LU86134A1 - PYRAZOLINE INSECTICIDES - Google Patents

Description

* 1 f ^ Pyrazoline insecticides.

The present invention relates to the field of chemical attack compositions; more particularly, it relates to new insecti-5. cides of pyrazolines, methods and intermediates for these insecticides, insecticidal compositions containing these pyrazolines, as well as the use of these pyrazolines to combat insects.

10 Pyrazolines are compounds with a pentagonal heterocyclic ring corresponding to the following formula and in which the atoms of the ring are numbered as follows:

H

In the insecticide art, it is known that certain derivatives of 1-carbamoyl-pyrazolines are insecticides. For example, in US Pat. No. 4,174,393, the insecticidal activity of 1-carbamoyl-pyrazolines is described which also has phenyl substituents in positions 3 and 4 of the pyrazoline ring.

The present invention provides pyrazolines having the following structural formula and exerting a pronounced insecticidal activity: ”" O- '

N ^ R.T

I / N

\ rc

It's w

35 where? 2 f f R. responds to the formula:

AT

“(JD-” '.

5 where R'A is chosen from the group comprising a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a halo-10 lower alkoxy group, a lower alkynyl-oxy group and a lower haloalkyl group; or 15 ^ where X represents a bridge of formula: - _ 7 ^ ° -'0R'AAR'AB> a- ° a'-ÎL- where a is equal to 1-3, a 'is equal to 0 or 1, a + a 'is equal to at least 2, but is not greater than 3.20 R'aa and r'ab are chosen independently of one another from a hydrogen atom, an atom d halogen and a lower alkyl group, while is selected from a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkoxy group and a lower haloalkyl group;

Rg represents a substituent 4 or 5 of formula: 30 ~ V ^ 7t R'b t /. '' Λ.

/ r 3 * ~ where R 'is chosen from a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group and a lower haloalkyl group; or 10 where Y represents a bridge of formula:

-E-ο- (cr 1 bar 1BB) b-ob, J

in which b is equal to 1-3, b 'is equal to 0 or 1, b + b' is equal to at least 2, but is not greater than 3, R'BA and R'BB are chosen independently from each other from a hydrogen atom, a halogen atom and a lower alkyl group, while R'bb is chosen from a hydrogen atom, a halogen atom, an alkyl group lower, lower alkoxy, lower haloalkoxy and lower haloalkyl; Rç responds to the formula:

; "-V

where Rp is selected from a hydrogen atom and a lower alkyl group, while R ^ is selected from a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkoxy halo group, a lower haloalkyl group, cyano group, nitro group, -NR ^ R ^ where R „and Rn 35 each independently of one another t 4 ί>

a lower alkyl group, as well as -SO R „where RH. n H

represents a lower alkyl group and n is 0-2; or where Z represents a bridge of formula:

./7o-(cr'car'gb)c-oc,J

10 in which c is equal to 1-3, c 'is equal to 0 or 1, c + c' is equal to at least 2, but is not greater than 3, R'ca and R'cb are chosen independently each other from a hydrogen atom, a halogen atom and a lower alkyl group and, in some compounds, R '^ A and R' ^ g do not both represent a hydrogen atom when c is equal to Λ 1 and c 'is equal to 1, while R'cc is chosen from a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a haloalkoxy group lower and lower haloalkyl; RN represents a hydrogen atom or a lower alkyl group; and V 'and W each independently represent an oxygen atom or a sulfur atom.

When used in this specification, the terms "halo" and "halogen" refer to fluorine, chlorine or bromine. The term "lower" modifying "alkyl", "alkoxy", "alkynyloxy" and the like implies a straight or branched hydrocarbon chain containing; 1-6 "preferably 1-4 carbon atoms; the term "halo" combined with another term means that 5 or more hydrogen atoms have been or have been replaced by a halogen atom.

# - 5

T

*. Among the aforementioned pyrazolines, the compounds in which W is an oxygen atom are preferred for most applications, in particular when R ′ is a substituent 4, preferably a halogen atom , for example, a chlorine atom or a fluorine atom, or a lower haloalkoxy group, for example, a difluoro-methoxy group. Pyrazolines in which R_ is a

D

substituent 4, are generally more active than the corresponding pyrazolines substituted in position 5 and the compounds in which Rg is a phenyl group comprising a substituent R'g, are of particular interest. In this regard, it is preferable that R'g is a substituent 4, in particular, a halogen atom, for example, a chlorine atom or a fluorine atom.

y

With regard to R ^, the most interesting insecticides usually derive from compounds comprising a 2,3-dihydro-2,2-dimethylbenzo-20 furan-5-yl group, a 2,3-dihydro-2,2 group, 3,3-tetrafluoro-benzofuran-5-yl, a 2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-6-yl group, a 2,2-difluoro-1,3-benzodioxol-5- group yl or a 2,2-dimethyl-1,3-benzodioxol-5-yl group, or else a 4-phenoxyphenyl group. In the latter case, it is preferable that Rg is a hydrogen atom and that R2 is a substituent 4, in particular, a lower haloalkoxy group.

Among the pyrazolines of the present invention exerting remarkable insecticidal activity, there is, for example, 3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) - 4-phenyl-ΐ pyrazoline-1-carboxamide, 3,4-bis- (4-fluorophenyl) - N-2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) pyra-- zoline -l-carboxamide, 3,4-bis- (4-fluorophenyl) -N- / 35 (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-

T

* 6 1-carboxamide, N- (2,3-dihydro-2,2,3,3-tetrafluoro-benzofuran-5-y1) -3- (4-difluoromethoxyphenyl) -4-phenylpyrazoline-1-carboxamide N- (2,2-difluoro- 1.3- benzodioxol-5-y1) -3- (4-difluoromé thoxyphenyl) -. 5 N-methyl-4-phenylpyrazoline-1-carboxamide, 3,4- bis- (4-chlorophény1) -N- (2,2-dimethyl1-1,3-benzodioxol- 5-yl) pyrazoline-1-carboxamide , N- (2,2-difluoro- 1.3- benzodioxol-5-yl) -3,4-bis- (4-fluorophenyl) pyra-zoline-1- ^ carboxamide, 3- (4-chlorophény 1) - N- (2,2-10 difluoro-1,3-benzodioxol-5-yl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide, 3- (4-difluoromethoxyphenyl) - N- (2, 3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -N-methyl-4-phenylpyrazoline-l-carboxamide, 3- (4-chlorophény1) 4- (4-difluoromethoxyphenoxy) phenylJ7-15 4 -phenylpyrazoline-1-carboxamide, N- £ "4- (4-difluoromethoxyphenoxy) phenylJ-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-tetrafluoro-benzofuran-6-yl) pyrazoline-1-carboxamide, 4- (4-chloropheny1) -N- (2,3-dihydro-2,2-dimé thylbenzofur an- 5- yl) -3-phenyl-pyrazoline-1-carboxamida, 3- (4-chloropheny1) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran- 5-yl) pyrazoline-1-carboxamide, 3- (4-difluoromethoxyphenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline- 1- carboxamide and 4- (4-chlorophenyl) -3- (4-difluoro-methoxyphenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.

Likewise, in the context of the present invention, insecticide compositions envisage are envisaged comprising, in an insecticide-effective amount, at least one of the aforementioned pyrazolines

T

, 7 mixed with a support acceptable from an agricultural point of view. Furthermore, the present invention encompasses a method for combating insects, this method comprising applying, at the point where it is desired to combat insects, at least one of the aforementioned pyrazolines in an amount which is effective from the point of view insecticide.

The pyrazolines of the present invention can be prepared by coupling an appropriate isocyanate or aromatic isothiocyanate with an appropriately substituted pyrazoline, i.e. a process falling within the scope of the present invention, namely:

"M

20 5

H

+ RC-N = C = W

25 ÿ 30 A Rß I / 35 W ^ Rc 1 W ^! i * 8

The product can be alkylated by s methods.

well known for forming the corresponding N-alkylated pyrazolines.

The suitably substituted starting pyrazolines are generally known materials. The required isocyanates and isothiocyanates can be prepared from the corresponding amines. A number of these amines are commercially available. Other interesting amines can be prepared by the methods described in the following examples.

EXAMPLE 1 3- (4-chlorophenyl) -N- / 74- (4-chlorophenoxy) phenylJ- 4-phenylpyrazoline-1-carboxamide Under heating of dry nitrogen for two days, the mixture was heated to 70 ° C. , a stirred mixture of 10.9 g (0.077 mole) of 4-fluoronitrobenzene, 9.95 g (0.077 mole) of 4-chlorophenol and 11.8 g (0.085 mole) of potassium carbonate in 175 ml of dimethyl sulfoxide. The reaction mixture was cooled and filtered. The filtrate was diluted with water until a volume of one liter was obtained.

This mixture was extracted with three 200 ml portions of diethyl ether. The combined ether extract was washed with water and then with a saturated aqueous solution of sodium chloride. The washed extract was dried over anhydrous sodium sulfate and filtered. By evaporation of the filtrate under reduced pressure, 13.5 g of 4- (4-chlorophenoxy) nitrobenzene were obtained (melting point: 67-70 ° C).

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

Jr 9 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) was added dropwise ) of tri-chloromethyl chloroformate in 20 ml of toluene. After the addition, the mixture was heated at 85 ° C for three hours. This mixture was cooled to room temperature and the solvent was evaporated under reduced pressure to obtain a residue. This was said to be under this residue in 25 ml of diethyl ether. This solution was added dropwise to a stirred slurry of 1 g (0.0034 mole) of 3- (4-chlorophenyl) - 4-phenylpyrazoline in diethyl ether. Three drops of triethylamine were added and the mixture was stirred at room temperature for two days. The solvent was evaporated from the mixture to obtain 0.92 g of 3- (4-chlorophenyl) -N- £ · 4- (4-chlorophenoxy) phenylJ7-4-phenylpyrazoline-1-carboxamide (melting point: 158-161 ° C).

20 Analysis:

Calculated: C 66.92; H 4.22 Found: C 66.06; H 4.95

Nuclear magnetic resonance spectrum: 8.06 parts per million (CDCl ^).

Example 2 3- (4-chloropheny1) -N- (2,3-dihydro-2,2-dimethylbenzo-furan-5-yl) -4-phenylpyrazoline-1-carboxamide

Over a period of one hour, an ice-cold mixture of 43 ml of concentrated nitric acid and 50 ml of concentrated sulfuric acid was added dropwise to 100 g (0.67 mole) of 2, 3-dihydro-2,2-dimethylbenzofuran while maintaining the temperature at 5 ° C. After the addition was complete, the mixture was stirred at 0 ° C for 2.5 hours. The reaction mixture was poured into ice water and *. 10 extract the whole with diethyl ether. The extract was dried over anhydrous magnesium chloride and filtered. By evaporation of the filtrate under reduced pressure, a black oil was obtained. By purifying this oil by column chromatography on silica gel, eluting with a 9: 1 mixture of toluene and n-hexane, 50 g of 2,3-dihydro-2,2-dimethyl-5- were obtained. nitrobenzofuran as a solid.

10 By hydrogenation of 20 g (0.1 mole) of 2,3-dihydro-2,2-dimethyl-5-nitrobenzofuran with a catalytic amount (0.2 g) of platinum oxide in 250 ml of methanol, obtained 16.6 g of 5-amino-2,3-dihydro-2,2-dimethyl-benzofuran.

A solution of 0.43 ml (0.0036 mole) of tri-chloromethyl chloroformate in 20 ml of toluene was added dropwise to a stirred solution of 0.56 g (0.0034 mole) of 5-amino -2,3-dihydro-2,2-dimethylbenzofuran in 20 ml of toluene. After the addition was complete, the mixture was heated at reflux for 3 hours. The mixture was cooled to room temperature and the solvent was evaporated under reduced pressure to obtain a residue. This residue was dissolved in 25 ml of dry diethyl ether and the solution obtained was added dropwise to a stirred mixture of 1 g (0.0034 mole) of 3- (4-chlorophenyl) -4-phenyl- pyrazoline and three drops of triethylamine in 25 ml of diethyl ether. The reaction mixture was stirred at room temperature for about 18 hours, after which time a solid of the mixture was filtered. A filter cake slurry was formed in ethanol and collected by filtration to obtain 0.47 g of 3- (4-chlorophenyl) -N- (2,3-dihydro-2,2- 35 dimethylbenzofuran-5-yl) -4-phenyl-pyrazoline-1-carbo-! - ·.

- 11> xamide (melting point: 160-162 ° C).

Analysis:

Calculated: C 70.00; H 5.43 Found: C 69.50; H 3.36 5. Nuclear magnetic resonance spectrum: 9 parts per million (dimethyl sulfoxide-dg).

Other members of the series which are prepared by similar techniques are given in the following additional examples. Melting points are indicated in degrees Celsius. In certain cases, the singlet of the nuclear magnetic resonance spectrum corresponding to the proton = NH characterizing these compounds is also indicated. Unless otherwise indicated, the solvent for the nuclear magnetic resonance spectrum is CDCl 4. In some cases, elementary analyzes are indicated.

Example 3 3.4- dipheny1-N- (4-phenoxyphenyl) pyrazoline-1-carboxamide-mide, melting point: 184-188 ° C, 9.17 parts per 20 million (dimethylsulfoxide-dg).

Example 4 N- / 7 4- (4-chlorophenoxy) pheny1J-3,4-diphenylpyrazoline-1-carboxamide, melting point: 146-149 ° C, 8.83 parts per million (dimethyl sulfoxide-dg).

Example 5 3- (4-chloropheny1) -N- (4-phenoxyphenyl) -4-phenylpyrazo-line-1-carboxamide, melting point: 163-166 ° C, 8.03 parts per million.

Example 6 N- (4-phenoxyphenyl) -4-pheny1-3- (4-trifluoromethylphenyl) pyrazoline-1-carboxamide, melting point: 188-190 ° C, 8.10 parts per million.

Example 7 3.4- bis- (4-chlorophény1) -N- (4-phenoxyphenyl) pyrazoline-35 1-carboxamide, melting point: 189-193 ° C, 8.20 parts - * 12 parts per million (CDClg / dimethylsulfoxide -dg).

Example 8 3- (4-chlorophenyl) -N- (3-methyl1-4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide, melting point: 5,151-157 ° C, 9.13 parts per million (dimethylsulfo- xyde-dg).

Example 9 3- (4-chlorophenyl) -N- £ "4- (2-fluorophenoxy) phenyl J - 4- phenylpyrazoline-1-carboxamide, melting point: 10 153-155 ° C, 8.16 parts per million.

Example 10 3- (4-chlorophenyl) -N- / J "4- (3-fluorophenoxy) phenyl" J- 4- phenylpyrazoline-1-carboxamide, melting point: 173-175 ° C, 9.33 parts per million (dimethylsulfoxide-dg).

Example 11 N-C4- (3-chlorophenoxy) phenylJ-3- (4-chlorophenyl) - 4-phenylpyrazoline-1-carboxamide, melting point: 169-174 ° C, 9.30 parts per million (dimethylsulfo-xyde -dg).

Example 12 3- (4-chlorophenyl) -N- ^ T 4- (4-fluorophenoxy) phenyl-4-phenylpyrazoline-1-carboxamide, melting point: 164-167 ° C, 8.13 parts per million.

Example 13 3- (4-chlorophenyl) -N- £ "4- (4-trifluorome thylphenoxy) -phenylJ7-4-phenylpyrazoline-1-carboxamide, melting point: 161-164 ° C, 8.03 parts per million .

Example 14 30 Ν- / Γ 4- (4-chlorophenoxy) phenyl> y-3- (4-difluoromethoxy-phenyl) -4-phenylpyrazoline-1-carboxamide, melting point: 103-107 ° C, 8.00 parts per million.

Example 15 3,4-bis- (4-chlorophenyl) -N- (3-me thy 1-4-phenoxyphenyl) - '35 pyrazoline-1-carboxamide, melting point: 188-190 ° C, ν' 13 s 9.23 parts per million (dimethyl sulfoxide-dg).

Example 16 3.4- bis- (4-chlorophenyl) -N- £ 4- (2-fluorophenoxy) phenylJ7-pyrazoline-1-carboxamide, melting point: 5,160-162 ° C, 8.10 parts per million.

Example 17 3.4- bis- (4-chlorophenyl) -N- £ "4- (3-fluorophenoxy) phe-nylJ7-pyrazoline-1-carboxamide, melting point: 144-146 ° G, 9.20 parts per million ( dimethylsulfo-xyde-dg).

Example 18 N — 4- (3-chlorophenoxy) pheny 1 "J-3,4-bis- (4-chloro-j phenyl) -pyrazoline-1-carboxamide, melting point: 135-140 ° C, 9.30 parts per million (dimethylsulfo-15 xyde-dg).

Example 19 3.4- bis- (4-chlorophenyl) -N- £ ”4- (4-fluorophenoxy) phe-nyl. 7-pyrazoline-1-carboxamide, melting point: 168-170 ° C, 9.23 parts per million (dimethylsulfoxide-dg).

Example 20 N-Γ4- (4-chlorophenoxy) phenyl27-3 »4 ~ bis- (4-chloro-phenyl) -pyrazoline-1-carboxamide, melting point: 154-156 ° C, 9.30 parts per million ( dimethylsulfo-25 xyde-dg).

Example 21 3.4- bis- (4-chlorophenyl) -Ν - ^ * 4- (4-trifluoromethyl-phenoxy) phenyl I7-pyrazoline-1-carboxamide, point of | mp: 191-194 ° C, 9.30 parts per million (dimethyl sulfoxide-dg).

Example 22 3- (4-chlorophenyl) -4-phenyl-N- (4-phenylthiophenyl) -pyrazoline-1-carboxamide, melting point: 157-162 ° C, 8.20 parts per million.

/ / Λ s * 14

Example 23 i ^ j 3,4-bis- (4-chlorophenyl) -N- (4-phenylthiophenyl) pyra- | zoline-1-carboxamide, melting point: 169-171 ° C, 8.20 parts per million.

5 Example 24.

3.5- bi s- (4-chlorophény1) -N- (4-phenoxypheny1) pyrazo-line-l-carboxamide, melting point: 168-170 ° C, 8.30 parts per million (CDClg / dimethylsulfoxide-dg).

Example 25 3- (4-chlorophenyl) -5- (4-trifluoromethylphenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide, melting point: 164-167 ° G, 8.00 parts per million.

Example 26 3.5- bis- (4-chloropheny 1) -N- ^ 4- (2-fluorophenoxy) pheny 1 "J -15 pyrazoline-1-carboxamide, melting point: 174-178 ° C; 8.50 parts per million.

Example 27 3.5- bis- (4-chlorophenyl) -N- £ * 4- (3-fluorophenoxy) phe-nylΌ-pyrazoline-1-carboxamide, melting point: 164-168 ° C, 9.00 parts per million (dimethylsulfoxide-dg).

! Example 28 3.5- bis- (4-chloropheny1) -N- £ 4- (4-fluorophenoxy) phe-nylj -pyrazoline-1-carboxamide, melting point: 165-167 ° C, 9.16 parts per million ( dimethylsulfoxide-dg).

Example 29 N- ^ "4- (4-chlorophenoxy) pheny1J-3,5-bi s- (4-chloro-phenyl) -pyrazoline-1-carboxamide, melting point: 30 142-144 ° C, 9.20 parts per million (dimethylsulfoxide-dg).

Example 30 3.5- bis- (4-chlorophenyl) -N- £ '4- (4-trifluoromethyl-phenoxy) phenyl ^ 7-pyrazoline-1-carboxamide, melting point: 155-158, 8.43 parts per million (CDClg / y dimethyl sulfoxide-dg).

Example 31 3- (4-chlorophenyl) -N- £ 4- (4-trifluoromethylphenoxy) -phenyl.7-5- (4-trifluoromethylphenyl) pyrazoline-1-5 carboxamide, melting point: 144-146 ° C, 8 , 06 parts per million.

Example 32 N- £ 4- (4-chlorophenoxy) pheny 1J-5- (4-chlorophenyl) - 3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide, melting point: 66-70 ° C, 8.60 parts per million (dimethyl sulfoxide-dg).

Example 33 5- (1,3-Benzodioxol-5-yl) -3- (4-chlorophenyl) -N- (4-phenoxyphenyl) -pyrazoline-1-carboxamide, melting point: 125 ° -128 ° C., 8.36 parts per million (CDClg / dimethylsulfoxide-dg).

Example 34 5- (1,3-benzodioxol-5-yl) -N- £ 4- (4-chlorophenoxy) phe-ny1J-3- (4-chlorophenyl) pyrazoline-1-carboxamide, melting point: 174- 175 ° C, 8.06 parts per million.

Example 35 N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -3,4-di-phenylpyrazoline-1-carboxamide, melting point: 139-143, 7.96 parts per million.

Example 36 3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2-di-methylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxa-mide, melting point: 75-82 ° C, 7.96 parts per million.

Example 37 (+) - 3,4-bis- (4-chlorophenyl) -N- (2,3-dihydro-2,2-di-methylbenzofuran-5-yl) pyrazoline-1-carboxamide, melting point: 134-137 ° C, 7.93 parts per million.

Example 38/35 3,5-bis- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethyl-16 benzofuran-5-yl) pyrazoline-1-carboxamide, melting point: 175- 180 ° C, 8.86 parts per million (dimethyl sulfoxide-dg).

Example 39 5 N- (1,4-Benzodioxan-6-y1) -3- (4-chlorophenyl) -4-phenyl-pyrazoline-1-carboxamide, melting point: 112-115 ° C, 7.96 parts per million.

Example 40 N- (1,4-benzodioxan-6-yl) -3,4-bis- (4-chlorophenyl) -10 pyrazoline-1-carboxamide, melting point: 140-145 ° C, 7.96 parts per million.

Example 41 3- (4-chlorophenyl) -N- (4-phenoxypheny1) -4-phenylpyra-zoline-1-carbothioamide, melting point: 105-110 ° C, 15 '10.30 parts per million (dimethyl sulfoxide-dg ).

Example 42 3,4-bis- (4-chlorophenyl) -N- (4-phenoxypheny1) pyrazo-line-1-carbothioamide, melting point: 151-153 ° C, 9.26 parts per million (dimethyl sulfoxide-dg) .

Example 43 N- / 7 4- (4-chlorophenoxy) pheny1J-3,4-bi s- (4-chloro-phenyl) -pyrazoline-1-carbothioamide, melting point: 179-183 ° C, 9.10 parts per million.

Example 44 3- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carbothioamide, melting point: 92-95 ° C , 10.12 parts per million (dimethyl sulfoxide-dg).

Example 45 3,4-bis- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) pyrazoline-1-carbothioamide, melting point: 149-154 ° C, 9.00 parts per million (dimethyl sulfoxide-dg).

Example 46 35 N- (1,4-benzodioxan-6-yl) -3,5-bis- (4-chlorophenyl) - 17 pyrazoline-1-carboxamide, melting point: 83-85 ° C, 9.33 parts per million (dimethyl sulfoxide-dg).

Example 47 5- (4-chlorophenyl) -3- (4-trifluoromethylpheny1) -N-5 [2 4- (4-tri f luoromy thy lphenoxy) pheny 1 ~ J pyrazoline-l- carboxamide, melting point: 183- 185 ° C, 8.77 parts per million (CDClg / dimethylsulfoxide-dg).

Example 48 N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -10 3- (4-difluoromethoxypheny1) -4-phenylpyrazoline-1-carboxamide

15 g (0.086 mole) of 2-chloro-4-nitrophenol, 11.9 g (0.086 mole) of potassium carbonate, 1.5 g 15 (0.02 mole) of propane were placed in a pressure bottle -thiol, 33.7 g (0.13 mole) of 1,2-dibromotetrafluoroethane and 115 ml of N, N-dimethyl-formamide. The pressure bottle was sealed and the mixture was stirred at 50 ° C for 48 hours. The pressure bottle was cooled to room temperature, opened and the contents poured into a separatory funnel. In the latter, about 200 ml of a 2N sodium hydroxide solution was added. The resulting mixture was extracted with four 300 ml portions of diethyl ether. The extracts were combined and washed with two 100 ml portions of 2N sodium hydroxide solution. The washed extract was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to obtain an oil. The reaction described above was repeated three times. The residual oils from the four experiments were combined and purified by column chromatography on silica gel eluting with. 95: 5 mixture of n-heptane and toluene to obtain 57.6 g of 3-chloro-4- (2-bromo-1,1,2,2-tetrafluorethoxy) nitrobenzene as an oil.

10 g (0.028 mole) of 3-chloro-4- (2-bromo-1,2,2,2-tetra-5 fluorethoxy) nitrobenzene, 9 g (0.14 mole) were placed in a pressure bottle copper powder (200 mesh), 0.45 g (0.0028 mole) of 2,2'-bipyridyl and 40 ml of dimethyl sulfoxide. The pressure bottle was sealed and the reaction mixture was stirred at 190-195 ° C for 2 hours. The pressure bottle was cooled to room temperature, opened and the contents poured into a separatory funnel. To this funnel was added about 200 ml of a 2N hydrochloric acid solution. The mixture was extracted with three 150 ml portions of diethyl ether. The extracts were combined and washed successively with 200 ml of a 2N hydrochloric acid solution, 200 ml of a saturated aqueous solution of sodium chloride 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 obtain an oil. The reaction described above was repeated six more times. The residual oils from the seven experiments were combined and subjected to column chromatography on silica gel eluting with toluene to obtain a yellow oil. This oil was dissolved in 125 ml of methyl cyclohexane and the solution was placed in a freezer for about 18 hours. Crystals formed which were collected by filtration to obtain 20.7 g of 2,2,3,3-tetrafluoro-5-nitrobenzofuran. The filtrate was evaporated under reduced pressure to obtain an oil. By distilling this oil under reduced pressure, an additional 3 g of product was obtained (boiling point: 75 ° C / 0.2 mm Hg). The hydrogenation of 2.15 g (0.011 mole) of 2,2,3,3-tetrafluoro-5-nitro-benzene with a catalytic amount (0.25 g) of platinum oxy-5 in 150 ml of methanol gave 2.15 g of 5-amino-2,2,3,3-tetrafluorobenzofuran.

To a stirred solution of 8 ml of 20% phosgene in toluene was added dropwise a solution of 0.75 g (0.0036 mole) of 5-amino-2,2,10 3,3-tetrafluorobenzofuran dissolved in 109 ml of toluene. When the addition was complete, the mixture was heated at reflux for two hours. The mixture was cooled and the solvent was removed by evaporation under reduced pressure to obtain a residue. This residue was dissolved in 15 ml of diethyl ether and the solution obtained was added to a stirred solution of 1.04 g (0.0036 mole) of 3- (4-difluoromethoxyphenyl) - 4-phenylpyrazoline and three drops of triethylamine in 100 ml of diethyl ether. At the end of the addition, the mixture was heated to reflux for one hour, then cooled to room temperature and stirred for about 18 hours. The solvent was removed from the reaction mixture by evaporation under reduced pressure to obtain a solid residue.

By recrystallization from ethanol, 0.99 g of N- (2,3-dihydro-2,2,3,3-tetrafluorobenzo-furan-5-yl) -3- (4-difluoromethoxyphenyl) was obtained. -4-pheny1-pyrazoline-1-carboxamide (melting point: 155-159 ° C). Analysis: 30 Calculated: C 58.58; H 3.29

Found: C 57.81; H 3.75.

Nuclear magnetic resonance spectrum: 8.16 parts per million.

| s! ^ / j i 20

Example 49 3,4-bis- (4-chlorophenyl) -N- (2,2-dlfluoro-1,3-benzo-dioxol-5-yl) pyrazoline-1-carboxamide To a cold solution (5-10 ° C ) of 24 ml 5 of 20% phosgene in toluene, a solution of 1.18 g (0.0068 mole) of prepared 5-amino-2,2-difluoro-1,3-benzodioxole was added dropwise by the method described in the literature and dissolved in 80 ml of tetrahydrofuran. After the addition was complete, the mixture was stirred at 2 ° C for one hour, then at reflux temperature for 2 hours. The solvent was evaporated under reduced pressure to obtain 1.4 g of a liquid residue. In a clean reaction flask, 0.68 g of this residue was added slowly to a stirred solution of 0.93 g (0.0032 mole) of 3,4-bis- (4-chlorophenyl) pyrazoline and three drops of triethylamine in 20 ml of diethyl ether. After the addition was complete, the mixture was stirred at room temperature for about 18 hours. A small amount of a solid was present in the reaction mixture and was removed by filtration. The filtrate was evaporated under reduced pressure to obtain a residue. Purification of this residue by column chromatography on silica gel eluting with a 1: 1 mixture of n-heptane and ethyl acetate gave 1.3 g of 3,4-bis- (4- chlorophenyl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) -pyrazo-line-1-carboxamide (melting point: 150-155 ° C). Analysis: Calculated: C 56.34; H 3.08

Found: C 57.16; H 2.89

Nuclear magnetic resonance spectrum: 8.10 parts per million.

21

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

Example 50 N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4-difluoro-5 methoxyphenyl) -4-pheny lpyrazoline-1-carboxamide, melting point: 135-138 ° VS ; 8.10 parts per million.

Example 51 3- (4-fluoropheny1) -N- (4-phenoxypheny1) -4-phenylpyrazo-. line-1-carboxamide, melting point: 187-191; 10 8.10 parts per million.

Example 52 3- (4-difluoromethoxyphenyl) -N- (4-phenoxypheny1) -4-phenylpyrazoline-1-carboxamide, melting point: 139-144 ° C; 8.10 parts per million.

* Example 53 3- (4-chloropheny 1) -N- / J4- (4-chlorophenoxy) -phenyl 'J- 4-phenylpyrazoline-1-carboxamide, melting point: 170-174 ° C; 8.10 parts per million.

Example 54 3- (4-chlorophenyl) -N- / 74- (4-nitrophenoxy) phenyl-4-phenylpyrazoline-1-carboxamide, melting point: 187-189 ° C; 8.30 parts per million.

Example 55 3- (4-chlorophenyl) -N- / 7 4- (4-methoxyphenoxy) phenyl J7 -25 4-phenylpyrazoline-1-carboxamide, melting point: 159-160 ° C; 8.07 parts per million.

Example 56 3- (4-chlorophenyl) -N- £ "4- (4-difluoromethoxyphenoxy) -phenyl" J-4-phenylpyrazoline-1-carboxamide, melting point: 181-184 ° C; 8.07 parts per million.

Example 57 Ν- / Γ4- (4-chlorophenoxy) phenyl "J-3- (4-trifluoromethyl thoxyphenyl) -4-pheny lpyrazoline-1-carboxamide, melting point: 132-134 ° C; 8.16 parts per million.

w / / i 22 ", Example 58 N- £ 4- (4-chlorophenoxy) phenyl ^ -4-phenyl-3- £ '4- (2-propynyloxy) phenyl 17pyrazoline-1-carboxamide, melting point: 160- 164 ° C; 8.13 parts per million.

Example 59 3- (1,3-Benzodioxol-5-y1) -N- (4-phenoxyphenyl) -4-pheny1-pyrazoline-1-carboxamide, melting point: 220-223QC; 8.06 parts per million.

Example 60 4- (4-chlorophenyl) -N- (4-phenoxyphenyl) -3-phenylpyrazoline-1-carboxamide, melting point: 153-155 ° C; 8.16 parts per million.

Example 61 3.4-bis- (4, -f luorophenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide, melting point: 194-198 ° C; 8.16 parts per million.

• ”Example 62

Nr £ "4- (2-chlorophenoxy) phenyl _7-3,4-bis- (4-chloro-: 'phenyl) -pyrazoline-1-carboxamide, melting point: 20 182-186 ° C; 8.10 parts per million.

Example 63 3.4- bis- (4-chlorophenyl) -Ν- / Γ 4- (4-methoxyphenoxy) phenyl, 7-pyrazoline-1-carboxamide; 8.20 parts per million.

Example 64 3- (4-chlorophenyl) -4- (4-fluorophenyl) -N- (4-phenoxy phenyl) pyrazoline-1-carboxamide, melting point: 178-179 ° C; 8.10 parts per million.

| Example 65 N-iC 4- (4-chlorophenoxy) pheny1J7 -3— (4-chlorophenyl) - 4- (4-fluorophenyl) pyrazoline-1-carboxamide, melting point: 143-145 ° C; 8.03 parts per million.

Example 66 3- (4-chlorophenyl) -4- (4-me thyIpheny1) -N- (4-phenoxy-phenyl) pyrazoline-1-carboxamide, melting point:; '23 I * ί i ί 165-168 ° C; 8.10 parts per million.

| "Example 67 N- ^ 4- (4-chlorophenoxy) phenyl_7 ~ 3- (4-chlorophenyl) - 4- (4-methoxyphenyl) pyrazoline-1-carboxamide, melting point: 169-173 ° C; 8.07 parts per million.

Example 68 I 4- (4-fluoropheny1) -3- (4-methoxyphenyl) -N- (4-phenoxyphenyl) pyrazoline-1-cart> oxamide, melting point: 184-187 ° C .; 8.17 parts per million.

Example 69 N-Γ4- (4-difluoromethoxyphenoxy) phenyl ^ 7-3- (4-difluo-romethoxyphenyl) -4- (4-fluorophény1) pyrazoline-1-carboxamide; 8.10 parts per million.

Example 70 N- / 74- (4-chlorophenoxy) phenylJ7-3- (4-chlorophenyl) - 4-phenylpyrazoline-1-thiocarboxamide, melting point: 179-183 ° C; 9.10 parts per million.

Example 71 - 3- (4-difluoromethoxyphenyl) -N- (4-phenoxyphenyl) -4- phenylpyrazoline-1-thiocarboxamide, melting point: 132-136 ° C; 9.13 parts per million.

Example 72 4- (4-chloropheny1) -N- (4-phenoxyphenyl) -3-phenylpyra-zoline-1-thiocarboxamide, melting point: 131-133 ° C; 25 9.16 parts per million.

Example 73 Ν-ΖΓ 4- (4-chlorophenylthio) phenyl J7-3,4-diphenylpyrazo-line-1-carboxamide, melting point: 186-190 ° C; 8.20 parts per million.

Example 74 3- (4-chlorophenyD-N-ZT 4- (4-chlorophenylthio) phenylJ- 4-phenylpyrazoline-1-carboxamide, melting point: 178-181 ° C; 8.23 parts per million.

w f i 24

Example 75 3- (4-difluoromethoxypheny1) -4-pheny1-N- (4-pheny1-thiophenyl) pyrazoline-1-carboxamide, melting point: -135-140 ° C; 8.13 parts per million.

Example 76 3.4- bis- (4-chlorophenyl) -N- £ T4- (4-fluorophény1thio) -phenylI7pyrazoline-1-carboxamide, melting point: 171-175 ° C; 8.20 parts per million.

Example 77 3,4-bis- (4-chlorophenyl) -N- £ 4- (4-chlorophenylthio) - phenyl. ^ Pyrazoline-1-carboxamide, melting point: 151-156; 8.13 parts per million.

Example 78 3.4- bis- (4-chlorophenyl) -N- £ ”4- (3-chlorophenoxy) -15 'phenylJ7-Pyrazoline-1-carboxamide, melting point: 135-140 ° C; 9.20 parts per million (dimethyl sulfoxide-dg). Example 79 3- (4-methoxypheny1) -N- (4-phenoxypheny1) -4-pheny1- "pyrazoline-1-carboxamide, melting point: 188-192 ° C; 8.46 parts per million (CDClg / dimethyl sulfoxide-dg).

Example 80 3- 3- ”4- (2-propynyloxy) phenylJ7-N ~ (4-phenoxypheny1) -4- phenylpyrazoline-1-carboxamide, melting point: 1212-126 ° C; 8.10 parts per million.

Example 81 3- (4-chlorophenyl) -N- (2,3-dihydrobenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide, melting point: 155-158 ° C; 7.93 parts per million.

Example 82 3- (4-difluorome thoxypheny1) -N- (2,3-dihydrobenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide; 7.93 parts per million.

Example 83 3.4- bis- (4-chlorophenyl) -N- (2,3-dihydrobenzofuran-5-35 yl) pyrazoline-1-carboxamide, mp: 214-216 ° C; 7.93 parts per million.

Example 84 3- (4-fluoropheny1) -N- (2,3-dihydro-2,2-dimethylbenzo-furan-5-yl) -4-phenylpyrazoline-1-carboxamide, melting point: 156-160 ° C ; 7.93 parts per million.

Example 85 3- (4-me thoxypheny1) -N- (2,3-dihydro-2,2-dimé thylbenzo-furan-5-yl) -4-phenylpyrazoline-1-carboxamide, melting point: 164-169 ° C; 8.00 parts per million.

Example 86, 3- (4-trifluoromethoxyphenyl) -N- (2,3-dihydro-2,2-di-methylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxa-mide, melting point: 81- 83 ° C; 7.98 parts per million.

Example 87 N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenyl- 3 - / ^ 4- (2-propynyloxy) phenyl Jpyrazoline-1-carboxamide, melting point: 175-179 ° C; 8.00 parts per million.

Example 88 20 3- (1,3-benzodioxol-5-yl) -N- (2,3-dihydro72,2-dimethyl-benzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide, melting point: 223 -227 ° C; 8.90 parts per million (dimethyl sulfoxide-dg).

Example 89 4- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -3-phenylpyrazoline-1-carboxamide; 8.00 parts per million.

Example 90 3,4-bis- (4-fluorophény1) -N- (2,3-dihydro-2,2-dimethyl-30 benzofuran-5-yl) pyrazoline-1-carboxamide, melting point: 161-166 ° VS ; 7.93 parts per million.

Example 91 3- (4-chlorophenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide, melting point: 169- 171 ° C; 7.96 parts per million.

26

Example 92 3- (4-chloropheny1) -4- (4-methylphenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide, melting point: 137-139 ° VS ; 7.96 parts per million.

Example 93 3- (4-chloropheny1) -4- (4-methoxypheny1) -N- (2,3-dihydro-2.2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide, melting point: 182-186 ° VS ; 7.93 parts per million.

Example 94 10 4- (4-fluoropheny1) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -3- (4-methoxyphenyl) pyrazoline-1-carboxamide, melting point: 179-182 ° C; 7.93 parts per million.

Example 95 4- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzo-furan-5-yl) -3- (4-methoxyphenyl) pyrazoline-1-carboxamide, dot melting: 157-160 ° C; 7.96 parts per million.

Example 96. 3- (4-difluoromethoxypheny1) -4- (4-fluoropheny1) -N- 20 (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline- 1-carboxamide, melting point: 169-172 ° VS ; 7.93 parts per million.

Example 97 • 4- (4-chlorophenyl) -3- (4-difluoromethoxypheny1) -N-25 (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide, melting point: 90 -95 ° C; 7.93 parts per million.

Example 98 3- (4-difluoromethoxypheny1) -N- (2,3-dihydro-2,2,3,3-30 tetrafluorobenzofuran-6-yl) -4-phenylpyrazoline-1-carboxamide, melting point: 152 -157 ° C; 8.33 parts per million.

Example 99 3- (4-difluoromé thoxyphenyl) -4- (4-fluorophény1) -N- (2,3-35 dihydro-2,2,3,3-tetrafluorobenzofuran-6-yl) pyrazoline-27 1-carboxamide, melting point: 110-114 ° C; 8.33 parts per million.

Example 100 * .......! I! I * 3- (4-difluoromethoxypheny1) -4- (4-fluorophény1) -N-5 (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) - pyrazoline-l-carboxamide, period mp: 155-159 ° C; 8.20 parts per million.

Example 101 3- (4-chlorophenyl) -N- (2,2-dimethyl-1,3-benzodioxol-10 5-yl) -4-phenylpyrazoline-1-carboxamide, melting point: 182-186 ° G; 7.96 parts per million.

Example 102 3- (4-difluoromethoxyphenyl) -N- (2,2-dimethyl-1,3-benzodioxol-5-yl) -4-phenylpyrazoline-1-carboxamide, melting point: 148-150 ° C; 7.93 parts per million.

Example 103 3,4-bis- (4-chlorophenyl) -N- (2,2-dimethyl1-1,3-benzo-dioxol-5-yl) -pyrazoline-1-carboxamide, melting point: 168-169 ° VS ; 7.93 parts per million.

Example 104 N- (1,4-benzodioxan-5-yl) -3- (4-difluorome thoxypheny1) - 4-phenylpyrazoline-1-carboxamide; 7.93 parts per million.

Example 105 N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4-difluoro methyl thoxyphenyl) -N-methyl-4-phenylpyrazoline-1-carbo-xamide, melting point : 110-114 ° C.

Example 106 4- (1,3-Benzodioxol-5-yl) -N- (4-phenoxyphenyl) -3-phenyl-pyrazoline-1-carboxamide, melting point: 195-197 ° C; 8.03 parts per million.

Example 107 3- (4-chlorophenyl) -N- ^ 4- ^ 4- (1,1-dimethylethyl) phenoxy J-phenyl_7-4-phenylpyrazoline-1-carboxamide, melting point: 192.5-194 ° C ; 8.03 parts per million.

28

Example 108 3- (4-chloropheny1) -4- (4-fluoropheny1) -N- £ A- (4-methyl-phenoxy) phenyl_7pyrazoline-1-carboxamide, melting point: 162-164 ° C; 8.03 parts per million.

Example 109 3- (4-chloropheny1) -A- (4-fluoropheny1) -N- £ “4 - / ^ 4- (1,1-dimethylethyl) phenoxy27phenyl ^ 7pyrazoline-1-carboxa-mide, melting point: 188-198 ° C; 8.03 parts per million. · Example 110 3- (4-chlorophenyl) -N- £ "4- £” 4- (1-methylethyl) phenoxy <| 7-phenyl. 7-4-phenylpyrazoline-1-carboxamide, melting point: 181 -182.5; 8.06 parts per million.

i

Example 111 15 3- (4-chloropheny1) -4- (4-fluoropheny1) -Ν- £ "4- £ T 4- (1- methylethyl) phenoxy JphenylJpyrazoline-1-carboxamide, melting point: 186-187 ° C ; 8.60 parts per million (CDClg / dimethylsulfoxide-dg).

Example 112 3- (4-chlorophenyl) -N- £ “4- (4-methylphenoxy) phenyl-4-phenylpyrazoline-1-carboxamide, melting point: 150-151 ° C; 8.06 parts per million.

Example 113 3- (4-chloropheny 1) -N - /! 7 "AC 4- (1-methylethoxy) phenoxy J-25 phenylJ7-4-phenylpyrazoline-1-carboxamide, melting point: 158-160.5 ° C ; 8.06 parts per million.

Example 114 3- (4-chloropheny 1) -A- (4-fluoropheny 1) -N- / C * 4- £ ”4- (1-; methylethoxy) phenoxÿ7phenylJ7pyrazoline-1-carboxamide, melting point: 213 -216 ° C; 8.66 parts per million (CDCl0 / dimethylsulfoxide-d_) o o

Example 115 3,4-bis- (4-fluorophenyl) -N- £ ‘A- £ 4- (1-methylethoxy) -phenoxy ^ 7phenylI7pyrazoline-1-carboxamide, melting point: 134-136 ° C; 8.06 parts per million.

29 ί}

Example 116 '3,4-bis- (4-fluoropheny1) -N- £ "4- (4-chlorophenoxy) phenylJ-pyrazoline-1-carboxamide, melting point: 197-198.5 ° C; 8, 70 parts per million (CDClg / dimethylsulfoxide-dg).

Example 117 J 3,4-bis- (4-fluorophenyl) -N- £ '4- £ 4- (1,1-dimethyl-! Ethyl) -phenoxy ^ phenyl ^ 7pyrazoline-1-carboxamide, [melting point: 189-192 ° C; 8.70 parts per million 10 (CDClg / dimethylsulfoxide-dg).

Example 118 3.4- bis- (4-fluoropheny1) -N- £ “4- (4-cyanophenoxy) phenyl J ^ pyrazoline-1-carboxamide, melting point: 198-200 ° C; 8.13 parts per million.

15 'Example 119 3.4- bis- (4-fluorophenyl) -N- / 7 4- £ * 4- (N, N-dimethylamino) - phenoxyJ7phenyl ^ 7pyrazoline-1-carboxamide, melting point: 148-150 ° C; 8.02 parts per million.

Example 120 3- (4-chloropheny1) -Ν- / Γ4- (4-cyanophenoxy) pheny1J-4-phenylpyrazoline-1-carboxamide, melting point: 170-172 ° C; 8.16 parts per million.

Example 121 * N- (1,4-benzodioxan-6-yl) -4- (4-chlorophény1) -3- (4-di-! Fluoromethoxyphenyl) pyrazoline-1-carboxamide, melting point: 124-128 ° VS ; 7.93 parts per million.

Example 122 3.4- bis- (4-chloropheny1) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -N-methylpyrazoline-1-carboxamide, or melting point: 150-155 ° C.

Example 123 N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3,4-diphenyl-pyrazoline-1-carboxamide, melting point: 214-216 ° C; 8.83 parts per million (CDClg / dimethylsulfoxide-35 dc).

b 30

Example 124 "N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3,4-bis- (4-fluorophenyl) pyrazoline-1-carboxamide, melting point: 178-180 ° C; 8.10 parts per million.

Example 125 3- (4-chlorophenyl) -N- (2,2-difluoro-1,3-benzodioxol- 5-y1) -4- (4-fluorophény1) pyrazoline-1-carboxamide, melting point: 147- 151 ° C; 8.06 parts per million.

Example 126 3- 3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -N-methyl-4-phenylpyrazo-line-1-carboxamide.

Example 127 3- (4-chlorophenyl) -4- (4-difluoromethoxyphenyl) -N-15 (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide, melting point: 155- 159 ° C; 7.96 parts per million.

Example 128 3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2-di-fluorobenzofuran-5-yl) -N-me thy1-4-phenylpyrazoline-1-carboxamide.

Example 129 4- (4-chlorophenyl) -N- (2,2-difluoro-1,3-benzodioxol-. 5-yl) -3- (4-difluoromethoxyphenyl) pyrazoline-1-carbo-xamide; 8.06 parts per million.

Example 130 4- (1,3-Benzodioxol-5-y1) -3- (4-chlorophenyl) -Ν- £ ”4- (4-f luoromé thoxyphenoxy) pheny 1J py razol ine-1 -carboxa-mide.

Example 131 4- (1,3-Benzodioxol-5-y1) -N- £ "4- (4-chlorophenoxy) phenylJ7-3- (4-chlorophenyl) pyrazoline-1-carboxamide.

Example 132 4- (1,3-benzodioxol-5-yl) -3- (4-chlorophenyl) -N- (2,2-35 dif luoro-1,3-benzodioxol-5-yl) pyrazoline-1-carboxamide .

31

Example 133 4- (1,3-Benzodioxol-5-yl) -3- (4-chlorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) py razoline- l-carboxamide.

Example 134 4- (1,3-benzodioxol-5-yl) -3- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-l- carboxamide .

j Example 135 10 4- (1,3-benzodioxol-5-yl) -N- ^ 7 4- (4-difluoromethoxyphenoxy) pheny1 J-3- (4-difluoromethoxypheny1) pyrazoline-1-carboxamide.

Example 136 4- (1, S-benzodioxol-S-ylJ-N- ^ 4- (4-chlorophenoxy) phe-nylJ7-3- (4-difluoromethoxyphenyl) pyrazoline-1-carbamide.

Example 137 4- (1,3-benzodioxol-5-yl) -N- (2,2-difluoro-1,3-benzodi-oxol-5-y1) -3- (4-difluoromethoxyphenyl) pyrazoline-1-20 carboxamide.

Example 138 4- (1,3-Benzodioxol-5-y1) -3- (4-di fluorome thoxypheny1) -N- (2,3-dihydro-2,2,3,3-té trafluorobenzofuran-5-yl) -pÿrazoline-l-carboxamide.

Example 139 4- (1,3-Benzodioxol-5-yl) -3- (4-difluorome thoxypheny1) -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-phenylpyrazoline-1-carboxamide.

Example 141 4- (1,3-Benzodioxol-5-yl) -N- (2,3-dihydro-2,2,3,3-tetra-f luorobenzof uran-5-yl) -3-phenylpyrazoline-1- carboxa-35 mide.

î __ s * 32

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

Example 143 5 4- (1,3-benzodioxol-5-yl) -N- £ "4- (4-difluoromethoxyphenoxy) phenyl 'J-3-phenylpyrazoline-1-carboxamide.

Example 144 4- (1,3-Benzodioxol-5-y1) -N- £ * 4- (4-chlorophenoxy) phe-nylJ7-3-phenylpyrazoline-1-carboxamide.

Example 145 4- (2,2-difluoro-1,3-benzodioxol-5-yl) -N- £ “4- (4-di-fluoromethoxyphenoxy) phenyl J-3- (4-fluorophenyl) py-razoline-1 -carboxamide.

Example 146 N- £ * 4- (4-chlorophenoxy) phenyl 7-4- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4-fluorophenyl) pyrazoline-1-carboxamide.

Example 147 4-N-bis- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4-20 fluorophenyl) pyrazoline-1-carboxamide.

Example 148 4- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4-fluoro-pheny 1) -N- (2, 3-dihy dro-2, 2, 3, 3 - tee t raf luorobenzof uran- 5- yl) pyrazoline-l-carboxamide.

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

Example 150 30 4- (2,2-difluoro-1,3-benzodioxol-5-y1) -N- £ ”4- (4-di-fluoromethoxyphenoxy) phenyl] 7 ~ 3-phenylpyrazoline-1-carboxamide.

Example 151 N- £ 7 4- (4-chlorophenoxy) phenyl J-4- (2,2-difluoro-1,3-. Benzodioxol-5-yl) -3-phenylpyrazoline-1-carboxamide.

i ^ ____ • 33>

Example 152 4-N-bis- (2,2-difluoro-1,3-benzodioxol-5-y1) -3-pheny1-pyrazoline-1-carboxamide.

Example 153 5 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-dffluoro-1,3-benzodioxol-5-yl) -N- (2,3-dihydro-10 2,3-dimethylbenzofuran-5-yl) -3-phenylpyrazoline-1- carboxamide .

Example 155 4- (2,2-difluoro-1,3-benzodioxol-5-yl) -N- / 7 4- (4-di-fluoromethoxyphenoxy) phenyl, 7-3- (4-difluoromethoxy-phenyl) pyrazoline -l-carboxamide.

Example 156 Ν-ΖΓ 4- (4-chlorophenoxy) phenyl J7 ~ 4- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) pyrazo-line-l-carboxamide.

Example 157 4-N-bis- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4-di-fluororné thoxypheny1) pyrazoline-1-c arboxamide.

Example 158 4- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4-difluoro-25 methoxypheny1) -N- (2,3-dihydro-2,2,3,3- tetrafluorobenzo-furan-5-yl) pyrazoline-1-carboxamide.

Example 159 4- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4-difluoro-methoxypheny1) -N- (2,3-dihydro-2,2-dimethylbenzofuran-30 5- yl) pyrazoline-1-carboxamide.

Example 160 4- (1,4-Benzodioxan-6-yl) -3- (4-chlorophenyl) -Ν- / Γ 4- {4-difluoromethoxyphenoxy) phenyl17pyrazoline-1-carboxamide.

/ # / __ ^ v 34

Example 161 4- (1,4-Benzodioxan-6-yl) -N- £ "4- (4-chlorophenoxy) phe-nylJ-3- (4-chlorophenyl) pyrazoline-1-carboxamide.

Example 162 5 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- 10 1-carboxamide.

Example 164 4- (1,4-Benzodioxan-6-y1) -3- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.

15 '“Example 165 4- (1,4-benzodioxan-6-yl) -N- £” 4- (4-difluoromethoxy- phenoxy) phenylJ7-3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide.

Example 166 20 4- (1,4-Benzodioxan-6-yl) -N- £ "‘ 4- (4-chlorophenoxy) phenylJ7- 3- (4-dlfluoromethoxyphenyl) pyrazoline-l-carboxamide.

Example 167 4- (1,4-Benzodioxan-6-y1) -N- (2,2-difluoro-1,3-benzodi-oxôl-5-yl) -3- (4-difluoromethoxyphenyl) pyrazoline-1- 25 carboxamide.

Example 168 4- (1,4-Benzodioxan-6-yl) -3- (4-difluorome thoxyphenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -pyrazoline -l-carboxamide.

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

* 35

Example 170 4- (1,4-Benzodioxan-6-yl) -N- £ 4- (4-difluoromethoxy-phenoxy) pheny 1 ZI-3-pheny lpyrazol ine-1 -carboxamide.

Example 171 5 4- (1,4-benzodioxan-6-yl) -N- £ ’4- (4-chlorophenoxy) phenyl. 7-3-phenylpyrazoline-1-carboxamide.

Example 172 4- (1,4-Benzodioxan-6-y1) -N- (2,2-difluoro-1,3-benzo-dioxol-5-yl) -3-phenylpyrazoline-1-carboxamide.

Example 173 4- (1,4-Benzodioxan-6-yl) -N- (2,3-dihydro-2,2,3,3-tetra-fluorobenzofuran-5-yl) -3-phenylpyrazoline-1-carboxamide .

Example 174 4- (1,4-Benzodioxan-6-yl) -N- (2,3-dihydro-2,2-dimethyl-15 * benzofuran-5-yl) -3-phenylpyrazoline-1-carboxamide.

Example 175 3- (1,3-benzodioxol-5-yl) -N- ^ ’4- (4-difluoromethoxyphé-noxy) pheny 1" J-4- (4-fluorophenyl) -N-methylpyrazoline-1-carboxamide.

Example 176 3- (1,3-Benzodioxol-5-y1) -N- £ * 4- (4-chlorophenoxy) phenyl J7-4- (4-fluorophenyl) pyrazoline-1-carboxamide.

Example 177 3- (1,3-benzodioxol-5-yl) -N- (2,2-difluoro-1,3-benzo-25 dioxol-5-yl) -4- (4-fluorophenyl) pyrazoline-l- carboxamide.

Example 178 3- (1,3-Benzodioxol-5-y1) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) pyrazoline- 1 -carboxamide.

Example 179 3- (1,3-Benzodioxol-5-yl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.

/ i ► * 36%

Example 180 3- (2,2-difluoro-1,3-benzodioxol-5-yl) -N- £ "4— (4-difluo-, romethoxyphenoxy) pheny1J-4- (4-fluorophenyl) pyrazoline-1-carboxamide .

Example 181 N- / J 4- (4-chlorophenoxy) phenyl "J -3- (2,2-dif luoro-1,3-benzodioxol-5-yl) -4- (4-fluorophenyl) -N-methylpyrazo -line-l-carboxamide.

Example 182 10 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-y1) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-15 (5-yl) pyrazoline-1-carboxamide.

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

Example 185 3- (1,4-benzodioxan-6-yl) -N- £ * 4- (4-difluoromethoxyphenoxy) phenyl _7-4-phenylpyrazoline-1-carboxamide.

Example 186 3- (1,4-Benzodioxan-6-yl) -N- £ * 4- (4-chlorophenoxy) phe-nyl "J-4-phenylpyrazoline-1-carboxamide.

Example 187 3- (1,4-benzodioxan-6-yl) -N- (2,2-difluoro-1,3-benzo-dioxol -5-yl) -N-methyl-4-phenylpyrazoline-l-carboxamide.

Example 188 30 3- (1,4-benzodioxan-6-yl) -N- (2,3-dihydro-2,2,3,3-tetra-fluorobenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide .

Example 189 3- (1,4-Benzodioxan-6-y1) -N- (2,3-dihydro-2,2-dimethyl-benzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide.

Λ 37

Example 190 Ν- £ "4- (4-difluoromethoxyphenoxy) phenyl ^ 7-3- (2,3-dihy-dro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide.

Example 191 Ν-Γ4 - (4-chlorophenoxy) pheny1J-3- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carbo-xamide.

Example 192 10 N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide .

Example 193 N- (2,3-dihydro-2,2,3,3-té trafluorobenzofuran-5-y1) -15 3- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -N- methyl-4-phenylpyrazoline-1-carboxamide.

Example 194 3- N-bis- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide.

Example 195 N- ^ 4- (4-difluoromethoxyphenoxy) phenyl ^ -4- (4-fluoro-phenyl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.

Example 196 1-C 4- (4-chlorophenoxy) pheny 1 "J-4- (4-fluoropheny 1) -25 3- (4-methylphenyl) pyrazoline-1-carboxamide.

Example 197 N- (2,2-difluoro-1,3-benzodioxol-5-yl) -4- (4-fluorophény 1) -3- (4-methylphenyl) pyrazoline-1-carboxamide.

Example 198 4- (4-fluoropheny1) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.

Example 199 4- (4-fluoropheny1) -N- (2,3-dihydro-2,2-dimethylbenzo-i furan-5-yl) -N-methyl-3- (4-methylphenyl) pyrazoline-1- * 38 carboxamide.

Example 200 N-Γ4- (4-difluoromethoxyphenoxy) phenyl, 7-4- (3-f luorophény l) -N-mé thy 1-3- (4-mé thy lphény 1) pyrazoline-l-5 carboxamide.

Example 201 Ν- £ * 4- (4-chlorophenoxy) phenylJ-4- (3-fluorophény1) - 3- (4-methylphenyl) pyrazoline-1-carboxamide.

Example 202 10 N- (2,2-difluoro-1,3-benzodioxol-5-yl) -4- (3-fluoro pheny 1) -3- (4-me thylpheny1) pyrazoline-1-carboxamide.

Example 203 4- (3-fluoropheny1) -N- (2,3-dihydro-2,2,3,3-tetrafluoro-benzofuran-5-y1) -3- (4-me thylpheny1) pyrazoline-1-car- 15 boxamide.

Example 204 ~ 4- (3-fluoropheny1) -N- (2,3-dihydro-2,2-dimé thylbenzofuran-5-yl) -3- (4-me thylpheny 1) pyrazoline-1-carboxamide.

Example 205 20 N- ^ 4- (4-difluoromethoxyphenoxy) phenyl J7 ~ 4- (2-fluoro pheny 1) -3- (4-methylpheny1) pyrazoline-1-carboxamide.

Example 206 N- / 4- (4-chlorophenoxy) phenylJ-4- (3-fluoropheny1) -N-methyl-3- (4-methylphenyl) pyrazoline-1-carboxamide.

Example 207 N- (2,2-difluoro-1,3-benzodioxol-5-yl) -4- (2-fluoropheny 1) -3- (4-methylphenyl) pyrazoline-1-carboxamide.

Example 208 4- (2-fluoropheny1) -N- (2,3-dihydro-2,2,3,3-tetrafluoro-benzofuran-5-yl) -3- (4-methylpheny1) pyrazoline-1-carboxamide.

Example 209 4- (2-fluoropheny1) -N- (2,3-dihydro-2,2-dimethylIbenzo-furan-5-yl) -3- (4-methylpheny1) pyrazoline-1-carboxa-35 mide.

39

Example 210 N- £ ”4- (4-difluoromé thoxyphenoxy) pheny1J-3- (3-fluoro-phenyl) -4- (4-fluorophény1) pyrazoline-1-carboxamide.

Example 211 5 N- £ 4- (4-chlorophenoxy) phenyl ^ - ^ “(S-fluorophenyl) - 4- (4-fluorophény1) pyrazoline-1-carboxamide.

Example 212 N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (3-fluoro-phenyl) -4, - (4-f luorophény 1) -N-methylpyrazol ine-1- 10 carboxamide.

Example 213 3- (3-fluoropheny1) -4- (4-fluoropheny1) -N- (2,3-dihydro- 2.2.3.3- tetrafluorobenzofuran-5-yl) pyrazoline-1-oarboxamide.

15 '* Example 214 3- (3-fluoropheny1) -4- (4-fluoropheny1) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.

Example 215 N-Γ4- (4-dlfluoromethoxyphenoxy) phenyl ^ 7-3- (2-fluoro-phenyl) -4- (4-fluorophény1) pyrazoline-1-carboxamide.

Example 216 N- / 7 4- (4-chlorophenoxy) phenyl, 7-3- (2-fluorophenyl) - 4- (4-fluorophény1) pyrazoline-1-carboxamide.

Example 217 25 N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (2-fluoro pheny 1) -4- (4-fluorophény1) pyrazoline-1-carboxamide.

Example 218 3- (2-fluoropheny1) -4- (4-fluoropheny1) -N- (2,3-dihydro-2.2.3.3- tetrafluorobenzofuran-5-y1) -N-me thyIpyrazo-30 line-1-carboxamide.

Example 219 3- (2-fluoropheny1) -4- (4-fluoropheny1) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide.

"

40

Example 220 3.4- bis- (4-fluorophenyl) -N- (2,3-dihydro-2,2,3,3,7-pentafluorobenzofuran-5-yl) pyrazoline-1-carboxamide.

Example 221 5 4- (4-chlorophenyl) -N- (2,3-dihydro-2,2,3,3,7-penta-fluorobenzofuran-5-yl) -3- (4-me thylpheny1) pyrazoline- 1 -carboxamide.

Example 222 N- (2,3-dihydro-2,2,3,3,7-pentafluorobenzofuran-5-yl) -10 3,4-diphenylpyrazoline-1-carboxamide.

Example 223 3- (4-difluoromé thoxyphény 1) -N- (2,3-dihy dro-2,2,3,3,7-pentafluorobenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide.

Example 224 3- (4-chloropheny1) -N- (2,3-dihydro-2,2,3,3,7-penta-fluorobenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide.

Example 225 3.4- bis- (4-fluorophenyl) -N- (2,2,6-trimaged thy1-1,3-benzo-dioxol-5-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 25 N- (2,2,6-trimethyl-1,3-benzodioxol-5-yl) -3,4-dipheny1-pyrazoline-1-carboxamide.

Example 228 3- (4-difluoromé thoxyphény 1) -N- (2,2,6-trimé thy 1-1,3-benzodioxol-5-yl) -4-pheny lpyrazoline-l-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-dimé thyl- / 1,3-benzodioxol-5-yl) pyrazoline-1-carboxamide.

- - 41

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

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

Example 233 3- (4-difluoromethoxypheny1) -N- (7-methoxy-2,2-dimethyl-1,3-benzodioxol-5-y1) -4-phenylpyrazoline-1-carboxamide.

Example 234 3- (4-chloropheny1) -N- (7-methoxy-2,2-dimethyl-1,3-benzo-dioxol-5-yl) -4-phenylpyrazoline-1-carboxamide.

Example 235 3.4- bis- (4-fluoropheny1) -N- £ "2,2-dimé thyl-7- (1-methyl1-ethyl) -1,3-benzodioxol-5-yl] 7pyrazoline-1-carboxamide.

Example 236 4- (4-chlorophenyl) -N- £ “2,2-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-yU -3,4-diphenylpyrazoline-1-carboxamide.

Example 238 3- (4-difluoromethoxypheny1) -N- £ * 2,2-dimethyl-7- (1-25 methylethyl) -l, 3-benzodioxol-5-yl, 7-4-phenylpyrazo-line-l-carboxamide .

Example 239 3- (4-chlorophenyl) -N- £ "2,2-dimethyl-7- (1-methylethyl) - 1,3-benzodioxol-5-yl .7-4-phenylpyrazoline-1-carboxamide.

Example 240 3.4- bis- (4-fluoropheny1) -N- (2,3-dihydro-7-ethyl1,2,2,3,3-tetrafluorobenzofuran-5-yl) pyrazoline-1-carboxamide.

S

"42

Example 241 4- (4-chlorophenyl) -N- (2,3-dihydro-7-ethyl-2,2,3,3-tetrafluorobenzofuran-5-yl) -3- (4-methylphenyl) pyra-zoline-1 -carboxamide.

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

Example 243 3- (4-Difluoromethoxypheny1) -N- (2,3-dihydro-7-ethyl-2,2,2,3,3-tetrafluorobenzofuran-5-y1) -4-phenylpyrazoline-1-carboxamide.

Example 244 3- (4-chlorophenyl) -N- (2,3-dihydro-7-ethy1-2,2,3,3-tetrafluorobenzofuran-5-yl) -4-phenylpyrazoline-l-15 'carboxamide.

Example 245 3- (4-chlorophenyl) -N- £ "4- (4-methylsulfonylphenoxy) -phenyl ^^ - phenylpyrazoline-1-carboxamide.

Example 246 3,4-bis- (4-fluorophenyl) -N- £ "4- (4-methylsulfonylphenoxy) phenyl. Azyazoline-1-carboxamide.

Example 247 3- (4-difluoromethoxypheny1) -N- £ 4- (4-methylsulfonyl-pftenoxy) phenyl ^ -4-phenylpyrazoline-1-carboxamide.

Example 248 3- (4-chlorophenyl) -4- (4-fluoropheny1) -Ν- / Γ 4- (4-methyl thulfonylphenoxy) phenyl J7pyrazoline-1-carboxamide.

Example 249 Ν- / Γ4 - (4-methylsulfonylphenoxy) phenyl J7 ~ 3> 4-diphenyl-30 pyrazoline-1-carboxamide.

Example 250 3,4-bis- (4-fluorophenyl) -N- (2,3-dihydro-7-difluoromé-thoxy-2,2-diméthylbenzofuran-5-yl) pyrazoline-1-carbo-xamide.

9 43; Example 251 4- (4-chlorophenyl) -N- (2,3-dihydro-7-difluoromethoxy-2,2-dimethylbenzofuran-5-yl) -3- (4-methylphenyl) pyra-! zoline-1-carboxamide.

Example 252 N- (2,3-dihydro-7-difluoromethoxy-2,2-dimethylbenzo-furan-5-yl) -3,4-diphenylpyrazoline-1-carboxamide.

Example 253 3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-7-difluoro-10 methoxy-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide.

Example 254 3- (4-chlorophenyl) -N- (2,3-dihydro-7-difluorome thoxy-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide.

Example 255 N- (7-chloromethyl-2,2-dimethyl-1,3-benzodioxol-5-yl) - 3,4-bis- (4-fluorophenyl) pyrazoline-1-carboxamide.

Example 256 20 N- (7-chloromethyl-2,2-dimethyl-1,3-benzodioxol-5-yl) - 4- (4-chlorophenyl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.

Example 257 lf- (7-chloromethyl-2,2-dimethyl-1,3-benzodioxol-5-yl) -25 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.

* 44

Example 260 N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -3- £ f 7- (l-methylethyl) -2,2-dimethyl-1,3-benzodioxol-5-ylJ- 4- phenylpyrazoline-1-carboxamide.

Example 261 N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -3- (7-methoxy-2,2-dimethyl1-1,3-benzodioxol-5-yl) -4-phenyl -pyrazoline-1-carboxamide.

Example 262 10 N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -3- (7- f luoro-2,2-dimethyl-1,3-benzodioxol-5-yl) -4- phenyl-pyrazoline-1-carboxamide.

Example 263 N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -3- (7-di-151 fluoromethoxy-2,2-dimethyl-1,3-benzodioxol-5-yl) -4 - phenylpyrazoline-1-carboxamide.

Example 264 N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4-fluoro-phenyl) -4- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl ) -20 pyrazoline-1-carboxamide.

Example 265 N- (-2,2-dif luoro-1,3-benzodioxol-5-yl) -3- (4-fluoro-phenyl) -4- (2,3-dihydro-2,2,3,3 -tetrafluorobenzofuran- 5- yl) pyrazoline-1-carboxamide.

Example 266 N-Z “3- (4-trifluoromethylphenoxy) pheny1J-3,4-bi s- (4-fluorophenyl) pyrazoline-1-carboxamide.

Example 267; N- £ T3- (4-fluorophenoxy) phenyl ^ -3,4 ^ 15- (4-fluorophen!! Nyl) pyrazoline-1-carboxamide.

Example 268 N- ^ T3- (4-difluoromethoxyphenoxy) phenyl ^ -3,4-bis- (4-fluorophenyl) pyrazoline-1-carboxamide.

45

Example 269 3,4-bis- (4-fluorophenyl) -N - / “3- (4-methylphenoxy) phe-nyl. 7-pyrazoline-1-carboxamide.

Example 270 5 3- (7-chloromethyl-2,2-dimethyl-1,3-benzodioxol-5-yl).

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

Example 271 N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4- / 7 7- (1-methylethyl) -2,2-dimethyl-1,3-benzodioxol-5-yl 10 3-phenylpyrazoline-1-carboxamide.

Example 272 N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4- (7-methoxy-2,2-dimethyl-1,3-benzodioxdL-5-yl) -3-phenyl- pyrazoline-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-pheny1 -pyrazoline-1-carboxamide.

; Example 274 20 N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4- (7-di-fluorome thoxy-2,2-dimé thy1-1,3-benzodioxol-5-y1) -3-phenylpyrazoline-1-carboxamide.

Example 275 4- (7-chloromethyl-2,2,2-dimethyl-1,3-benzodioxol-5-yl) -25 3-N-bis- (4-fluorophenyl) pyrazoline-1-carboxamide.

In the normal use of the insecticide pyrazolines of the present invention, the pyrazolines are usually not used without mixing or dilution, but are usually used in an appropriately formulated composition compatible with the application process and comprising a pyrazoline in an insecticide effective amount. Like most pesticidal agents, the pyrazolines of the present invention can be mixed with the carriers 1 w - - - _ ^ 46 and the agriculturally acceptable surfactants normally used to facilitate the dispersion of the active ingredients while admitting the fact that the formulation and the mode of application of an insecticide can influence the activity of the material. The pyrazolines of the present invention can be applied, for example, in the form of sprays, dust or granules on the surface where it is desired to carry out a pesicide control, the type of application obviously varying depending on the pest and the environment. Thus, the pyrazolines of the present invention can be formulated in the form of granules in large particles, in the form of powdery dust, in the form of wettable powders, in the form of emulsifiable concentrates, in the form of solutions and the like.

The granules may comprise porous or non-porous particles such as, for example, sand or attapulgite clay serving as supports for the pyrazolines. The particles of the granules are relatively large and specifically have a diameter of about 400-2,500 microns. The particles are impregnated with pyrazoline in solution or they are coated with this pyrazoline sometimes using an adhesive. The granules generally contain 0.05-10%, preferably 0.5-5% of active ingredient as an insecticide effective amount.

30 Dusts are mixtures of pyra zolines with finely divided solids such as talc, attapulgite clay, kieselguhr, pyrophyllite, chalk, diatomaceous earth, calcium phosphates, calcium carbonates and ^ __ J35 of magnesium, sulfur, flours, as well as other very solid organic and inorganic β * acting as carriers for the insecticide. These finely divided solids are in particles with an average granularity of less than about 50 microns. A specific dust formulation which is useful for insect control contains a part of pyrazoline such as 3- (4-chlorophenyl) -N- £ * 4- (4-chlorophenoxy) phenyl J-4 -phenylpyrazoline- l-carboxamide and 99 parts of talc. The pyrazolines of the present invention can be made into liquid concentrates by dissolution or emulsification in suitable liquids, as well as solid concentrates by mixing with talc, clays and other known solid 15 '* carriers used in the art. pesticide technology. Concentrates are compositions containing, as an insecticide effective amount, about 5-50% pyrazoline such as 3- (4-chlorophenyl) -N- (2,3-dihydro-2,2 -dimethylbenzo-20 furan-5-yl) -4-phenylpyrazoline-1-carboxamide and 95-50% of an inert material comprising wetting agents, emulsifiers and surface-active dispersants, however that even higher concentrations are active ingredient can be used mentally. The concentrates are diluted with water or other liquids to apply them practically in the form of sprays or with an additional solid in order to use them in the form of dust.

Among the specific carriers for solid concentrates (also known as wettable powders) are fuller's earth, clays, silicas, and other highly absorbent and easily impregnated inorganic diluents. . A solid concentrate formulation which is * * 48 useful for insect control, each contains 1.5 parts of sodium lignosulfonate and sodium lauryl sulfate as wetting agents, 25 parts of 3- (4-chlorophenyl) -N - (2,3-dihydro-2,2-5 dimethylbenzofuran-5-yl) -4- (4-chlorophenyl) pyrazoline-1-carboxamide and 72 parts of attapulgite clay.

Manufactured concentrates are useful for transporting the low melting point products of the present invention. These concentrates are prepared by melting the low melting solid products together with 1% or more of a solvent to obtain a concentrate which does not solidify upon cooling to the freezing point of the pure product or below.

15 ”Among useful liquid concentrates are emulsifiable concentrates which are homogeneous liquid or pasty compositions easily dispersed in water or other liquid carriers. They may consist entirely of pyrazoline with a liquid or solid emulsifier or they may also contain a liquid carrier such as xylene, heavy aromatic naphthas, isophorone and other relatively non-volatile organic solvents. For application, these concentrates are dispersed in water or other liquid carriers and are normally applied as sprays to the areas to be treated.

Among the specific surface active emulsifiers, dispersants and wetting agents used in pesticidal formulations are, for example, alkyl and alkyl aryl sulfates and sulfonates, as well as their sodium salts; alkylamide sulfonates, in particular fatty methyl taurides; 3.5 alkylaryl-polyether-alcohols, higher alcohols! "* 49 laughing sulfates, polyvinyl alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide adducts of these esters; as well as the adducts of ethylene oxide and long chain mercaptans.

Many other types of useful surfactants are commercially available. When used, the surfactant normally represents about 1-15% by weight of the insecticidal composition.

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

An insecticide-effective amount of pyrazoline in an insecticide composition which is diluted for application is normally in the range of from about 0.001% to about 8% by weight. Many variations of spray and dust compositions known in the art can be used by substituting the pyrazolines of the present invention in compositions known or evident in the art.

The insecticide compositions of the present invention can be formulated with other active ingredients, including other insecticides, nematocides, acaricides, fungicides, plant growth regulators, fertilizers, etc. When using the compositions for insect control, it suffices simply to apply pyrazoline in an insecticide-effective amount at the point where it is desired to carry out this control. This place can be, for example, the insects themselves, the plants on which the ins; Sects feed or insect habitat.

When the aforementioned location is soil, for example, soil in which agricultural crops are or will be planted, the active compound can be applied to and optionally incorporated into the soil. For most applications, an insecticide effective amount will be between about 10 75 and 4,000 g per hectare, preferably between 150 g and 3,000 g per hectare.

The insecticidal activity of pyrazolines, the preparation of which is described above, was evaluated as follows: The compounds were tested in applications on leaves with different concentrations: concentrations in aqueous solutions containing 10% acetone and 0.25% octyl-phenoxypolyethoxy-ethanol. Pinto 20 bean plants were placed on a rotary table rotating in a hood and the test solutions were applied with a sprayer. Test solutions were applied to the upper and lower surfaces of the plant leaves until dripping. Then the plants were allowed to dry and cut at the base of the stem. Each rod was introduced into the water through a paper bowl. Ten individuals of the appropriate insect species were placed in each bowl and each was covered.

30 For the evaluation, Spodoptera eridania, Epilachna varivestis, Spodoptera exigua and Trichoplu-sia ni were used. After 4 days at 26 ° C and 50% relative humidity, the mortality was read. The results of the tests are shown in Table 35 below. Insect mortality was general- ”? 51 less when the test readings were taken more prematurely.

A number of the pyrazolines were also active against Diabrotica undecimpunctata 5 howardi Barber when applied to the soil and those tested were also very effective on Leptinotara decemlineata Say.

BOARD

-Evaluation on sheets 10 Compound Application Insects (mortality,%) _ (parts by MBB SAW BAW CL _million) _ 1 500 100 100 2 500 100 100 15 3 500 100 100 4 500 100 100: 5 500 100 87 100 6 500 70 65 90 7 500 100 50 90 20 8 500 100 85 9 500 90 70 10 500 100 35 11 500 85 15 '12 500 100 100 25 13 500 93 50 90 14 500 100 100 15 500 100 90 16 500 100 17 500 100 35 30 18 500 90 55 19 500 100 100 20 500 80 40 21 500 70 15 22 500 100 100 35! v 52 TABLE (continued)

Evaluation on leaves Compound Application Insects (mortality,%).

(parts by MBB SAW BAW CL

5 _ million) _ 23,500 40 30 24 250 95 100 25,500 30 75 26. 500 80 65 10 27 500 75 95 28 500 95 90 29 500 10 90 30 500 5 64 60 31 500 5 65 70 15 32 500 100 50 33 500 100 80 - 34 500 10 75 35 500 100 100 36 8 100 98 45 90 20 37 32 98 98 97 100 38 500 95 80 39 500 100 25 40 500 100 100 '41 128 95 70 25 42 128 95 100 43 500 100 100 44 500 100 100 45 32 100 100 100 100 46 500 30 40 30 47 500 5 10 48 8 100 100 100 95 49 500 100 100 50 500 100 100 51 100 40 60 35 52 500 100 95? 53 4 TABLE (continued)

Evaluation on leaves Compound Application Insects (mortality,%)

(parts by MBB SAW BAW CL

5. _million) _ 53 500 100 10 54 500 100 85 55 500 100 80 56. 500 100 100 10 57 250 100 100 58 500 100 40 59 500 100 100 60 200 100 60 61 32 45 100 55 90 15 '' 62 500 95 95 63 500 100 95: 64 500 100 100 65 500 100 100 66 500 100 100 20 67 500 85 95 68 500 100 0 69 8 100 60 5 100 70 500 100 100 71 200 60 10 25 72 200 100 30 73 500 100 90 74 500 100 80 75 200 100 45 76 200 95 100 30 '77 500 80 200 0 95 78 500 90 55 79 200 95 60 80 500 100 100 35 81 250 100 100 * 54 TABLE (continued) 'Evaluation on sheets

Insect Application Compound (mortality,%) (parts per MBB SAW BAW CL 5 _million) _ 82 128 100 90 83 250 85 100 84 100 100 90 85 200 100 100 10 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 15 '' 91 32 100 100 100 100 92 500 100 100 93 500 100 100 94 500 100 100 95 200 100 90 20 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 25 101 1,000 100 100 102 128 100 100 103 16 90 95 15 100 105 16 100 100 | 106 256 100 70: 30 107 1,000 45 0! 108 1,000 100 75! ! 109 1,000 0 0 I = 110 1,000 70 0 111 1,000 0 0 I 35 112 1,000 100 90 1 '- —- 55 TABLE (continued)

Evaluation on leaves Compound Application Insects (mortality,%) (parts per

5 million) _MBB SAW BAW CL

113 1,000 100 10 114 1,000 100 30 115 1,000 100 15 116 500 100 100 10 117 500 55 0 118 500 100 100 119 500 100 95 120 500 100 100 121 500 95 100 15 '122 64 100 100 123 64 15 0 124 64 100 100 125 64 '100 100 MBB = Epilachna varivestis 20 SAW = Spodoptera eridania BAW = Spodoptera exigua CL = Trichoplusia ni.

/ m L-

Claims (32)

56 "1. Pyrazoline insecticide, characterized in that it corresponds to the formula: ^ N ^ I_ / Rn yjr1" "N ^ Ni 2. Compound according to claim 1, characterized in that W represents oxygen. 3. Compound according to claim 1, characterized in that R ′ ^ represents a halogen atom or a lower haloalkoxy group. 4. Compound according to claim 1, characterized in that R 'represents a substituent 4. D 5 NL / Rn W ^ Rc in which 10 corresponds to the formula: 15 in which R '^ is chosen from a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkoxy group , a lower alkynyl-oxy group and a lower haloalkyl group; or 20 where X represents a bridge of formula: ^ ° - <CR, AAR, AB) a- ° a 'J where a is equal to 1-3, a' is equal to 0 or 1, a + a 'is 30 equal to at least 2, but not greater than 3, R'aa and r'ab son ^ chosen independently from each other from a hydrogen atom, a halogen atom and an alkyl group lower, while R '^ is selected from a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkoxy group and a lower haloalkyl group; Rg is a substituent 4 or 5 of the formula: wherein R'g is selected from a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group and a lower haloalkyl group; or • ^ / ~ V ^ r'bc where Y is a bridge of formula: Zr ° - (CR, BAR, BB) b- ° b · ^ ί 20! where b is equal to 1-3, b 'is equal to 0 or! 1. b + b 'is equal to at least 2, but is not greater than 3, R'g ^ and R'gg are chosen independently of one another from a hydrogen atom, a 25 d atom halogen and a lower alkyl group, while R'bc is selected from a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkoxy group and a lower haloalkyl group; 30. responds to the formula: f! T / i ^! - Z * f. ¥ 64 's in which R ^ is chosen from a hydrogen atom and a lower alkyl group; Rg is selected from a lower alkyl group, a halogen atom, a lower alkoxy group, a lower haloalkoxy group, a lower haloalkyl group, a cyano group, a nitro group, an -NRpRç group, where Rp and RG each independently represents a lower alkyl group, as well as a group -S0 Ru n H where Rg represents a lower alkyl group and n is 15 'equal to 0-2; or 20 where Z represents a bridge of formula: r ° - (c r'car'cb> c- ° c '^ 25 in which c is equal to 1-3, c' is equal to 0 or 1, c + c 'is equal to at least 2, but is not greater than 3, R'A and R'pn are chosen independently of one another from a hydrogen atom, a halogen atom and an alkyl group lower, with the proviso that R '^ and R' ^ g do not both represent a hydrogen atom when c is equal to 1 and that c 'is equal to 1, while R' __ is chosen from an atom hydrogen, a halogen atom, a lower alkyl group, a lower alkoxy group, a jr 35 lower haloalkoxy group and a haloalkyl group; '65 ί i!: lower; i Rn represents a hydrogen atom or a group lower alkyl; and V and W each independently represent one of; 5. the other an oxygen atom or a sulfur atom, 5. Compound according to claim 1, characterized. in that Rg responds to the formula: 6. A compound according to claim 5, characterized in that R'ß represents a halogen atom. 7. A compound according to claim 1, characterized in that R ^, corresponds to the formula: re or is chosen from the 2,3-dihydro-2,2-dimethylbenzofuran-5-yl, 2,3- groups dihydro-2,2,3,3-tetra-fluorobenzofuran-5-yl, 2,3-dihydro-2,2,3,3-tetra-fluorobenzofuran-6-yle, 2,2-difluoro-1,3 -benzodioxol-5-yl and 2,2-dimethyl-1,3-benzodioxol-5-yl. 8. Compound according to claim 1, characterized in that corresponds to the formula: 30 (θ) ~ ϋ - (ô) - re 9. Compound according to claim 8, characterized in that R_ represents a halo-lower alkoxy group. 60 N 10. 3- (4-Difluoromethoxypheny1) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazo-line-1-carboxamide which is a compound according to claim 1. 10. KC in which Ra corresponds to the formula:: where R'a is chosen from a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkoxy group, a lower alkynyl-oxy group and lower haloalkyl group; or where X is a bridge of formula: Æ- (CR, AAR Va-V J 30 where a is equal to 1-3, a 'is equal to 0 or 1, a + a' is equal to at least 2; but not greater than 3, R'ab are chosen independently of one another from a hydrogen atom, a halogen atom and a lower alkyl group, while R'Aq is chosen from a hydrogen atom , a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkoxy group and a halo-lower alkyl group; Rg is a substituent 4 or 5 of the formula: in which R'g is chosen from an atom of hydrogen, a halogen atom, a lower alkyl group, a lower alkoxy group and a lower haloalkyl group; or: "" C "| where Y is a bridge of formula: 20 rtMCR'BARWb-'W where b is equal to 1-3, b 'is equal to 0 or 1, b + b' is equal to at least 2, but not greater than 3, R 'and dA are chosen independently of one another i JdJd I 25 from a hydrogen atom, a halogen atom and a group lower alkyl, while R '_ is chosen rSL>. if from a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkoxy group and a lower haloalkyl group; Rç corresponds to the formula: * 58 in which RD is chosen from a hydrogen atom and a lower alkyl group; is selected from a lower alkyl group, a halogen atom, a lower alkoxy group, a lower haloalkoxy group, a lower haloalkyl group, a cyano group, a nitro group, a group -NRpRç where Rp. and Rq are chosen independently of one another from a lower alkyl group, as well as a group -SOnRH where.Rh represents a lower alkyl group 10 and n is equal to 0-2; or WT "- 15 'where Z represents a bridge of formula: ^ - <CR, aAR, CB> o- ° c ^ 20 in which c is equal to 1-3, c' is equal to 0 or 1, c + it is equal to at least 2, but is not greater than 3, R'ga and R'çg are chosen independently of one another from a hydrogen atom, a drhalogen atom and an alkyl group lower, with the proviso that R'CA and R'CB do not both represent a hydrogen atom when c is equal to 1 and that c 'is equal to 1, while R'qq is chosen from an atom d hydrogen, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkoxy group and a lower haloalkyl group; R 1 represents a hydrogen atom or a lower alkyl group; and V and W each represent independently of one another an oxygen atom or a sulfur atom. 11. 3,4-bis- (4-fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) pyrazoline-1-carboxamide which is a compound according to claim 1. 12. 3,4-bis- (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carboxamide which is a compound according to claim 1. 13. The N- (2,3-dihydro-2,2,3,3-tetrafluoro-benzofuran-5-yl) -3- (4-difluorome thoxypheny1) -4-pheny1-15 pyrazoline-1-carboxamide which is a compound according to claim 1. 14. N- (2,2-difluoro-1,3-benzodioxol-5-y1) -3- (4-difluoromethoxyphenyl) -N-methyl-4-phenyl-pyrazoline-1-carboxamide which is a compound according to 20 claim 1. 15. 3,4-bis- (4-chlorophenyl) -N- (2,2-dimethyl-1,3-benzodioxol-5-yl) pyrazoline-1-carboxa-mide which is a compound according to claim 1. 16. N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3,4-bis- (4-fluorophenyl) pyrazoline-1-carboxamide which is a compound according to claim 1. 17. 3- (4-chlorophenyl) -N- (2,2-difluoro- 1,3-benzodioxol-5-y1) -4- (4-fluorophenyl) pyrazoline- 1-carboxamide which is a compound according to the claims - 30 tion 1. 18. 3- (4-difluoromethoxypheny1) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -N-methyl-4-phenylpyrazoline-1-carboxamide which is a compound according to claim 1. w / i * 61 19. 3- (4-chloropheny1) -N- / 74- (4-difluo-romethoxyphenoxy) phenylJ7-4-phenylpyrazoline-1-carbo-xamide which is a compound according to claim 1. 20. N- ^ 4- (4-difluoromethoxyphenoxy) - phenyl 4-dif luoromethoxyphenyl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide which is a compound according to claim 1. 21. 3- (4-difluoromethoxyphenyl) -4- (4-fluoropheny1) -N- (2,3-dihydro-2,2,3,3-té trafluoro-benzofuran-5-yl) pyrazoline-l- carboxamide which is a compound according to claim 1. 22. The 3- (4-difluoromethoxyphenyl) -4- (4-fluoropheny1) -N- (2,3-dihydro-2,2,3,3-tetrafluoro-benzofuran-6-yl) pyrazoline-1-carboxamide is a compound according to claim 1. 23. 4- (4-chloropheny1) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -3-phenylpyrazoline-1-carboxamide which is a compound according to claim 1. 24. 3- (4-chloropheny1) -4- (4-fluoro pheny 1) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -pyrazoline-1-carboxamide which is a compound according to claim 1. R 1 each represents independently of each other a lower alkyl group, as well as a group -S0nR 1 where Rh represents a lower alkyl group and n is equal to 0-2; or ^ V — Z; / • 35 where Z represents a bridge of formula: /. ▼ 68 a in which c is equal to 1-3, c 'is equal to O or 1, c + c' is equal to at least 2, but is not greater than 5, R1 ^ and R1 ^ are chosen independently of one another from a hydrogen atom, a halogen atom and a lower alkyl group, with the proviso that R '^ and R' ^ g do not both represent a hydrogen atom when c is equal to 1 and 10 when c 'is equal to 1, while R'cc is chosen from a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkoxy group and a lower haloalkyl group; 15. represents a hydrogen atom or a lower alkyl group; and V and W each independently of one another represents an oxygen atom or a sulfur atom. 25. 3- (4-difluoromethoxyphenyl) -4- (4-fluoropheny1) -N- (2,3-dihydro-2,2-dimethylbenzofuran- 5-yl) pyrazoline-1-carboxamide which is a compound according to the claim 1. 26. · 4- (4-chloropheny1) -3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2-dimethylIbenzofuran 5-yl) pyrazoline-1-carboxamide which is a compound according to claim 1. 27. Insecticidal composition, characterized in that it contains, in a mixture with a support acceptable in agriculture and in an effective amount 35 from the insecticidal point of view, at least one pyrazoline "62 insecticide corresponding to the formula:‘ Vy "b y 28. Composition according to claim 27, characterized in that W represents an oxygen atom. 29. Composition according to claim 10 27, characterized in that R '^ represents a halogen atom or a lower haloalkoxy group. 30. Composition according to claim 27, characterized in that R ^ represents a substance killing 4. 31. A method for combating sects, characterized in that it consists in applying, to the place where it is desired to carry out this struggle and in an insecticide-effective amount, a pyrazoline of formula:: 20 ra \ _ _ ty ^ NL / R "26 /" V, W RC in which R ^ corresponds to the formula: "in which R'A is chosen from a hydrogen atom, a halogen atom , a lower alkyl group, a lower alkoxy group, a lower haloalkoxy group, a lower alkynyl-oxy group and a lower haloalkyl group; or where X represents a bridge of the formula: ° - (CR, AAR'AB> a- ° ai? Where a is equal to 1-3, a 'is equal to 0 or 1, a + a' is equal to at least 2, but is not greater at 3, R '^ and R'ab are chosen independently of one another from a hydrogen atom, a halogen atom and a lower alkyl group, while R'ac is chosen from a d atom hydrogen, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkoxy group and a lower haloalkyl group; Rg is a substituent 4 or 5 of the formula: wherein R'g is selected from a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group and a lower haloalkyl group; or 30 r'bc 7 35 i * 67 * J- in which Y represents a bridge of formula: £ -0- (CR'BAR'BB) b-0b, 7 in which b is equal to 1-3, b ' is equal to 0 or 5 1, b + b 'is equal to at least 2, but is not greater than 3, R'. and R 'are chosen independently of one another from a hydrogen atom, a halogen atom and a lower alkyl group, while R'gç is chosen from a hydrogen atom, a 10 atom halogen, lower alkyl, lower alkoxy, lower haloalkoxy and lower haloalkyl; R c corresponds to the formula: in which R ^ is chosen from a hydrogen atom and a lower alkyl group; R £ is chosen from a lower alkyl group, a halogen atom, a lower alkoxy group, a lower haloalkoxy group, a lower haloalkyl group, a cyano group, a nitro group, a group -NR-R ^ where R „and Γ U Γ 32. Process for the preparation of an insecticide pyrazoline 20, characterized in that a compound of formula: RC-N = C = W is reacted with a compound of formula: ra 25 "ΊΓV" "BH 30 and optionally subjected the product obtained when alkylated to obtain an insecticidal pyrazoline of formula: "/ i / * · V * 69% * RA> -cwc in which corresponds to the formula: in which R '^ is chosen from a hydrogen atom , 15 'a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkoxy group, a lower alkynyl-oxy group and a lower haloalkyl group; or 25 in which X represents a bridge of formula: £ ° - (CR'AARVa- ° a ': 7 in which a is equal to 1-3, a' is equal to 0 or 1, a + a 'is equal to at least 2, but not greater than 3, R '^ and R' ^ ß are chosen independently from one another from a hydrogen atom, a halogen atom and an alkyl group lower, while <R'Ac is ^ selected from a hydrogen atom, a halogen atom *, a lower alkyl group, a lower alkoxy group, a lower haloalkoxy group and / s * '70 ν 'rv a lower haloalkyl group; i Rg represents a substituent 4 or 5 of formula: = in which R'B is chosen from a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group and a lower haloalkyl group; or where Y represents a bridge of the formula: 3 £ ° - (CR, BARWb- ° b'7 20 in which b is equal to 1-3, b 'is equal to 0 or 1, b + b 'is equal to at least 2, but is not greater than 3, and R'gg are chosen independently initiate each other from a hydrogen atom, a halogen atom and a lower alkyl group, while R '„is selected from a hydrogen atom, a JUU halogen atom, a lower alkyl group, lower alkoxy group, lower haloalkoxy group and lower haloalkyl group; Rc corresponds to the formula: 30 35 '71 + t i -5 in which RD is chosen from a hydro- atom! gene and lower alkyl group; Rg is chosen from a lower alkyl group, a halogen atom, a lower alkoxy group, a halo-5 lower alkoxy group, a lower haloalkyl group, a cyano group, a nitro group, a group -NR „R„ Γ Lx where Rp, and Rq each independently represent a lower alkyl group, as well as a group -SC> nRH where Rg represents a lower alkyl group and n is 0-2; or WP 15 '' —.Z where Z represents a bridge of formula:; ^ o- (cr, car, cb) c- ° c · ^ '20 where c is equal to 1-3, c' is equal to 0 or 1, c + c 'is equal to at least 2, but n 'is not greater than 3, R'CA and R10B are chosen independently of one another from a hydrogen atom, a cT'halogen atom and a lower alkyl group, with the proviso that R'CA and R 'Cg do not both represent a hydrogen atom when c is equal to 1 and c' is equal to 1, while R'cc is chosen from a hydrogen atom, a halogen atom, an alkyl group lower, lower alkoxy, lower haloalkoxy and lower haloalkyl; R ^ represents a hydrogen atom or a lower alkyl group; and V and W each independently of one another represent an oxygen atom or a sulfur atom.