyllite, chalk, diatomaceous earth, calcium phosphates, calcium and magnesium carbonates, sulfur, flours and other organic and inorganic solids, which act as carriers for the insecticide. These finely divided solids have an average particle size of less than approx. 50 µm. A typical dust formulation useful for insect control contains 1 part pyrazoline, such as 3- (4-chlorophenyl) -N- [4- (4-chlorophenoxy) phenyl] phenylpyrazoline-1-carboxamide, and 99 parts Talc.

The pyrazolines according to the invention can be processed into liquid concentrates by dissolving or emulsifying them in suitable liquids and can be processed into solid concentrates by mixing with talc, clays and other known solid carriers which are used in pest control. The concentrates are pre5

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parate, the insecticidally effective amount about 5 to 50% pyrazoline, such as 3- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) - phenylpyrazolin-1- carboxamide, and 95 to 50% inert material, including surfactants, emulsifiers and wetting agents, but experimentally even higher concentrations of the active ingredient component can be used. The concentrates are diluted with water or other liquids for practical use as sprays or diluted with an additional solid carrier for use as dusts.

Typical carriers for solid concentrates (also called wettable powders) include fuller earth, clays, silicon dioxide and other highly absorbent, easily wettable inorganic diluents. A solid concentrate formulation that is suitable for controlling insects contains 1.5 parts of sodium lignosulfonate and sodium umlauryl sulfate as wetting agents, 25 parts of (3- (4-chlorophenyl) -N- (2,3-dihydro-2,2) -dimethylbenzofuran-5-yl) - 4- (4-chlorophenyl) -pyrazoline-1-carboxamide and 72 parts of attapulgite clay.

The preparation of concentrates is useful for the transport of low-melting products according to the invention. Such concentrates are made by melting the low melting solid products together with 1% or more of a solvent to produce a concentrate which does not solidify on cooling to or below the freezing point of the pure product.

Useful liquid concentrates include the emulsifiable concentrates, which are homogeneous liquid or paste-like preparations that are easily dispersed in water or other liquid carriers. They can consist entirely of the pyrazoline with a liquid or solid emulsifier, or they can also contain a liquid carrier such as xylene, heavy aromatic naphthas, isophorone and other relatively non-volatile organic solvents. For use, these concentrates are dispersed in water or other liquid carriers and are normally applied as sprays to the areas to be treated.

Typical surfactant wetting, dispersing and emulsifying agents used in pest control formulations are e.g. the alkyl and alkylarylsulfonates and sulfates and their sodium salts; Alkyl amide sulfonates, including fatty acid methyl taurides; Alkylaryl polyether alcohols, sulfated higher alcohols, polyvinyl alcohols; Polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; Fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition products of long chain mercaptans and ethylene oxide. Many other types of useful surfactants are commercially available. The surfactant, when used, normally makes up about 1 to 15% by weight of the insecticidal preparation.

Other useful formulations include simple solutions of the active ingredient in a solvent in which it is fully soluble at the desired concentration, such as acetone or other organic solvents.

An insecticidally effective amount of pyrazoline in an insecticidal preparation that has been diluted for use will normally range from about 0.001 to about 8% by weight. Many variations of spray and dust preparations which are known to the person skilled in the art can be used by using the pyrazolines according to the invention instead of the active compounds of known or those which are obvious to the person skilled in the art.

The insecticidal preparations according to the invention can be formulated with other active ingredient components, including other insecticides, nematocides, acaricides, fungicides, plant growth regulators, fertilizers, etc. When using the insect control preparations, it is only necessary to apply an insecticidally effective amount of pyrazoline to the location where control is desired. Such a position can e.g. be the insects themselves, plants on which the insects feed, or the habitat of the insects. If the site is the ground, e.g. Soil in which agricultural crops have been planted or are to be planted, the active compound can be applied to the earth and, if desired, incorporated into the earth. For most applications, an insecticidally effective amount is approximately 75 to 4000 g per ha, preferably 150 to 3000 g per ha.

The insecticidal activity of the pyrazolines, the preparation of which is described above, was assessed as follows:

The compounds were tested in leaf applications at various concentrations in aqueous solutions containing 10% acetone and 0.25% octylphenoxypolyethoxyethanol. Spotted field bean plants were placed in a hood on a rotating turntable, and the test solutions were applied to the top and bottom surfaces of the plant leaves until draining. The plants were then allowed to dry and severed at the base of the stem. Each stem was placed in water through a paper cup. 10 individuals of the corresponding insect species were placed in each cup and the cups were covered. “Southern armyworm” (Spodoptera eridania), “Mexican bean beetle” (Epilachna varivestis), “Beet armyworm” (Spodoptera exigua) and “Cabbage looper” (Trichoplusia ni) were used for the assessment. After 4 days at 26 ° C and 50% relative humidity, the mortality was registered. The results of the tests are summarized in Table 1. Insect mortality was generally lower when the tests were evaluated much sooner.

A number of pyrazolines were also active against Southern com rootworm larvae (Diabrotica undecimpuncta-ta howardi Barber) when applied to the earth, and the pyrazolines tested were also very effective against Colorado potato beetle (Leptinotara decemlineata Say ).

Table 1

Leaf rating

Concentrate

Insects (% killing)

Connection

dung

(ppm)

MBB

SAW BAW

CL

1

500

100

100

2nd

500

100

100

3rd

500

100

100

4th

500

100

100

5

250

100

87

100

6

500

70

65

90

7

500

100

50

90

8th

500

100

85

9

500

90

70

10th

500

100

35

11

500

85

15

12

500

100

100

13

500

93

50

90

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

666 029

20th

Table 1

! Continuation)

70

500

100

100

71

200

60

10th

Leaf rating

72

200

100

30th

Concentrate

Insects (%

Killing)

73

500

100

90

Connection

5 74

500

100

80

dung

(ppm)

MBB

SAW

BAW

CL

75

200

100

45

14

500

100

100

76

200

95

100

15

500

100

90

77

500

80

16

500

100

200

0

95

17th

500

100

35

10 78

500

90

55

18th

500

90

55

79

200

95

60

19th

500

100

100

80

500

100

100

20th

500

80

40

81

250

100

100

21st

500

70

15

82

128

100

90

22

500

100

100

15 83

250

85

100

23

500

40

30th

84

100

100

90

24th

250

95

100

85

200

100

100

25th

500

30th

75

86

16

95

95

26

500

80

65

87

500

100

100

27th

500

75

95

20 88

100

100

25th

28

500

95

90

89

200

100

100

29

500

10th

90

90

16

100

100

30th

500

5

64

60

91

32

100

100

31

500

5

65

70

92

500

100

100

32

500

100

50

25 93

500

100

100

33

500

100

80

94

500

100

100

34

500

10th

75

95

200

100

90

35

500

100

100

96

32

100

100

36

8th

100

98

45

90

97

8th

100

100

37

32

98

98

97

100

30 9g

16

100

40

38

500

95

80

99

16

100

100

39

500

100

25th

100

32

100

100

40

500

100

100

101

1000

100

100

41

128

95

70

102

128

100

100

42

128

95

100

35103

16

90

95

43

500

100

100

105

16

100

100

44

500

100

100

106

256

100

70

45

32

100

100

100

100

107

1000

45

0

46

500

30th

40

108

1000

100

75

47

500

5

10th

40 109

1000

0

0

48

8th

100

100

100

95

110

1000

70

0

49

500

100

100

111

1000

0

0

50

500

100

100

112

1000

100

90

51

100

40

60

113

1000

100

10th

52

500

100

95

43 114

1000

100

30th

53

500

100

10th

115

1000

100

15

54

500

100

85

116

500

100

100

55

500

100

80

117

500

55

0

56

500

100

100

118

500

100

100

57

250

100

100

5 ° n9

500

100

95

58

500

100

40

120

500

100

100

59

500

100

100

121

500

95

100

60

200

100

60

122

64

100

100

61

32

45

100

55

90

123

64

15

0

62

500

95

95

55 124

64

100

100

63

500

100

95

125

64

100

100

64

500

100

100

65

500

100

100

MBB

= Epilachna varivestis

66

500

100

100

SAW

= Spodoptera eridania

67

500

85

95

60 BAW

= Spodoptera exigua

68

500

100

0

CL

= Trichoplusia ni

69

8th

100

60

5

100

40

10th

100 100

85 85 35 90 100

15

100

85

90 100

95

80 85 100

100

65

C.

O

Claims (17)

666 029 PATENT CLAIMS 1. Insecticidal pyrazolines of the formula: V- SN w \ rc where Ra for a group of the formula: A where RA 'is selected from hydrogen, halogen, lower alkyl, lower alkoxy, halogen lower alkoxy, lower alkynyloxy and halogen lower alkyl, or for a group of the formula: where X stands for a bridge of the formula: [0 ~ (CR'AAR'AB) a_0a '] where a is 1 to 3, a 'is 0 or 1, a + a' is at least 2 but not greater than 3, R'AA and R'ab> which are the same or different, each from hydrogen, Halogen and lower alkyl are selected and R'ac is selected from hydrogen, halogen, lower alkyl, lower alkoxy, halogen-lower alkoxy and halogen-lower alkyl, RB for a 4- or 5-substituent of the formula: R B where RB 'is selected from hydrogen, halogen, lower alkyl, lower alkoxy and halogeno lower alkyl, or for a 4- or 5-substituent of the formula: BC where Y is a bridge of the formula: [0- (CR'BAR'BB) b-Ob <] where b is 1 to 3, b 'is 0 or 1, b + b' is at least 2 but not greater than 3, R'BA and R'BB, which are the same or different, each from hydrogen, Halogen and lower alkyl are selected and R'BC is selected from hydrogen, halogen, lower alkyl, lower alkoxy, halogen lower alkoxy and halogen lower alkyl, Rc for a group of the formula: where RD is selected from hydrogen and lower alkyl and RE from lower alkyl, halogen, lower alkoxy, halogenated lower alkoxy, halogenated lower alkyl, cyano, nitro, groups of the formula -NRFRG, wherein RF and RG, which are the same or different, each represent lower alkyl, and Groups of the formula -SOnRH, in which RH is lower alkyl and n is 0 to 2, are selected, or for a group of the formula: CC where Z stands for a bridge of the formula: [0- (C R'ca R'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, which are the same or different, each from hydrogen, Halogen and lower alkyl are selected, provided that R'ca and R'CB are not both hydrogen when c is 1 and c 'is 1 and R'cc is hydrogen, halogen, lower alkyl, lower alkoxy, halogeno lower alkoxy and Halogen lower alkyl is selected, Rn is hydrogen or lower alkyl and V and W, which are the same or different, each represent oxygen or sulfur. 2. Compounds according to claim 1, characterized in that W represents oxygen. 3. Compounds according to claim 1 or 2, characterized in that R'a represents halogen or halogen-lower alkoxy. 4. Compounds according to any one of claims 1 to 3, characterized in that RB stands for a 4-substituent. 5. Compounds according to any one of claims 1 to 4, characterized in that Ra for a group of the formula: stands. 6. Compounds according to claim 5, characterized in that R'b represents halogen. 7. Compounds according to any one of claims 1 to 6, characterized in that Rc for a group of the formula: stands or from 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, 2,2-difluoro-1,2-benzodi- 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 oxol-5-yl and 2,2-dimethyl-1,3-benzodioxol-5-yl is selected. 8. Compounds according to one of claims 1 to 6, characterized in that Rc for a group of the formula: H stands. 9. Compounds according to claim 8, characterized in that Re represents halogen lower alkoxy. 10. 3- (4-difluoromethoxyphenyl) - N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide, 3,4-bis- (4- £ luorphenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) pyrazolin-1-carboxamide, 3,4-bis- (4-fiuorphenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazolin-1-carboxamide, N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -3- (4-difluoromethoxyphenyl) -4-phenylpyrazoline-1-carboxamide, N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) -N-methyl-4-phenylpyrazoline-1-carboxamide, 3,4-bis- (4th -chlorophenyl) -N- (2,2-dimethyl-l, 3-benzodi-oxol-5-yl) -pyrazolin-1-carboxamide, N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3,4-bis- (4-fluoro-phenyl) -pyrazoline-1-carboxamide, 3- (4-chlorophenyl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) -4- (4-fluorophenyl) pyrazoline-l-carboxamide, 3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -N-methyI-4-phenylpyrazoIin-l-carboxamide, 3- (4-chlorophenyl) -N- [4- (4-difhiormethoxyphenoxy) phenyl] -4-phenylpyrazoline-1-carboxamide, N- [4- (4-difluoromethoxyphenoxy) phenyl] -3- (4-difluoro-methoxyphenyl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide, 3- (4-difluoromethoxyphenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) pyrazoline-l-carboxamide, 3- (4-difluoromethoxyphenyl) -4- (4-fluorophenyl) - N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-6-yl) pyrazoline carboxamide, 4- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yI) -3-phenylpyrazoIin-l-carboxamide, 3- (4-chlorophenyl) -4- (4-fluorophenyl) - N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide, 3- (4-difluoromethoxyphenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide and 4- (4-chlorophenyl) -3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide as compounds according to claim 1. 11. Insecticidal preparation, characterized in that, in a mixture with an agriculturally acceptable carrier, it contains an insecticidally effective amount of at least one insecticidal pyrazoline of the formula: ) ~ K? w \ Rc 666 029 contains, wherein RA for a group of the formula: A R'A is selected from hydrogen, halogen, lower alkyl, lower alkoxy, halogen-lower alkoxy, lower alkynyloxy and halogen-lower alkyl, or for a group of the formula: where X stands for a bridge of the formula: [0- (CR'AAR'AB) a-Oa <] in which a is 1 to 3, a 'is 0 or 1, a + a' is at least 2 but not greater than 3, R'aa and R'AB, which are the same or different, each from hydrogen, Halogen and lower alkyl are selected and R'AC is selected from hydrogen, halogen, lower alkyl, lower alkoxy, halogen lower alkoxy and halogen lower alkyl, RB for a 4- or 5-substituent of the formula: R B where R'ß is selected from hydrogen, halogen, lower alkyl, lower alkoxy and halogeno lower alkyl, or for a 4- or 5-substituent of the formula: BC where Y is a bridge of the formula: [0- (CR'BAR'BB) b-CW where b is 1 to 3, b 'is 0 or 1, b + b' is at least 2 but not greater than 3, R'BA and R'bb, which are the same or different, each from hydrogen, Halogen and lower alkyl are selected and R'Bc is selected from hydrogen, halogen, lower alkyl, lower alkoxy, halogen lower alkoxy and halogen lower alkyl, Rc for a group of the formula: where RD is selected from hydrogen and lower alkyl and Re from lower alkyl, halogen, lower alkoxy, halogeno lower alkoxy, halogeno lower alkyl, cyano, nitro, groups of the formula -NRFRG, in which RF and RG, which are the same or different 3rd 5 10th 15 2a 25th 30th 35 40 45 50 55 60 65 666 029 are different, each stand for lower alkyl, and groups of the formula -SOnRH, in which RH stands for lower alkyl and n stands for 0 to 2, or for a group of the formula: where Z is a bridge of the formula: [0- (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, which are the same or different, are each from hydrogen, Halogen and lower alkyl are selected, provided that R'ca and R'cb are not both hydrogen when c is 1 and c 'is 1 and R'Cc is hydrogen, halogen, lower alkyl, lower alkoxy, halogeno lower alkoxy and Halogen lower alkyl is selected, Rn is hydrogen or lower alkyl and V and W, which are the same or different, each represent oxygen or sulfur. 12. A preparation according to claim 11, characterized in that W stands for oxygen. 13. A preparation according to claim 11 or 12, characterized in that R'a represents halogen or halogen-lower alkoxy. 14. Preparation according to one of claims 11 to 13, characterized in that RB stands for a 4-substituent. 15. A method for controlling insects, characterized in that an insecticidally effective amount of a pyrazo-lin of the formula: in which RA for a group of the formula: A R'A is selected from hydrogen, halogen, lower alkyl, lower alkoxy, halogen-lower alkoxy, lower alkynyloxy and halogen-lower alkyl, or for a group of the formula: AC where X stands for a bridge of the formula: [0- (CR'aa R'A B) a-0Il] where a is 1 to 3, a 'is 0 or 1, a + a' is at least 2 but not greater than 3, R'AA and R'AB, which are the same or different, are each selected from hydrogen, halogen and lower alkyl and R'AC is selected from hydrogen, halogen, lower alkyl, lower alkoxy, halogen-lower alkoxy. and halogeno lower alkyl is selected, RB for a 4- or 5-substituent of the formula: where R'B is selected from hydrogen, halogen, lower alkyl, lower alkoxy and halogeno lower alkyl, or for a 4- or 5-substituent of the formula: BC where Y is a bridge of the formula: [0- (CR'BAR'BB) b ~ 0b '] where b is 1 to 3, b 'is 0 or 1, b + b' is at least 2 but not greater than 3, R'BA and R'BB, which are the same or different, each from hydrogen, Halogen and lower alkyl are selected and R'BG is selected from hydrogen, halogen, lower alkyl, lower alkoxy, halogen lower alkoxy and halogen lower alkyl, Rc for a group of the formula: where RD is selected from hydrogen and lower alkyl and RE from lower alkyl, halogen, lower alkoxy, halogeno lower alkoxy, halogeno lower alkyl, cyano, nitro, groups of the formula -NRFRG, in which RF and RG-, which are the same or different, each represent lower alkyl, and groups of the formula -SOnRH, in which RH is lower alkyl and n is 0 to 2, or a group of the formula: where Z stands for a bridge of the formula: [0- (CR'CAR'CB) = - 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, which are the same or different, each from hydrogen, Halogen and lower alkyl are selected, provided that R'ca and R'CB are not both hydrogen when c is 1 and c 'is 1 and R'Cc is hydrogen, halogen, lower alkyl, lower alkoxy, halogeno lower alkoxy and Halogen lower alkyl is selected, Rn for hydrogen or lower alkyl 4th s 10th 15 20th 25th 30th 35 40 45 50 55 60 65 and V and W, which are the same or different, each represent oxygen or sulfur. 16. Process for the preparation of an insecticidal pyrazo-lin of the formula: w \ Rc where Ra for a group of the formula: A R'A is selected from hydrogen, halogen, lower alkyl, lower alkoxy, halogen-lower alkoxy, lower alkynyloxy and halogen-lower alkyl, or for a group of the formula: where X is a bridge of the formula: [0- (CR / AAR'AB) a-Oa '] where a is 1 to 3, a 'is 0 or 1, a + a' is at least 2 but not greater than 3, R'AA and R'ab, which are the same or different, each from hydrogen, Halogen and lower alkyl are selected and R'ac is selected from hydrogen, halogen, lower alkyl, lower alkoxy, halogeno lower alkoxy and halogeno lower alkyl, Rb for a 4- or 5-substituent of the formula: R B where R'B is selected from hydrogen, halogen, lower alkyl, lower alkoxy and halogeno lower alkyl, or for a 4- or 5-substituent of the formula: where Y is a bridge of the formula: [0- (CR'BAR'BB) b-Ob.] where b is 1 to 3, b 'is 0 or 1, b + b' is at least 2 but not greater than 3, R'ba and R'BB, which are the same or different, are each from hydrogen, Halogen and lower alkyl are selected and R'BG from hydrogen, halogen, lower alkyl, lower alkoxy, halogen lower alkoxy 666 029 and halogeno lower alkyl is selected, Rc for a group of the formula: where RD is selected from hydrogen and lower alkyl and RE from lower alkyl, halogen, lower alkoxy, halogenated lower alkoxy, halogenated lower alkyl, cyano, nitro, groups of the formula -NRFRG, wherein RF and RG, which are the same or different, each represent lower alkyl, and Groups of the formula -SOnRH, in which RH is lower alkyl and n is 0 to 2, are selected, or for a group of the formula: where Z is a bridge of the formula: [0- (CR'caR'cb) c-Oc.] in which 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'gb, which are the same or different, each from hydrogen, Halogen and lower alkyl are selected, provided that R'ca and R'CB are not both hydrogen when c is 1 and c 'is. 1 is, and R'cc is selected from hydrogen, halogen, lower alkyl, lower alkoxy, halogen-lower alkoxy and halogen-lower alkyl, Rn is hydrogen and V and W, which are the same or different, each represent oxygen or sulfur, characterized in that one Connection of the formula: R <r-N = C = W with a compound of the formula: N H implements. 17. Process for the preparation of an insecticidal pyrazo-lin of the formula: w \ Rc where Ra for a group of the formula: A 5 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 666 029 R'A is selected from hydrogen, halogen, lower alkyl, lower alkoxy, halogen-lower alkoxy, lower alkynyloxy and halogen-lower alkyl, or for a group of the formula: where X stands for a bridge of the formula: [0- (CR'AAR'AB) a-Oa <] where a is 1 to 3, a 'is 0 or 1, a + a' is at least 2 but not greater than 3, R'AA and R'ab, which are the same or different, each from hydrogen, Halogen and lower alkyl are selected and R'ac is selected from hydrogen, halogen, lower alkyl, lower alkoxy, halogen-lower alkoxy and halogen-lower alkyl, RB for a 4- or 5-substituent of the formula: where R'B is selected from hydrogen, halogen, lower alkyl, lower alkoxy and halogeno lower alkyl, or for a 4- or 5-substituent of the formula: BC where Y stands for a bridge of the formula: [0- (CR'BAR'bb) b-Ob '] where b is 1 to 3, b 'is 0 or 1, b + b' is at least 2 but not greater than 3, R'BA and R'BB, which are the same or different, each from hydrogen, Halogen and lower alkyl are selected and R'Bc is selected from hydrogen, halogen, lower alkyl, lower alkoxy, halogen lower alkoxy and halogen lower alkyl, Rc for a group of the formula: , where Z is a bridge of the formula: [0- (CR'caR'cb) c-Oc-1 s is 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, which are the same or different, are each from hydrogen , Halogen and lower alkyl are selected, with the condition that R'CA and R'cb are not both hydrogen when c is 1 and i 'and c' is 1, and R'cc is hydrogen, halogen, lower alkyl, lower alkoxy, Halogen-lower alkoxy and halogen-lower alkyl is selected, Rn stands for lower alkyl and V and W, which are the same or different, each represent oxygen or sulfur, characterized in that ei-15 ne compound of the formula: Rc-N = C = W with a compound of the formula: 20th 25th and the compound obtained, in which RN is hydrogen, is alkylated to the corresponding compound, in which RN is lower alkyl. 30th