NL8502913A - PYRAZOLINE INSECTICIDES. - Google Patents

Description

** γ «^ ν: //. ". -1-

Pyrazoline insecticides.

The invention is in the field of biologically active chemical compositions - more particularly, it relates to novel pyrazoline insecticides, methods and intermediates thereof, insecticide compositions containing the pyrazolines, and the use of the pyrazolines for insect control.

Pyrazolines are five-membered heterocycles of the formula and the ring atom numbering, indicated on the formula sheet under 1.

It is known in the field of insecticides that certain 1-carbamoylpyrazoline derivatives are insecticides.

For example, U.S. Patent 4,174,393 discloses the insecticidal activity of 1-carbamoylpyrazolines, which also contain phenyl substituents at the 3 and 4 positions of the pyrazoline ring.

The invention relates to pyrazolines of the structural formula 2 of the formula sheet, which have a pronounced insecticidal activity.

This application is a continuation in part of the application Serial No. 709,626 filed March 8, 1985, which is a continuation in part of the application. Serial No.

664,674, filed October 25, 1984.

The invention relates to the field of biologically active chemical compositions; more particularly, it relates to novel pyrazoline insecticides, methods and intermediates thereof, insecticidal compositions containing the pyrazolines, and the use of the pyrazolines for insect control.

Pyrazolines are 5-membered heterocyclic compounds of the formula and ring atom numbering shown under 1 on the formula sheet.

* -i * *. » . ► y \ ’·· 'We W ·.

i I

<-2- \

It is known in the field of insecticides that certain 1-carbamoylpyrazoline derivatives are insecticides. For example, U.S. Patent 4,174,393 discloses the insecticidal activity of 1-carbamoylpyrazolines, which also contain phenyl substituents at the 3 and 4 positions of the pyrazoline ring.

It has now been found that pyrazolines of the formula II structure of the formula sheet exhibit a pronounced insecticidal activity. In this formula, R. has the formula 3

a

10 of the formula sheet, wherein R 'is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, lower alkynyloxy and lower haloalkyl, or the formula 4 of the formula sheet, wherein X is a bridge of the formula f "- VabW 2 15 in which a 1-3, a '0 or 1, a + af is at least 2 but not more than 3, R' ^ and R '^ g are independently selected from hydrogen, halogen and lower alkyl, and R1 'is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl; 20

Rg is a 4 or 5 substituent of the formula 5 of the formula sheet, wherein R 'is selected from hydrogen, halogen,

D

lower alkyl, lower alkoxy and lower haloalkyl; or a group of the formula 6 of the formula sheet, wherein Y is a bridge of the formula wherein b 1 - 3, b '0 or 1, b + b' is at least 2 but not more than 3, R 'and R' independently are selected from hydrogen, halogen and lower alkyl, and R '' is selected from dL30 hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl; R_ has the formula 7 of the formula sheet, where \ j

Rp is selected from hydrogen and lower alkyl, and R ^ is selected from halogen, lower alkyl, lower alkoxy, lower halo-35 alkoxy, lower haloalkyl, cyano, nitro, -NR ^ Rg, where Rp is € 302913 / - 3 - » - ^> and RQ are independently lower alkyl and -sonRH <- where R is lower alkyl and n is 0-2? or a group with the formula 8 Ξ from the formula sheet / where Z is a bridge with the formula / ~ 0- (CR 'R') -0.7 - v CA CBJ c c- 5 where c is 1-3 / c '0 or 1, c + c1 is at least 2 but no more than 3, R' and R 'are independently selected from hydrogen, halogen WA UO 1 and lower alkyl, in certain compounds R' and R'CB with both hydrogen when c is 1 and c 'is 1, and R' is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower halo-10 alkoxy and lower haloalkyl;

Rn is hydrogen or lower alkyl? and V and W independently of each other are oxygen or sulfur.

The term "halogen" used herein means fluorine, chlorine or bromine. The term "lower" in "alkyl", "alkoxy", "alkynyloxy" and the like denotes a straight or branched chain hydrocarbon having 1-6, preferably 1-4 carbon atoms - "halogen" linked to another term means that one or more hydrogen atoms have been replaced by halogen.

Of the aforementioned pyrazolines, the compounds in which W is oxygen are preferred for most applications, especially when R '& is a 4 substituent, preferably halogen, eg chlorine or fluorine, or lower haloalkoxy, eg difluoromethoxy . The pyrazolines, wherein R_ is a 4-substituent, are generally more active than the corresponding 5-substituted pyrazolines, and the compounds wherein R is phenyl with a substituent R 'are particularly attractive. In this context it is preferable,

that R "is a 4 substituent, especially halogen, at-B

Example chlorine or fluorine.

Regarding Rc, the most attractive insecticides are usually derived from those compounds containing either a 2,3-dihydro-2,2-dimethylbenzofuran-5-yl, 2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5 -yl, 2,3-dihydro- 3502813 v -4- *% 2.2.3.3-tetrafluorobenzofuran-6-yl, 2,2-difluoro-1,3-benzodioxol-5-yl or 2,2-dimethyl-1 , 3-benzodioxol-5-yl group, or a 4-phenoxyphenyl group. In the latter case, it is preferred that it be hydrogen and that it be a 4-substituent, especially lower haloalkoxy.

Pyrazolines of the invention with remarkable insecticidal activity include, for example, 3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2-dimethylbenzo-furan-5-yl) -4-phenylpyrazoline-1-carboxamide, 3, 4-bis-10 (4-fluorophenyl) -N-2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) pyrazoline-1-carboxamide, 3,4-bis (4-fluorophenyl) - N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide, N- (2,3-dihydro-2,2,3,3-tetrafluoroben * ofuran-5-y 1 ) -3- (4-difluoromethoxyphenyl) -4-phenyl pyrazole ine-1-carbox-15 amide, N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4 -difluoro-methoxyphenyl) -N-methyl-4-phenylpyrazoline-1-carboxamide, 3,4-bis (4-chlorophenyl) -N- (2,2-dimethyl-1,3-benzodioxol-5-yl) pyrazoline- 1-carboxamide, N- (2,2-difluoro-1,3-benzo-dioxol-5-yl) -3,4-bis (4-fluorophenyl) pyrazoline-1-carboxamide, 20 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-tetrafluorobenzofuran-5-yl) -N-methyl-4-phenylpyrazole ine-1-carboxamide, 3- (4-chlorophenyl) -N- / L4- (4-difluoromethoxyphenoxy) phenyl7-4-phenylpyrazole ine-1-25 carboxamide, /- / 4- (4-dif fluoromethoxyphenoxy) phenyl J-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) pyrazoline-1-carboxamide, 3- (4-difluoromethoxyphenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2,3, 3-tetrafluorobenzofuran-6-yl) pyrazoline-1-carboxamide, 4- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -3-phenyl-pyrazoline-1- carboxamide, 3- (4-chlorophenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -pyrazoline-1-carboxamide, 3- (4-difluoromethoxyphenyl) ) -4- 35 (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) - OJV .2 »VI V V '-5- * * 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 includes insecticide compositions containing an insecticidally effective amount of at least one of the aforementioned pyrazolines mixed with an agriculturally acceptable carrier. In addition, the invention includes a method of controlling insects which includes applying to the site where control is desired using insecticidically effective amount of at least one of the aforementioned pyrazolines.

Pyrazolines according to the invention can be prepared by coupling an appropriate aromatic isocyanate or isothiocyanate with an appropriately substituted pyrazoline, a method encompassed by the invention, namely on the formula sheet shown under A.

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

The suitably substituted pyrazoline starting materials are generally known materials. The required isocyanates and isothiocyanates can be prepared from the corresponding amines. Some of the amines are commercially available. Other important amines can be prepared according to the methods described in the following examples.

Example 1 3- (4-Chlorophenyl) -N - / 4- (4-chlorophenoxy) phenyl-7-4-phenyl-30-pyrazoline-1-carboxamide.

Under a dry nitrogen atmosphere, a stirred mixture of 10.9 g (0.077 mol) 4-fluomitrobenzene, 9.95g (0.077 mol) 4-chlorophenol and 11.8g (0.085 mol) potassium carbonate in 175 ml dimethyl sulfoxide was added for 2 days hit at 70 ° C far-35. The reaction mixture was cooled and filtered. The 30 ml filtrate was diluted with water until a volume of one liter was obtained. This mixture was extracted with three 200 ml portions of diethyl ether. The combined ether extract was washed with water, followed by 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 13.5g of 4- (4-chlorophenoxy) nitrobenzene (melting point 67-70 ^ 0).

Hydrogenating 13.5g (0.054 mol) 4- (4-chlorophenoxy) -10 nitrobenzene with a catalytic amount (0.15g) platinum oxide in 250ml tetrahydrofuran gave a quantitative yield of 4- (4-chlorophenoxy) aniline.

To a stirred solution of 0.75g (0.0034 mol) 4- (4-chlorophenoxy) aniline in 25 ml toluene was added dropwise a solution of 0.43 ml (0.0036 mol) trichloromethyl chloroformate in 20 ml toluene . After complete addition, the mixture was heated at 85 ° C for 3 hours. This mixture was cooled to room temperature and the solvent was evaporated under reduced pressure to leave a residue. The residue was dissolved in 25 ml of diethyl ether. This solution was added dropwise to a stirred slurry of 1.0g (0.0034 mol) 3- (4-chlorophenyl) -4-phenylpyrazoline in diethyl ether. Three drops of triethyl amine were added and the mixture was stirred at room temperature for 2 days. The solvent was evaporated from the mixture and 0.92g of 3- (4-chlorophenyl) -N- / ¾- (4-chlorophenoxy) pheayl-Uphenylpyrazoline-1-carboxamide (mp 158-161 ° C) were obtained. .

Analysis: Calculated C 66.92; H 4.22 found C 66.06; H 4.95.

nmr: 8.06 ppm (CDCl 3) S5C2813, -7-

iA

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

Over a 1 hour period, 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 2,3-dihydro-2,2-dimethylbenzofuran, with the temperature 5 ° C was held. After complete addition, the mixture was stirred at 0 ° C for 2.5 hours. The reaction mixture was poured into ice water and the total was 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-15 gel eluting with toluene: n-hexane (9: 1) gave 50 µg of 2,3-dihydro-2,2-dimethyl-5-nitrobenzourane as a solid.

Hydrogenating 20.0 g (0.1 mole) of 2,3-dihydro-2,2-dimethyl-5-nitrobenzofuran with a catalytic amount of (0.2 g) platinum oxide in 250 ml of methanol gave 16.6 g of 5-amino-2 .3-20 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 stirred solution of 0.56 g (0.0034 mol) of 5-amino-2,3-dihydro-2,2 dimethyl benzofuran in 20 ml of toluene.

After completed addition, the mixture was refluxed for 3 hours. The mixture was cooled to room temperature and the solvent was evaporated under reduced pressure to leave a residue. The residue was dissolved in 25 ml of dry diethyl ether and the solution was 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. The reaction mixture was stirred at room temperature for about 18 hours, after which a solid was filtered from the mixture. The filter cake was slurried in ethanol and recovered f *. Μ λ -J. . : J1 * -8- by filtration, whereby 0.47 g of 3- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylb and so furan-5-yl) -4-phenylpyrazoline-1 -carboxamide (melting point 160-162 ° C) were obtained.

Analysis: Calculated C 70.00; H 5.43 found C 69.50; H 3.36 nmr: 9.00 ppm (DMS0-dg)

Other members of the group prepared by similar techniques are shown in the following examples. The melting points are stated in degrees Celsius. The nmr singlet corresponding to the = NH proton, characteristic of these compounds, has also been reported in some cases. Unless otherwise stated, the nmr solvent is CDCl 4. In some cases the basic analysis has been given.

15

Example 3 3,4-Diphenyl-N- (4-phenoxyphenyl) pyrazoline-1-carboxamide, melting point 184-188. 9.17 ppm (DMSO-dg)

Example 4 N-Z4- (4-Chlorophenoxy) phenyl-3,4-diphenylpyrazoline-1-carboxamide, melting point 146-149. 8.83 ppm (DMSO-dg)

Example 5 3- (4-Chlorophenyl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide, melting point 163-166. 8.03 ppm.

Example 6 N- (4-Phenoxyphenyl) -4-phenyl-3- (4-trifluoromethylphenyl) -pyrazoline-1-carboxamide, melting point 188-190. 8.10 ppm. Example 7 13,4-Bis (4-Chlorophenyl) -N- (4-phenoxyphenyl) pyrazoline-1-30 carboxamide, melting point 189-193. 8.20 ppm (CDCl 4 / DMSO-dg).

Example 8 3- (4-Chlorophenyl) -N- (3-methyl-4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide, melting point 151-157. 9.13 ppm (DMSO-dg).

f ^ Λ V V I Ö m% -9-

Example 9 3- (4-Chlorophenyl) -N- / 4- (2-fluorophenoxy) phenyl-4-phenylpyrazoline-1-carboxamide, melting point 153-155. 8.16 ppm.

Example 10 5- (4-Chlorophenyl) -N- / 4- (3-fluorophenoxy) phenyl-7-4-phenyl-pyrazoline-1-carboxamide, melting point 173-175. 9.33 ppm (DMSO-dg).

Example 11 N-Z4 "(3-Chlorophenoxy) enyl7-3- (4-chlorophenyl) -4-phenyl-10-pyrazoline-1-carboxamide, melting point 169-174. 9.30 ppm (DMSO-dg).

Example 12 3- (4-Chlorophenyl) -N-Z.4- (4-fluorophenoxy) phenyl -4-4-phenyl-pyrazoline-1-carboxamide, melting point 164-167. 8.13 ppm 15 Example 13 3- (4-Chlorophenyl) -N- ^ 4- (4-trifluoromethylphenoxy) -phenyl7-4-enylpyrazoline-1-carboxamide, melting point 161-164. 8.03 ppm Example 14 N - $ - (4-Chloro-enoxy) phenyl-3- (4-difluoromethoxyphenyl) -4-20 phenylpyrazoline-1-carboxamide, mp 103-107. 8.00 ppm.

Example 15 3.4-Bis (4-Chlorophenyl) -N- (3-methyl-4-phenoxyphenyl) -pyrazoline-1-carboxamide, melting point 188-190. 9.23 ppm (DMSO-dg).

Example 16 3,4-Bis (4-Chlorophenyl) -N- / 4- (2-fluorophenoxy) phenyl-pyrazoline-1-carboxamide, melting point 160-162. 8.10 ppm.

Example 17 3.4-bis (4-Chlorophenyl) -N-4- (3-fluorophenoxy) phenyU-pyrazoline-1-carboxamide, melting point 144-146. 9.20 ppm 30 (DMSO-dg)

Example 18 N- 4- (3-Chlorophenoxy) phenyl 17-3,4-bis (4-chlorophenyl) -pyrazoline-1-carboxamide, melting point 135-HO. 9.30 ppm (DMSO-dg)

Example 19 3,4-b is (4-Chlorophenyl) -N-Z.4- (4-fluorophenoxy) phenyl-7-pyrazole-1-carboxamide, melting point 168-170. 9.23 ppm (DMSO-dg) f * * .- »^ c 1

-J '·: / va * "J J' V

»1 -10-

Example 20 N ** Z4 ”(4-Chlorophenoxy) phenyl-3,4-bis (4-chlorophenyl) -pyrazoline-1-carboxamide, melting point 154-156. 9.30 ppm (DMSO-dg) 5 Example 21 3.4-bis (4-Chlorophenyl) -N- / 4 "(4-trifluoromethylphenoxy) pheny L / pyrazoline-1-carboxamide, melting point 191-194. 9.30 ppm (DMSO-dg)

Example 22 10 3- (4-Chlorophenyl) -4-phenyl-N- (4-phenylthio-phenyl) pyrazoline-1-carboxamide, melting point 157-162. 8.20 ppm Example 23 3.4-bis (4-Chlorophenyl) -N- (4-phenylthiophenyl) pyrazoline-1-carboxamide, melting point 169-171. 8.20 ppm 15 Example 24 3.5-bis (4-Chlorophenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide, melting point 168-170. 8.30 ppm (CDCl ^ / DMSO-dg)

Example 25 3- (4-Chlorophenyl) -5- (4-trifluoromethylphenyl) -N- (4-phenoxy-20-phenyl) pyrazoline-1-carboxamide, melting point 164-167. 8.00 ppm.

Example 26 3.5-bis (4-Chlorophenyl) -N-Z4- (2-fluorophenoxy) phenyl-pyrazoline-1-carboxamide, melting point 174-178. 8.50 ppm

Example 27 3,5-Bis (4-Chlorophenyl) -N - / - 4- (3-fluorophenoxy) phenyl-pyrazolin-1-carboxamide, melting point 164-168. 9.00 ppm (DMSO-dg) Example 28 3.5-bis (4-Chlorophenyl) -N- 4- (4-fluorophenoxy) pheny 17-pyrazoline-1-carboxamide, melting point 165-167. 9.16 ppm (DMSO-dg) 30 Example 29 NZ.4- (4-Chlorophenoxy) phenyl 17-3,5-bis (4-chlorophenyl) -pyr azo-line-1-carboxamide, melting point 142- 144. 9.20 ppm (DMSO-dg) Example 30 3.5-b is (4-Chlorophenyl) -N-Z.4- (4-trifluoromethylphenoxy) phenyl 17 ”35 pyrazoline-1-carboxamide, melting point 155-158. 8.43 ppm (CDCl3 / DMS0-dg) 8502 913 m * -11-

Example 31 3- (4-Chlorophenyl) -N- / 4- (4-trifluoromethylphenoxy) -phenyl7-5- (4-trifluoromethylphenyl) pyrazoline-1-carboxamide, melting point 144-146. 8.06 ppm.

Example 32 N-Z4- (4-Chlorophenoxy) phenyl J-5- (4-chlorophenyl) -3- (4-difluoro-methoxyphenyl) pyrazoline-1-carboxamide, melting point 66-70.

8.60 ppm (DMSO-dg)

Example 33 10- (1,3-Benzodioxol-5-yl) -3- (4-chlorophenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide, melting point 125-128. 8.36 ppm (CDCl3 / DMS0-d6)

Example 34 5- (1,3-Benzodioxol-5-yl) -N-Z.4- (4-chlorophenoxy) phenyl-3-15 (4-chlorophenyl) pyrazoline-1-carboxamide, melting point 174-175.

8.06 ppm.

Example 35 N- (2,3-Dibydro-2,2-dimethyl-benzofuran-5-yl) -3,4-diphenyl-pyrazoline-1-carboxamide, melting point 139-143. 7.96 ppm.

Example 36 3- (4-Difluoromethoxyphenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide, melting point 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, melting point 134-137.

7.93 ppm.

Example 38 3,5-Bis (4-Chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzo-30-furan-5-yl) pyrazoline-1-carboxamide, melting point 175-180.

8.86 ppm (DMSO-dg)

Example 39 N - (1,4-Benzodioxan-6-yl) -3- (4-chloro-enyl) -4-phenylpyrazoline-1-carboxamide, melting point 112-115. 7.96 ppm.

• Λ τ®; \ try, * - * i -. » &.-o * * · -12- »'i

Example 40 N - (1,4-Benzodioxan-6-yl) -3,4-bis (4-chlorophenyl) pyrazoline-1-carboxamide, mp 140-145. 7.96 ppm.

Example 41 5 3- (4-Chlorophenyl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carbothioamide, mp 105-110. 10.30 ppm (DMS0-dg) Example 42 3.4-b is (4-Chlorophenyl) -N- (4-phenoxyphenyl) pyrazole-1-carbothioamide, mp 151-153. 9.26 ppm (DMSO-dg) Example 43 N- (4- (4-Chlorophenoxy) phenyl] 3,4-bis (4-chlorophenyl) pyrazoline-1-carbothioamide, melting point 179-183. 9.10 ppm.

Example 44 3- (4-Chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -15 4-phenylpyrazoline-1-carbothioamide, melting point 92-95.

10.12 ppm (DMSO-dg)

Example 45 3.4-bis (4-Chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carbothioamide, melting point 149-154.

20 9.00 ppm (DMSO-dg)

Example 46 N - (1,4-Benzodioxan-6-yl) -3,5-bis (4-chlorophenyl) pyrazoline-1-carboxamide, melting point 83-85. 9.33 ppm (DMS0-dg)

Example 47 5- (4-Chlorophenyl-3- (4-trifluoromethylphenyl) -N- / 4- (4-trifluoromethylphenoxy) phenylpyrazoline-1-carboxamide, melting point 183-185. 8.77 ppm (CDCl 4 DMSO-) dg)

Example 48 N- (2,3-Dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -3-30 (4-difluoromethoxyphenyl) -4-phenylpyrazoline-1-carboxamide

Pressurized into a pressure bottle were 15.0g (0.086 mol) 2-chloro-4-nitrophenol, 11.9g (0.086 mol) potassium carbonate, 1.5g (0.02 mol) propane thiol, 33.7g (0.13 mol) 1 , 2-di-bromo-tetrafluoroethane and 115 ml of Ν, Ν-dimethylformamide. The

The pressure bottle was closed and the mixture was heated at 50 ° C for 48 hours

850 2 9 1 3 »f * -13- stirred. The dropper bottle was cooled to room temperature, opened and the contents poured into a separatory funnel.

About 200 ml of a 2N sodium hydroxide solution was added to the separating funnel. The resulting mixture was extracted with 4 300 ml portions of diethyl ether.

The extracts were combined and washed with two 100 ml portions of a 2N sodium hydroxide solution. The washed extract was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to leave an oil. The reaction described above was repeated three more times. The residual oils from the four runs were combined and purified by column chromatography over silica gel, eluting with n-heptane: toluene (95: 5), to obtain 57.6g of 3-chloro-4- (2-15 bromo-1, 1,2,2-tetrafluoroethoxy) nitrobenzene as an oil.

10.0g (0.028 mol) 3-chloro-4- (2-bromo-1,1,2,2-tetrafluoroethoxy) nitrobenzene, 9.0g (0.14 mol) copper powder (200 mesh) were charged into a pressure bottle, 0.45 g (0.0028 mol) 2,2'-bipyridyl and 40 ml dimethyl sulfoxide. The pressure bottle 20 was closed and the reaction mixture was stirred at 190-195 ° G for 2 hours. The pressure bottle was cooled to room temperature, opened and the contents were poured into a separatory funnel. About 200 ml of a 2N hydrochloric acid solution was added to the separating funnel. The mixture was extracted with 350 ml portions of diethyl ether,

The extracts were combined and washed successively with 200 µl of a 2N hydrochloric acid solution, 200 ml of a saturated aqueous sodium chloride solution and 200 ml of a 2N sodium hydroxide solution. The washed extract was dried over anhydrous magnesium sulfate and filtered. The solvent was evaporated under reduced pressure to leave an oil. The above reaction was repeated six times. The residue oils from the seven runs were combined and subjected to silica gel column chromatography, eluting with toluene, to give the? * I- · ’::. · 'J Λ * 1 -14- obtain a yellow oil. This oil was dissolved in 125 ml of methylcyclohexane and the solution was placed in a freezer for about 18 hours. Crystals were formed, which were collected by filtration and 20.7 g of 2,2,3,3-tetrafluoro-5-nitrobenzofuran were obtained.

The filtrate was evaporated under reduced pressure to leave an oil. Distilling this oil under reduced pressure gave 3.0 g of product (boiling point 75 ° C / 0.2 mm Hg). Hydrogenation of 2.15g (0.011 mol) 2,2,3,3-tetrafluoro-10-nitrobenzene with a catalytic amount (0.25g) of platinum oxide in 150ml of methanol gave 2.15g of 5-amino-2,2, 3,3-tetrafluorobenzofuran.

A solution of 0.75g (0.0036 mol) 5-amino-2,2,3,3-tetrafluorobenzofuran, dissolved in 109ml toluene, was added dropwise to a stirred solution of 8.0ml 20% phosgene in toluene . After completed addition, the mixture was heated to reflux for 2 hours. The mixture was cooled and the solvent was removed by evaporation under reduced pressure to leave a residue. This residue was dissolved in 15 ml diethyl ether and added to a stirred solution of 1.04 g (0.0036 mol) 3- (4-difluoromethoxyphenyl) -4-phenylpyrazoline and three drops of triethylamine in 100 ml diethyl ether. After completed addition, the mixture was heated to reflux for 1 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 to leave a solid residue. Recrystallization from ethanol gave 0.99g of N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -30 3- (4-difluoromethoxyphenyl) -4-phenylpyrazoline-1-c arboxamide (melting point 155-159 ° C).

Analysis:

Calculated C 58.58; H 3.29 found C 57.81; H 3.75, 35 nmr: 8.16 ppm: 7,; J «3 -15- i \

Example 49 3,4-Bis (4-Chlorophenyl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) -pyrazoline-1-carboxamide

A solution of 1.18g (0.0068 mol) 5-amino-2,2-di-5 fluoro-1,3-benzodioxole, prepared according to the method described in the literature and dissolved in 80 ml tetrahydrofuran, was added dropwise to a cold (5-10 ° C) solution of 24 ml of 20% phosgene in toluene. After complete addition, the mixture was stirred at 2 ° C for 1 hour, then refluxed for 2 hours. The solvent was evaporated under reduced pressure to leave 1.4g of a liquid residue. In a clean reaction flask, 0.68 g of this residue were slowly added to a stirred solution of 0.93 g (0.0032 mol) of 3,4-bis (4-chloro-15-phenypyrazoline and three drops of triethylamine in 20 ml of diethyl ether). The mixture was stirred at room temperature for about 18 hours A small amount of solid was contained in the reaction mixture and was removed by filtration The filtrate was evaporated under reduced pressure to leave a residue.

Purification of this residue by column chromatography on silica gel, eluting with n-heptane: 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, (mp 150-155 ° C).

25 Analysis:

Calculated C 56.34; H 3.08 found C 57.16; H 2.89.

nmr: 8.10 ppm.

The compound of Example 50 was prepared in the same manner.

Example 50 N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3- (4-difluoromethoxy-phenyl) -4-phenylpyrazoline-1-carboxamide, melting point 135-138. 8.10 ppm 35 Example 51 3- (4-Fluorophenyl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1- - -O *. * * Vl * - * • 'v -Γ mJ ^

* X

., -16-carboxamide, melting point 187-191. 8.10 ppm

Example 52 3- (4-Difluoromethoxyphenyl) -N- (4-phenoxyphenyl) -4-phenyl-pyrazoline-1-carboxamide, melting point 139-144. 8.10 ppm 5 Example 53 3- (4-Chlorophenyl) -N- / 4- (4-chlorophenoxy) -phenyl7-4-phenyl-pyrazoline-1-carboxamide, melting point 170-174. 8.10 ppm Example 54 3- (4-Chlorophenyl) N-Z4 ~ (4-nitrophenoxy) phenyl-7-phenyl-10-pyrazoline-1-carboxamide, melting point 187-189. 8.30 ppm

Example 55 3- (4-Chlorophenyl) -N- / 4- (4-methoxyphenoxy) pheny 1J-4-phenyl-pyrazoline-1-carboxamide, melting point 159-160. 8.07 ppm

Example 56 3- (4-Chlorophenyl) -N- / 4- (4-difluoromethoxyphenoxy) -phenyl 0-4-phenylpyrazoline-1-carboxamide, melting point 181-184. 8.07 ppm Example 57 N-Z.4- (4-Chlorophenoxy) phenyl 17 "3- (4-trifluoromethoxyphenyl) -4-phenylpyrazoline-1-carboxamide, melting point 132-134. 8.16 ppm. Example 58 N-Z5- (4-Chlorophenoxy) pheny7-4-phenyl-3- / 4- (2-propynyloxy) -phenyl / pyrazoline-1-carboxamide, melting point 160-164. 8.13 ppm

Example 59 3- (1,3-Benzodioxol-5-yl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide, melting point 220-223. 8.06 ppm

Example 60 4- (4-Chlorophenyl) -N- (4-phenoxyphenyl) -3-phenylpyrazoline-1-carboxamide, melting point 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-Z4- (2-Chlorophenoxy) phenyl-3,4,4-bis (4-chlorophenyl) -pyrazoline-1-carboxamide, melting point 182-186. 8.10 ppm, 2 313 t -17-; - ^ / s

Example 63 3,4-bis (4-Chlorophenyl) -N- / 4- (4-methoxyphenoxy) phenyl / pyrazoline-1-carboxamide. 8.20 ppm

Example 64 5 3- (4-Chlorophenyl) -4- (4-fluorophenyl) -N- (4-enoxyphenyl) pyrazoline-1-carboxamide, melting point 178-179. 8.10 ppm

Example 65 N-Z4- (4-Chlorophenoxy) phenyl-3- (4-chlorophenyl) -4- (4-fluoro-phenyl) pyrazoline-1-carboxamide, melting point 143-145. 8.03 ppm 10 Example 66 3- (4-Chlorophenyl) -4- (4-methylphenyl) -N- (4-phenoxyphenyl) -pyrazoline-1-carboxamide, melting point 165-168. 8.10 ppm

Example 67 N- 4- (4-Chlorophenoxy) phenyl-7-3- (4-chlorophenyl) -4- (4-methoxy-15-phenyl) pyrazoline-1-carboxamide, melting point 169-173. 8.07 ppm

Example 68 4- (4-Fluorophenyl) -3- (4-methoxyphenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide, mp 184-187. 8.17 ppm

Example 69 N-Z4- (4-Difluoromethoxyphenoxy) phenyl7-3- (4-difluoromethoxyphenyl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide. 8.10 ppm Example 70 N-Z4 ”(4-Chlorophenoxy) phenyl-3- (4-chlorophenyl) -4-phenyl-pyrazoline-1-thiocarboxamide, melting point 179-183. 9.10 ppm Example 71 3- (4-Difluoromethoxyphenyl) -N- (4-phenoxyphenyl) -4-phenyl-pyrazoline-1-thiocarboxamide, melting point 132-136. 9.13 ppm

Example 72 4- (4-Chlorophenyl) -N- (4-phenoxyphenyl) -3-phenylpyrazoline-1-thiocarboxamide, melting point 131-133. 9.16 ppm

Example 73 N- 4- (4-Chlorophenylthio) phenyl-3,4-diphenylpyrazoline-1-carboxamide, melting point 186-190. 8.20 ppm

Example 74 35 3- (4-Chlorophenyl) -N- / 4 ~ (4-chlorophenylthio) phenyl / 4-phenyl-

.- Λ .- -'Z

- :. 4. pyrazoline-1-carboxamide, mp 178-181. 8.23 ppm

Example 75 3- (4-Difluoromethoxyphenyl) -4-phenyl-N- (4-phenylthio phenyl) -pyrazoline-1-carboxamide, melting point 135-140. 8.13 ppm 5 Example 76 3.4-bis (4-Chlorophenyl) -N-ZA- (4-fluorophenylthio) -phenyl7-pyrazoline-1-carboxamide, melting point 171-175. 8.20 ppm

Example 77 3.4-Bis (4-Chlorophenyl) -N - / 4- (4-Chlorophenylthio) -1-enyl-7-pyrazoline-1-carboxamide, melting point 151-156. 8.13 ppm

Example 78 3.4-bis (4-Chlorophenyl) -N- 4- (3-chlorophenoxy) pheny17-pyrazoline-1-carboxamide, mp 135-140. 9.20 ppm

Example 79 3- (4-Methoxyphenyl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide, melting point 188-192. 8.46 ppm (CDCl ^ / DMSO-dg)

Example 80 3- (4-(2-Propynyloxy) phenyl) 7-N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide, melting point 121-126. 8.10 ppm 20 Example 81 3- (4-Ch. 1-phenyl) -N- (2,3-dihydrob etc or uran-5-yl) -4-phenyl-pyrazoline-1-carboxamide, melting point 155- 158. 7.93 ppm

Example 82 3- (4-Difluoromethoxyphenyl) -N- (2,3-dihydrob enzofuran-5-yl) -4-25 phenylpyrazoline-1-carboxamide 7.93 ppm

Example 83 3.4-bis (4-Chlorophenyl) -N- (2,3-dihydrob enzo furan-5-yl) -pyrazoline-1-carboxamide, melting point 214-216. 7.93 ppm

Example 84 3- (4-Fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide, melting point 156-160. 7.93 ppm

Example 85 3- (4-Methoxyphenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide, melting point 164-169.

35 8.00 ppm Λ cis ^ ίΐ Λ. · "J \ l X" <

Y Y Y 0 5 O

19 -19-

Example 86 3- (4-Trifluoromethoxyphenyl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide, melting point 81-83. 7.98 ppm 5 Example 87 N- (2,3-Dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenyl-3- / 4- (2-propynyloxy) phenyl-7-pyrazoline-1-carboxamide, melting point 175-179. 8.00 ppm

Example 88 10 3- (1,3-Benzodioxol-5-yl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoin-1-carboxamide, melting point 223- 227. 8.90 ppm (DMSO-dg)

Example 89 4- (4-Chlorophenyl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -3-phenyl-pyrazoline-1-carboxamide. 8.00 ppm

Example 90 3,4-Bis (4-Fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzo-furan-5-yl) pyrazoline-1-carboxamide, melting point 161-166.

7.93 ppm 20 Example 91 3- (4-Chlorophenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide, melting point 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, melting point 137-139. 7.96 ppm

Example 93 3- (4-Chlorophenyl) -4- (4-methoxyphenyl) -N- (2,3-dihydro-2,2-30 dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide, melting point 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, melting point 35 179-182. 7.93 ppm T * ..f * ^ ƒ i '4. j ^: v '«-20-

Example 95 4- (4-Chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -3- (4-methoxyphenyl) pyrazoline-1-carboxamide, melting point 157-160. 7.96 ppm 5 Example 96 3- (4-Difluoromethoxyphenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide, melting point 169- 172. 7.93 ppm

Example 97 4- (4-Chlorophenyl) -3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide, mp 90-95. 7.93 ppm

Example 98 3- (4-Difluoromethoxyphenyl) -N- (2,3-dihydro-2,2,3,3-tetra-15-fluorobenzofuran-6-yl) -4-phenylpyrazoline-1-carboxamide, melting point 152-157. 8.33 ppm

Example 99 3- (4-Difluoromethoxyphenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2.2.3.3-tetrafluorobenzofuran-6-yl) pyrazoline-1-carboxamide, melting point 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, melting point 155-159. 8.20 ppm. Example 101 3- (4-Chlorophenyl) -N- (2,2-dimethyl-1,3-benzodioxol-5-yl) -4-phenylpyrazoline-1-carboxamide, melting point 182-186. 7.96 ppm Example 102 3- (4-Difluoromethoxyphenyl) -N- (2,2-dimethyl-1,3-benzodioxol-5-yl) -4-phenylpyrazoline-1-carboxamide, melting point 148-150.

7.93 ppm

Example 103 3,4-Bis (4-Chlorophenyl) -N- (2,2-dimethyl-1,3-benzodioxol-5-yl) pyrazoline-1-carboxamide, melting point 168-169. 7.93 ppm. '- · * · »1% an .1 i y 1 Ó -21-

Example 104 N- (1,4-Benzodioxan-5-yl) -3- (4-difluoromethoxyphenyl) -4-pheaylpyrazoline-1-carboxamide. 7.93 ppm Example 105 5 N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) -N-methyl-4-phenylpyrazoline-1-carboxamide, melting point 110- 114.

Example 106 4- (1,3-Benzodioxol-5-yl) -N- (4-phenoxyphenyl) -3-phenylpyrazoline-10 t-carboxamide, melting point 195-197. 8.03 ppm

Example 107 3- (4-Chlorophenyl) -N- / 4- / 4- (1,1-dimethylethyl) phenoxy] phenyl] 4-phenylpyrazoline-1-carboxamide, melting point 192.5-194.

8.03 ppm. Example 108 3- (4-Chlorophenyl) -4- (4-fluorophenyl) -N- / 4- (4-methylphenoxy) -phenyl-7-pyrazoline-1-carboxamide, melting point 162-164. 8.03 ppm

Example 109 3- (4-Chlorophenyl) -4- (4-fluorophenyl) -N- / 4- / 4- (1,1-dimethyl-20 ethyl) phenoxy-phenyl-pyrazoline-1-carboxamide, melting point 188 -198. 8.03 ppm

Example 110 3- (4-Chlorophenyl) -N- / 4- / 4 "(1-methylethyl) phenoxyphenyl-4-phenylpyrazoline-1-carboxamide, melting point 181-182.5. 8.06 ppm Example 111 3- (4-Chloro-phenyl) -4- (4-fluorophenyl) -N- / 4- / 4- (1-methyl-ethyl) phenoxy-phenyl-7-pyrazoline-1-carboxamide, melting point 186-187.

8.60 ppm (CDCl3 / DMS0-d6)

Example 112 3- (4-Chlorophenyl) -N- / 4- (4-methylphenoxy) phenyl-4-phenyl-pyrazoline-1-carboxamide, melting point 150-151. 8.06 ppm

Example 113 3- (4-Chlorophenyl) -N- / 4- / 4- (1-methylethoxy) phenoxy-7-phenyl-7-phenylpyrazoline-1-carboxamide, melting point 158-160.5. 8.06 ppm 'p P Λ V 1 Μ τ. ν -} ij i 0 * »-22-

Example 114 3- (4-Chlorophenyl) -4- (4-fluoropheny 1) -N- / 4- / 4- (1-methyl-ethoxy) phenoxy-7-phenyl-7-pyrazoline-1-carboxamide, melting point 213-216.

8.66 ppm (CDCl3 / DMSO-d6) Example 115 3.4-bis (4-Fluorophenyl) -N- / 4- /. 4- (1-methyl ethoxy) phenoxyphenyl /? pyrazoline-1-carboxamide, melting point 134-136. 8.06 ppm

Example 116 3.4-Bis (4-Fluorophenyl) -N- / 4- (4-chlorophenoxy) phenyl / pyrazoline-1-carboxamide, melting point 197-198.5. 8.70 ppm (CDCl ^ / DMSO-dg)

Example 117 3.4-bis (4-Fluorophenyl) -N- / 4-Z4 "(1,1-dimethylethyl) phenoxy7 phenyl7pyrazoline-1-carboxamide, melting point 189-192. 8.70 ppm (CDCl3 / DMSO-d6) Example 118 3.4-bis (4-Fluorophenyl) -N- / 4- (4-cyanophenoxy) phenyl / pyrazoline-1-carboxamide, melting point 198-200. 8.13 ppm

Example 119 3.4-bis (4-Fluorophenyl) -N- / 4- / 4 "(N, N-dimethylamino) phenoxy] phenylpyrazoline-1-carboxamide, melting point 148-150. 8.02 ppm

Example 120 3- (4-Chlorophenyl) -N- [h- (4-cyanophenoxy) phenyl L7-4-phenyl-pyrazoline-1-carboxamide, melting point 170-172. 8.16 ppm

Example 121 N - (1,4-Benzodioxan-6-yl) -4- (4-chlorophenyl) -3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide, melting point 124-128.

7.93 ppm

Example 122 3.4-Bis (4-Chlorophenyl) -N- (2,3-dihydro-2,2-dimethyl-benzo-furan-5-yl) -N-methylpyrazoline-1-carboxamide, mp 150-155.

Example 123 N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3,4-diphenylpyrazoline-1-carboxamide, melting point 214-216. 8.83 ppm - '0 ^ f' λ * y • (i ί ύ -23-

Example 124 N- (2,2-Diuror-1,3-benzodioxol-5-yl) -3-, 4-bis (4-fluorophenyl) pyrazoline-1-carboxamide, melting point 178-180. 8.10 ppm

Example 125 5 3- (4-Chlorophenyl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) -4- (4-fluoro-enyl) pyrazoline-1-carboxamide, melting point 147- 151.

8.06 ppm

Example 126 3- (4-Difluoromethoxyphenyl) -N- (2,3-dihydro-2,2,3,3-tetra-10-fluorobenzofuran-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, melting point 155-159 . 7.96 ppm

Example 128 3- (4-Difluoromethoxyphenyl) -N- (2,3-dihydro-2,2-difluorobenzofuran-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-carboxamide. 8.06 ppm

Example 130 4- (1,3-Benzodioxol-5-yl) -3- (4-chlorophenyl) -N-Z4- (4-fluoromethoxyphenoxy) phenyL-pyrazoline-1-carboxamide.

Example 131 4- (1,3-Benzodioxol-5-yl) -N-M- (4-chlorophenoxy) phenyl7-3- (4-chlorophenyl) pyrazoline-1-carboxamide.

Example 132 4- (1,3-Benzodioxol-5-yl) -3- (4-chlorophenyl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) pyrazoline-1-carboxamide.

Example 133 4- (1,3-Benzodioxo-5-yl) -3- (4-chlorophenyl) -N- (2,3-dihydro- 2,2,3,3-tetrafluorobenzofuran-5-y1) pyrazoline- 1-carboxamide. Example 134 35 4- (1,3-Benzodioxol-5-yl) -3- (4-chlorophenyl) -N- (2,3-dihydro- 3 i 3 -24- 2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide. Example 135 4- (1,3-Benzodioxol-5-yl) "N" Z4- (4-difluoromethoxyphenoxy) enyl7- 3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide.

Example 136 4- (1,3-Benzodioxol-5-yl) -N - / * 4- (4-chlorophenoxy) phenyl-7-3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide.

Example 137 4- (1,3-Benzodioxol-5-yl) "N- (2,2-difluoro-1,3-benzodioxol-5-10 yl) -3- (4-difluoromethoxyphenyl) pyrazoline-1- carboxamide.

Example 138 4- (1,3-Benzodioxol-5-yl) -3- (4-difluoromethoxypheny-1) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl pyrazoline-1-carboxamide.

Example 139 4- (1,3-Benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2-dimethylbenzuran-5-yl) pyrazoline-1-carboxamide .

Example 140 4- (1,3-Benzodioxol-5-yl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -3-phenylpyrazoline-1-carboxamide.

Example 141 4- (1,3-Benzodioxol-5-yl) -N- (2,3-dihydro-2,2,3,3-tetrafluoro-benzofuran-5-yl) -3-phenylpyrazoline-1-carboxamide.

Example 142 4- (1,3-Benzodioxol-5-yl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3-phenylpyrazoline-1-carboxamide.

Example 143 4- (1,3-Benzodioxol-5-yl) -N-Z.4- (4-difluoromethoxyphenoxy) -30 phenyl7-3-phenylpyrazoline-1-carboxamide.

Example 144 4- (1,3-Benzodioxol-5-yl) -N- / 4- (4-chlorophenoxy) phenyl-3-phenylpyrazoline-1-carboxamide.

Example 145 35 4- (2,2-Difluoro-1,3-benzodioxol-5-yl) -N - ^ - (4-difluoro- A i Q vi | 5 * '.? V SA V 1 V / -25 methoxyphenoxy) phenyl-3- (4-fluorophenyl) pyrazoline-1-carboxamide.

Example 146 N- / 4- (4-Chlorophenoxy) phenyl-4- (2,2-difluoro-1,3-benzodioxol-5 5-yl) -3- (4-fluorophenyl) pyrazoline-1-carboxamide.

Example 147 4, N-bis (2,2-Difluoro-1,3-benzodioxol-5-yl) -3- (4-fluorophenyl) pyrazoline-1-carboxamide.

Example 148 10 4- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3- (4-fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran- 5-yl) pyrazoline-1-carboxamide.

Example 149 4- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3- (4-fluorophenyl) -N-15 (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.

Example 150 4- (2,2-Difluoro-1,3-benzodioxol-5-yl) -N- / 4- (4-difluoro-methoxyphenoxy) phenyl / 3-phenylpyrazo 1-in-1-carboxamide.

Example 151 N-Z & - (4-Chlorophenoxy) phenyl-4- (2,2-difluoro-1,3-benzodioxol-5-yl) -3-phenylpyrazoline-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-y1) -3-phenylpyrazoline- 1-carboxamide. Example 154 30- (2,2-Difluoro-1,3-benzodioxol-5-yl) -N- (2,3-dihydro-2,3-dimethyl-benzofuran-5-yl) -3-phenyl-pyrazoline-1- carboxamide. Example 155 4- (2,2-Difluoro-1,3-benzodioxol-5-yl) -N-Z4- (4-difluoro-methoxyphenoxy) phenyl7-3- (4-difluoromethoxyphenyl) pyrazoline-1-35 carb oxamide.

jv I ó φ -26- '

Example 156 N- / 4- (4-Chlorophenoxy) phenyi-4- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide. Example 157 5, 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-difluoromethoxy-phenyl) -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-difluoromethoxy-phenyl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl pyrazoline-1-carboxamide.

Example 160 4- (1,4-Benzodioxan-6-yl) -3- (4-chlorophenyl) -N-Z4- (4-difluoromethoxyphenoxy) phenyl / pyrazoline-1-carboxamide.

Example 161 4- (1,4-Benzodioxan-6-yl) -N- / 4- (4-chlorophenoxy) phenyl] 3-20 (4-chlorophenyl) pyrazoline-1-carboxamide.

Example 162 4- (1,4-Benzodioxan-6-yl) -3- (4-chlorophenyl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) pyrazoline-1-carboxamide.

Example 163 4 - (1,4-Benzodioxan-6-yl) -3- (4-chlorophenyl) -N- (2,3-dihydro-2.2.3.3-tetrafluorobenzofuran-5-yl) pyrazoline-1-carboxamide. Example 164 4- (1,4-Benzodioxan-6-yl) -3- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.

Example 165 4- (1,4-Benzodioxan-6-yl) -N- / 4- (4-difluoromethoxyphenoxy) pheny17- 3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide.

Example 166 4- (1,4-Benzodioxan-6-yl) -N- / 4- (4-chlorophenoxy) phenyl-7-3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide.

1 ~ ΰ 2 9 13 t -27-

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 5 4- (1,4-Benzodioxan-6-yl) -3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) pyrazoline- 1-carboxamide ♦

Example 169 4- (1,4-Benzodioxan-6-yl) -3- (4-difluoromethoxyphenyl) -N-10 (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.

Example 170 4-Cl (4-Benzodioxan-6-yl) -N- / 4- (4-difluoromethoxyphenoxy) -phenyl-3-phenylpyrazoline-1-carboxamide.

Example 171 4- (1,4-Benzodioxan-6-yl) -N-Z4- (4-chlorophenoxy) phenyl2-3-phenylpyrazoline-1-carboxamide.

Example 172 4- (1,4-Benzodioxan-6-yl) -N- (2,2-difluoro-1,3-benzodioxol-5-20 yl) -3-phenylpyrazoline-1-carboxamide.

Example 173 4- (1,4-Benzodioxan-6-yl) -N- (2,3-dihydro-2,2,3,3-tetrafluoro-benzofuran-5-yl) -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) -phenyl7-4- (4-fluorophenyl) -N-methylpyrazoline-1-carboxamide.

Example 176 3- (1,3-Benzodioxol-5-yl) -N - /. 4 ”(4-chlorophenoxy) phenyl7-4- (4-fluorophenyl) pyrazoline-1-carboxamide &

Example 177 3- (1,3-Benzodioxol-5-yl) -N- (2,2-difluoro-1,3-benzodioxol-5-35 yl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide.

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Example 178 3- (1,3-B enzodioxo-5-yl) -4- (4-fluorophenyl) -N- (2,3-dihydro- 2,2,3,3-tetrafluorobenzofuran-5-yl) pyrazoline -1-carboxamide. Example 179 5- (1,3-Benzodioxol-5-yl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide. Example 180 3- (2,2-Difluoro-1,3-benzodioxol-5-yl) -N- / 4- (4-difluoro-methoxyphenoxy) pheny1J-4- (4-fluorophenyl) pyrazoline-1-carbox -10 amide.

Example 181 N- / 4- (4-Chlorophenoxy) pheny1 / -3- (2,2-difluoro-1,3-benzodioxol-5-yl) -4- (4-fluorophenyl) -N-methylpyrazoline-1-carboxamide . Example 182 3, N-bis (2,2-Difluoro-1,3-benzodioxol-5-yl) -4- (4-fluorophenyl) -pyrazoline-1-carboxamide.

Example 183 3— (2,2-Difluoro-1,3-benzodioxol-5-yl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5) -yl) pyrazoline-20-1-carboxamide.

Example 184 3- (2,2-Difluoro-1,3-benzodioxol-5-yl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-y1) pyrazoline-1-carboxamide.

Example 185 3 - (1,4-Benzodioxan-6-yl) -N - /. 4 "(4-difluoromethoxyphenoxy) -phenyl 7-4-phenylpyrazoline-1-carboxamide.

Example 186 3- (1,4-Benzodioxan-6-yl) -N - / 4- (4-chlorophenoxy) phenyl 17-4-30 phenylpyrazoline-1-carboxamide.

Example 187 3- (1,4-Benzodioxan-6-yl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) -N-methyl-4-phenylpyrazoline-1-carboxamide.

Example 188 35 3 - (1,4-Benzodioxan-6-yl) -N- (2,3-dihydro-2,2,3,3-tetrafluoro-: *; "-? Q 1 * -29-benzofuran- 5-yl) -4-phenylpyrazoline-1-carboxamide.

Example 189 3- (1,4-Benzodioxan-6-yl) -N- (2,3-dihydro-2,2-dimethylbenzo-furan-5-yl) -4-phenylpyrazo line-1-carboxamide.

Example 190 N-Z4- (4-Difluoromethoxyphenoxy) phenyl2-3- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide. Example 191 N-M '(4-Chlorophenoxy) phenyl-7-3- (2,3-dihydro-2,2-dimethyl-10-benzofuran-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 15 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-phenyl-20-pyrazoline-1-carboxamide.

Example 195 N- / 4- (4-Difluorometboxyphenoxy) phenyl7-4- (4-fluorophenyl) -3- (4-methylphenyl) pyrazoline-1-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-fluorophenyl) -3- (4-methylphenyl) pyrazoline-1-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-dimethyl-benzofuran-5-35 yl) -N-methyl-1-3- (4-methylphenyl) -pyrazine-1-carboxamide.

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Example 200 N- [k- (4-Diofluoromethoxyphenoxy) phenyl] -4 - (3-phenylphenyl) -N-methyl-3- (4-methylphenyl) pyrazoline-1-carboxamide.

Example 201 5 N- / 4- (4-Chlorophenoxy) phenyl-4- (3-fluorophenyl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.

Example 202 N- (2,2-Difluoro-1,3-benzodioxo-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-5-15 yl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.

Example 205 N-Z4- (4-Difluoromethoxyphenoxy) pheny 1J-4- (2-fluorophenyl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.

Example 206 N- / 4- (4-Chlorophenoxy) phenyl-7-4- (3-fluorophenyl) -N-methyl-1-3- (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-tetrafluorobenzofuran-5-yl) -3- (4-methylpheny1) pyrazoin-1-carboxamide . Example 209 4- (2-Fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-30 yl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.

Example 210 N-44- (4-D ifluoromethoxyphenoxy) phenyl-3- (3-fluorophenyl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide.

Example 211 35 N-Z <4- (4-Chlorophenoxy) f eny 1J-3- (3-fluoro enyl) -4- (4-fluoro-

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Example 212 N- (2,3-Difluoro-1,3-benzodioxol-5-yl) -3- (3-fluorophenyl) -4- (4-fluorophenyl) -N-methylpyrazoline-1-carboxamide.

Example 213 3- (3-Fluorophenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2> 2,3,3-tetrafluorobenzofuran-5-yl) pyrazoline-1-carboxamide. Example 214 3- (3-Fluorophenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2-10-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.

Example 215 N-14- (4-Difluoromethoxyphenoxy) phenyt-3- (2-fluorophenyl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide.

Example 216 N-Z4- (4-Chlorophenoxy) phenyl-3- (2-fluoro-enyl) -4- (4-fluoro-phenyl) pyrazoline-1-carboxamide.

Example 217 N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3- (2-fluorophenyl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide.

Example 218 3- (2-Fluorophenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -N-methylpyrazoline-1-carboxamide .

Example 219 3- (2-Fluorophenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.

Example 220 3,4-Bis (4-Fluorophenyl) -N- (2,3-dihydro-2,2,3,3,7-pentafluoro-benzofuran-5-yl) pyrazoline-1-carboxamide.

Example 221 4- (4-Chlorophenyl) -N- (2,3-dihydro-2,2,3,3,7-pentafluoro-benzofuran-5-yl) -3- (4-methylphenyl) pyrazoline-1- carboxamide.

Example 222 N- (2,3-Dihydro-2,2,3,3,7-pentafluorobenzofuran-5-yl) -3,4- -32-diphenylpyrazoline-1-carboxamide.

Example 223 3- (4-Difluoromethoxyphenyl) -N- (2,3-dihydro-2,2,3,3,7-penta-fluorobenzofuran-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-benzodioxol-5-10 yl) pyrazoline-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 15 N- (2,2,6-Trimethyl-1,3-benzodioxol-5-yl) -3,4-diphenylpyrazoline-1-carboxamide.

Example 228 3- (4-Differic thoxyphenyl) -N- (2,2,6-trimethyl-1,3-benzo-dioxol-5-yl) -4-phenylpyrazoline-1-carboxamide.

Example 229 3- (4-Chlorophenyl) -N- (2,2,6-trimethyl-1,3-benzodioxol-5-yl) -4-phenylpyrazoline-1-carboxamide.

Example 230 3.4-bis (4-Fluorophenyl) -N- (7-methoxy-2,2-dimethyl-1,3-benzo-dioxol-5-yl) pyrazoline-1-carboxamide.

Example 231 4- (Chlorophenyl) -N- (7-methoxy-2,2-dimethyl-1,3-benzodioxol-5-yl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.

Example 232 N- (7-Methoxy-2,2-dimethyl-1,3-benzodioxol-5-yl) -3,4-diphenylpyrazoline-1-carboxamide.

Example 233 3- (4-Difluoromethoxyphenyl) -N- (7-methoxy-2,2-dimethyl-1,3-benzodioxol-5-yl) -4-phenylpyrazoline-1-carboxamide.

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Example 234 3- (4-Chlorophenyl) -N- (7-methoxy-2,2-dimethyl-1,3-benzodioxol-5-yl) -4-phenylpyrazoline-1-carboxamide.

Example 235 3,4-bis (4-Fluorophenyl) -N - / * 2,2-dimethyl-7- (1-methyl-ethyl) -1,3-benzodioxol-5-yl, 7-pyrazoline-1-carboxamide.

Example 236 4- (4-Chlorophenyl) -N- Q., 2-dimethyl-7- (1-methylethyl) -1,3-benzodioxol-5-yl_7-3- (4-methylphenyl) pyrazoline-1-carboxamide .

Example 237 N- / 2,2-Dimethyl-7- (1-methylethyl) -1,3-benzodioxol-5-ylJ-3,4-diphenylpyrazoline-t-carboxamide.

Example 238 3- (4-Difluoromethoxyphenyl) -N- / 2,2-dimethyl-7- (1-methyl ethyl) -15 1,3-benzodioxol-5-yl-4-phenylpyrazoline-1-carboxamide.

Example 239 3- (4-Chlorophenyl) -N- / 2,2-dimethyl-7- (1-methyl-ethyl) -1,3-benzodioxol-5-yl7-4-phenylpyrazoline-1-carboxamide.

Example 240 3,4-Bis (4-Fluorophenyl) -N- (2,3-dihydro-7-ethyl-2,2,3,3-tetrafluorobenzofuran-5-yl) pyrazoline-1-carboxamide.

Example 241 4- (4-Chlorophenyl) -N- (2,3-dihydro-7-ethyl-2,2,3,3-tetrafluorobenzofuran-5-yl) -3- (4-methylphenyl) pyrazoline-1 - 25 carboxamide.

Example 242 N- (2,3-Dihydro-7-ethyl-2,2,3,3-tetrafluorobenzofuran-5-yl) 3,4-diphenylpyrazoline-1-carboxamide.

Example 243 3- (4-Difluoromethoxyphenyl) -N- (2,3-dihydro-7-ethyl-2,2,3,3-tetrafluorobenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide. Example 244 3- (4-Chlorophenyl) -N- (2,3-dibydro-7-ethyl-2,2,3,3-tetrafluorobenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide.

1 "" Λ "7 -" J * ij -34-

Example 245 3- (4-Chlorophenyl) -N- / 4- (4-methylsulfonyl-enoxy) -enyl-4-phenylpyrazoline-1-carboxamide.

Example 246 3,4-bis (4-Fluorophenyl) -N- [k- (4-methylsulfonylphenoxy) phenyl-7-pyrazoline-1-carboxamide.

Example 247 3- (4-Difluoromethoxyphenyl) -N- / 4- (4-methylsulfonylphenoxy) -phenyl7 "4-phenylpyrazoline-1-carboxamide.

Example 248 3- (4-Chlorophenyl) -4- (4-fluorophenyl) -N- / 4- (4-methylsulfonyl-phenoxy) phenyl-7-pyrazoline-1-carboxamide.

Example 249 N- / 4- (4-Methylsulfonylphenoxy) phenyl7,4,4-diphenylpyrazoline-1-15 carboxamide.

Example 250 3,4-Bis (4-Fluorophenyl) -N- (2,3-dihydro-7-difluoromethoxy-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.

Example 251 4- (4-Chlorophenyl) -N- (2,3-dihydro-7-difluoromethoxy-2,2-dimethylbenzofuran-5-yl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.

Example 252 N- (2,3-Dihydro-7-difluoromethoxy-2,2-dimethylbenzofuran-5-yl) -25 3,4-diphenylpyrazoline-1-carboxamide.

Example 253 3- (4-D ifluoromethoxyphenyl) -N- (2,3-dihydro-7-difluoromethoxy-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-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-1,3-benzodioxol-5-yl) -3,4-35 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-Chloromethyl-2,2-dimethyl-1,3-benzodioxol-5-yl) -3,4-diphenylpyrazoline-1-carboxamide.

Example 258 N- (7-Chloromethyl-2,2-dimethyl-1,3-benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) -4-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- (1-15 methyl ethyl) -2,2-dimethyl-1,3-benzodioxol-5-ylJ -4-phenylpyrazoline-1-carboxamide.

Example 261 N- (2,3-Dihydro-2,2-dimethyl-benzofuran-5-yl) -3- (7-methoxy-2,2-dimethyl-1,3-benzodioxol-5-yl) -4-phenylpyrazoline-1 - 20 carboxamide.

Example 262 N- (2,3-Dihydro-2,2-dimethylbenzofuran-5-yl) -3- (7-fluoro-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-difluoro-methoxy-2,2-dimethyl-1,3-benzodioxol-5-yl) -4 -phenyl-pyrazoline-1-carboxamide.

Example 264 30 N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3- (4-fluorophenyl) -4- (2,3-dihydro-2,2-dimethylb enzofuran-5-y1) pyrazoline-1-carboxamide.

Example 265 N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3- (4-fluorophenyl) -4-35 (2,3-dihydro-2,2,3,3-tetrafluorobenzo furan-5-yl) pyrazoin-

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-36- S * 1-carboxamide.

Example 266 N-Z3 "(4-Trifluoromethylphenoxy) phenyl7" 3,4-bis (4-fluorophenyl) -pyrazoline-1-carboxamide.

Example 267 N- / 3- (4-Fluorophenoxy) phenyl-3,4-bis (4-fluorophenyl) pyrazoline-1-carboxamide.

Example 268 N - / 3- (4-Difluoromethoxyphenoxy) phenyl 7-3,4-bis (4-fluorophenyl) -10 pyrazoline-1-carboxamide.

Example 269 3,4-Bis (4-Fluorophenyl) -N- ^ 3- (4-methylphenoxy) phenyl-7-pyrazoline-1-carboxamide.

Example 270 15- (7-Chloromethyl-2,2-dimethyl-1,3-benzodioxol-5-yl) -4, N-b is (4-fluorophenyl) pyrazoline-1-carboxamide.

Example 271 N- (2,3-Dihydro-2,2-dimethylbenzofuran-5-yl) -4- / 7- (1-methyl-ethyl) -2,2-dimethyl-1,3-benzodioxol-5-yl7 -3-phenyl-20-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-fluoro-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 -phenyl-pyrazoline-1-carboxamide.

Example 275 4- (7-Chloromethyl-2,2-dimethyl-1,3-benzodioxol-5-yl) -3, N-35 bis (4-fluorophenyl) pyrazoline-1-carboxamide.

; J 2 S 1 3 -37-

In the normal application of the insecticidal pyrazolines of the invention, the pyrazolines will usually not be used except in a mixture or dilution. They will usually be used in a suitably formulated composition adapted to the method of use and containing an insecticidically effective amount of pyrazoline. The pyrazolines of the invention, like most pesticides, can be mixed with agriculturally acceptable surfactants and carriers, which are normally used to facilitate dispersion of the active ingredients, taking into account the accepted fact that the formulation and the mode of application of an insecticide can affect the activity of the material. The present pyrazolines can be used, for example, as sprays, dusts or granules in the area where pest control is desired, the type of application obviously varying with the pest and the environment. Thus, the pyrazolines of the invention can be formulated as large sized granules, as powder, as wettable powders, as emulsifiable concentrates, as solutions, and the like.

Granules can contain porous and non-porous particles, such as attapulgite clay or sand, for example, which serve as carriers for the pyrazolines. The granular particles are relatively large, typically about 400-2500 µm in diameter. The particles are either impregnated with the pyrazoline from solution or coated with the pyrazoline, sometimes using adhesive. The granules generally contain 0.05-10, preferably 0.5-5% active ingredient as the insecticidally effective amount.

Substance is a mixture of the pyrazolines with finely divided solids, such as talc, attapulgite clay, kieselguhr, pyrophyllite, lime, diatomaceous earth, calcium C 'Λ Λ λ 1' f

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-38- phosphates, calcium and magnesium carbonates, sulfur, powder 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 about 50 µm. A typical compound formulation useful for insecticide control contains 1 part pyrazoline, such as 3- (4-chlorophenyl) -N- / A ~ (4-chlorophenoxy) phenyl / 4-phenylpyrazoline-1-carboxamide and 99 parts talc .

The pyrazolines of the invention can be prepared as liquid concentrates by dissolving or emulsifying in suitable liquids and as solid concentrates by mixing with talc, clay and other known solid carriers used in the pesticides field. The concentrates are compositions containing as insecticidally effective amount about 5-50% pyrazoline, such as 3- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) - 4-phenylpyrazoline-1-carboxamide and 95-50% inert material containing surfactant dispersants, emulsifiers and wetting agents, but even higher concentrations of active ingredients can be used experimentally. The concentrates are diluted with water or other liquids for practical application for spraying or with an additional solid carrier for use as a substance.

Typical solid concentrate carriers (also called wettable powders) include Volker earth, clay, silica and other highly absorbent, easily wettable inorganic diluents. A solid concentrate formulation suitable for insect control contains 1.5 parts each of sodium lignosulfonate and sodium 30 lauryl sulfate as a humectant, 25 parts 3- (4-chlorophenyl) -N- (2,3- dihydro-2,2-dimethylbenzofuran-5-yl) -4- (4-chlorophenyl) pyrazoline-1-carboxamide and 72 parts attapulgite clay.

The preparation of concentrates is suitable for the transport of low-melting products according to the invention.

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Such concentrates are prepared by melting the low-melting solid products together with 1% or more of a solvent to prepare a concentrate that does not solidify on cooling to the freezing point of the pure product or less.

Suitable liquid concentrates include the emulsifiable concentrates, which are homogeneous liquid or pasty compositions that are readily dispersed in water or other liquid carriers. They can consist entirely of the pyrazoline with a liquid or solid emulsifying agent, and 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 normally used for spraying on the area to be treated.

Typical surfactant wetting, dispersing and emulsifying agents used in pesticide formulations include, for example, the alkyl and alkyl aryl sulfonates and sulfates and the sodium salts thereof; alkyl amide sulfonates, including fatty acid methyl taurides; alkyl aryl 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 suitable surfactants are commercially available. The surfactant when used is about 1-15% by weight of the insecticide composition.

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

* - ^ x - -40- *

An insecticidically effective amount of pyrazoline in an insecticide composition diluted before use is normally in a range from about 0.001 to about 8% by weight. Many known variations of spray and spray compositions can be employed by incorporating the pyrazolines of the invention into known or obvious compositions.

The insecticidal compositions of the invention can be formulated with other active ingredients, including other insecticides, nematicides, acaricides, fungicides, plant growth regulators, fertilizers, etc. When using insect control compositions, it is only necessary that an insecticidically effective amount of pyrazoline is applied to the site where control is desired. Such a place can for instance be the insects themselves, plants on which the insects feed or the growing place of the insects. Where the place is good, for example soil in which agricultural crops have been planted or will be planted, the active compound can be applied to and, if desired, incorporated into the soil. For most applications, an insecticidically effective amount will be about 75 to 4000 g per hectare, preferably 150 to 300 g per hectare.

The insecticidal activity of the pyrazolines, of which the preparation has been described above, was evaluated as follows.

The compounds were tested in foliar applications at various concentrations in aqueous solutions containing 10% acetone and 0.25% octylphenoxy polyethoxyethanol. Pinto bean plants were placed on a rotating turntable in a hood and the test solutions were applied with an atomizer. The test solutions were applied to the top and bottom surfaces of the plant leaves to flow. The plants were then allowed to dry and then degraded at the base of the stem. Each trunk was put into water through a paper cup. Ten individuals of the insect species were placed in each beaker and the beaker covered. Evaluated were 5 southern annyworm (Spodoptera eridania), Mexican bean beetle (Epilachna varivestis) beet armyworm (Spodoptera exigua) and cabbage looper (Trichoplusia ni). Mortality was determined after 4 days at 26 ° C and 50% relative humidity.

The results of the tests are shown in Table 1. The insect mortality was generally lower when the tests were previously read.

Some of the pyrazolines were also active against Southern corn rootworm larvae (Diabrotica undecimpunctata howardi Barber) when applied to the soil, and the pyrazolines investigated were also very effective on Colorado potato beetle (Leptinotara decemlineata Say).

Table

Evaluation sheet 20 Compound Insect quantity (% killed)

(ppm) MBB SAW BAW CL

1 500 100 100 2 500 100 100 3 500 100 100 25 4 500 100 100 5 250 100 87 100 6 500 70 65 90 7 500 100 50 90 8 500 100 85 30 9 500 90 70 10 500 100 35 11 500 85 15 12 500 100 100 13 500 93 50 90 35 14 100 100 ^ ·>> __ -i— '- +. * ~ .Y rJD' ™ »v * -42-

Table (continued)

Sheet evaluation

Compound Quantity Insects _ (% killed)

(ppm) MBB SAW BAW _CL

5 15 500 100 90 16 500 100 17 500 100 35 18 500 90 55 19 500 100 100 10 20 500 80 40 21 500 70 15 22 500 100 100 23 500 40 30 24 250 95 100 15 25 500 30 75 26 500 80 65 27 500 75 95 28 500 95 90 29 500 10 90 20 30 500 5 64 60 31 500 5 65 70 32 500 100 50 33 500 100 80 34 500 10 75 25 35 500 100 100 36 8 100 98 45 90 37 32 98 98 97 100 38 500 95 80 39 500 100 25 30 40 500 100 100 41 128 95 70 42 128 95 100 43 500 100 100 44 500 100 100 35 45 32 100 100 100 100 rv rae 4¾ Λ ^ q sar • a Λ '- : 15: -J * · - *? -43 *

Table (continued)

Sheet evaluation

Compound Quantity Insects _ (% killed)

MBB SAW BAW CL

5 46 500 30 40 47 500 5 10 48 8 100 100 100 95 49 500 100 100 50 500 100 100 10 51 100 40 60 52 500 100 95 53 500 100 10 54 500 100 85 55 500 100 80 15 56 500 100 100 57 250 100 100 58 500 100 40 59 500 100 100 60 200 100 60 20 61 32 45 100 55 90 62 500 95 95 63 500 100 95 64 500 100 100 65 500 100 100 25 66 500 100 100 67 500 85 95 68 500 100 0 69 8 100 60 5 100 70 500 100 100 30 71 200 60 10 72 200 100 30 73 500 100 90 74 500 100 80 75 200 100 45 35 76 200 95 100 - -j ~ ϋ I o -44- '* ·

Table (continued)

Sheet evaluation

Compound Quantity Insects _ (% killed)

_ ^ dpm) MBB SAW BAW CL

5 77 500 80 200 0 95 78 500 90 55 79 200 95 60 80 500 100 100 10 81 250 100 100 82 128 100 90 83 250 85 100 84 100 100 90 85 200 100 100 15 86 16 95 95 40 100 87 500 100 100 88 100 100 25 10 85 89 200 100 100 90 16 100 100 100 90 20 91 32 100 100 100 100 92 500 100 100 93 500 100 100 94 500 100 100 95 200 100 90 25 96 32 100 100 85 95 97 8 100 100- 85 98 16 100 40 35 80 99 16 100 100 90 85 100 32 100 100 100 100 30 101 1000 100 100 102 128 100 100 103 16 90 95 15 100 105 16 100 100 106 256 100 70 35 107 1000 45 o 0552913 -45-

Table (continued)

Sheet evaluation

Compound Quantity Insects _ (% killed)

(ppm) MBB SAW BAW CL

5 108 1000 100 75 109 1000 0 0 110 1000 70 0 111 1000 0 0 112 1000 100 90 10 113 1000 100 10 114 1000 100 30 115 1000 100 15 116 500 100 100 117 500 55 0.

15 118 500 100 100 119 500 100 95 120 500 100 100 121 500 95 100 122 64 100 100 20 123 64 15 0 124 64 100 100 125 64 100 100 MBB = Mexican bean beetle 25 SAW = southern armyworm BAW = beet armyworm CL = cabbage looper

, ~ t? i J

Claims (21)

Insecticide pyrazoline, characterized by the formula 2 of the formula sheet, wherein R. has the formula 3 of the formula sheet, wherein R 'is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, lower alkynyloxy and lower haloalkyl; or the formula 4 of the formula sheet, wherein X is a bridge with the formula wherein a 1-3, a '0 or 1, a + a' is at least 2 but not greater than 10, R '^ and R' ^ g are independently selected from hydrogen, halogen and lower alkyl, and R * 1 is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower halooxy and lower haloalkyl; Rg is a 4 or 5 substituent of the compound of the formula V of the formula sheet, wherein R 'is selected from D hydrogen, halogen, lower alkyl, lower alkoxy and lower haloalkyl; or of a compound of the formula 6 of the formula sheet, wherein Y is a bridge of the formula Z ° - (CE Wb-V ^ 20 where b 1-3, b '0 or 1, b + b' at least 2 but not is greater than 3, R 'and R' are independently selected from hydrogen, halogen and lower alkyl and R'gC is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl; R_ has the formula 7 of the formula sheet, wherein L Rg is selected from hydrogen and lower alkyl; Rg is selected from lower alkyl, halogen, lower alkoxy, lower haloalkoxy, lower haloalkyl, cyano, nitro, -NR ^ R ^ where Rp and Rg are independently lower alkyl and -SO ^ Rg, where R ^ is lower alkyl and n is 0-2; or the formula 8 of the formula sheet, where Z is a bridge of the formula ^ - (CE'cAE'cB> c- ° c'2 where c is 1-3, c 'is 0 or 1, c + c' at least 2 but not greater than 3, R 'and K ·' ™, are independently selected from LA Ld ƒ "ƒ * η λ <5 7» V -47- ψ m hydrogen, halogen and lower alkyl, provided that R1 ^ and R1 ^ are not both hydrogen when c is 1 and c 'is 1, and RT ^ C is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower halo-5 alkyl; R ^ is hydrogen or lower alkyl, and V and W independently of each other are oxygen or sulfur. 2. A compound according to claim 1, characterized in that W is oxygen. Compound according to claim 1, characterized in that R 1 is halogen or lower haloalkoxy. Compound according to claim 1, characterized in that Rg is a 4-substituent. Compound according to claim 1, characterized in that Rg has the formula 9 of the formula sheet. Compound according to claim 5, characterized in that R 'is halogen. D 7. A compound according to claim 1, characterized in that R has the formula 10 of the formula sheet or is selected 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-1,3-benzo-dioxol-5-yl and 2,2-dimethyl-1 , 3-benzodioxol-5-yl. A compound according to claim 1, characterized in that R 1 has the formula 11 of the formula sheet. Li Compound according to claim 8, characterized in that Rg is lower haloalkoxy. 10. 3- (4-Difluoromethoxyphenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide, a compound according to claim 1. 11. 3.4 -bis (4-Fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorob enzofuran-5-y1) pyrazoin-1-carboxamide, a compound according to claim 1. Λ 'i * t - 48-12. 3,4-Bis (4-Fluorophenyl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) pyrazoline-1-carboxamide, a compound according to claim 1. N- (2,3-Dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -5- (4-difluoromethoxyphenyl) -4-phenylpyrazoline-1-carboxamide, a compound according to claim 1. N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3- (4-difluoro-methoxyphenyl) -N-methyl-4-phenylpyrazoline-1-carboxamide, a compound according to claim 1. 15. 3,4-bis (4-Chlorophenyl) -N- (2,2-dimethyl-1,3-benzodioxol-5-yl) pyrazoline-1-carboxamide, a compound according to claim 1. N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3,4-bis- (4-fluorophenyl) pyrazoline-1-carboxamide, a compound according to claim 1. 17. 3 - (4-Chlorophenyl) -N- (2,2-difluoro-1,3-benzo-dioxol-5-yl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide, a compound according to claim 1. 18. 3- (4-Difluoromethoxyphenyl) -N- (2,3-dihydro-2,2,3,3-20-tetrafluorobenzofuran-5-yl) -N-methyl-4-phenyl-pyrazoline-1-carboxamide, a compound of claim 1. 19. 3- (4-Chlorophenyl) -N- £ 4- (4-difluoromethoxyphenoxy) -phenyl / -4-phenylpyrazoline-1-carboxamide, a compound according to claim 1. 20. N- / 4- ( 4-Difluoromethoxyphenoxy) phenyl / -3- (4-difluoromethoxyphenyl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide, a compound according to claim 1. 21. 3- (4-Difluoromethoxyphenyl) —4— ¢ 4 -fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) pyrazoline-1-30 carboxamide, a compound according to claim 1. 22. 3- (4-Difluoromethoxyphenyl) - 4- (4-fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-6-yl) pyrazoline-1-carboxa mide, a compound according to claim 1. 23. 4- (4-Chlorophenyl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -3-phenylpyrazoline-1-carboxamide, a compound of 3 '-J t 9 -49- compound according to claim 1. 24. 3- (4-Chlorophenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2 2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide, a compound according to claim 1. 25 25.- (4-Difluoromethoxyphenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2 2-dimethylbenzofuran-5-yl) -pyrazoline-1-carboxamide, a compound according to claim 1. 26. 4- (4-Chlorophenyl) -3- (difluoromethoxyphenyl) -I- (2,3-dihydro-2,2 dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide, a compound according to claim 1. 27. Insecticidal composition, characterized in that mixed with an agriculturally acceptable carrier is mixed an insecticidically effective amount of at least one insecticide pyrazoline of the formula 2 of the formula sheet, wherein R. has the formula 3 of the formula sheet, wherein R 'is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, lower alkynyloxy and lower haloalkyl; or the formula 4 of the formula sheet, wherein X is a bridge of the formula 20 1 in which a 1 - 3, af 0 or 1, a + a 'is at least 2 but not more than 3, R' ^ and R '^ g are independently selected from hydrogen, halogen and lower alkyl, and R 10 is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl; Rg is a 4 or 5 substituent of the formula 5 of the formula sheet wherein R 'is selected from hydrogen, D halogen, lower alkyl, lower alkoxy and lower haloalkyl; or with the formula 6 of the formula sheet, in which Y is a bridge 30 of the formula ^ ”^ CR, BAR, BB ^ b-0b '3 in which b 1 - 3, b' 0 or 1, b + b1 at least 2 but is not greater than 3, R'g ^ and R'BB are independently selected from hydrogen, halogen and lower alkyl, and R 'is J5L - - 4 1. . -J? -J-, -50- selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl; Β.β has the formula 7 of the formula sheet, where Rp is selected from hydrogen and lower alkyl; R ^, is selected from lower alkyl, halogen, lower alkoxy, lower halogen alkoxy, lower haloalkyl, cyano, nitro, -NR ^ R ^ where Rp and Rg are independently lower alkyl and -SO ^ Rjj where Rjj is lower alkyl and n is 0-2, or the formula 8 of the formula sheet, wherein Z is a bridge of the formula 10--WuFcih-0 ''! where c is 1-3, c 'is 0 or 1, c + c' is at least 2 but not more than 3, R'c ^ are independently selected from hydrogen, halogen and lower alkyl, with the proviso that R 'and R' 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 lower alkyl, and V and W independently are oxygen or sulfur. The composition according to claim 27, characterized in that W is oxygen. 29. A composition according to claim 27, characterized in that R 1 is halogen or lower haloalkoxy. The composition according to claim 27, characterized in that Rg is a 4-substituent. 31. A method of controlling insects, characterized by applying to the site where control is desired} an insecticidically effective amount of pyrazoline of the formula 2 of the formula sheet, wherein R has the formula 3 of the formula sheet, wherein R ' . A 'A is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, lower alkynyloxy and lower haloalkyl; or the formula 4 of the formula sheet, where 35 X is a bridge with the formula Γ: "^ O -3"? v v v CJ «? 1 'J -51- ^ - (CR VabW 1 where a 1 - 3, a' O or 1, a + a 'is at least 2 but not more than 3, R' ^ and R '^ g are chosen independently from hydrogen, halogen and lower alkyl, and R 'is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl; Rg is a 4 or 5 substituent of the formula V in which R is selected from hydrogen, O halogen, lower alkyl, lower alkoxy and lower haloalkyl; or the formula 6 of the formula sheet, wherein Y is a bridge of the formula ----? ° - ^ bae Vt, - ° b> 3 wherein b 1 - 3, b '0 or 1, b + b' is at least 2 but not more than ~ - "than 3, R'g ^ and R '^ g are independently selected from hydrogen, halogen and lower alkyl, and R '' is i) C selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl; R 1, has the formula 7 of the formula sheet, wherein R 1 is selected from hydrogen and lower alkyl R1 is selected from lower alkyl, hal no, lower alkoxy, lower haloalkoxy, lower haloalkyl, cyano, nitro, -NRg, Rg wherein Rp and Rg are independently lower alkyl and -SO4Rg, wherein lower is alkyl and n is 0-2; or the formula 8 of the formula sheet, where Z is a bridge of the formula 25 -7 where c 1 3, c '0 or 1, c + cr is at least 2 but not more than 3, R' ^ and R '^ independently from each other are selected from hydrogen, halogen and lower alkyl, with the proviso that and are hydrogen when c 1 is 30 and c * 1, and R 1 is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl; Rjj. hydrogen or lower alkyl; and V and W are independently oxygen or sulfur. ; ., 7 r. $ E -52-n 32. A method of preparing an insecticidal pyrazoline, characterized by reacting a compound of the formula RC-N = C = W 5 with a compound of the formula 12 of the formula sheet and optionally alkylating the product to obtain an insecticide pyrazoline of formula 2 of the formula sheet, wherein R ^ has the formula 3 of the formula sheet, wherein R 10 is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, lower alkynyloxy and lower haloalkyl; or the formula 4 of the formula sheet, where X is a bridge with the formula r ° - (CR'MR'ABW 7 15 where a 1 - 3, a '0 or 1, a + a' at least 2 but not more than 3 R '^ and R' ^ g are independently selected from hydrogen, halogen and lower alkyl, and R '^ is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl; Rg is a 4 or 5 substituent of the formula 5 of the formula sheet wherein R'g is selected from hydrogen, halogen, lower alkyl, lower alkoxy and lower haloalkyl; or the formula 6 of the formula sheet, where Y is a bridge with the formula 25 ^ "VbbW 7 where b 1 - 3, b '0 or 1, b + b' is at least 2 but not more than 3, R'g ^ and R'gg are independently selected from hydrogen, halogen and lower alkyl, and R * is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl; R ^ has the formula 7 of the formula sheet, wherein Rp is selected from hydrogen and lower alkyl; R ^ is selected from lower alkyl, halogen, lower alkoxy, lower haloalkoxy, lower haloalkyl, cyano, nitro, -NR ^ R ^ where 85 02 S 1 3 1 -53- - Rp and Rg are independently lower alkyl, and -SO 1 Rg wherein R 1 is lower alkyl and n is 0-2; or the formula 8 of the formula sheet, where Z is a bridge with the formula wherein c 1 - 3, c '0 or 1, c + cf is at least 2 but not more than 3, R'. and R '' are independently selected uA Ld from hydrogen, halogen and lower alkyl, with the proviso that R '. and R "is not both hydrogen when c 1 is CA Ld 10 and c" 1, and R "is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl; Rj is hydrogen or lower alkyl; and V and W are independently oxygen or sulfur. 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