FR2572400A1 - INSECTICIDES OF PYRAZOLINE - Google Patents

Abstract

1. PYRAZOLINE INSECTICIDE CHARACTERIZED BY THE FORMULA (CF DRAWING IN BOPI) IN WHICH R MEETS THE FORMULA (CF DRAWING IN BOPI) IN WHICH R IS CHOSEN AMONG HYDROGEN, A HALOGEN, A RADICAL ALKYL INFERIEUR, ALCOYXY INFALCOERIE INFERIE , LOWER ALCYNYLOXY AND LOWER HALOALKYL.

Description

2 2572400

INSECTICIDES OF PYRAZOLINE

  This invention relates to the field of

  chemical compositions affecting life; eLlte

  In particular, there are novel pyrazoline insecticides, methods and intermediates therefor, insecticidal compositions containing the pyrazotins, and the use of pyrazotins.

to fight against insects.

  Pyrazotines are heterogeneous compounds

  Five-link cycles with the formula and numbering scheme of the following ring atoms:

  It is known in the art of insect

  ticides, that certain derivatives of 1-carbamoyt pyra-

  zoline are insecticides. For example, the patent

  U.S. 4,174,393 discloses insecticidal activity.

  1-carbamoyl pyrazoline compounds also bearing phenyl substituents at the 3- and 4-positions of the pyrazoline ring. The present invention provides pyrazolines

  presenting the formula developed below, which

  sedent a pronounced insecticidal activity: R W-RB

--N RN

\ W Rc

  This patent application is a continuation

  partial application of a US patent application.

  not'; 709,626, filed March 9, 1985, which is a

  partial continuation of the patent application

  No. 664,674 filed on October 25, 1984. The invention belongs to the field of

  chemical compositions affecting life; it is

  In particular, new pyrazotine insecticides, methods and intermediates for pyrazotines, insecticidal compositions containing pyrazolines and the use of pyrazoLines are also

Fight against insects.

  Pyrazotines are heterogeneous compounds

  CycLics at Five Mayons Presenting The Formula and Cycle Numbering Scheme of the Cycle Followed H

  He is known in The Insect Technique

  ticides that certain 1-carbamoyl pyrazoline derivatives are insecticides. For example, The breve

  U.S.A. 4,174,393 discloses the activity of

  of 1-carbamoyl pyrazoLines also bearing phenyl substituents at positions 3 and 4 of

pyrazoline nucleus.

  It has now been found that pyrazolines having the following structural formula have a pronounced insecticidal activity: ## STR2 ## In this formula, RA corresponds to the formula in which R'A is selected from hydrogen, halogen and lower alkyl. lower alkoxy, lower haloalkoxy, lower alkynyloxy and lower haloalkyl; or R AC x X is a bridge of formula 40- (CR 'AAR RAB) a-Oa, wherein j. is 1-3, a 'is 0 or 1, a + a' is at least 2, but no more than 3, R'AA and R'AB are independently selected from hydrogen, halogen and lower alkyl, and R'AC is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower alkoxy and lower haloalkyl radical;

  RB is a 4- or 5-member substituent

  According to your formula: in which R 'is selected from hydrogen, halogen, lower alkyl. lower atcoxy and lower hatoalkyte; or w BC in which Y is a bridge of the formula O (CR'BARI BB) b Ob + in which b is 1-3, b 'is 0 or 1, b + b' is at least 2 but not greater than 3, R'BA and R'BB are independently selected from hydrogen, halogen, and lower alkyl, and R'BC is selected from hydrogen, halogen, lower alkoxy, haloalkoxy, haloalkoxy; lower and lower haloalkyl; Rc corresponds to the formula wherein R 1 is selected from hydrogen and a lower alkyl radical, and RE is selected from

  halogen, a lower alkyl radical, lower alkoxy

  lower haloalkoxy, lower haloalkyl, cyano, nitro, -NRFRG o RF and RG are independently a lower alkyl radical, and -SOnRH o RH is a lower alkyl radical and n is 0-2; or R cc Z'CC o Z is a bridge of the formula + O- (CR 'AR' C -) cc where c is 1-3, c is 0 or 1, c + c 'is at least 2 but no more than 3, R'CA and R'CB are independently selected from hydrogen, halogen and lower alkyl, in some compounds R'CA and R'CB are not both hydrogen when c is 1 and c 'is 1, and R'Cc is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, and lower haloalkyl; R is hydrogen or a lower alkyl radical; N and

  V and W are independently oxygen or sulfur.

  The terms "halo" and "halogen" refer to

  here fluorine, chlorine or bromine. The term "

  The term "alkyl", "alkoxy", "alkynyloxy", etc., denotes a linear or branched C1-C6, preferably C1-C4, hydrocarbon chain, "halo" associated with another term means one or more

  Hydrogen atoms have been replaced by halogens.

  Among the above pyrazolines, the compounds wherein W is oxygen are preferred for most applications, particularly when R'A is a 4-, preferably a halogen substituent, e.g. chlorine or fluorine, or

  a lower haloalkoxy radical, for example difluorinated

  methoxy. The pyrazoLines in which RB is a 4- substituent are generally more active than the 5- substituted pyrazolines, and the compounds wherein RB is a phenyl radical bearing

  Substituent R 'are particularly interesting.

  In this context, it is preferred that R'B be a substitute

  killing in 4-, especially a halogen, for example

chlorine or fluorine.

  As far as RC is concerned, the most interesting insecticides are usually derived from

  compounds with either a 2,3-dihydro-2,2-dimethyl-

  benzofuran-5-yl, a 2,3-dihydro-2,2,3,3-tetrafluoro-

  benzofuran-5-yl, a 2,3-dihydro-2,2,3,3-tetrafluoro-

  benzofuran-6-yl, a 2,2-difluoro-1,3-benzodioxol-5-

  yl, 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 4-substituent, in particular a haloalkoxy

24 lower.

  The pyrazolines of the invention having a notable insecticidal activity include, for example

  3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2-

  dimethylbenzofuran-5-yl) -4-phénylpyrazoline-1-

  carboxamide, 3,4-bis (4-fluorophenyl) -N-2,3-dihydro-

  2,2,3,3-tétrafluorobenzofurane-5-yl) pyrazoline-1

  carboxamide, 3,4-bis (4-fluorophenyl) -N- (Z, 3-dihydro-

  2,2-diméthytbenzofurane-5-yl) pyrazoline-1-carboxamide,

  N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl)

  3- (4-difluoromethoxyphenyl) -4-phenylpyrazoline-1-carboxamide,

2'57240O

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

  méthoxyphénytl) -N-methyl-4-phényLpyrazoline-1-carboxamide

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

  benzodioxol-5-yl) pyrazotine-1-carboxamide, the N- (2,2-

  difluoro-1,3-benzodioxol-5-yl) -3,4-bis (4-fluorophenyl)

  pyrazoline-1-carboxamide, 3- (4-chlorophenyl) -N-

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

  pyrazoLine-1-carboxamide, 3- (4-difluoromethoxy)

  phenyl) -N- (2,3-dihydro-2,2,3,3-tétrafluorobenzofurane-

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

  phenyl] -4-phenylpyrazoline-1-carboxamide, N- [4 (4-

  difluorométhoxyphénoxy) phenyl] -3- (4-diftuorométhoxy-

  phenyl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide, the

  3- (4-difluoromethoxyphenyl) -4- (4-fluorophenyl) -N- (2,3-

  dihydro-2,2,3,3-tétrafluorobenzofurane-5-yl) pyrazoline-

  1-carboxamide, 3- (4-difluoromethoxyphenyl) -4- (4-

  fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tétrafluorobenzo-

  furan-6-yl) pyrazoline-1-carboxamide, the 4- (4-chloro)

  phenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -

  3-phenylpyrazoline-1-carboxamide, 3- (4-chlorophenyl) -

  4- (4-fluorophenyl-N- (2,3-dihydro-2,2-diméthytbenzo-

  furan-5-yl) pyrazoline-1-carboxamide, 3- (4-difluoro-

  methoxyphenyl) -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. The present invention also contemplates insecticidal compositions comprising a quantity

  effective as an insecticide of at least one of the pyrazol

  above lines in admixture with an acceptable carrier in agriculture. In addition, this invention covers the insect control method of applying to the location where control is desired an insecticidally effective amount of at least

one of the pyrazotines above.

  The pyrazoLines of the invention can

  be prepared by coupling an isocyanate or an iso-

  Suitable aromatic thiocyanate with a suitably substituted pyrazotine, a method within the scope of the invention, namely: H aRB lD_ N R

\ R

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

  Pyrazotines appropriately substituted -

  used as starting materials are materials

  generally known. Isocyanates and isothiocyanates

  Nates needed can be prepared from the corresponding amines. A number of amines

  exist in the trade. Other amines of interest

  can be prepared by the methods described

in the following examples.

ExempLe 1

  3- (4-chlorophenyl) -N- [4- (4-chlorophenoxy) phenyl] -4-

  In a dry nitrogen atmosphere, a stirred mixture of 10.9 g (0.077 mol) of 4-fluoronitrobenzene, 9.95 g (0.077 mol) of 4-chlorophenol and 11, 8 g (0.085 mol) of potassium carbonate in 175 ml of dimethylsulfoxide. The reaction mixture is cooled and filtered. The filtrate is diluted with water until a volume of 1L is obtained. This mixture is extracted

  with three portions of 200 mL of diethyl ether.

  The combined ether extracts are washed with water and then with a saturated aqueous solution of sodium chloride. The washed extract is dried over anhydrous sodium sulfate and filtered. Evaporation of the filtrate under reduced pressure gives 13.5 g of 4- (4-chlorophenoxy)

nitrobenzene (mp 67-70 ° C).

  Hydrogenation of 13.5 g (0.954 mol) of 4- (4-chlorophenoxy) nitrobenzene with a catalytic amount (0.015 g) of platinum oxide in 250 mL of tetrahydrofuran gives a quantitative yield.

4- (4-chlorophenoxy) aniline.

  To a stirred solution of 0.75 g (0.0034 mole) of 4- (4-chlorophenoxy) aniline in 25 ml of toluene, a solution of 0.43 ml (0.0036 mole) of chloroformate is added dropwise. trichloromethyl

  in 20 ml of toluene. When the addition is complete

  The mixture was heated at 85 ° C. for three hours.

  This mixture is cooled to room temperature, and the solvent is evaporated under reduced pressure, leaving a residue. The residue is dissolved in 25 ml of diethyl ether. This solution is added dropwise to a stirred slurry of 1.0 g (0.0034 mole) of 3- (4-chlorophenyl) -4-phenylpyrazoline in

  diethyl ether. Three drops of triethyl

  amine and mixed at room temperature for two days. The solvent is evaporated from the mixture,

  which gives 0.92 g of 3- (4-chlorophenyl) -N- [4- (4-

  chlorophenoxy) phenyl] -4-phénylpyrazoline-1-carboxamide

(Mp 158-161 ° C).

  Compound C, 66.92; H, 4.22

Found C, 66.06; H, 4.94.

NMR: 8.06 ppm (CDCl 3).

Example 2

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

  furan-5-yl) -4-phenylpyrazolin-1-carboxamide For one hour, an ice-cold mixture of 43 ml of nitric acid and 50 ml of concentrated sulfuric acid at 100.0 is added over one hour. g (0.67 moles) of 2,3-dihydro-2,2-dimethylbenzofuran, while maintaining the temperature at 5 ° C. When the addition is complete, the mixture is stirred at 0 ° C. for two and a half hours. The reaction mixture is poured into ice water and extracted with diethyl ether. The extract is dried

  on anhydrous magnesium chloride and filtered.

  Evaporation of the filtrate under reduced pressure

  duit a black oil. Purification of this oil by column chromatography on silica gel, eluting with toluene: n-hexane (9: 1), gives

  0 g of 2,3-dihydro-2,2-dimethyl-5-nitrobenzoate

furan in the form of a solid.

  Hydrogenation of 20.0 g (0.1 mol) of 2,3-dihydro-2,2-dimethyl-5-nitrobenzofuran with a catalytic amount (0.2 g) of platinum oxide in

  ml of methanol produces 16.6 g of 5-amino-2,3-dihydro-

  2,2-dimethylbenzofuran. 257240i A solution is added dropwise

  0.43 mL (0.0036 mole) of trifluoromethyl chloroformate

  chloromethyl in 20 ml of toluene to a solution

  stirred with 0.56 g (0.0034 mol) of 5-amino-2,3-di-

  hydro-2,2-dimethylbenzofuran in 20 ml of toluene. When the addition is complete, heat the

  mixture under reflux for three hours. We cool

  The mixture is warmed to room temperature and the solvent is evaporated under reduced pressure to leave a residue. The residue is dissolved in 25 ml of dry diethyl ether and the solution is added dropwise to a stirred 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.

  lic. The reational metangeat is agitated: at the temperature

  room temperature for about eighteen hours,

  at the end of which a solid is filtered from the mixture.

  The filter cake is slurried in ethanol and collected by filtration.

  which gives 0.47 g of 3- (4-chlorophenyl) -N- (2,3-di-

  hydro-2,2-dimethylbenzofuran-5-yl) -4-phénylpyra-

  zoline-1-carboxamide (F = 160-162 ° C).

  Caulculated Composition C, 70.00; H, 5.43

Found this 69.50; H, 3.36.

NMR. 9.00 ppm (DMSO-d6).

  Other members of the series prepared by similar techniques are represented by the following additional examples. Dots

  melting point are indicated in degrees CeLsius. The sin-

  NMR glue corresponding to the proton = NH, characteristic of these compounds, is also given in

  certain cases. Unless otherwise indicated, the

  NMR is CDCL3. Elementary compositions

are given in * some cases.

EXAMPLE 3

  3,4-Diphenyl-N- (4-phenoxyphenyl) -1-carbox- pyraz1oline

  amide, F-188-188. 9.17 ppm (DMSO-d)

Example 4

  N- [4- (4-Chlorophnnoxy) phenyl] -3,4-diphenylpyrazoline-1

  carboxamide, mp = 146-149. 8.83 ppm (DMSO-d6) Example 5

  3- (4-Chlorophenyl) -N- (4-phénoxyphény1) -4-phényl1pyrazo-

  line-1-carboxamide, mp 163-166. 8.03 ppm

Example 6

  N- (4-phenoxyphenyl) -4-phenyl-3- (4-trifluoromethyl

  phenyl) pyrazoline-1-carboxamide, mp 188-190. 8.10 ppm

Example 7

  3,4-bis (4-Chlorophenyl) -N- (4-phénoxyphényl1) pyrazoline-

  1-carboxamide, mp 189-193. 8.20 ppm (CDCl3 / DMSO-d6)

Example 8

  3- (4-Chlorophenyl) -N- (3-methyl-4-phenoxyphenyl) -4-

  phenylpyrazoline-1-carboxamide, mp 151-157. 9.13 ppm (DMSO - d6)

Example 9

  3- (4-Chlorophenyl) -N- [4- (2-fluorophenoxy) phenyl] -4-

  phenylpyrazoline-1-carboxamide, mp 153-155. 8.16 ppm

Example 10

  3- (4-Chlorophenyl) -N- [4- (3-fluorophenoxy) phenyl] -4-

  phenylpyrazoline-1-carboxamide, mp 173-175. 9.33 ppm (DMSO-d6) Example 11

  N- [4- (3-chlorophenoxy) phenyl] -3- (4-chlorophenyl) -4-

  phenylpyrazoline-1-carboxamide, mp 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

Example 13

  3- (4-Chlorophenyl) -N- [4- (4-trifluoromethylphenoxy) -

  phenyl] -4-phenylpyrazoline-1-carboxamide, mp = 161-164.

8.03 ppm

Example 14

  N- [4- (4-chlorophenoxy) phenyl] -3- (4-difluoromethoxy

  phenyl) -4-phenylpyrazoline-1-carboxamide, mp 103-107.

8.00 ppm Example 15

  3,4-bis (4-Chlorophenyl) -N- (3-methyl-4-phenoxyphenyl) -

  pyrazoline-1-carboxamide, mp 188-190. 9.23 ppm (DMSO-d6)

Example 16

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

  pyrazoline-1-carboxamide, mp 160-162. 8.10 ppm

Example 17

  3,4-bis (4-Chlorophenyl) -N- [4- (3-fluorophenoxy) phenyl] -

  pyrazoline-1-carboxamide, mp = 144-146. 9.20 ppm (DMSO-d6)

Example 18

  N- [4- (3-chlorophenoxy) phenyl] -3,4-bis (4-chlorophény1) -

  pyrazoline-1-carboxamide, mp: 135-140. 9.30 ppm (DMSO-d6)

Example 19

  3,4-bis (4-Chlorophenyl) -N- [4- (4-fluorophenoxy) phenyl] -

  pyrazoline-1-carboxamide, mp 168-170. 9.23 ppm (DMSO-d6) Example 20

  N- [4- (4-chlorophenoxy) phenyl] -3,4-bis (4-chlorophenyl) -

  pyrazoline-1-carboxamide, mp 154-156. 9.30 ppm (DMSO-d6)

Example 21

  3,4-bis (4-Chlorophenyl) -N- [4- (4-trifluorométhylphén-

  oxy) phenyl] -pyrazoline-1-carboxamide, mp 191-194.

9.30 ppm (DMSO-d6)

Example 22

  3 - (- 4-Chlorophenyl) -4-phenyl-N- (4-phenylthiophenyl) pyra-

  zoline-1-carboxamide, mp = 157-162. 8.20 ppm

Example 23

  3,4-bis (4-Chlorophenyl) -N- (4-phenylthiophenyl) pyrazo-

  line-1-carboxamide, mp 169-171. 8.20 ppm

Example 24

  3,5-bis (4-Chlorophenyl) -N- (4-phenoxyphenyl) pyrazoline-

  1-carboxamide, mp 168-170. 8.30 ppm (CDCl3 / DMSO-d6)

Example 25

  3- (4-Chlorophenyl) -5- (4-trifluoromethylphenyl) -N- (4-

  phenoxyphenyl) pyrazoline-1-carboxamide, mp 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)

Example 28

  3,5-bis (4-Chlorophenyl) -N- [4- (4-fluorophenoxy) phenyll-

  pyrazoline-1-carboxamide, mp 165-167. 9.16 ppm (DMSO-d6)?

Example 29

  N- [4- (4-chlorophenoxy) phény1] -3,5-bis (4-chlorophenyl) -

  pyrazoline-1-carboxamide, mp 142-144. 9.20 ppm (DMSO-d6) Example 30

  3,5-bis (4-Chlorophenyl) .N- [4- (4-trifluorométhylphén-

  oxy) phenyl) l] pyrazoline-1-carboxamide, mp 155-158. -

8.43 ppm (CDCl3 / DMSO-d6)

* Example 31

  3- (4-Chlorophenyl) -N- [4- (4-trifluoromethylphenoxy) -

  phenyl) -S- (4-trifluoromethylphenyl) pyrazolin-l-carbox-

  amide, mp = 144-146. 8.06 ppm Exept 32

  N- [4- (4-chlorophenoxy) phnyl] -S5-4-ch1ôrophenyl) -3- (4-

  difluoromethoxyphenyl) pyrazoline-1-carboxamide, mp 66-70. 8.60 ppm (DMSOd6)

Example 33

  (1,3-Benzodioxol-5-yl) -3- (4-chlorophenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxaamide, mp 125-128. 8.36 ppm (CDCl3 / DMSO-d6)

Example 34

  - (1,3-benzodioxol-5-yl) - N- [4- (4-chlorophenoxy) phenyl] -

  3- (4-chlorophenyl) pyrazoline-1-carboxamide, mp 174-175.

8.06 ppm Example 35

  N- (2,3-Dihydro-2,2-dimethylbenzofuran-5-yl) -3,4-di-

  phenylpyrazoline-1-carboxamide, mp 139-143. 7.96 ppm

- Example 36

  3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2-di-

  methylbenzofuran-5-yl) -4-phenyipyrazoline-1-carbohydrate

amide, mp 75-82. 7.96 ppm

Example 37

  (+) - 3,4-bis (4-Chloroph6nyl) -N- (2,3-dihydro-2,2-di-

  methylbenzofuran-5-yl) -4-phenylpyrazoline-1-carbox-

amide. F 134-137. 7.93 ppm

Example 38

  3,5-bis {4-Chlorophenyl) -N- (2,3-dihydro-2,2-dimethyl-

  benzofuran-5-yl) pyrazoline-1-carboxamide, mp = 175-180.

8.86 ppm (DMSO-d6) Example 39

  N- (1,4-benzodioxan-6-yl-3- (4-chlorophenyl) -4-phenyl

  pyrazoline-1-carboxamide, mp 112-115. 7.96 ppm

Example 40

  N- (1,4-Benzodioxan-6-yl) -3,4-bis (4-chlorophenyl) pyra-

  zoline-1-carboxamide, mp 140-145. 7.96 ppm

Example 41

  3- (4-Chlorophény1) -N- (4-phenoxyphenyl) -4-phénylpyrazo-

  line-1-carbothioamide, mp 105-110. 10.30 ppm (DMSO-d6)

Example 42

  3,4-bis (4-Chlorophény1) -N- (4-phenoxyphenyl) pyrazoline-

  1-carbothioamide, mp 151-153. 9.26 ppm (DMSO-d6)

Example 43

  N- [4- (4-chlorophenoxy) phenyl] -3,4-bis (4-chlorophenyl) -

  pyrazoline-1-carbothioamide, mp 179-183. 9.10 ppm Example 44

  3- (4-Chlorophényl1) -N- (2,3-dihydro-2,2-diméthylbenzo-

  furan-5-yl) -4-phenylpyrazolin-1-carbothioamide, m.p. 92-95. 10.12 ppm (DMSO-d6)

Example 45

  3,4-bis (4-Chlorophenyl) -N- (2,3-dihydro-2,2-dimethyl-

  benzofuran-5-yl) pyrazoline-1-carbothioamide, mp 149-154. 9.00 ppm (DMSOd6)

Example 46

  N- (1,4-Benzodioxan-6-yl) -3,5-bis (4-chlorophenyl) pyra-

  zoline-1-carboxamide, mp 83-85. 9.33 ppm (DMSO-d6)

Example 47

  - (4-Chlorophenyl-3- (4-trifluoromethylphenyl) -N- [14- (4trifluoromethylphenoxy) phenyl] pyrazoline-1-carboxamide, mp = 183-185.8.87 ppm (CDCl3 / DMSO-d6)

Example 48

  N- (2,3-dihydro-2,2,3,3-tétrafluorobenzofurane-5-yl) -3-

  (4-difluoromethoxyphenyl) -4-phénylpyrazoline-1-carbox-

  In a pressure flask, 0 g (0.086 moles) of 2chloro-4-nitrophenol, 11.9 g (0.086 moles) of potassium carbonate, 1.5 g (0.02 moles) of propanethiol, are added. 7 g (0.13 mol) of

  1,2-dibromotetrafluoroethane and 115 ml of N, N-dimethyl-

  formamide. The bottle is sealed under pressure and the mixture is stirred at 50 ° C. for forty-eight hours. The pressure flask is cooled to room temperature, opened, and the contents are poured into a separatory funnel. About 200 ml of a 2N solution of sodium hydroxide are introduced into the separating funnel. The resulting mixture is extracted with four 300 ml portions of diethyl ether. The extracts are combined and washed with two 1 ml portions of a 2N solution of sodium hydroxide. The washed extract is dried over anhydrous magnesium sulfate and filtered. The filtrate is evaporated under reduced pressure, leaving an oil. We repeat

  three times the reaction described above.

  above. The residual oils from the four experiments are pooled and purified by column chromatography on silica gel eluting with n-heptane: toluene (95: 5) to give 57.6 g.

  3-chloro-4- (2-bromo-1,1,2,2-tetrafluoroethoxy) nitro-

benzene in the form of an oil.

  In a pressure bottle, we introduce

  0 g (0.028 mol) of 3-chloro-4- (2-bromo-1,1,2,2-

  tetrafluoroethoxy) nitrobenzene, 9.0 g (0.14 mol) of copper powder (0.074 mm), 0.45 g (0.0028 mol) of

  2,2'-bipyridyl and 40 ml of dimethylsulfoxide.

  Seal the pressure bottle and shake the mixture

  reaction at 190-195 C for two hours. We cool

  The pressure flask is told at room temperature, opened and poured into a separating funnel. 200 ml of a 2N solution of hydrochloric acid are added to the separating funnel, and the mixture is extracted with three 150 ml portions of diethyl ether. The extracts are combined and washed successively with 200 ml of a 2N solution of hydrochloric acid, 200 ml of a saturated aqueous sodium chloride solution, and 200 ml of a 2N solution of sodium hydroxide. The washed extract is dried over anhydrous magnesium sulfate and filtered. The solvent is evaporated under reduced pressure, leaving an oil. The reaction described above is repeated six more times. The residual oils from the seven experiments are pooled and subjected to column chromatography on silica gel,

  eluting with toluene, giving a yellow oil.

  This oil is dissolved in 125 ml of methylcyclo

  hexane, and the solution is placed in a freezer for about eighteen hours. Crystals form, which are collected by filtration, which

  gives 20.7 g of 2,2,3,3-tetrafluoro-5-nitrobenzo-

  furan. The filtrate is evaporated under reduced pressure, leaving an oil. Distillation of

  this oil under reduced pressure provides 3.0 g

  additional product (Eb = 75 C / O, mm Hg). The hydro-

  2.15 g (0.011 mol) of 2,2,3,3-tetrafluoro

  nitrobenzene with a catalytic amount (0.25 g) of platinum oxide in 150 ml of methanol produced

  2.15 g of 5-amino-2,2,3,3-tetrafluorobenzofuran.

  A solution of

  0.75 g (0.0036 mole) of 5-amino-2,2,3,3-tetrafluoroethylene

  benzofuran in 109 ml of toluene to a solution

  stirred with 8.0 ml of 20% phosgene in toluene.

  When the addition is complete, the mixture is heated

257240 (

  under reflux for two hours. The mixture was cooled and the solvent removed by evaporation under reduced pressure, leaving a residue. This residue is dissolved in 15 ml of diethyl ether and added to a stirred solution of 1.04 g.

  (0.0036 moles) 3- (4-difluoromethoxyphenyl) -4-

  phenylpyrazoline and three drops of triethylamine in 100 ml of diethyl ether. When the addition

  is complete, the mixture is heated under reflux

  one hour, then cool to the temperature

  ambient and stirred for about eighteen hours.

  The solvent is removed from the reaction mixture and evaporated.

  poration under reduced pressure, which leaves a

  solid residue. Recrystallization in ethanol

  provides 0.99 g of N- (2,3-dihydro-2,2,3,3-tetra-

  fluorobenzofuran-5-yl) -3- (4-difluoromethoxyphenyl) -

  4-phenylpyrazoline-1-carboxamide (mp 155-159 ° C).

  Composition Calculated C, 58.58; H, 3.29

Found C, 57.81; H, 3.75.

NMR: 8.16 ppm.

Exemp -

  3,4-bis (4-chlorophenyl) -N- (2,2-difluoro-1,3-benzo

  dioxol-5-yl) pyrazoline-1-carboxamide A solution of

  1.18 g (0.0068 mole) of 5-amino-2,2-difluoro-1,3-benzoate

  dioxol prepared by the process described in the literature.

  dissolved in 80 ml of tetrahydrofuran, to a cold solution (5 to 10 C) of 24 ml of phosgene

  % in toluene. When the addition is ter-

  The mixture is stirred at 2 ° C. for one hour,

  then under reflux for two hours. We evaluate

  The sotvant under reduced pressure, which leaves 1.4 g of a liquid residue. In a clean reaction flask, 0.68 g of this residue is slowly added to a stirred solution of 0.93 g (0.0032 mole) of 3,4-bis (4-chlorophenyl) pyrrolidine and three drops of triethylamine in 20 g. ml of diethyl ether. When the addition-is over, one

  The mixture is stirred at room temperature

  about eighteen hours. A small amount

  solids is present in the reaction mixture

  net and is removed by filtration. We evapo-

  The filtrate under reduced pressure, which leaves

  a residue. Purification of this residue by chroma-

  Silica gel column chromatography, eluting with n-heptane: ethyl acetate (1: 1)

  produced 1,3 g of 3,4-bis-4-chlorophenyl) -N- (2,2-

  difluoro-1,3-benzodioxot-5-yl) pyrazoline-1-carbox-

amide (mp = 150-155 ° C). Composition Calculated C, 56.34; H, 3.08

Found C, 57.16; H, 2.89.

NMR: 8.10 ppm.

  The compound of Example 50 is prepared

in the same way.

257240C

Example 50

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

  methoxyphenyl) -4-phényLpyrazoline-1-carboxamide,

F = 135-138. 8.10 ppm.

Example 51

  3- (4-Fluorophenyl) -N- (4-phenoxyphenyl) -4-phénylpyra-

  zoline-1-carboxamide, mp 187-191. 8.10 ppm.

Example 52

  3- (4-Di-fluoromethoxyphenyl) -N- (4-phenoxyphenyl) -4-

  phenylpyrazoline-1-carboxamide, mp 139-144.

8.10 ppm.

Example 53

  3- (4-Chlorophenyl) -N- [4- (4-chlorophenoxy) -phenyl] -4-

  phenylpyrazoline-1-carboxamide, mp 170-174.

8.10 ppm.

Example 54

  3-4 (Chlorophenyl) -N- [4- (4-nitrophenoxy) phenyl] -4-

  phenylpyrazoline-1-carboxamide, mp 187-189. 8.30 ppm.

Example 55

  3- (4-Chlorophenyl) -N- [4- (4-methoxyphenoxy) phenyl] -4-

  phenylpyrazoline-1-carboxamide, mp 159-160. 8.07 ppm.

Example 56

  3- (4-Chtorophényl) -N- [4- (4-difLuorométhoxyphénoXy) -

  phenyl] -4-phenylpyrazoline-1-carboxamide, mp 181-184.

8.07 ppm.

Example 57

  N- [4- (4-chlorophenoxy) phenyl] -3- (4-trifluoromethoxy

  phenyl) -4-phenylpyrazoline-1-carboxamide, mp = 132-134.

8.16 ppm Example 58

  N- [4- (4-chlorophenoxy) phenyl] -4-phenyl-3-14- (2-pro-

  pynyloxy) phenyllpyrazoline-1-carboxamide, mp 160-164.

8.13 ppm

Example 59

  3- (1,3-benzodioxol-5-yl) -N- (4-phenoxyphenyl) -4-phenyl

  pyrazoline-1-carboxamide, mp 220-223. 8.06 ppm

Example 60

  4- (4-Chlorophenyl) -N- (4-phenoxyphenyl) -3-phénylpyrazo-

  line-1-carboxamide, mp 153-155. 8.16 ppm Example 61

  3,4-bis (4-Fluorophenyl) -N- (4-phenoxyphenyl) pyrazoline-

1-carboxamide, mp 194-198. 8.16 ppm

Example 62

  N- [4- (2-chlorophenoxy) phenyl] -3,4-bis (4-chlorophény1) -

  pyrazoline-1-carboxamide, mp 182-186. 8.10 ppm

Example 63

  3,4-bis (4-Chlorophenyl) -N- [4- (4-methoxyphenoxy) phenyl] -

pyrazoline-1-carboxamide. 8.20 ppm

Example 64

  3- (4-Chlorophenyl) -4- (4-fluorophenyl) -N- (4-phenoxy

  phenyl) pyrazoline-1-carboxamide, F-178-179. 8.10 ppm

Example 65

  N- [4- (4-chlorophenoxy) phenyl] -3- (4-chlorophenyl) -4-

  (4-fluorophenyl) pyrazoline-1-carboxamide, mp 143-145.

8.03 ppm

Example 66

  3- (4-Chlorophenyl) -4- (4-methylphenyl) -N- (4-phenoxy

  phenyl) pyrazoline-1-carboxamide, mp = 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) ON- (4-phenoxy

  phenyl) pyrazoline-1-carboxamide, mp 184-187. 8.17 ppm

Example 69

  N- [4- (4-Difluoromêthoxyphénoxy) phenyl] -3- (4-difluoro-

  methoxyphenyl) -4- (4-fluorophenyl) pyrazoline-1-carbox-

amide. 8.10 ppm

Example 70

  N- [4- (4-chlorophenoxy) phenyl] -3- (4-chloroph6nyl) -4-

  phenylpyrazoline-1-thiocarboxamide, mp 179-183.

9.10 ppm ExEmp 71

  3- (4-difluoromethoxyphenyl) -N- (4-phenoxyphenyl) -4-

  phenylpyrazoline-1-thiocarboxamide, mp = 132-136.

9.13 ppm Example 72

  4- (4-Chlorophény1) -N- (4-phenoxyphenyl) -3-phénylpyrazo-

  line-1-thiocarboxamide, m.p. 131-133. 9.16 ppm

Example 73

  N- [4- (4-chlorophenylthio) phenyl] -3,4-diphénylpyrazo-

  line-1-carboxamide, mp 186-190. 8.20 ppm

Example 74

  3- (4-Chlorophenyl) -N- [4- (4-chlorophenylthio) phenyl] -4-

  phenylpyrazoline-1-carboxamide, mp 178-181. 8.23 ppm

Example 75

  3- (4-Difluoromêthoxyph6nyl) -4-phenyl-N- (4-phenylthio

  phenyl) pyrazoline-1-carboxamide, mp: 135-140. 8.13 ppm

Example 76

  3,4-bis (4-Chlorophenyl) -N- [4- (4-fluorophenylthio) -

  phenyl] pyrazoline-1-carboxamide, mp 171-175. 8.20 ppm

Example 77

  3,4-bis (4-Chlorophenyl) -N- [4- (4-chlorophenylthio) -

  phenyl pyrazoline-1-carboxamide, mp 151-156. 8.13 ppm

Example 78

  3,4-bis (4-chlorophenyl) -N- [4- (3-chlorophenoxy) phenyl] pyrazoline-1-carboxamide, mp: 135-140. 9.20 ppm (DMSO-d6)

Example 79

  3- (4-methoxyphenyl) -N- (4-phenoxyphenyl) -4-phényl1pyrazo-

  line-1-carboxamide, mp 188-192. 8.46 ppm (CDCl3 / DMSO-d6)

Example 80

  3- [4-t 2 -propynyloxy) phenyl-N - (4-phenoxyphenyl) -4-

  phenylpyrazoline-1-carboxamide, mp 121-126. 8.10 ppm

Example 81

  3- (4-Chlorophenyl) -N- (2,3-dihydrobenzofuran-5-yl) -4-

  phenylpyrazoline-1-carboxamide, mp 155-158. 7.93 ppm

Example 82

  3- (4-Difluorométhoxyphény1) -N- (2,3-dihydrobenzofuran-5-

  yl) -4-phénylpyrazoline-1-carboxamide. 7.93 ppm Example 83

  3,4-bis (4-Chlorophenyl) -N- (2,3-dihydrobenzofuran-5-

  yl) pyrazoline-1-carboxamide, mp 214-216. 7.93 ppm

Example 84

  3- (4-Fluorophenyl) -N- (2,3-dihydro-2,2-diméthylbenzo-

  furan-5-yl) -4-phenylpyrazoline-1-carboxamide, mp = 156-160.

7.93 ppm

Example 85

  3- (4-Methoxyphenyl) -N- (2,3-dihydro-2,2-dimethylbenzoate)

  furan-5-yl) -4-phenylpyrazoline-1-carboxamide, mp 164-169.

8.00 ppm

Example 86

  3- (4-trifluoromethoxyphenyl) -N- (2,3-dihydro-2,2-di-

  methylbenzofuran-5-yl) -4-phenylpyrazoline-1-carbox-

amide, mp 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, mp 175-179. 8.00 ppm Example 88

  3- (1,3-benzodioxol-5-yl) -N- (2,3-dihydro-2,2-dimethyl-

  benzofuran-S-yl) -4-phenylpyrazolin-1-carboxamide, mp 223-227. 8.90 ppm (DMISO-d6)

Example 89

* 4- (4-Chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzoate)

  furan-5-yl) -3-phénylpyrazoline-1-carboxamide. 8.00 ppm

Example 90

  3,4-bis (4-Fluorophenyl) -N- (2,3-dihydro-2,2-dimethyl-

  benzofuran-5-yl) pyrazoline-1-carboxamide, mp = 161-166.

7.93 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) pyrazoline-1-carboxamide, mp 137-139. 7.96 ppm

Example 93

  3- (4-Chlorophenyl) -4- (4-methoxyphenyl) -N- (2,3-dihydro-

  2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide, mp 182-186. 7.93 ppm

Example 94

  4- (4-Fluorophenyl) -N- (2,3-dihydro-2,2-diméthylbenzo-

  furan-5-yl) -3- (4-methoxyphenyl) pyrazoline-1-carbox-

amide, mp 179-182. 7.93 ppm

Example 95

  4- (4-Chlorophenyl) -N- (2,3-dihydro-2,2-diméthylbenzo-

  furan-5-yl) -3- (4-methoxyphenyl) pyrazoline-I-carbox-

amide, mp = 157-160. 7.96 ppm

Example 96

  3- (4-difluoromethoxyphenyl) -4- (4-fluorophenyl) -N- (2,3-

  dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-car-

  boxamide, mp 169-172. 7.93 ppm Example 97

  4- (4-Chlorophenyl) -3- (4-difluoromethoxyphenyl) -N- (2,3-

  dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-car-

boxamide, F = 90-95. 7.93 ppm

Example 98

  3- (4-Difluorométhoxyph6nyl) -N- (2,3-dihydro-2,2,3,3

  tetrafluorobenzofuran-6-yl) -4-phenylpyrazoline-1-car-

boxamide, mp 152-157. 8.33 ppm

Example 99

  3- (4-Difluorométhoxyphényl1) -4- (4-fluoropheényl) -N- (2,3-

  2,2,3,3-tetrafluorobenzofuran-6-yl) pyrazoline

1-carboxamide, mp 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-phenylpyrazolin-1-carboxamide, mp 182-186.

7.96 ppm Example 102

  3- (4-difluoromethoxyphenyl) -N- (2,2-dimethyl-1,3-benzo

  dioxol-5-yl) -4-pheenylpyrazoline-1-carboxamide, mp = 148-150.

7.93 ppm

Example 103

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

  oxol-5-yl) -pyrazolin-1-carboxamide, m.p. 168-169.

7.93 ppm

Example 104

  N- (1,4-Benzodioxan-5-yl) -3- (4-difluoromethoxyphenyl) -

  4-phénylpyrazoline-1-carboxamide. 7.93 ppm

Example 105

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

  methoxyphenyl) -N-methyl-4-phénylpyrazoline-1-carbox-

amide, mp 110-114.

Exemxle 106

  4- (1,3-benzodioxol-S-yl) -N- (4-phenoxyphenyl) -3-phenyl-

  pyrazoline-1-carboxamide, mp 195-197. 8.03 ppm Example 107

  3- (4-Chlorophenyl) -N- [41 [4- (1,1-dimethylethyl) phenoxy] -

  phenyl] -4-phenyl-pyrazoline-1-carboxamide, mp 192.5-194. 8.03 ppm

Example 108

  3- (4-Chlorophényl1) -4- (4-fl-fluorophenyl) -N- [4- (4-methyl-

  phenoxy) phenyl] pyrazoline-1-carboxamide, mp = 162-164.

8.03 ppm

Example 109

  3-C (4-Chloro.phényl) -4- (4-fluorophenyl) -N- [4- [4- (l, 1-di-

  methylethyl) phenoxy] phenyl] pyrazolinel-1-carboxamide, mp 188-198. 8.03 ppm Exe.mple 110

  3- (4-Chlorophenyl) -N- [4- [4- (1-methylethyl) phenoxy] -

  phenyl] -4-phenylpyrazoline-1-carboxamide, mp 181-182.5.

8.06 ppm

Example 111

  3- (4-Chlorophenyl) -4- (4-fluorophenyl) -N- [4- [4- (1-

  methylethyl) phenoxy] phenylpyrazolin-1-carboxamide, mp 186-187. 8.60 ppm (CDCl3 / DMSO-d6)

Example 112

  3- (4-Chlorophenyl) -N- [4- (4-methylphenoxy) phenyl-4-

  phenylpyrazoline-1-carboxamide, mp = 150-151. 8.06 ppm

Example 113

  3- (4-Chlorophenyl) -1- [4- [4- (1-methylethoxy) phenoxy] -

  phenyl] -4-phenylpyrazoline-1-carboxamide, mp 158-160.5.

8.06 ppm

Example 114

  3- (4-Chlorophenyl) -4- (4-fluorophenyl) -N- [4- [4- (1-

  Methyl (methoxy) phenoxy phenyl] pyrazoline-1-carboxamide, mp 213-216. 8.66 ppm (CDCl3 / DMSO-d6) Example 115

  3,4-bis (4-Fluorophêny1) = N- [4- [4- (1-m6thy1éthoxy) phen

  oxy] phenyl] pyrazoline-1-carboxamide, mp = 134-136.

8.06 ppm

Example 116

  3,4-bis (4-Fluorophenyl) -N- [4- (4-chlorophenoxy) phenyl] -

  pyrazoline-1-carboxamide, mp 197-198.5. 8.70 ppm (CDCl3 / DMSO-d6)

Example 117

  3,4-bis (4-fluorophenyl) -N- [4- [4- (1,1-dimethylethyl) -

  phenoxy] phenyl] pyrazoline-1-carboxamide, mp 189-192.

8.70 ppm (CDCl3 / DMSO-d6)

Example 118

  3,4-bis (4-Fluorophenyl) -N- [4- (4-cyanophenoxy) phenyl] -

  pyrazoline-1-carboxamide, mp 198-200. 8.13 ppm Example 119 3,4-Bis (4Fluorophenyl) -N-14- [4- (N, N-dimethylamino).

  phenoxy] phenyl] pyrazoline-1-carboxamide, mp = 148-150.

8.02 ppm

Example 120

  3- (4-Chlorophenyl) -N- [4- (4-cyanophenoxy) phenyl] -4-

  phenylpyrazoline-1-carboxamide, mp 170-172. 8.16 ppm

Example 121

  N- (1,4-Benzodioxan-6-yl) -4- (4-chlorophenyl) -3- (4-di-

  fluoromethoxyphenyl) pyrazoline-1-carboxamide, F 124-128.-

7.93 ppm

Example 122

  3,4-bis (4-Chlorophény1) -N- (2,3-dihydro-2,2-dimethyl-

  benzodioxan-5-yl) -N-methylpyrazoline-1-carboxamide,

F = 150-155.

Example 123

  N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3,4-diphenyl

  pyrazoline-1-carboxamide, mp 214-216. 8.83 ppm (CDCl3 / DMSO-d6) Example 124

  N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3,4-bis (4-fluoro-

  phenyl) pyrazoline-1-carboxamide, mp 178-180. 8.10 ppm

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

  tetrafluorobenzofuran-5-yl) -N-methyl-4-phenylpyrazo

line-l-carboxamide.

Example 127

  3- (4-Chlorophenyl) -4- (4-diflu6rométhoxyphényl) -N- (2,3-

  dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-car-

  boxamide, mp 155-159. 7.96 ppm Example 128

  3- (4-Difluorométhoxyph6nyl) -N- (2,3-dihydro-2,2-di-

  fluorobenzofuran-5-yl) -N-methyl-4-phenylpyrazoline

1-carboxamide.

Example 129

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

  yl) -3- (4-difluoromethoxyphenyl) pyrazoline-1-carbox-

amide. 8.06 ppm

Example 130

  4- (1,3-benzodioxol-5-yl) -3- (4-chlorophenyl) -N- [4- (4-

  fluorométhoxyphénoxy) phenyl] pyrazoline-1-carboxamide.

Example 131

  4- (1,3-benzodioxol-5-yl) -N- [4- (4-chlorophenoxy) phenyl] -

  3- (4-chlorophenyl) pyrazoline-1-carboxamide.

Example 132

  4- (1,3-benzodioxol-5-yl) -3- (4-chlorophenyl) -N- (2,2-di-

  fluoro-1,3-benzodioxol-5-yl) pyrazoline-1-carboxamide.

Example 133

  4- (1,3-benzodioxol-5-yl) -3- (4-chlorophényl1) -N- (2,3-di-

  hydro-2,2,3,3-tétrafluorobenzofurane-5-yl) pyrazoline-1

carboxamide. Example 134

  4- (1,3-benzodioxol-5-yl) -3- (4-chlorophenyl) -N- (2,3-di-

  hydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carbox-

amide.

Example 135

  4- (1,3-benzodioxol-5-yl) -N-14- (4-difl1uorométhoxyphén-

  oxy) phenyl] -3- (4-difluoromethoxyphenyl) pyrazoline-1

carboxamide.

Example 136

  4- (1,3-benzodioxol-5-yl) -N- [4- (4-chlorophenoxy) phenyl] -

  3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide.

Example 137

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

pyrazoline-l-carboxamide.

Example 139

  4- (1,3-benzodioxol-S-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-phénylpyrazoline-l-carboxamide.

Example 141

  4- (1,3-benzodioxol-5-yl) -N- (2,3-dihydro-2,2,3,3-tetra-

  fluorobenzofuran-5-yl) -3-phenylpyrazoline-1-carbox-

amide.

Example 142

  4- (1,3-benzodioxol-5-yl) -N- (2,2-difluoro-1,3-benzo4i-

  oxol-5-yl) -3-phénylpyrazoline-l-carboxamide.

Example 143

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

Example 144

  4- (1,3-benzodioxol-5-yl) -N- [4- (4-chlorophenoxy) phény1] -

  3-phénylpyrazoline-1-carboxamide. Example 145

  4- (2,2-Difluoro-l, 3-benzodioxol-5-yl) -N- [4- (4-difluoro-

  methoxyphenoxy) phenyl] -3- (4-fluorophenyl) pyrazoline-1

carboxamide.

Example 146

  N- [4- (4-chlorophenoxy) phenyl] -4- (2,2-difluoro-3-ben

  zodiool-S-yl) -3- (4-fluorophenyl) pyrazoline-1-carbox-

amide.

Example 147

  4, N-bis (2,2-Difluoro-1,3-benzodioxol-5-yl) -3- (4-fluoro-

phenyl) pyrazoline-l-carboxamide.

Example 148

  4- (2,2-Difluoro-1,3-benzodioxol-S-yl) -3- (4-fluoro-

  phenyl) -N- (2,3-dihydro-2,2,3,3-tétrafluorobenzofurane-

  yl) pyrazoline-l1-carboxamide. Exm the 149

  4- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3- (4-fluoro-

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

Example 150 -

  4- (2,2-Difluoro-1,3-benzodioxol-5-yl) -N- [4- (4-di-

  fluorométhoxyphenoxy) phenyl] -3-phénylpyrazoline-1-

carboxamide.

Example 151

  N-14- (4-chlorophenoxy) phenyl] -4- (2,2-difluoro-1,3-

  benzodioxol-S-yl) -3-phénylpyrazoline-1-carboxamide.

Example 152

  4, N-bis (2,2-Difluoro-1,3-benzodioxol-5-yl) -3-phenyl-

pyrazoline-1-carboxamide.

Example 153

  4- (2,2-Difluoro-1,3-benzodioxol-5-yl) -N- (2,3-dihydro-

  2,2,3,3-tetrafluorobenzofuran-5-yl) -3-phenylpyrazoline

1-carboxamide.

Example 154

  4- (2,2-Difluoro-1,3-benzodioxol-5-yl) -N- (2,3-dihydro-

  2,3-dimethylbenzofuran-5-yl) -3-phenylpyrazoline-1

carboxamide.

Example 155

  4- (2,2-Difluoro-1,3-benzodioxol-5-yl) -N-14- {4-difluoro-

  methoxyphenoxy) & ph nyl] -3- (4-difluoromethoxyphenyl) -

pyrazoline-l-carboxamide.

Example 156

  N- [4- (4-Chiorophénoxy) 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-l, 3-benzodioxol-5-yl) -3- (4-di-

  fluorométhoxyph6nyl) pyrazoline-1-carboxamide.

Example 158-

  4- (2,2-Difluoro-l, 3-benzodioxol-5-yl) -3- (4-difluoro-

  méthoxyphényl'-N- (2,3-dihydro-2,2,3,3-tétrafluorobenzo-

  furan-5-yl) pyrazoline-1-carboxamide.

Example 159

  4- (2,2-Difluoro-l, 3-benzodioxol-S-yl) -3- (4-difluoro-

  methoxyphenyl) -N- (2,3-dihydro-2,2-dimethylbenzofurane-

5-yl) pyrazoline-l-carboxamide.

Example 160

  4- (1,4-Benzodioxan-6-yl) 3- (4-chlorophenyl) -N-14- (4-

  difluorométhoxyphénoxy) phenyl] pyrazoline-l-carboxamide.

Example 161

  4- (1,4-benzodioxan-6-yl) -N- [4- (4-chlorophenoxy) phényl1-

  3- (4-chlorophenyl) pyrazoline-l-carboxamide.-

Example 162

  4- (1,4-Benzodioxan-6-yl) -3- (4-chlorophenyl) -N- (2,2-di-

  fluoro-1,3-benzodioxol-5-yl) pyrazoline-1-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-Benzodioxane-6-yl) -3- (4-chlorophenyl) -N- (2,3-di-

  hydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-l-carbox-

amide.

Example 165

  4- (1,4-Benzodioxan-6-yl) -N-t4- (4-difluoromethoxyphenyl)

  oxy) phenyl] -3- (4-difluoromethoxyphenyl) pyrazoline-1

carboxamide.

Example 166

  4- (1,4-Benzodioxan-6-yl) -N- [4- (4-chlorophenoxy) phenyl] -

  3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide.

Example 167

  4- (1,4-benzodioxan-6-yl) -N- (2,2-difluoro-1,3-benzodi-

  oxol-5-yl) -3- (4-difluoromethoxyphenyl) pyrazoline-1

carboxamide.

Example 168

  4- (1,4-benzodioxan-6-yl) -3- (4-difl1uorométhoxyphény1) -

  N- (2,3-dihydro-2,2,3,3-tétrafluorobenzofurane-5-yl) -

pyrazol ine-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-difluorométhoxyphén-

  oxy) phenyl] -3-phénylpyrazoline-1-carboxamide.

Example 171

  4- (1,4-benzodioxan-6-yl) -N- [4- (4-chlorophenoxy) phényvl] -

3-phénylpyrazoline-1-carboxamide.

Example 172

  4- (1,4-Benzodioxan-6-yl) -N- (2,2-difluoro-1,3-benzodio)

  oxol-5-yl) -3-phénylpyrazoline-l-carboxamide.

Example 173

  4- (1,4-Benzodioxan-6-yl) -N- (2,3-dihydro-2,2,3,3-tetrahydrate)

  fluorobenzofuran-5-yl) -3-phenylpyrazoline-1-carbox-

amide.

Example 174

  4- (1,4-Benzodioxan-6-yl) -N- (2,3-dihydro-2,2-dimethyl)

  benzofuran-5-yl) -3-phénylpyrazoline-1-carboxamide.

Example 17S -

  3- (1,3-benzodioxol-5-yl) -N- [4- (4-difluorométhoxyphén-

  oxy) phenyl] -4- (4-fluorophenyl) -N-méthylpyrazoline-1-

carboxamide. Example 176

  3- (1,3-benzodioxol-5-yl) -N- [4- (4-chloroph'noxy) phenyl] -

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

Example 177

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

  oxol-5-yl) -4- (4-fluorophenyl) pyrazoline-l-carboxamide.

Example 178

  3- (1,3-benzodioxol-5-yl) -4- (4-fluorophenyl) -N- (2,3-di-

  hydro-2,2,3,3-tetrafluorobenzofuran-5-yl) pyrazoline-1

carboxamide. Example 179

  3- (1,3-benzodioxol-5-yl) -4- (4-fluorophenyl) -N- (2,3-di-

  hydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carbox-

amide.

Example 180

  3- (2,2-Difluoro-l, 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-3-ben

  zodioxol-5-yl) -4- (4-fluorophenyl) -N-methylpyrazoline-l-

carboxamide.

Example 182

  3, N-bis (2,2-Difluoro-1,3-benzodioxol-5-yl) -4- (4-fluoro-

phenyl) pyrazoline-1-carboxamide.

Example 183

  3- (2,2-Difluoro-1,3-benzodioxol-5-yl) -4- (4-fluoro-

  phenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofurane-

yl) pyrazolinel-carboxamide.

Example 184

  3- (2,2-Difluoro-1,3-benzodioxol-5-yl) -4- (4-fluoro)

  phenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -

pyrazoline-1-carboxamide.

Example 185

  3- (1,4-Benzodioxan-6-yl) -N- [4- (4-difluoromethoxyphenyl)

  oxy) phenyl] -4-ph6nylpyrazoline-l-carboxamide.

Example 186

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

Example 187

  2- (1,4-Benzodioxan-6-yl) -N- (2,2-difluoro-1,3-benzodio)

  oxol-5-yl) -N-methyl-4-phénylpyrazoline-1-carboxamide.

Example 188

  3- (4-Benzodioxan-6-yl) -N- (2,3-dihydro-2,3,3,3-tetra);

  fluorobenzofuran-5-yl) -4-phenylpyrazoline-1-carbox-

amide.

Exeple 189

  3- (1,4-Benzodioxan-6-yl) -N- (2,3-dihydro-2,2-dimethyl)

  benzofuran-5-yl) -4-phénylpyrazoline-1-carboxamide.

Example 190

  N- 4- (4-Difluoromethoxyphenoxy) phenyl] -3- (2,3-dihydro)

  2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-car-

carboxamide.

Example 191

  N- [4- (4-chlorophenoxy) phenyl] -3- (2,3-dihydro-2,2-di-

  Methylbenzofuran-5-yl) -4-phenylpyrazoline-1-carbox-

amide.

Example 192

  N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3- (2,3-dihydro-

  2,2-dimethylbenzofuran-5-yl) -4-phénylpyrazoline-1-

carboxamide. Example 193

  N- (2,3-Dihydro-2,2,3,3-tétraf1uorobenzofurane-5-yl) -3-

  (2,3-Dihydro-2,2-dimethylbenzofuran-5-yl) -N-methyl-4-

  phénylpyrazoline-1-carboxamide. Example 194

  3, N-bis (2,3-Dihydro-2,2-dimétbylbenzofurane-5-yl) -4-

phénylpyrazoline-l-carboxamide.

Example 195

  N- [4- (4-Difluoromèthoxyphénoxy) phenyl] -4- (4-fluoro-

  phenyl) -3- (4-methylphenyl) pyrazoline-l-carboxamide.

Example 196

  N- [4- (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-fluoro-

  phenyl) -3- (4-methylphenyl) pyrazol1ine-l-carboxamide.

Example 198

  4- (4-Fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluoro-

  benzofuran? -5-yl) -3-t4-methylphenyl) pyrazolin-l-carbox-

amide.

Example 199

  4- (4-Fluorophenyl) -N- (2,3-dihydro-2,2-diméthylbenzo-

  furan-5-yl) -N-methyl-3- (methylphenyl) pyrazolin-1-

carboxamide. Example 200

  N- 4- (4-Difluoromethoxyphenoxy) phenyl -4- (3-fluoro)

  phenyl) -N-methyl-3- (4-methylphenyl) pyrazolin-l-ca-r-

carboxamide.

Example 201

  N- [4- (4-chlorophenoxy) phenyl] -4- (3-fluorophenyl) -3-

  (4-méthylphényvli) pyrazoline-1-carboxamide.

Example 202

  N- (2,2-Difluoro-l, 3-benzodioxol-S-yl) -4- (3-fluoro-

  phenyl) -3- (4-methylphenyl) pyrazoline-l-carboxamide.

Example 203

  S 4- (3-Fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluoro-

  benzofuran-5-yl) -3- (4-methylphenyl) pyrazolin-1-carbox-

amide.

Example 204

  4- (3-Fluorophenyl) -N- (2,3-dihydro-2,2-diméthylbenzo-

  furan-5-yl) -3- (4-methylphenyl) pyrazoline-l-carboxamide.

Example 205

  N- [4- (4-Difluorométhoxyphénoxy) phenyl] -4- (2-fluoro-

  phenyl) -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-l, 3-benzodioxol-5-yl) -4- (2-fluoro-

  phenyl) -3- (4-methylphenyl) pyrazoline-l-carboxamide. Example 208

  4- (2-Fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluoro-

  benzofuran-5-yl) -3- (4-methylphenyl) pyrazolin-l-car-

carboxamide.

Example 209

  4- (2-Fluorophenyl) -N- (2,3-dihydro-2,2-diméthylbenzo-

  furan-5-yl) -3- (4-methylphenyl) pyrazoline-l-carboxamide.

Example 210

  N- [4- (4-Difluorométhoxyphénoxy) phenyl] -3- (3-fluoro-

  phenyl) -4- (4-fluorophenyl) pyrazoline-l-carboxamide. Example 211

  N- [4- (4-chlorophenoxy) phenyl] -3- (3-fluorophenyl) -4-

  (4-fluorophenyl) pyrazoline-l-carboxamide.

Example 212

  N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3- (3-fluoro-

  phenyl-4- (4-fluorophenyl) -N-1-carbox- méthylpyrazoline-

amide.

Example 213

  3- (3-F1luorophényl) -4- (4-fluoroph'nyl) -N- (2,3-dihydro-

  2,2,3,3-tetrafluorobenzofuran-5-yl) pyrazoline-1-car-

carboxamide. Example 214

  3- (3-Fluorophenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-

  2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.

Example 215

  N- [4- (4-Difluorométhoxyphénoxy) phenyl] -3- (2-fl1uoro-

  phenyl) -4- (4-fluorophenyl) pyrazoline-l-carboxamide.

Example 216

  N- [4- (4-chlorophenoxy) phenyl] -3- (2-fluorophenyl) -4-

  (4-fluorophenyl) pyrazoline-l-carboxamide.

Example 217

  N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3- (2-fluoro-

  phenyl) -4- (4-fluorophenyl) pyrazoline-l-carboxamide.

Example 218

  3- (2-Fluorophenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-

  2,2,3,3-tétrafluorobenzofurane-5-yl) -N-méthylpyrazo-

line-l-carboxamide.

Exe.mple 219

  3- (2-Fluorophenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-

  2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.

Example 220

  3.4: bis (4-Fluorophenyl) -N- (2,3-dihydro-2,2,3,3,7-penta-

  fluorobenzofuran-5-yl). pyrazoline-1-carboxamide.

Example 221

  4- (4-Chlorophenyl) -N- (2,3-dihydro-2,2,3,3,7-penta-

  fluorobenzofuran-5-yl) -3- (4-methylphenyl) pyrazoline

1-carboxamide.

Example 222

  N- (2,3-Dihydro-2,2,3,3,7-pentafluorobenzofurane-5-yl) -

  3,4-diphenylpyrazoline-l-carboxamide. EXAMPLE 223

  3- (4-Difluorométhoxyph6nyl) -N- (2,3-dihydro-2,2,3,3,7-

  Pentafluorobenzofuran-5-yl) -4-phnrylpyrazoline-1

carboxamide. Example 224

  3- (4-Chlorophenyl) -N- (2,3-dihydro-2,2,3,3,7-penta-

  fluorobenzofuran-5-yl) -4-phénylpyrazoline-1-carbox-

amide.

Example 225

  3,4-bis (4-Fluorophenyl) -N- (2,2,6-trimethyl-l, 3-benzo-

  dioxol-5-yl) pyrazoline-l1carboxamideo

Example 226

  4- (4-Chlorophnyl) -N = (2,2,6-trimethyl-l, 3-benzodioxol

  S-yl) -3- (4-methylphenyl) pyrazoline-l-carboxamide.

Example 227-

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

-Exemple_228

  3- (4-Difluorométhoxyph & nyl) -N- (2,2,6-trimethyl-3-

  benzodioxol-5-yl) -4-phenylpyrazoline-l-carboxamide.

Example 229

  3- (4-Chlorophenyl) -N- (2,2,6-trimethyl-l, 3-benzodioxol

  yl) -4-phénylpyrazoline-l-carboxamide.

Example 230

  3,4'bis (4-Fluorophenyl) -N- (7-methoxy-2,2-dimethyl-1,3-

  benzodioxol-5-yl) pyrazoline-locarboxamide '

Example- 231

  4- (Chlorophenyl) -N- (7-methoxy-2, 2-dimethyl-1,3-benzodi-

  oxol-S-yl) -3- (4-methylphenyl) pyrazoline! 1-carboxaTnide. Example 232

  N- (7-Methoxy-2,2 = diméthylI-1,3-benzodioxol-5-yl) -3, 4-

diphenylpyrazoline-1-carboxamide.

Example 233

  3- (4-Difluoromethoxyphenyl) N- (7-methoxy-2,2-dimethyl)

  1,3-benzodioxol-5-yl) -4-phénylpyrazoline-1-carboxamide.

Example 234

  3- (4-Chlorophenyl) -N- (7-methoxy-2,2-dimethyl-l, 3-benzo-

  dioxol-5-yl) -4-phényipyrazoline-l-carboxamide.

Example 235

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

Example 236

  4- (4-Chlorophenyl) -N- [2,2-dimethyl-7- (l-methylethyl) -

  l, 3-benzodioxol-5-yl] -3- (4-methylphenyl) pyrazolin-1-

carboxamide.

Example 237

  N- [2,2-Dimethyl-7- (1-methylethyl) -1,3-benzodioxol-5-

  yl] -3,4-diphenyl1pyrazoline-l-carboxamide.

Example 238

  3- (4-difluoromethoxyphenyl) -N- [2,2-dimethyl-7- (l-

  methylethyl) -l, 3-benzodioxol-5-yl] -4-phénylpyrazo-

line-l-carboxamide.

* Example 239

  3- (4-Chlorophenyl) -N- [2,2-dimethyl-7- (l-methylethyl) -

  l, 3-benzodioxol-5-yl] -4-phénylpyrazoline-l-carboxamide.

Example 240

  3,4-bis (4-Fluorophenyl) -N- (2,3-dihydro-2,2,3,3-7-4thyl

  tetrafluorobenzofuran-5-yl) pyrazoline-1-carboxamide.

Example 241 4- (4-Chlorophenyl) -N- (2,3-dihydro-7-ethyl-2,2,3,3-

  tetrafluorobenzofuran-5-yl) -3- (4-methylphenyl) pyrazo

l-1-carboxamide.

Example 242

  N- (2,3-Dihydro-7-ethyl-2,2,3,3-tétrafluorobenzofurane-5-

  yl) -3,4-diphénylpyrazoiine-l-carboxamide.

Example 243

  3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-7-ethyl-

  2,2,3,3-tetrafluorobenzofurane-5-yl) -4-phénylpyrazo-

line-l-carboxamide.

Example 244

  3- (4-Chlorophenyl) -N- (2,3-dihydro-7-ethyl-2,2,3,3

  tetrafluorobenzofuran-5-yl) -4-phenylpyrazol ine-1

carboxamide.

Example 245

  3- (4-Chlorophenyl) -N- [4- (4-methylsulfonylphenoxy) -

  phenyl] -4-phénylpyrazoline-l-carboxamide.

Example 246

  3,4-bis (4-Fluorophenyl) -N- [4- (4-methylsulfonylphenoxy) -

phenyl] pyrazoline-l-carboxamide.

Example 247

  3- (4-difluoromethoxyphenyl) -N- [4- (4-methylsulfonyl

  phenoxy) phenyl] -4-phénylpyrazoline-l-carboxamide.

Example 248

  3- (4-Chlorophenyl) -4- (4-fluorophenyl) -N- [4- (4-methyl-

  sulfonylphénoxy) phenyl] pyrazoline-l-carboxamide.

Example 249

  N- [4- (4-methylsulfonylphenoxy) phenyl] -3,4-diphenyl

  pyrazoline-l-carboxamide. Example 250

  3,4-bis (4-Fluorophenyl) -N- (2,3-dihydro-7-difluorométh-

  oxy-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carbox-

amide.

Example 251

  4- (4-Chlorophenyl) -N- (2,3-dihydro-7-difluoromethoxy-

  2,2-diméthylbenzofurane'-5-yl) -3- (4-methylphenyl) pyrazo-

line-l-carboxamide.

Example 252

  N- (2,3-Dihydro-7-difluoromethoxy-2,2-diméthylbenzo-

  30. furan-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-phénylpyrazo-

line-l-carboxamide.

Example 254

  3- (4-Chlorophenyl) -N- (2,3-dihydro-7-difluoromethoxy-

  2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1

carboxamide. Example 255

  N- (7-Chloromethyl-2,2-dimethyl-l, 3-benzodioxol-5-yl) -

  3,4-bis (4-fluorophenyl) pyrazoline-1-carboxamide.

Example 256

  N- (7-Chloromethyl-2,2-dimethyl-l, 3-benzodioxol-5-yl) -

  4- (4-chlorophenyl) -3- (4-methylphenyl) pyrazolin-1-

carboxamide.

Example 257

  N- (7-Chloromethyl-2,2-dimethyl-l, 3-benzodioxol-5-yl) -

  3,4-diphenylpyrazoline-l-carboxamide. Example 258

  N- (7-Chloromethyl-2,2-dimethyl-l, 3-benzodioxol-S-yl) -

  3- (4-difluoromethoxyphenyl) -4-phénylpyrazoline-1-

carboxamide.

Example 259

  N- (7-Chloromethyl-2,2-dimethyl-l, 3-benzodioxol-5-yl) -

  3- (4-chlorophenyl) -4-phénylpyrazoline-l-carboxamide.

Example 260

  N- (2,3-Dihydro-2,2-dimethylbenzofuran-5-yl) -3- [7- (1-

  methylethyl) -2,2-dimethyl-l, 3-benzodioxol-5-yl] -4-

phénylpyrazoline-l-carboxamide.

Example 261

  N- (2,3-Dihydro-2,2-dimethylbenzofuran-5-yl) -3- (7-

  m'thoxy-2,2-dimethyl-l, 3-benzodioxol-5-yl) -4-phenyl

  pyrazoline-l-carboxamide. Example 262

  N- (2,3-Dihydro-2,2-dimethylbenzofuran-5-yl) -3- (7-

  fluoro-2,2-dimethyl-l, 3-benzodioxol-5-yl) -4-phenyl

pyrazoline-l-carboxamide.

Example 263

  N- (2,3-Dihydro-2,2-dimethylbenzofuran-5-yl) -3- (7-di-

  fluoromethoxy-2,2-diméthylll, 3-benzodioxolo-S-yl) -4-

  phênylpyrazoline-l-carboxamide. Example 264

  N- (2,2-Difluoro-1,3-benzodioxol-S-yl) -3- (4-fluoro-

  phenyl) -4- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl)

pyrazoline-l-carboxamide.

Example 265

  N- (2,2-Difluoro-1,3-benzodioxol-S-yl) -3- (4-fluoro-

  phenyl) -4- (2,3-dihydro-2,2,3,3-tétrafluorobenzofurane-5-

yl) pyrazoline-l-carboxamide.

Example 266

  N- [3- (4-trifluoromethylphenoxy) phenyl] -3,4-bis (4-

  fluorophenyl) pyrazoline-l-carboxamide.

Example 267

  N- [3- (4-fluorophenoxy) phenyl] -3,4-bis (4-fluorophenyl) -

pyrazoline-l-carboxamide.

Example 268

  N- [3- (4-Difluorométhoxyphénoxy) phenyl] -3,4-bis (4-

  fluorophenyl) pyrazoline-l-carboxamide.

Example 269

  3,4-bis (4-Fluorophenyl) oN-13o (4-methylphenoxy) phenyl] -

  pyrazoline-l-carboxamide. Example 270

  3- (7-Chloromethyl-2,2-dimethyl-1,3-benzodioxol-5-yl) -

  4, N-bis (4-fluorophenyl) pyrazoline-l-carboxamide.

Example 271

  N- (2,3-Dihydro-2,2-dimethylbenzofuran-5-yl) -4- [7- (l-

  methylethyl) -2,2-dimethyl-l, 3-benzodioxol-5-yl] -3-

phénylpyrazoline-l-carboxamide.

Example 272

  N- (2,3-Dihydro-2,2-dimethylbenzofuran-5-yl) -4- (7-meth-

  oxy-2,2-dimethyl-l, 3-benzodioxol-5-yl) -3-phénylpyrazo-

line-l-carboxamide.

Example 273

  N- (2,3-Dihydro-2,2-dimethylbenzofuran-5-yl) -4- (7-

  fluoro-2,2-dimethyl-1,3-benzodioxol-5-yl) -3-phényt-

  pyrazotine-1-carboxamide. Example 274

  N- (2,3-Dihydro-2,2-dimethylbenzofuran-5-yl) -4- (7-

  difluoromethoxy-2,2-dimethyl-1,3-benzodioxoLt-5-yl) -3-

  phénylpyrazoline-1-carboxamide. Exempt 275

  4- (7-Chtorométhyl-2,2-dimethyl-1,3-benzodioxol-5-yl) -

  3, N-bis (4-ftuorophényl) pyrazoline-1-carboxamide. In the normal use of the insecticidal pyrazolines of the present invention, pyrazotines will not usually be used without mixing or disruption, but will usually be used.

  in a properly formulated composition,

  tible with the application method and comprising a

  effective amount as an insecticide of pyrazoline.

  The pyrazolines of the invention, like most pesticidal agents, can be mixed with

  surfactants and acceptable carriers in agriculture

  culture normally used to facilitate the dispersal

  active ingredients, taking into account the fact that the form and manner of application of a

  insecticide can affect the activity of your material.

  The pyrazolines of the invention can be applied, for example, in the form of sprays, dusts or granules to the region in which it is desired to fight against parasites. The type of application

  obviously with the parasite and the environment.

  is lying. Thus, the pyrazotines of the invention can be formulated as granules of large particle sizes, in the form of powdery dusts such as wettable powders, in the form of emulsifiable concentrates, in the form of solutions, etc.

  The granules may comprise

  porous or non-porous particles such as attapulgite clay and sand, for example, which serve as

  supports for pyrazolines. Particles of

  The numbers are relatively large, usually about 400 to 2500 microns in diameter. The particles are either impregnated with pyrazoline from a solution or coated with pyrazoline, an adhesive sometimes being used. The granules generally contain 0.05-10%, preferably 0.5-5% of ingredient

  active as effective amount as insecticide.

  The dust is a mixture of pyra-

  zolines with finely divided solids such as talc, attapulgite clay, kieselguhr, pyrophyllite, chalk, diatomaceous earth, calcium phosphates, calcium and magnesium carbonates, sulfur, flours and dusts. other inorganic and organic solids which act as carriers for the insecticide. These solids finely

  divided have an average particle size of

  than about 50 microns. A typical dust formulation usable for insect control contains 1 part of a pyrazoline, such as

  3- (4-chlorophenyl) -N- [4- (4-chlorophenoxy) phenyl] -4-

  phenylpyrazoline-1-carboxamide, and 99 parts of talc.

  The pyrazolines of the present invention

  can be transformed into liquid concentrates by.

  dissolution or emulsification in suitable liquids, and solid concentrates by mixing with talc, clays, and other known solid carriers used in the pesticide art. The

  concentrates are compositions containing, as a

  as an insecticide, about 5-50% of

  pyrazoline, such as 3- (4-chlorophenyl) -N- (2,3-

  dihydro-2,2-dimethylbenzofuran-5-yl) -4-phénylpyrazo-

  line-1-carboxamide, and 95-50% of inert material which

  comprises surfactants, dispersing agents, emulsifiers

  and wetting, but it is possible to use

  rementally even higher concentrations of active ingredient. The concentrates are diluted with water or other liquids for practical application in the form of sprays, or with a solid

  extra for use as dust.

  Typical carriers for solid concentrates (also called wettable powders) include diatomaceous earth, clays, silicas and other highly mineral diluents.

  absorbent, easily wetted. A concentration formula

  The solid used for insect control contains 1.5 parts of sodium lignosulfonate and 1.5 parts of sodium lauryl sulphate 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 clay

  pulgite. Manufacturing concentrates are useful for shipping the products of the invention down

  Fusion point. These concentrates are prepared in

  solid products with a low melting point with

  1% or more of a solvent to produce a concentration

  which does not solidify by cooling to

  freezing point of the pure product or below.

  Usable liquid concentrates include emulsifiable concentrates, which are compositions in the form of homogeneous liquids or pastes, easily dispersed in water, or other

  liquid carriers. They can be made up entirely

  pyrazoline with a liquid or solid emulsifier, or they may also contain a

  liquid carrier such as xylene, aromatic naphthas

  heavy materials, isophorone and other solvents

  relatively nonvolatile organic. For the application

  These concentrates are dispersed in water or other liquid carriers and normally applied

  as sprays on the regions to be treated.

  Wetting surfactants, dispersing

  and emulsifiers used in pesticide formulations include, for example, alkyl and alkyl aryl sulfonates and sulfates and their sodium salts; alkylamide sulfonates, including methyl taurides

  alkylaryl polyether alcohols, the higher alcohols

  sulphated alcohols, polyvinyl alcohols; the

  polyethylene oxides; animal and vegetable oils

  sulphonated tales; sulphonated petroleum oils; fatty acid esters of polyalcohols and adducts with ethylene oxide of these esters; and long chain mercaptan adducts and ethylene oxide. Many other types of surfactants that can be used are commercially available. The surfactant, when used, normally comprises about 1 to 15% by weight of the

insecticidal composition. -

  Other useful formulas include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone or other

organic solvents.

  An effective insecticidal amount of pyrazoline in a dilute insecticidal composition for application is normally in the range of about 0.001% to about 8% by weight. Many

  variants of spray compositions and

  dusting known in the art can be used

  substituted by substituting the pyrazotines of the invention in compositions known or obvious in the art. The insecticidal compositions of the invention may be formulated with other active ingredients including other insecticides, nematocides, acaricides, fungicides, plant growth regulators, fertilizers, etc. When using

  to fight against insects, it suffices

  applied a quantity of pyrazoline effective as an insecticide on the site where it is desired to fight. This location may for example be The insects themselves, The plants whose

  insects feed on, or the habitat of the insect.

  Where the site is the soil, for example a soil in which agricultural crops are or will be planted, the active compound may be applied to the soil and, if desired, incorporated therein. For most applications, an insecticidally effective amount will be from about 75 to 4000 g per hectare,

  preferably from 150 to 3000 g per hectare.

  The insecticidal activity of the pyrazoLines of which the preparation is described above was evaluated as follows:

  The compounds have been tested in

  Foliar cations at various concentrations in aqueous solutions containing 10% acetone and 0.25% octyl phenoxypolyethoxy ethanol. Seedlings

  "Pinto" beans were placed on a turntable

  in a hood, and the test solutions were applied with a puLverizer. The test solutions were applied on the upper faces

  and lower leaves of the plant until heard

  LEMENT. The plants were then allowed to dry and then cut at the base of the stem. Each stem has been

  inserted through a paper cup in water.

  Ten individuals of the appropriate insect species were placed in each cup and the cup was covered. The evaluation used the southern military worm (Spodoptera eridania), the Mexican bean beetle (Epilachna varivestis), the military beet worm (Spodoptera exiqua). and cabbage looper (Trichoplusia ni). After four days at 26 C, and 50% RH, the mortality was read. The results

  tests are given in Table 1. Mortality

  Insect resistance is generally lower if

essays are read much earlier.

  A number of the pyrazolines were also active against the southern corn rootworm (Diabrotica undecimDunctata howardi Barber) when applied to the soil, and those tested were also very effective on the Colorado potato beetle.

(LeDtinotara decemlineata Say).

TABLE 1

  Foliar Rate Rate Insects (% of killed) Compound (ppm) MBB SAW BAW CL

1500 100 100

2,500 100 100

3,500 100 100

4,500 100 100 100

250 to 100 87 100

6 500 70 65 90

7,500 100 50 90

8 500 100 85

9 500 90 70

500 100 35

11 500 85 15S

12 500 100 100

13,500 93 50 90

14 500 100 100

500 100 90

16 500 100

17 500 100 35

18 500 90 55

19 500 100 100

500 80 40

21 500 70 15

22 500 100 100

  Table 1 (Continued) Foliar Evaluation Rate Insects (% killed) Compound (pm) MB SAW BAW C

23 500 40 30

24 250 95 100

500 30 75

26 500 80 65

27 500 75 95

28 500 95 90

29 500 10 90

500 S 64 60

31,500 5 65 70

32 500 100 50

33 500 100 80

34,500 10 75

500 100 100

36 8 100 98 45 90

* 37 32 98 98 97 100

38,500 95,80

39 500 100 25

500 100 100

41 128 95 70

42,128 95,100

  Table 1 (Continued) Eva Foal Count Rate Insects (% of killed) Compound (ppm) MBB SAW BAW _L

43 500 100 100

44 500 100 100

32 100 100 100 100

46 500 30 40

47,500 5 10

48 8 100 100 100 95

49 500 100 100

500 100 100

51 100 40 60

52 500 100 95

53 500 100 10

54 500 100 85

500 to 100

56 500 100 100

57 250 100 100

58 500 100 40

59 500 100 100

200 to 100

61 32 45 100 55 90

62 500 95 95

63 500 100 95

64 500 100 100

  Table 1 (Continued) Foliar Evaluation Rate Insects (% killed) Compound (ppm) MBB SAW BAW CL

500 100 100

66 500 100 100

67 500 85 95

68 500 100 0

69 8 100 60 5 100

500 100 100

71 200 60 10

72 200 100 30

73 500 100 90

74 500 100 80

200 to 100

76,200 95,100

77 500 80

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

  Table 1 (Continued) Foliar Evaluation Rate Insects (% of killed) Compound (ppm) MBB SAW BAW CL

86 16 95 95 40 100

87 500 100 100

88 100 100 25 10 85

89 200 100 100

16 100 100 100 90

91 32 100 100 100 100

92 500 100 100

93 500 100 100

94 500 100 100 '

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

32 100 100 100 100

101 1000 100 100

102 128 100 100

103 16 90 95 15 100

16 100 100

106 256 100 70

107 1000 45 0

108 1000 100 75

  Table 1 (Continued) Foliar Rate Rate Insects (% of killed) Compound {pDm) MBB SAW BAW CL

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 IS

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 i0o 100 0 125 64 100o 100 MBB = Mexican bean beetle SAW = South Military Worm BAW = Army Beet Worm

CL = Cabbage looper.

Claims (32)

  1. An insecticidal PyrazoLine characterized by the formula R Pc N -W a, wherein RA has formula A in which RIA is selected from hydrogen, a   halogen, a lower alkyl radical, lower alkoxy   lower haloalkoxy, lower alkynyloxy and lower haloalkyl; or y / vR AC wherein X is a bridge of the formula [O- (CR'AAR 'AB) a-Oa] wherein a is 1-3, a' is O or 1, a + a 'is at minus 2, but not greater than 3, R'A and R'BB are AA 'BB   independently selected from hydrogen, halogen and lower alkyl, and R'AC is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl; RB is a 4- or 5- substituent of the formula BR B wherein R'B is selected from hydrogen, halogen, lower alkyl, lower alkoxy and lower haloalkyl; or R 'REBC wherein Y is a bridge of the formula: [O- (CR'BAR'BB) -Ob [0- (CR'BAR BB) b b'] wherein b is 1-3, b ' is O or 1, b + b 'is at least 2, but not greater than 3, R'BA and R' BB are BB   independently selected from hydrogen, halogenated   gene and a lower alkyl radical and R'BC is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl; RC is according to the formula ## STR2 ## wherein RD is selected from hydrogen and a lower alkyl radical, RE is selected from lower alkyl, halogen, lower alkoxy, lower haloalkoxy, lower haloalkyl, cyano, nitro, -NRFRG, RF and RG are independently a lower alkyl radical, and -SOnRH, where RH is a lower alkyl radical and n is 0-2, or CC in which Z is a bridge of the formula [O- ( Wherein c is 1-3, c is 0 or 1, c + c 'is at least 2, but no more than 3, R'CA and R'CB are independently selected from hydrogen, a halogen and a lower alkyl radical, provided that R'CA and R'CB are not both hydrogen when   c is 1 and c 'is 1, and R'C is selected from hydro-   CC gene, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl;   RN is hydrogen or an alkyl radical   laughing; and V and W are independently oxygen or sulfur.   2. The compound of claim 1, characterized in that W is oxygen.   3. The compound of claim 1, characterized   rised in that R'A is a halogen or a radical lower haloalkoxy.   4. The compound of claim 1, characterized   in that RB is a 4- substituent.   5. The compound of claim 1, characterized   rised in that RB meets the formula   6. The compound of claim 5, characterized   in that RIB is a halogen.   7. The compound of claim 1, characterized   rised in that RC responds to the 0R formula RD RE   or is selected from 2,3-dihydro-2,2-dimethylbenzoate   furan-5-yl, 2,3-dihydro-2,2,3,3-tetrafluorobenzoate   furan-5-yl, 2,3-dihydro-2,2,3,3-tetrafluorobenzoate   furan-6-yl, 2,2-difluoro-1,3-benzodioxol-5-yl and   2,2-dimethyl-1,3-benzodioxol-5-yl.   8. The compound of claim 1, wherein RC has the formula H - 9. The compound of claim 8, characterized   in that RE is a lower haloalkoxy radical.   10. 3- (4-Difluoromethoxyphenyl) -N- (2,3-   dihydro-2,2-diméthytbenzofurane-5-yl) -4-phenyl   pyrazoline-1-carboxamide, compound of claim 1.   11. 3,4-bis (4-Fluorophenyl) -N- (2,3-dihydro-   2,2,3,3-tétrafluorobenzofurane-5-yl) -1- pyrazotine   carboxamide compound of claim 1.   12. 3,4-bis (4-Fluorophenyl) -N- (2,3-dihydro)   2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide, compound of claim 1.   13. N- (2,3-Dihydro-2,2,3,3-tetrafluorobenzoate   furan-5-yl) -3- (4-diftuorométhoxyphényl) -4-phénytpyra-   zoline-1-carboxamide, compound of claim 1.   14. N- (2,2-Difluoro-1,3-benzodioxot-5-yl) -   3- (4-difluoromethoxyphenyl) -N-methyl-4-phénylpyrazotine-   1-carboxamide compound of claim 1.   15. 3,4-bis (Chlorophenyl) -N- (2,2-dimethyl-1,3-   benzodioxol-5-yl) pyrazoLine-1-carboxamide, composed of claim 1.   16. N- (2,2-Difluoro-1,3-benzodioxot-5-yl) -3,4-   bis- (4-fluorophenyl) pyrazoLine-1-carboxamide compound of claim 1.   17. 3- (4-Chtorophenyt) -N- (2,2-diftuoro-1,3-   benzodioxot-5-yl) -4- (4-fluorophenyl) -1- pyrazotine   carboxamide compound of claim 1.   18. 3- (4-Diftuoromethoxyphenyl) -N- (2,3-dihydro-   2,2,3,3-tétrafLuorobenzofurane-5-yl) -N-methyl-4-phenyl   pyrazoLine-1-carboxamide, compound of claim 1.   19. 3- (4-Chlorophenyl) -N-1 [4- (4-difluoromethoxy)   phenoxy) phenyl] -4-phenylpyrazoline-1-carboxamide, compound of claim 1.   20. N- [4- (4-Difluoromethoxyphenoxy) phenyl] -3-   (4-difluoromethoxyphenyl) -4- (4-fluorophényt) pyrazotine-   1-carboxamide, composed of the claim i.   21. 3- (4-Difluoromethoxyphenyl) -4- (4-fluorophenyl)   phenyl) -N- (2,3-dihydro-2,2,3,3-tétrafluorobenzofurane-   -yl) pyrazoline-1-carboxamide, composed of cation 1. - 257240 (   22. 3- (4-Difluoromethoxyphenyl) -4- (4-fluoro)   phenyl) -N- (2,3-dihydro-2,2,3,3-tétrafluorobenzofurane-   6-yl) pyrazoline -1-carboxamide, composed of the 1.   23. 4- (4-Chlorophenyl) -N- (2,3-dihydro-2,2-   dimethylbenzofuran-5-yl) -3-phénylpyrazoline-1-carbox-   amide compound of claim 1.   24. 3- (4-Chlorophenyl) -4- (4-fluorophenyl) -   N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-   1-carboxamide compound of claim 1.   25. 3- (4-Difluoromethoxyphenyl) -4- (4-fluorophorone)   phenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl)   pyrazoline-1-carboxamide, composed of the 1.   26. 4- (4-Chlorophenyl) -3- (4-difluoromethoxy)   phenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl)   pyrazoline-1-carboxamide, compound of claim 1.   27. An insecticidal composition, characterized in that it contains, in admixture with an agriculturally acceptable carrier, an insecticidally effective amount of at least one insecticidal pyrazoline having the formula > RBR   wherein w.C wherein R A is of the formula RA in which R 'is selected from hydrogen, A   halogen, a lower alkyl radical, lower alkoxy   lower haloalkoxy, lower alkynyloxy and lower haloalkyl; or R 'RAC wherein X is a bridge of the formula [O- (CR' AAR 'AB) a-Oa,] wherein a is 1-3, a' is 0 or 1, a + a 'is at at least 2, but no more than 3, R'AA and R'AB are independently selected from hydrogen, halogen, lower alkyl, and R'AC is selected from hydrogen, halogen, lower alkyl lower alkoxy, lower haloalkoxy and haloalkyl; inferior. RB is a substituent in 4- or 5- corresponding to the formula - X R'B   B in which R'B is selected from hydrogen, a   halogen, a lower alkyl radical, lower alkoxy   lower haloalkyl; or BC wherein Y is a bridge of the formula [O- (CR'BAR BB) bb wherein b is 1-3, b 'is 0 or 1, b + b' is at least 2, but not greater than 3, R'I and R 'are BA 'BB   independently selected from hydrogen, halogenated   gene and a lower alkyl radical, and R 'BC is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl radical; RC responds to the formula -   RD g.V RE wherein RD is selected from hydrogen and a lower alkyl radical; RE is selected from lower alkyl, halogen, lower alkoxy, lower haloalkoxy, lower haloalkyl, cyano, nitro, -NRFRGo RF and RG are independently a lower alkyl radical, and -SOnRH o RH is a lower alkyl radical and -n is 0-2; or Rc 'wherein Z is a bridge of formula [O- (CR' CAR CB) c] wherein c is 1-3, it is 0 or 1, c + c 'is at least 2, but not greater than 3, RCA and R "are CA: CB   independently selected from hydrogen, halogen and lower alkyl, provided that RICA CA and RI are not both hydrogen when CB   c is 1 and c 'is 1, and R'CC is selected from hydro-   Cc gene, a halogen, a lower alkoxy radical, alkoxy   lower haloalkoxy and lower haloalkyl   laughing; RN is hydrogen or a lower alkyl radical; and V and W are independently oxygen or sulfur.   28. The composition of claim 27, wherein   characterized in that W is oxygen.   29. The composition of claim 27, characterized in that R'A is a halogen or a lower hatoatoxy radical.   30. The composition of claim 27,   characterized in that RB is a 4- substituent.   31. A method of controlling insects, characterized in that it applies to the location o   It is desired to fight an effective amount   ticide of a pyrazoLine in Formula R A A RB W XR   wherein RA has formula AA in Laquette R'A is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower alkanoloxy, lower alkynyloxy and lower haloalkyl; or R 'AC wherein X is a bridge of formula [O- (CR'AAR AB) a-a] wherein a is 1-3, a' is 0 or 1, a + a 'is at least 2 , but not greater than 3, R'AA and R'AB are   independently selected from hydrogen, halogenated   gene and a lower alkyl radical, and R'AC is ACes selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl; RB is a 4- or 5- substituent of formula B. wherein R 'is selected from hydrogen, B   halogen, a lower alkyl radical, lower alkoxy   lower haloalkyl; or R 'BC wherein Y is a bridge of the formula [O- (CR'BAR' BB) b-0 b '] wherein b is 1-3, b' is 0 or 1, b + b 'is at least 2, but not greater than 3, R'BA and R 'are independently selected from hydrogen, halogen and lower alkyl, and R'BC is selected from hydrogen, halogen, a lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl radical; RC has the formula C DP R wherein RD is selected from hydrogen and lower alkyl; RE is selected from lower alkyl, halogen, lower alkoxy, lower haloalkoxy, lower haloalkyl, cyano, nitro, -NRFRG, o RF and RG are independently a lower alkyl radical, and -SOnRH, where RH is a radical lower alkyl and n is 0-2; or Rc wherein Z is a bridge of the formula [OO- (CR'CAR 'CB) c Oc] wherein c is 1-3, where c is 0 or 1, c + c' is at least 2, but no greater than 3, R'CA and R'CD are   independently selected from hydrogen, halogenated   gene and a lower alkyl radical, provided that R'CA and R'CB are not both hydrogen when c is 1 and c 'is 1, and R'C is selected from CC hydrogen, halogen, a lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl radical; 25724C   RN is hydrogen or an alkyl radical; and V and W are independently oxygen and sulfur. -   32. A process for producing an insecticidal pyrazoline, characterized in that a compound having the formula Rc -N = C = W is reacted with a compound of formula RA RB H and, if desired, The product for producing an insecticidal pyrazoline having the formula RA eRB w RC wherein RA has formula A in which R'A is selected from hydrogen, a   halogen, a lower alkyl radical, lower alkoxy   lower haloalkoxy, lower alkynyloxy and lower haloalkyl; or Re AC wherein X is a bridge of the formula [O- (CR AAR AB) a-0a wherein a is 1-3, a 'is 0 or 1, a + a' is at least 2, but not greater than 3, R'A and R'BB are independently selected from hydrogen, halogen and lower alkyl, and R 'AC is selected from hydrogen, halogen, lower alkyl, lower alkoxy, haloalkoxy lower and lower haloalkyl; RB is a 4- or 5- substituent of the formula R 'B wherein R'B is selected from hydrogen, a   halogen, a lower alkyl radical, lower alkoxy   laughter and lower halogen; or R 'RBC wherein Y is a bridge of the formula [O- (CR'BAR' BB) b-0b '] wherein b is 1-3, b' is 0 or 1, b + b 'is at minus 2, but not more than 3, R'BA and R 'BB are independently selected from hydrogen, halogen and lower alkyl, and R'BC is selected 257240C   among hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl; RC has the formula RE wherein R is selected from hydrogen and lower alkyl; RE is selected from a lower alkyl radical, a halogen, an alkoxy radical   lower, lower haloalkoxy, lower haloalkyl   cyano, nitro, -NRFRG, o RF and RG are inde-   pendentially a lower alkyl radical, and -SOnRH o RH is a lower alkyl radical and n is 0-2; or wherein Z is a bridge of the formula wherein R is 1-3, where 0 is 0 or 1, c + c is at least 2, but no more than 3, R'CA and R'CB are independently selected from hydrogen, halogen and lower alkyl, provided that R'CA and R'CB are not both hydrogen when c is 1 and it is 1, and R'Cc is selected from hydrogen, halogen, lower alkyl, alkoxy   lower haloalkoxy and lower haloalkyl   laughing; RN is hydrogen or a lower alkyl radical; and V and W are independently oxygen or sulfur.