CS252497B2 - Insecticide and method of efficient substances production - Google Patents

Description

The invention relates to chemical agents affecting biological functions, in particular to novel insecticidally active pyrazoline derivatives, to a process for their preparation and to the necessary intermediates, to insecticidal compositions containing these pyrazolines and to their use for controlling insects.

Pyrazolines are five-membered ring-containing heterocyclic compounds with the following structure and number by ringing single atoms

H

It is known in the art of insecticides that certain 1-carbonyl compounds are effective. Thus, for example, the U.S. Pat. No. 4,174,393 discloses the insecticidal activity of 1-carbamoolpyrazolines bearing at the 3 and 4 positions of the pyrazone ring also phenyl phenyl.

The invention provides pyrhzouinl of formula I

in which

^p pose a ^b yte of ^the formula wherein represents hydrogen, fluorine or chlorine, mmthoxyskupinu, iifjooreethoxlskupinu, trijUuoreetUoxystupinu 2-řropinylu) xyskupinu or Trifu ^ Orlova, or R ¹ ^ e ^ ^b ytek camel of formula

R is a substituent at the 4 or 5 position of the formula wherein

R ** represents a hydrogen, fluorine or chlorine atom, a methyl group, a methyl group, a trifluoromethyl group or a fluoro-ethyloxyxurea 20 or R represents a radical of formula

represents the remainder of the formula

where

R represents a hydrogen atom or a methyl group,

R ³ is C 1 -C 4 alkyl, fluoro or chloro, C 1 -C 3 alkoxy, difluoromethoxy, trifluoromethyl, cyano, nitro or dimethylamino, or

R3 represents a radical of formula

where

Z is a bridge of formula [o- (CR ³¹ R ³² ) _c -O _c -J wherein c is a number from 1 to 2, c is a number from 0 or 1, where the sum of c + c ": is at least 2,

32

R and R are each independently hydrogen, fluorine or methyl, then R ³¹ and R ³² do not mean that when c is 1 and ^r is 1, both present hydrogen, is hydrogen or methyl and

In each case, W is, independently of one another, an oxygen or sulfur atom having a significant insecticidal activity.

From the above pyrazolinS.jsou for most applications, preferred compounds are those wherein ^{W BC} n ^d s ^t jiujn atom ^alkyl sl ^Cart ua Pa ^s especially ^{for those} HV ^{and HZ} c represents R ^{10 and} the substituent at the ^4-position, _{with the} 2 preferably chloro or fluoro, or difluoromethoxy. Those pyrazolines in which R represents with the 4-position at the 4-position are generally more effective than the corresponding 5-sulfated pyrazolines, and those compounds in which R represents a phenyl radical bearing a sub-20 _: 20 substituent R are of particular interest. In this context, it is preferred that R is in the 4 position, especially chlorine or fluorine.

When ^the UD regards slbst tlnnt ^with R ^3. odvozuií you are not jzajímavíS ^ ^^ with thrombin, are suitable ^EFFECTIVE variables ^alkyl acrylate of ^{b e} interpreted from those compounds which contain either a 2,3-ditydro dieethylSenzofuran-2,2-5-yl, 2,3-dihydro-2,2 2,3-dihydro-2,2-3-3-tetrafluorosulfonanillyl, 2,2-dihydro-1,3-benzodioxole-5-yl-2,2-dihydro-2,2,3-dihydro-2,2,3-dihydro-2,2,3-tetrahydro-sulfonate; A 1,3-benzodioxol-5-yloxy group, or a 4-methoxyphenyl group. In the latter case, it is preferable to condense the hydrogen atom and R ⁵ represents a substituent in the 4-position, in particular a difluoroethoxy group.

Pyrazines according to the invention having remarkable insecticidal activity include, for example, la.d.

3- (4-Difluoromethoxyphenyl) -N- (2,3-dihydro-2,2-dimethybenzenuron-n-yl) -4-phenylpyra-aoyl-1-carboyanil.il 3

3,4-bis- (4-elloreblyl) -N- (2,3-dihydro-2,2,33-tetriazolidin-4-yzrazazine-1 H -tarboxamide),

3,4-bis- (4-11 -orphenyl) -N- (2,3-dihydro-2,2-dimethylbenzenouuraz-1-yl) yyrazoline-tarpxamide,

N- (2,3-dihydro-2,2,3,3-tetrafluorobenoofuran-df) -3- (4-difluoromethoxyphenyl) -4-rehydrofuran-4-ylcarbonyl-amine (i,

N- (2,2-difluoro-1,3-benzenesol-d-df) d3- (4-difluoromethylbenzene) -N-methyl-4-phenylyrazazole-1-tarboxamide,

3,4-bis-4-chlorophenyl-N- (2,2-dimethyl-1,3-benzenesulfonyl-1-ylamino) -1-zirconamide,

N- (2,2-difluoro-1,3-benzoyl-5-di) -3,4-bis (4-fluorophenyl) yyzzolin-1-carboxyamide,

3- (4-chloroanilino) -N- (2,2-difluoro-1,3-benoxiooyl-d-df) -4- (4-fluoro-1H-azrazole-1-carboxamide),

3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2,3-trifluorobenzenoborane-b) -N- (11,1-a-4-enyl) pyrimidine ,

3- (4-Chloro-phenyl) -N- 4- (4-difluoromethoxy-brenoxy) -methyl-4-biphenyl-pyrazole-1-carboxylic acid

N- 4- (4-difluoromethoxyphenoxy) phenyl -3- (4-difluoromethoxyphenyl) -4- (4-difluoromethoxyphenyl) -4- (4-difluoromethoxyphenyl) -4- (4-difluoromethoxyphenyl) -4- (4-difluoromethoxyphenyls) -4- (4-difluoromethoxyphenyl) -4- ) -N- (2,3-dihydro-2,2,3,3-tetraljorrbenooeuran-5-) 1) pyrazolin-1-aaboxaamide,

3- (4-difluoromethoxyphenyl) -4- (4-eluorophenyl) -N- (2,3-dihidro-2,2,3-tetralorotenooruran-6-) -1) pyrazoline-1-caboyxamide,

4- (4-Chloro-phenyl) -N- (2,3-dihydro-2,2-dimethylamino-5-yl) -13-benzynyl-benzoyl-trichloride amide,

3- (4-Chloro-phenyl) -4- (4-dichloro-phenyl) -N- (2,3-dihydro-2,2-dimethyl-benzyl-furan-5-yl) -pyrazzoin-1-carboxamide,

3- (4-difluoromethoxyoxyphenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylphenol-5-ol) -5-yyrazine-taaboyxamide; and

4- (4-Chloro-phenyl) -3- (4-difluoromethyl-oxyphenyl) -N- (2,3-dihydro-2,1-dimethoxy) -1db (4-difluoro-5-di) -yrazoline-aaboyxamide.

The present invention provides an insecticidal composition which comprises an insecticidally effective amount of at least one of said pyrazoline derivatives in admixture with a conventional carrier.

In addition, the present invention provides a method of insect control comprising applying an insecticidally effective amount of at least one of the aforementioned yyrazoline derivatives to a particular site where the insect is to be killed,

In accordance with the invention, the above-mentioned pyrazoles can be prepared by reacting a flavored isocyanate or a subsequent reaction isothiocyanate with an appropriately substituted pyrazoline, according to the scheme:

The product is pyrazolines.

they can then be methylated in a known manner to give the corresponding N-methylated

Starting appropriately substituted pyrazolines are generally known. The necessary isocyanates and isithiocyanates can be prepared from the corresponding amines, many of which are commercially available. Other of these amines may be prepared by the methods described in the following examples, but are not intended to limit the scope of the invention in any way.

Example 1

3- (S-Chloro-phenyl) -N- ^[4 - ⁽⁴ -chlirfeiixy) feiyl ^j 44_finy ^of pyvaZi; ⁱⁱ nlj; ariovamid

A mixture of 10.9 g (0.077 mol) of 4-fluornltioeinzeil, 9.95 g (0.077 mol) of 4-chlirfeiill and 11.8 g (0.085 mol) of potassium ^ ШПаги dimeehhУsulfixidu in 175 ml in a nitrogen atmosphere for 2 days mícliání heated ^and to ⁷⁰ ° C.

water to a volume of 1 liter.

The reaction mixture thus formed was filtered ^P by cooling and diluted three times with 200 ml of ether and the ether extracts were then saturated aqueous sodium chloride solution, dried

The mixture 'was extracted with ^p CTI promysly first with water over anhydrous sodium sulfate and filtered. After evaporation filrrátu under reduced pressure afforded ^{13.5 g} of 4- (4 - chlirfeiliX ^{s) r} ii iobenzeit of te ^pl ol ^of melting point 67-70 ° C.

Hydrogenation of 13.5 g (0.054 mol) of 4- (4-chlorophenyl) sulfobenzene in 250 ml of tetrahydrifurvr in an amount of catalytic (0.15 g) of sulfur dioxide yielded 4- (4-chlorophenyl) aviiii in a quantitative yield.

To a stirred solution of 0.75 g (0.0034 mol) of 4- (4-chloro (4-chlorophenyl) aviliite in 25 ml of toluene) was added dropwise a solution of 0.43 ml (0.036 mol) of trihloromethylchloride in 20 ml of toluene. After the id ^ s ^^ ^{3 h,} the mixture Odin ^{y also} play at ^A 8 ⁵ ° C, ^P and ^K was cooled to te ^beta] -ol místnooti and solvent from ^ ii vacuo.

The residue is dissolved in 25 ml of diethyl ether, the solution is added dropwise to a stirred suspension of 1.0 g (0.0034 mol) of 3- (4-chlorophenyl) -4-phenylacetyl in diethyl ether, 3 drops of triethylamine are added and the mixture is stirred for two days at room temperature. After evaporating the solvent from the reaction mixture Zis ^m Ei ^{ka 0.92} g [3- (4-chlorophenyl) -N- [4- ^(4-chloro-l irfeiixy) phenyl ^iУ | -4-fei ^yloy rvzo ^II IL-karbixamidu of te ^ ot ^ ^otání

Mp 158-161 ° C.

Analysis: Calculated Found

66.92

% C, 66.06;% H, 4.22;

% C, 4.95% H.

NMR: 8.06 ppm (deochlorochirifirm).

Ϊ52497

Pi lad

3- (4-Chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-55-yl) -4-phenylpyrazoline-1-carboxamide

To 100.0 g (0.67 mole) _{2/3-dihydro-2,2-dimethylbenzofurar!} U maintaining the temperature at ^O C ^{was added} · It runs straight ^h em hotíiny after 1 ^h kapkác it towers chilled ^ n ^{d s} smeús 43 ml of concentrated ^1- nitric acid and 50 ml of concentrated sulfuric acid. After addition ee RTA CNI eměe stirred for 2.5 h ^p s ^p te ture 0 ° C ^for PA ee vyHje ^{d dy} in the ice and výslt e ^{d n, and} the mixture extracted with diethyl ee ^hy lttherem.

The extract was dried with anhydrous magnesium chloride and filtered. Evaporation of the filtrate under reduced pressure gave a black oil which was purified by chromatography on a column of silica gel using toluene / n-hexane (9: 1) as eluent to give 50.0 g of a solid. 2,3-dihydro-2,2-dimethyl-5-nitro-benzene.

Hydrogenation of 20.0 g (0.1 mol) of 2,3-dihydrf ^{diaeth-2,2-yl-5-ittfctenzffurniu} in 250 ml aathanofuvpřífomnofSi -atalyti-ééhf ϋο νί ^ (0.2 g) of plntičtééhf ee zís- Г 16.6 g

5-morphol-2,3-dihydro-2'-dimethyl-2-methane.

To a stirred solution of 0.56 g (0.0034 mml) of 5-naphine-2,3-dihydro-2,2,2-diaethylbenzofuran in 20 ml of toluene was added dropwise a solution of 0.43 ml (0.0036 mol) of trihloromethyl chloroformate in 20 ml. toluene. After the addition was complete, the reaction mixture was refluxed for 3 hours, then cooled to room temperature and the solvent was evaporated under reduced pressure.

The residue was dissolved in 25 ml of dry diethyl ether and the solution was added dropwise to the stirred mixture.

1.0 g (0.0034 mol) of 3- (4-chlorophenyl) -4-phenylpyridinoline and 3 drops of triethylamine in 25 ml of diethyl ether. The reaction mixture was stirred at room temperature for about 18 hours, whereupon a solid material was formed which was filtered.

The cake was suspended in ethanol and further filtered to give 0.47 g of 3- (4-chloro-4-N-1,3-dihydrof-2,2-diabutylbenzofluoro-5-yl) -4. -ftnylpyrnzflin-l-ol karfxaaaidu ^ lo ^ ^{TR 160} and the ^from L ⁶² ° C.

Analysis:

C, 70.00; H, 5.43.

found: 69.50% C, 3.36% H.

NMR: 9.00 ppm (ppm).

Other compounds of this group prepared in a similar manner are set forth in the following Examples. In some cases, the NMR speetra singlet corresponding to the proton of the = NH group, which is chant-n-tetstic for these compounds, is reported for the products produced. Unless otherwise indicated, this NMR spectrum was measured in deuttrochlfrofcrau (CDD11). The abbreviation DMSO-dg denotes perdeιlUerodfmaehh1ssUffxid.

Example 3

^3-f dtien ^- 1-N- (4: ^phenoxy phen ^{n y} l) p-l- ^yl razclii ^and TLR ^of xxaai ^d ^ o ^ th ^ fence ¹⁸⁴ to ¹⁸⁸ ° C.

NMR: 9.17 ppm (DMSO-dd).

Example 4

1 - [[4- (4-chlfrfeiXf ^χ) fee ^I1] - ^{3, 4-d} IFTIM ^{y y} razflin LP-l ^{-a Arf} Xaa ^ ^id of the PLO ≤ ^t ≤ ^r n ^e and ^{146 f}

Mp 149 ° C.

166

NMR: 8.83 ppm (DMSO-d ₆ ).

5

3- (4-Chlorophenyl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide, m.p.

NMR: 8.03 ppm.

6

N- (4-Phenoxyphenyl) -4-phennyl-3- (4-trifluoromethylphenyl) pyrazoline-1-carocamide, m.p. 188-190 ° C.

NMR: 8.10 ppm.

7

193

3,4-biphenyl-4- (fibroxyphenynyl) pbrbZ (ilin-α-roxbomadide, m.p. 189 DEG-C).

NMR: 8.20 ppm (CDCl 3 / DMSO-d 6). .

a d 8

3- (4-4-chlorophenyl) -N- (3-methyl-4-phenoxyphenyl) -4-phenylamino-1-aarookamide, m.p. 151-157 ° C.

temperature

NMR: 9.13 ppm (DMSO - d P Píkl ad 9

3- (řcídoofen ^) -N- 4- £ p ^ enyl ffluoiienooy ^ - ^ ^ tf nylpyrkzoMn-l-te kaibokamid the ^p counting Lote 153 KŽ 155 ° C.

NMR:

8.16 ppm

Rikli kd P 10 ³ - (CH ^{4 l} oo fn ^{f nl) N} - ^[4 - ⁽³ - ^fluoro enooy ^{f) f} fnyl] - ⁴ - ^phenyl yrkzol ^{P i n)} - ^L - Ar ^{to O d} mesh on te ^pl ol ^of melting point 173 KŽ 175 ° C.

NMR ! 9.33 ppm (MMO-d6).

Example 11

N- [4- (3-4-chlorophenoxy) phenyl] -4- (4-chlorophenyl) -4-phenylpyrrolidine-carboxylic acid, m.p. 169-174 ° C.

NMR: 9.30 ppm (DMMO-dd

He said to d 12

3- (4-chlorophenyl ⁿ⁾ -N- ^[4 - ^(4-fluoro eiooy ^{f) f fnyl]]} -4- NNY ^{f l i} d-pyrazol ^l -carboxylic ^{O into} immediate counting / 164 KŽ 167 ° C .

te ^p te ture ^{of pl} ot

NMR: 8.13 ppm.

Example 1 a <1 I 2

3- (4-Chlorophenyl) -N-1- 4- (4-trifluoromethylphenoxy) phenyl] -4-phenylpyrazoline-1-carboxamide, m.p. 161-164 ° C.

NMR: 8.03 ppn.

P g i 1 <i d 14

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

fence ti (hí 10 3 a NMR: 8. , 00 ppm. í к 1 and d 15 Dec

3,4-bis (4-chlorophenyl) -N- (3-methyl-4-phenoxyphenyl) pyrazoline-1-carboxamide, m.p. 188-190 ° C.

NMR: 9.23 ppm (DMSO-d6).

Example 16

3,4-bis) 4-chlorophenyl) -N-Q4- (2-fluorophenoxy) phenyl] pyrazoline-1-carboxamide, m.p. 160-162 ° C.

NMR: 8.10 ppm.

Example 17

3,4-bis (4-chlorophenyl) -N- [4- (3-fluorophenoxy) phenyl] pyrazoline-1-carboxamide, m.p. 144-146 ° C.

NMR: 9.20 ppm (DMSO-d6).

Example 18

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

NMR: 9.30 ppm (DMSO-d6).

Example 19

3,4-bis (4-chlorophenyl) -N- [4- (4-fluorophenoxy) phenyl] pyrazoline-1-carboxamide, m.p. 168-170 ° C.

NMR: 9.23 ppm (DMSO-d6).

Example 20

N- [4- (4-chlorophenoxy) phenyl] -3,4-bis (4-chlorophenyl) pyrazoline-1-carboxamide, m.p. 154-156 ° C.

NMR: 9.30 ppm (DMSO-d 6).

Example 21

3,4-bis (4-chlorophenyl) -N- [4- (4-trifluoromethylphenoxy) phenyl] pyrazoline-1-carboxamide, m.p. 191-194 ° C.

NMR: 9.30 ppm (DMSO-d6).

Example 22

3- (4-Chlorophenyl) -4-phenyl-N- (4-phenylthiophenyl) pyrazoline-1-carboxamide, m.p.

Mp 157-162 ° C.

NMR: 8.20 ppm.

Example 23

3,4- bis (4-chlorophenyl) -N- (4-phenylthiophenyl) pyrazolo-1-carboxamide, m.p. 169-171 ° C.

NMR: 8.20 ppm.

Example 24

3,5-bis (4-chlorophenyl) -N- (4-phenoxyphenyl) trans-amino] -1-carboam: m.p.

170 [deg.] C.

NMR: 8.30 ppm (CDCl ₃ / DMSO-d ₆ ).

Example 25

3- (4-chlorophenyl) -5- (4-trifluoromethylphenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide, m.p. 164-167 ° C.

NMR: 8.00 ppm.

Example 26

3,5-bis (4-chlorophenyl) -N- [4- (2-fluorophenoxy) phenyl] pyrazoline-1-carboxamide, m.p.

Mp 174-178 ° C.

NMR: 8.50 ppm.

Example 27

3,5-bis (4-chlorophenyl) -N- [4- (3-fluorophenoxy) phenyl] pyrazoline-1-carboxamide, m.p.

Mp 164-168 ° C.

NMR: 9.00 ppm (DMSO-d6).

Example 28

3,5-bis (4-chlorophenyl) -N- [4- (4-fluorophenoxy) phenyl] pyrazoline-1-carboxamide, m.p.

Mp 165-167 ° C.

NMR: 9.16 ppm (DMSO-d6).

Example 29

N- (4-H-chlorophenoxyphenyl) -1H-bis-Cd-chlorophenyl pyrazolinil-carboxamide, m.p. 142-144 ° C.

NMR: 9.20 ppm.

Example 30 ^3-f-Bishi cdfeteny ¹⁾ -N- ^£ 4- ^(4-tr i ^ ^f ^ et ^ LORM h ^y1f ylethoxy) ^phenoxy-y 1 ^y razclínil jp ^ te kteoxamid of ^p lot ^of point 155 ^to F . ' 158 ° C.

NMR: 8.43 ppm (CDCC ₃ / DMSO-d ₆ ).

EXAMPLE 31 ^{3 (4-chlorophenyl} ennl) ^ιΝ - £ 4-- ⁽⁴ - ^. Ίίlorrme ^t h ^y1f enooy) ^y en ⁿ LL-5-H-three. domett ^ly1f en ^y1) дотоШd ^ te ^p arboxamid of Mount Yōtei reading Ш to ¹⁴⁴ ° C.

NMR: 8.06 ppm.

Example 32

N1 [s- ^(s -chlorfeiob ^yl) phen l ^{l n -} 5- (4-Choro enyd ^{f d} 3 ^"(41d if ^l rormet ^h en ^yl oy ^{Y1) p and} i yrkzol ^11" -krroyamid of te ^p l .otě T ^and the ⁶⁶ to ⁷⁰ ° C.

NMR: δ, 60 ppm (CMSO-dg).

Example 33

5- (1,3-Renio-6-oxoyl-15dl) -3- (S-chlorophenyl) -N- (S-phenyloxyphenyl) pyrrolidine-1-hydroxamide, m.p. 125-128 ° C.

NMR: 8.36 ppm (CDCl 3 / DMSO-d 6).

Example 34

5- (1,3-benioOioxoУr5-yl) y1N1 ⁴ - (S-chlrrfeiory) Уenill13 "(S-chlrrfenyl) pyokzrlin-З к ^ ^ ГтУamid of ^p te ture T ^and the ¹⁷⁴ and ^{of 175} ° C.

NMR: 8.06 ppm.

EXAMPLE 35

N- (2,3-ddhysbdOo2,2-dimeehllbenioruroki1-yУ) 13-S-difenylpyrkzoli111 kor0yχamid counting a temperature of 143 ^and 139 ° C.

NMR: 7.96 ppm.

Example 36

3- (S-diflbormetloxyfenilУ -N- (2,3-d.ihydro-2,2 · 1dimeehylreniorurakn5-yl) -4-phenyl-гот11 у ^ - te aorbyamid of ^p lot ^of T ^and the ⁷⁵ and ⁸² ° C.

NMR: 7.96 ppm.

Amide Example 37 of melting (0) -3,4-bis (4ychlorfenyl) -N - (2,2-2,3yiihyiiro diiΠiehy1bbnioluran-5-1 l) pyrzzolin' 1-kzrboxtá ^nus 134 ^and 137 ° C. .

NMR: 7.93 ppm.

Examples of amides of ^t e ^pl of ^thee

3,5-bis (4-chlorfeny1) -N- (2,3-d: IHY ^ 2 ^^ (^ - 2,2-uranium-DNC ^ ^ 5 ^ yHpyyazolin -karboxtání 1 ^{75 F} 18G and C .

NMR: 8.86 d d

112

N - (1,4-benzoano-66-yl-3- (4-chlorophenyl) -4-phenylpyrazoline-1-aaroxoxamide, m.p. 115 DEG C.).

NMR: 7.96 ppm.

PIHO

N- (1,4'-benzolioxalin-6-yl) -3,4-bis (4-chlorophenyl) pyrrole-1-carboxmidide, m.p. 145 ° C. .

NMR: 7.96 ppm.

1 · k 1 and d 41 j 05

J53

3- (4-Chlorophenyl) -N- (4-phenoxyphenyl) -4-phenylphenylpyrazoline- [eta] < 4 &gt;'Oamid melting ^and from 110 ° C.

NMR: 10.30 ppm (DMSO - d _r).

Example 42

3,4-l-ni (4'-chlorophenyl) -1'-N (4-phenoxy-4'-thienyl) -4-arythiol-4-ol. - ^ ^ lio _<mi.io m.p. 151 DEG C.

NMR: 9.26 ppm (DMSO-d6).

Example 43

N- [4- ⁽⁴ -chlorřenoxy) ► ^{f] -3, 4-bis (4-chlorfei yl) py} rzoo ^L yn-L.-karboth ^L Aamod a lot ^{of p} te mp 179-183 ° C.

NMR: 9.10 ppm.

Example 44

3- (4-chlorophenyl) yn (2,3-dihydro-2,2-Lmeeř ^ ^ ^ hH ennoofran-5-yy) -L-L-fcnnlppyrzolln karbot.hioam ⁰ to ^t e ^pl of ^thee m.p. ⁹² to &gt; 5 ° C.

NMR: 10.12 ppm (D 2 SO 4).

and

5? 4 9 /

3, 4-1? [α]: (4α-uro: -1 / -1) -1- (1-hydroxy-2,2-dimethyl by hen-η-δ-yl) pyrazolin-1- carbothioumi d ('t (·, li'l ti ₍ .in i i 4 4, i. (.

NMR: 9.00 ppi? (DE:, (> - <

l · r ϊ k · Ι a d 4 6

N- (1,4-benzodioxa-C-yl) -3,9-bis-4-carbonyl ^; 83 DEG-85 DEG C. 1-carboxamide.

NMR: 9.3 _L- pr (DMU, alpha).

Example 4 7 ^- (4 ^- chlorophenyl or ^{f l y} one ^{1 - 3- (4-CR1} Fluc Li ^{Y? 1} en ^{1 yl)} -4- (4-Trifluoro luorett ^Yy -ooY ^e l ^y) of the tone ^^ razolin ^{- |} - ^- arluxanui 'a temperature between approximately ¹⁸³ to TA ^s] h ^- ° ^C.

NMR: 8.77 ppmi (CDCl 3 / Mei-R).

Example 48

N - (2-3-dihidro-2,2,3,3-tetramethylphenyl) -3-1,4-difluoromethoxyphen-11-l-4-piperazoline- ¹ -carboxainide

15.0 g (0.086 mol) of 2-chloro-4-nitrophenol, 11.9 g (0.086 mol) of potassium carbonate, 1.5 g (0.02 mol) of propanediol, 33.7 g (0) 13 mol) of 1,2-dibromo-thiophthalic acid and 115 ml of N, N-dimethylamino standard _; IDF, pressure vessel with a septum Vv and the mixture was stir ^for 48 hours at rt ^{t h} e ^{pl of} 50 ° C.

After cooling to a temperature of one minute, the pressure vessel was opened and the contents were poured into a separatory funnel. Next, about 200 mL of 2N sodium hydroxide solution was added to the separatory funnel, and the resulting mixture was extracted four times with 300 mL of diethyl ether each time.

The extracts were combined and washed twice with 100 ml of 2N sodium hydroxide solution each time. The washed extract was dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated under reduced pressure to give an oily residue. The above reaction was repeated three more times.

The oily residues from these four experiments were combined and purified by chromatography on a silica gel column using n-hepotin / toluene (95: 5) as eluent. 57.6 g of oily 3-chloo-4- (2-bromo-1,1,2,2-tetrahydro-oxo-oxyl) -niroobenzene are obtained.

10.0 g (0.028 mol) of 3-chloro-4- (2-bromo-, Ι-β-β-ω-ω-ω-oxo) nitoobenzene, 9.0 g (0.14 mol) of powdered powder are introduced into a pressure vessel. copper (200 meeh), 0.45 g (0.0028 mol) of 2,2 '^^ ^ γΠάγ and 40 ml drmπeh ^y lsull: oordf'

Tlatová utensil and ^b is closed and the re-mixture 2 FRUs throw stirred ^{1 s t} tp ¹ about ^{the 190} to ¹⁹⁵ ° C. After cooling to room temperature, the pressure vessel was opened and the contents were poured into a separatory funnel to which about 200 mL of 2N hydrochloric acid solution was added. The resulting mixture was extracted three times with 150 ml of 150 ml each.

The extracts were combined and washed successively with 200 ml of 2N hydrochloric acid solution, 200 ml of saturated aqueous sodium chloride solution and 200 ml of 2N sodium hydroxide solution. The washed extract was dried over anhydrous magnesium sulfate and filtered.

"in

The solvent was evaporated under reduced pressure to give an oily residue. From above, the oily remnants of seven of these attempts will be silicified.

The reaction is repeated six more times. it is subjected to chromium (III) columnar yellow oily material. which can be ripped in 125 ml for 18 hours in the freezer. By filtering the precipitate off with toluene, methylcyclohexane is obtained and a solution of the rough crystals yields 20.7 g of 2,2,3,3-tetrafluoro-5-aitzobeazzfuraau. The filtrate was evaporated at ambient pressure and the oily residue was subjected to suction. iesSί] tii-BN for gust pressure to be zíbká ^^ dl 3.0 ^g of ^t ^ e duct ^{ol ee} Boiling of ⁷⁵ ° C ^{/ 27} mbar.

By hydrogenation of 2.15 g (0.011 mol) of 2,2,3,3-tetrafluoro-5-air-benzene in 150 ml of methanol in the presence of catalytic mannose! (0.25 g) of oxide is pure 2.15 g of 5-amino-1,2,3,3-tetralbenzobenzofuran.

A solution of 0.75 g was added dropwise to a stirred solution of the gene in toluene (8.0 ml of a 20% solution).

After the addition was added and the solvent was (0.0036 mol) of 5-amino-2,2,3,3-tetrafluorobenzofuran at 109m for 2 hours, it was heated to reflux for 2 hours, then evaporated under reduced pressure.

1 of toluene, cooled BE BE added to three drops treehh ^y taíiau 100 ml

The residue was dissolved in 15 ml of diethyl ether and stirred (0.0036 mol) of 3- (4-difluoromethoxyphenyl) -4-phenylpyrrolidine and the mixture was heated to reflux for 1 hour under stirring.

of a solution of 1.04 g of diethyl ether. After the condenser, after the addition is complete, the reaction is cooled to room temperature and evaporated under reduced pressure and

Zífek-á. be 0.99 g of N- (2,3-dihydro-2,2,3,3-tetrafluoromethyl-4-phenyylpyrazulin-ketaxamine), m.p. 155-159 &apos;

The solvent solid residue was recrystallized from ethanol.

5 --—) -3- (4-difluoromethylphenyl) Analysis: calculated

% C, 58.58;% H, 3.29;

57.81% C, 3.75% H.

NMR: 8.16

OOm.

3,4-bis (4-chlorophenyl) -N- (2,2-difluorobenzyl):

o1 ~ 5-yl) oyrazzlin-kka40oxamie odro? · ol. i. /. ' Solution treated with 1.18 g (0.0068 mol) of 5-darkness (? -2,2-d; fluoro) oenz.i 0 > uosa.ným in literature, in 80 ml eetrahydrzfuranš be added dropwise to 24 ml Luen-cooled at ^{5 and 10} ° C.

After the addition was complete, the mixture was stirred at 2 ° C for 1 hour and then at reflux for 2 hours. The solvent was evaporated under reduced pressure to give 1.4 g of a liquid residue. 0.68 g of this residue is slowly added to a stirred solution of 0.93 g (0.0032 mol)

3.4-4is (4-chlorophenyl) pyrazzium and three drops of erythhylammonium in 20 ml of diethyl ether.

After the addition was complete, the mixture was stirred at room temperature for about 18 hours, and the filtrate was filtered off and the filtrate was evaporated under reduced purification by silica gel column chromatography, leaving off the usual acetate as eluent.

low pressure. The remainder of the residue was α-heoethanol and ethyl. Zinc is 1.3 g of 3,4-b4b (4-chlorophenyl) -N- (2,2-difluoro-3-4-benzazinyl-5-yl) pyrazolium-1-carboxamide of the title compound. ^ ^f = ¹⁵⁰ and ¹⁵⁵ ° C.

Analysis:

calculated: 56.34% C, 3.08% B;

Found: C, 57.16; C, 2.89.

NMR: 8.10 ppm.

In a similar manner, the compounds of the following Examples were prepared.

Example 50

N- (2,2-difluoro-1,3'-benízOUoooO-5-yl) -3 - (4-ciif luormeťhoxyfeny 1) -4-fenylpyaaZGl ίη-ΐ-ΐ ^ τ ΐ »· ^AMI on te ^p Lot ^of mp ^{13 5-138} ° C.

NMR: 8.10 ppm.

Example 51

3- (- fluorophenyl) - N - (- phenolylbenzyl) -4-pyrazole-1-carboxamide, m.p. 187-191 ° C.

NMR: 8.10 ppm,

Example 52

3- (trifluoromethoxyphenyl) -N- (- phenoxyphenyl) -4-phenylpyrazoline-C-caroxamine, m.p. 139-144 ° C.

NMR: 8.10 ppm.

Example 53

3- (4-Chlorophenyl) -N- £ 4- (4-chlorophenoxy) ffi ^y L '] ^y lp --- phen ^yl-C razolin karOyχamiU counting a temperature of 174 ¹⁷⁰ ° C.

NMR: 8.10 ppm.

Example 54 ³ (-CH ^{4 h} or ^f fny ^{f) - £} N- 4- ^(4-nitro fnoyy ^{f) f fnyl]} - ^4c - ^{f y} en lp razolin ^{y l} l- ^and r ⁰ · УaamiU mp 187 to 189 ° C.

NMR: 8.30 ppm.

EXAMPLE 1 ad 55 _ ^{3 (4-chlorophenyl yl)} -N ⁴⁴ "H metěoyje noxylfeejj ^ NJ ^ -phenyl-i-razolin aarbyxamid · m.p. 159-160 ° C.

NMR: 8.07 ppm.

Example 56

3- H-chlorfenj) -N- £ 4- ^{(4 L} c ^{in the} IF oormft ^h oxyfennx ^s) fee ^{IF] -} -ffn ^ylpy IXzo ^{if χ} n ^l l- r ^{0 e} ot ^even УXím pl ^of 181 to thee Counting 184 ° C.

NMR: 8.07 ppm.

Example 57 melting point

N- [4- (4-chlorophenoxy) phenyl] -3- (4-trifluoromethyl unnrnet ^{of the e} oxy) -4- NNY ^{p e n} n pyrazol-Lakar ^of oxamide 132 XZ 134 ° C.

NMR:

8.16 ppm.

said ad

N- [4- (4-Chloro-phenoxy) -phenyl] -444-phenyl-4- 4- (2-propynyloxy) -phenyl] -pyrazoline-1-carboxylate x 164 ° C.

O

P

te ^p lot ^of thaw 160 NMR: 8.13 ppm he said. ad 59

. (1,3-rerlio0ioool-L-Lp) of lN- (44fenoxyfeniP) l4lfenylpyrrzolin L-rar0oramid melting Subtraction 220 ^x 223 ° C.

NMR: 8.06 ppm.

said x d 60

155

4- (4-chlorophenyl) -N- (4-phenooyphenyl) -3-phenylpyrrzolin-1-oloramide, m.p.

NMR: 8.16 ppm.

r d 61

198

3,4-Ris (4-fluorophenyl) -N- (1-phenoxyphenyl) pyrazolino-carbo-amide, m.p.

NMR: 8.16 ppm.

said 62

182 t ^{N p} i ^ - ^ ^r ^ loríenoo e ^ ⁿ ^ ^{pl] 'i3 iri} 4 ^K-1 chlonenyl ot ot ^ e ^ ^{pl of} T ^and the XZ 186 ° C.

NMR: 8.10 ppm.

IKL xd 63 ³ .4- ^RI (4-c ^h LORF en ^yl) -N- [4- (4-mehhoo ^{yl-phenoxy) -phenyl-l} ^ rrzolin ^ rr ^ xamid

NMR: 8.20 ppm.

said 64

3- (4-these-ENN)) -4- (4flforfenyl) -N- (4ffnnooyrfnyl) ρyrrzolin-íxnrboxémid temperature of 178 ^x counting from 179 ° C.

NMR: 8.10 ppm.

5 2 4 9

P i * Í к .1 <. н (-5

Μ-, 4- (4-chlorophenyl) phenyl; -3- (4-chlorophenyl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide

At the temperature Mp 143-345 ° C. NMR: 8.03 ppm. Example 1 d 66 -

3- (4-Chlorophenyl) -4- (4-methylphenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide, m.p.

Mp 165-168 ° C.

NMR: 8.10 ppm.

Example 67

N- (4- (4-chlorophenoxy) phenyl) -3- (4-chlorophenyl) -4- (4-methoxyphenyl) pyrazoline-1-carboxamide, m.p. 169-173 ° C.

NMR: 8.07 ppm.

Example 68

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

NMR: 8.17 ppm.

Example 69

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

NMR: 8.10 ppm.

Example 1 a d 70

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

NMR: 9-10 ppm

Example 71

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

NMR: 9.13 ppm.

Example 72

4- (4-chlorophenyl) -N- (4-phenoxyphenyl) -3-phenylpyrazoline-1-thiocarboxamido m.p.

Mp 131-133 ° C.

NMR: 9.16 ppm.

said a d 73

190

N - ^ - U ^ cdoi enXtdoHeoyl] ^{l3, 4-} d ^f lpyrkZol phen ^{y y} n ^- - ⁰ Уkar ^to Ar ^and the temperature T in ° C ^and OI.

¹⁸⁶ až

NMR: 8.20 ppm.

Example 74 ³ ~ (4-ch ⁰ or ^ph en ^oy ) lN ·· ^([4 - ( ⁴ lC ⁰ loo ^e eyylt ⁰ io) ^e ey ^y lг ^lfC Уly ^iyo kazol ^y - · l ^- -carbùcarid o ta 178 mp 181 ° C.

temperature

NMR: 8.23. ppm.

Example 75

3- (4-difIoormet0oyyfeoyl) -4-N-feoyl -fenyltOiofeof 1) ^{p-Y-L-rkzolin} karOyχamid. mp 135-140 ° C.

temperature

NMR: 8.13 ppm.

Example 76

3,4-bis (4-chloro-phenoxy) -N- [4- (4-phenoxyphenoxy) phenoxy] pyrrolidinyl-1- (-4-) at a temperature of between 171 ^and 175 Deň: 32 ° C.

NMR: 8.20 ppm.

Example 77

3,4-ris (4-cycloofeoyl (-N-Q4- (4-cycloofeoylthio) phyl) cyclo-choline-1 H -carbeamide, m.p. 151-156 ° C.

NMR: 8.13 ppm.

and d 78

135

3,4-Iris ^{(4-chlorophenyl} eoyl) ^- N ^{- [4- (3} -c ⁰ lorfeooo ^{y) f} eoy? Q ^ razoliy-l-Korn. Layiid of ^t ^ e ^p lo ^of téoí. ^to 140 ° C.

NMR: 9.20 ppm (CCMSO-d 6).

and d 79

192

3- (4-Methoxyphenyl) -N- (4-phenooyphenyl) -4-phenylpyrazoline-1-caroxamide, m.p. . '

NMR: 8.46 ppm (CDCl 3 / DMOO-R).

and d 80

3 - [% - (2-prypin ^y lox ^y) FeO ^yl] LNL (4-feyoУ ^y FeO ^y f) (- · 4lfeoylpyokzolУo -l-korbyxarid táoí temperature of 121-126 ° C.

NMR: 8.10 ppm.

and

Example 81

3- (4-chlorophenyl) -N- (2,3-dihydrobenzofuran-55-yl) -4-phenylpyrazolinilecarboxamide, m.p. 155-158 ° C.

NMR: 7.93 ppm.

Example 82

3- (4-Difluoromethoxyleeyl) -N- (2,3-dilydrobeeyoburanyl) 54-5-phenylpyrnoolinyl-naphthalide.

NMR: 7.93 ppm.

Example 83

3, 4-b (454-cbУurneyy -) - N- (2,3 · 5dilydrorennoburann5-yl) pyrnoblnn15-nrr0 <? Xamid a temperature T ^y d 214-216 ° C.

NMR: 7.93 ppm.

Example 84

3- (4-fluorfeyy У) -Ы- (2, ^I-3 dilldro-, dimethllЬenzoburrnn5 2-yl) -4-feyylpyrnooУiy5-1 - nrrbУ5 amide of ^p te lo tW ^{I 156 Z 16} and 0 ° C.

NMR: 7.93 ppm.

Example 85

3- (4-methloyУueyl) -N- (2-S-dilldro, dimeetilbrenoforan 2-n-51) --- fenyУppyanolly-l-amide of knrroy5 te ^pl OTE mp ^164-169 ° C.

NMR: 8.00 ppm.

P Pikl a d 86

3- (4-trfflbormetlbyyfenyУ) -N- (2,3 · 2,2-5dilydro dimeehllbrnУofuran-У-51) 4-y ¹ fenyУpyranolin5 5 ^- ^ a] ^ ^r ^ ^d oxamL ^pl of TE EREV mp ^{8 1-83} ° C.

NMR: 7.98 ppm.

Example 87

Un-N-dilldron, 277imeehylbryzofuraa-5-yl) -4-feyy1-3- [4- (2-propiyyloyy) feyyy] oxadiazol-PLR NL- ^{n n} r ^of ynam ^even the yot ^{P AY E} t ¹ and 75 ^mp 179 ° C.

NMR: 8.00 ppm.

Peak a d 88

3- (1,35beyzobiobol-yl) -N- (2S, 5-dimethyl-1,2-dimethoxybenzobenzin-5-yl) -4-phenylpyrazole-5-ol

karboyami -IL-te ^ o ^p J.ot ^{of Tay 223 and} 2 ²⁷ ° C. '

NMR: 8.90 ppm (DMSO-d6).

Peaks a d 89

4- (4-chlorfeayl) -N- (2-dilldro ^ 2 · 5dimethylreУzofrrnn-5-y1) - ^{3--feyylpyrnobУny15} arr0oxnmid.

NMR: 8.00 ppm.

he said a d 90

Mp 161-166 ° C.

thaw

3,4-bis (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-55-yl) pyrazoline-1-carboxamide-temperature

NMR:

7.93 ppm.

said ad

3- (4-chhooftnnl) -4- (4-fluorftnyl) -N- (2,3-dihydro-2,2-dieethyΊbrniofuraki5-yl) ^p yraaofiny yl karfoxamid of ttplotě mp 169-171 ° C.

NMR: 7.96 ppm.

Example 92

3- (4 'chhorftnnl) -4 H methylfennll-N- (2,3 - dihydro-2,2' dimethhlbrtnoOfrann55yl) pyraaofin5 ^ -carboxamide tt ^P Lot ^{1 of} mp 37 ^DEG-9 DEG C. I3.

NMR: 7.96 ppm.

Example 93

3- (4-chhorftnnl) -4- (4-menhhfoУunyl) -N- (2,3-dihydsro 2-z ^ ^f] ^ N _L ¹⁵ - ^{and the} rr ^ Ox ml of ^D by? ^P lo the ^{I th 182 ≥} 18 and ⁶ ° C.

2-diethylene-2-furan-5-yl) pyaa5

NMR: 7.93 ppm

he said

4- (4-UlUfrfnnyl) 5N- (2,3-of dihydro-2,2-dieenhylbenioOurakn5lin-l- ^ aOoaaeid of t ^{p t} fo ^ ^e ^ u 179 and ¹⁸² ° C.

-1) ι3- (4ymenhoooУθrliУ) ^p yakOfy

he said

NMR:

7.93 ppm

4- (4-ohуorftnyi) -N- (2,3-dihydro-2,2-diňethylrenioOurann5-yl) -3Ю ¹ l of aOoxamid ^ tt ^ ^p lot ^of the pools ¹⁵⁷ and ^{Z 160} ° C. '(4 · 5menhoooУenil) ^p yaaofy

NMR: 7.96 ppm

Example 96

3- (4 · ldifUuorenthoxyfenil) 4- (4-UluorUniyl) -N- (2,3-dihydro-2,2-dieethylbeniofurakn5-yl) ^ raaolin ij. ^ Tt aOoxaeíd of ^p lot ^of pools ¹ and 69 ^{out of 172} Deň: 32 ° C.

NMR: 7.93 ppm.

ř í

3-Dihydro-2,2-dimethylmethyl-furanoyl-4- (4-chloro-phenyl) -3- (4-difluoromethoxy-ethoxyl) -N- (2,2-pyrzoline-1-carfoxae), m.p. 90-95 ° C.

NMR: 7.93 ppm.

1 'í k 1 << c ή; ·

3- (4-difluoro-d-hexylphenyl) -N (2,3-dilydro-2,2,3,3-tetrafluorobenzofuran-6-yl) -4-phenylpyrazole-1 H- carbox / mi.id, m.p. -1.52-157 ° C.

NMR: 8.33 ppm.

Example 99

3- (4-difluoromethoxy-phenyl luornethoxy y 1-4- (4-f] uxrfeiy]) -N- (2,3-dihydro-2,2,3,3-tetraflorbbe-zofura- ^- 6 ^- yl) pyrazoj , in ^- l ^- karboxíwiid mp ^110-114 ° C.

NMR: 8.33 ppm.

Example 100

3- (4-iifloorniethoxyfe-y1) '4-- (4-flufrfenyl) -N- (2,3-dihydjío-2 / 2,3,3-tetrafluoro lorbeenzofura - 5- ^yl) p ^y razolii-- L-karboxamiě a temperature between approximately t: a-I ¹⁵⁵ to ¹⁵⁹ ° C.

NMR: 8.20 ppm.

Píli or even 101

3- (4-Chloophen-yl) -N- (2,2'-dihexyl) -b (4'-chloro-4 ', 5'-5') -4-yl-4'-yl] -1 ''; m.p. 182 DEG -18 DEG C .;

NMR: 7.9 ppm.

Example 102

3- (4-Difloxrrethoxyphenyl) -N- (2,2-direehlyl) -phenylpyrrole-1-

- ^{k b} ^ xr ^ oo ^ XMLData of te ^ t ^p JLotě ^and -I and ^{148 of the 150} ° C.

NMR: 7.93 ppm.

Píli and i 103

3 bb (4 (С-сИог-суу-) -N- (2,2-direfthУ-l, 3--be · zo0iolxl - 5-yl) lyrxzllnnfl-XarOxxímid tiepdte about Ta ^- 1-8 d ^{χ ζ} 5 ° C.

NMR: 7.93 ppm.

Example 104

N- (1,4-Benzolinyl-5-yl) -3- (4-difloxethoxyphenyl) -4-H-yl-oxooxole-1-XorOxxaride.

NMR: 7.93 ppm.

Pril and 105

N- (2,2-diffuor ^{benzo0iooxlf5--1,3-yl)} -3- (4-diffuorrreholχУee УJ-N? -Mthyl · --- 4-ernУplУaxolin dXxrboxxmid of te rt ^{fc of 110} -I ^{th mp 114} ° C.

Píli a i 106

4- (1,3-beenolixoxl ---- УJ -N- (4-phenyl-ox ^y fennУ) -3-phenyl-yllyrxoolZnfl "XarOxxmid a temperature T ^- even from 197 ^and 195 ° C.

NMR: 8.03 ppm.

Example 107

3- (4-chlorophenyl) -N- [4- [4- (1,1-dimethylethyl) phenoxy] phenyl] -4-phenylpyrazoline-1-carboxamide, m.p. 192.5-194 ° C.

NMR: 8.03 ppm.

Example 108

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

NMR 8.03 ppm.

Example 109

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

NMR: 8.03 ppm.

Example 110

3- (4-chlorophenyl) -N- [4- [4- (1-methylethyl) phenoxy] phenyl] -4-phenylpyrazoline-1-carboxamide, m.p. 181-182.5 ° C.

NMR: 8.06 ppm.

Example 111

3- (4-chlorophenyl) -4- (4-fluorophenyl) -N- [4- [4- (1-methylethyl) phenoxy] phenyl] pyrazoline-1-carboxamide, m.p. 186-187 ° C.

NMR: 8.60 ppm (CDCl ₃ / DMSO-d ₆ ).

Example 112

3- (4-chlorophenyl) -N-Q4- (4-methylphenoxy) phenyl-4-phenylpyrazoline-1-carboxamide, m.p. 150-151 ° C.

NMR: 8.06 ppm.

• Example 113

3- (4-chlorophenyl) -N- [4- [4- (1-methylethoxy) phenoxy] phenyl] -4-phenylpyrazoline-1-carboxamide, m.p. 158-160.5 ° C.

Example 114

3- (4-chlorophenyl) -4- (4-fluorophenyl) -N- [4- [4- (1-methylethoxy) phenoxy] phenyl] pyrazoline-1-carboxamide, m.p. 213-216 ° C.

NMR: 8.66 ppm (CDCl ₃ / DMSO-d ₆ ).

Example 115

3,4-bis (4-fluorophenyl) -N- [4- [4- (1-methylethoxy) phenoxy _j phenyl] pyrazoline-1-carboxamide, m.p. 134-136 ° C.

NMR: 8.06 ppm.

Example 116

3,4-bis (4-fluorophenyl) -N - [-4- (4-chlorophenoxy) phenyl 13py ^{RA2 'o} ii ^{_ N_} l k ^and carboxamido m.p.

Mp 197-198.5 ° C.

NMR: 8.70 ppm (CDCl 3 / DMSO-d 6).

Example 117

3,4-bis (4-fluorophenyl) -N- [4- [4- (1,1-dimethylethyl) phenoxy] phenyl] pyrazoline-1-carboxamide, m.p. 189-192 ° C.

NMR: 8.70 ppm (CDCl ₃ / DMSO-d ₆ ).

Example 118

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

Mp 198-200 ° C.

NMR: 8.13 ppm.

Example 119

3,4-bis (4-fluorophenyl) -N- [4- [4- (4'-dimethylamino) phenoxy] phenyl pyrazoline-1-carboxamide, m.p. 148-150 ° C.

NMR: 8.02 ppm.

Example 120

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

NMR: 8.16 ppm.

Example 121

N- (1,4-benzodioxan-6-yl) -4- (4-chlorophenyl) -3- (4-difluoromethoxyphenyl) pyrazoline-1-carboxamide, m.p. 124-128 ° C.

NMR: 7.93 ppm.

Example 122

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

214

Deposit 123

N- (2,2-Difluoro-1,3-benzoyl-yloxy) -3,4-diphenyl-pyrimidin-1-carboxylic acid, m.p. 216 ° C.

NMR: 8.83 ppm (CDCl 3 / DMSO 4).

and d 124

N- (2,2'-difluoro-1,3,3-benzophenol-5-yl) -3,4-biphenyl (4-fluorophenyl) yyazolin-1-yl] acetonitrile

Z 180 ^and 178 ° C.

NMR:

8.10 ppm.

said ad

125

3- (4-chhorfeno1) -N- (2,2-díflloual 3-beenoUiouol --- yУ) -4- (4-flluafenyl) oУajzoUio ^1-d Karboom of te ^ o ^ t ^and RI ¹⁴⁷ and ^{f 151 [} deg.] C.

NMR: 8.06 ppm.

Example 126

3- (4-difluoromethoxyphenyls) -N- (2,3-difluoro-2,2,3,3-tetrifluorobenzen-5-yl) -N-methyl-4-phenylpyrazoin-1-aarboacidide as a yellowish gum.

Analysis: Calculated Found

% C, 58.32;% H, 3.57;% N, 7.85;% C, 58.08;% N, 7.61.

Example

127

3- (4-Chloro-4-chloro) -4- (4-difluoromethoxy-ethanol) -N- (2,3-dihydro-2,2-dimethylamino-triazol-1-yl) -basic acid. Xam ^ o teptató ^th eye ¹⁵⁵ and ^{from 159} ° C.

NMR: 7.96 ppm.

Example 128

4- (4-Chloropheno-N- (2,2-difluoro-1,3-benzoylol-55-η) -3- (4-fluoroethoxyoylphoyl) pyrazole-4-yl-amide.

NMR: 8.06 ppm.

Example 129

3,4-SiS · 14 - flluafenyl) -N- (2,3- (2,2,3,3-dihydro-5-tetrjfluobbeozuflrjn yУ) -oyrjzouio-1 ^- ^ ^r kai) ooam. ^D o te ^ OTO t ^and RI ^{156 Z 16} and 0 ° C.

NMR: 8.23 ppm.

The insecticidally active pyrazolines of the invention are not normally used as such, but are generally used in the form of a composition appropriate to the selected application method and comprising the insecticidally effective amount of the pyrazolium of the invention. The pyraazines of the present invention, like most pesticide active ingredients, can be rendered more readily acceptable by surfactants and carriers normally used to facilitate dispersion of the active ingredients,

5 2 4 9 7 is possible. . In the case of the surfactants and carriers normally used, the active substances are generally used, and the active substances are employed, and it is to be understood that this is a characteristic of the present invention. . The route of administration of the insecticide may affect the activity of the active ingredient. For example, the cast iron may be applied, for example, in the form of spraying, dusting or granulates to a mini-mold, where the coating may be damaged in a dramatic manner, the method of application varies considerably depending on the pest control and the surrounding environment. conditions.

The pyraalines according to the invention can be formulated into granules with a large particle size, dusted, mixed powders, emulsifiable concentrates, solutions and the like.

The granules may be porous or non-porous particles, for example, aluminum or sand phase particles, which serve as carriers for the proactive pyrazolines. These granules are relatively large - typically having a diameter of about 400 to 2500 µm. These particles are either applied with a pyrazolic solution or pyrazolite, sometimes using adhesives. Generally, the grandat contains 0.05-10%, preferably 0.5-5% of the active ingredient, which is insecticidally effective

Dusts are mixtures of the pyrazolites according to the invention with finely divided solids such as talc, attapulgite clay, diatomaceous earth, pyrroolfylite, chalk, itfusori clays, calcium phosphates, calcium carbonates? and magnesium, sulfur, flours and other organic and inorganic solids which serve as a carrier for the insecticide. ’

These finely divided solids have an average particle size of less than about 50 µm. A typical dust formulation useful for controlling insects contains 1 part pyrazolicu as 3 ^{- (4-chlorophenyl} lcylj ^τ ^ - ^{[4 4 (4-chlorophenyl} xy-ethoxy) ^{f r} LNY] ^{-4-et l} in ^rliy rαzo ^L - ^{α 0} OxAm ^id nr l ^{and 99} ^ d of talc.

The pyrazoles according to the invention can be processed by liquid concentrates by dissolving or emulsifying them in suitable liquids, and solid concentrated formulations by mixing with talc, clay and other known solid carriers used in the pesticide art.

These concentrates contain about 5 to 50% of the pyrazolic acid according to the invention, such as 3- (4-chloro-phenyl) -N- (2,3-dihydro-2,2-dimelhyrbenzoic acid) -4-phenylthylamino-arrioxamide, and 95 to 50% of an inert material which includes surfactants such as dispersants, emulsifiers and wetting agents.

Experimentally, higher concentrations of the active ingredient can also be used. Said concentrates for dilution are diluted with water or other liquids and suitably concentrated spray or other solid co-suitably concentrated dusts.

Typical carriers for the preparation of solid concentrates, also referred to as wettable powders, include clay, various clays, diatomaceous earths, and other scadco wettable inorganic inorganic materials having a high adsorbency.

A suitable solid concentrated insecticide composition comprises 1.5 parts of sodium ligtosulfate and 1.5 parts of sodium lauryl sulfate as a stearate, 25 parts of 3- (4-chlorophecyl) -N- (2,3-dihydro-2,2). diethylbenzothoxyl-4- (4-chlorophenyl) irazrazole-3-trichloride and 72 parts of carbon black.

Industrial terminates are used for the shipping of the heavy products according to the invention. These ends are prepared by melting the foreign-solid product with 1% or more of the solution to give a concentrate which, upon cooling to the freezing point of the pure product or even lower. does not solidify.

Useful liquid ends include emulsifiable concentrates which are homogeneous liquid or paste formulations dispersed in water or other liquid carriers.

These preparations may consist only of pyrophosphite and a liquid or solid emulsifier, or may also contain a liquid carrier such as xylene, aromatic petroleum fractions, itfrot and other, relatively volatile organic solvents.

For application purposes, these concentrates are dispersed in water or other liquid liquid onto the area to be treated, normally applied post-spray.

Typical surface-active surfactants, dispersants and emulsifiers used in pesticidal compositions include, for example, alkyl and alkylarylsilphonates and sulfates, and their salt salts, alkyl amide sulfonates, including the fatty acid alcohols; animal and vegetable oils, petroleum oils, esters of polyhydric alcohols with fatty acids and addition products of these esters with ethylene oxide, as well as addition products of long-chain mercaptan and ethylene oxide.

Numerous other types of useful surfactants are available on the market.

When a surfactant is used, the surfactant comprises an amount of the surfactant typically in the range of from about 1% to about 15% of moisture.

Other usable formulations are also completely soluble in the desired solvent.

simple solutions of the active ingredient in a solvent, concentrations such as acetone or other effective amount of the active ingredient; The pyrtzolite in the diluent composition diluted for application purposes normally ranges from about 0.001 to 8% by weight. The pyrazdines of the invention can be used in the form of a wide variety of other spray formulations and dusts known in the art.

The compositions according to the invention may contain, in addition to the pyrtzolites described above, other active ingredients, such as other insecticides, non-insulins, alcohols, fungicides, plant growth regulators, fertilizers and the like.

In the insect control compositions of the present invention, it is only necessary that the insecticidally effective insecticide is applied to the place where the insect is to be exterminated. This place may be the insect itself, the plants on which the insect feeds, or the environment of the insect. If this place is an agricultural crop, it can be corrected.

soil, for example, soil in which the attitude or cultivation of the active ingredient is carried out on the soil and then optionally into the soil

For most applications, preferably from 150 to 3000 g / ha.

The effective amount is approximately 75 to 4,000 kg,

The idiopathic efficacy of the pyrazolines described above was tested as follows.

Test compounds are applied to the leaf in the form of variously concentrated aqueous solutions containing 10% acetone and 0.25% octylSenoxypolyethoxyxyethanol. The procedure is as follows:. The bean plants are mixed on a turntable in a digestor and the test solutions are sprayed onto them.

The test solutions were applied to the upper and lower leaf surfaces of the test run. Rofthity is allowed to dry, then cut off above the root and each stalk in a paper cup pushed into the water.

up to the holes

In each of these cups, 10 dmd of each insect species were placed and the cup was covered. Spoddotera ζγϊΙ ^ Η (SE), Epilachna vatovest ^

I i

252497 26 (EV), Spodoptera exigua (SEX), and Trichoplusia ni (TN). After 4 days, when ro ^ tli ^ y ^ y hrnyudržují t ^ ho ^p ture of 26 ° C, the ^p grazing ^{characterized} hodnn> ^P s and detection ^ 50% Mortl ^l - ^t a. Results The ^{thanks to} the achieved in this The test results are given in Table 1 below. If the test is evaluated earlier, the molarity of the mass is generally lower.

Many pyridines of the invention also show efficacy against the larvae of Diabrotica undecimptuniata howardi (Barber) when applied to the soil, and those which have been tested are also. very effective against manCo.licce potato (Lcptinotarsa Oec · emlineatr Say).

Table 1

Insecticidal activity in foliar application

Compound (ppm) Mott ^ alLta (%) experimental SEX insect TN EV SE 1 500 100 ALIGN! 100 ALIGN! 2 500 100 ALIGN! 100 ALIGN! 3 500 100 ALIGN! 100 ALIGN! 4 500 100 ALIGN! 100 ALIGN! 5, 250 100 ALIGN! 87 100 ALIGN! 6 500 70 65 90 7 500 100 ALIGN! 5 0 90 8 500 100 ALIGN! 85 9 500 90 70 10 500 100 ALIGN! 35 11 500 8 5 1 5 12 500 .1 00 100 ALIGN! 13 500 93 50 90 14 500 100 ALIGN! 100 ALIGN! 15 Dec 500 100 ALIGN! 90 16 500 1 00 17 500 ] (> 0 35 18 500 90 55 19 Dec 500 100 ALIGN! 100 ALIGN! 20 May 500 80 40 21 500 70 15 Dec 22nd 500 100 ALIGN! 100 ALIGN! 23 500 40 30 24 250 95 100 ALIGN! 25 500 30 75 26 500 80 65 27 Mar: 500 75 95 28 500 95 90 29 500 10 90 30 500 5 64 60 31 500 5 65 70 32 500 100 ALIGN! 50 33 500 100 ALIGN! 80 34 500 10 75 35 500 100 ALIGN! 100 ALIGN! 36 8 100 ALIGN! 98 45 90 37 32 98 98 97 100 ALIGN! 38 500 95 80 39 500 100 ALIGN! 25 40 500 100 ALIGN! 100 ALIGN!

continuation of Table

Compound Concentration of M% (%) of test insects

(ppm) EV SE SEX TN 41 128 95 70 42 128 95 100 ALIGN! 43 500 100 ALIGN! 100 ALIGN! 44 500 100 ALIGN! 100 ALIGN! 45 32 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 46 500 30 40 47 500 5 10 48 8 100 ALIGN! 100 ALIGN! 100 ALIGN! 95 49 500 100 ALIGN! 100 ALIGN! 50 500 100 ALIGN! 100 ALIGN! 51 100 ALIGN! 40 60 52 500 100 ALIGN! 95 53 500 100 ALIGN! 10 54 500 100 ALIGN! 85 55 500 100 ALIGN! 80 56 500 100 ALIGN! 100 ALIGN! 57 250 100 ALIGN! 100 ALIGN! 58 500 100 ALIGN! 40 59 500 100 ALIGN! 100 ALIGN! 60 200 100 ALIGN! 60 61 32 45 100 ALIGN! 55 90 62 500 95 95 63 500 100 ALIGN! 95 64 500 100 ALIGN! 100 ALIGN! 65 500 100 ALIGN! 100 ALIGN! 66 500 100 ALIGN! 100 ALIGN! 67 500 85 95 68 500 100 ALIGN! 0 69 8 100 ALIGN! 60 5 100 ALIGN! 70 500 100 ALIGN! 100 ALIGN! 71 200 60 10 72 200 100 ALIGN! 30 73 500 100 ALIGN! 90 74 500 100 ALIGN! 80 75 200 100 ALIGN! 45 76 200 95 100 ALIGN! 77 500 80 200 0 95 78 500 90 55 79 200 95 60 80 500 100 ALIGN! 100 ALIGN! 81 250 100 ALIGN! 100 ALIGN! 82 128 100 ALIGN! 90 83 250 85 100 ALIGN! 84 100 ALIGN! 100 ALIGN! 90 85 200 100 ALIGN! 100 ALIGN! 86 16 95 95 40 100 ALIGN! 87 500 100 ALIGN! 100 ALIGN! 88 100 ALIGN! 100 ALIGN! 25 10 85 89 200 100 ALIGN! 100 ALIGN! 90 16 100 ALIGN! 100 ALIGN! 100 ALIGN! 90

8 continued Table I

Compound

Concentration ¹

Mentality (%) of experimental insects

(ppm) SE SEX TN ’91 32 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 92 500 100 ALIGN! 100 ALIGN! 93 500 100 ALIGN! 100 ALIGN! 94 500 100 ALIGN! 100 ALIGN! 95 200 100 ALIGN! 90 96 32 100 ALIGN! 100 ALIGN! 85 95 97 8 100 ALIGN! 100 ALIGN! 85 98 16 100 ALIGN! 40 35 80 99 16 100 ALIGN! 100 ALIGN! 90 85 100 ALIGN! 32 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 101 1 000 100 ALIGN! 100 ALIGN! 102 128 100 ALIGN! 100 ALIGN! 103 16 90 95 15 Dec 100 ALIGN! 105 16 100 ALIGN! 100 ALIGN! 106 256 100 ALIGN! 70 107 1 000 45 0 108 1 000 100 ALIGN! 75 109 1 000 0 0 110 1 000 70 0 111 1 000 0 0 112 1 000 100 ALIGN! 90 113 1 000 100 ALIGN! 10 114 1 000 100 ALIGN! 30 115 1 000 100 ALIGN! 15 Dec 116 500 100 ALIGN! 100 ALIGN! 117 500 55 0 118 500 100 ALIGN! 100 ALIGN! 119 500 100 ALIGN! 95 120 500 100 ALIGN! 100 ALIGN! 121 500 95 100 ALIGN! 122 64 100 ALIGN! 100 ALIGN! 123 64 15 Dec 0 124 64 100 ALIGN! 100 ALIGN! 125 64 100 ALIGN! 100 ALIGN! 126 8 100 ALIGN! 100 ALIGN! 127 64 100 ALIGN! 90 128 64 100 ALIGN! 100 ALIGN! 129 8 100 ALIGN! 100 ALIGN!

Claims (24)

OBJECT OF THE INVENTION is an amount of at least one pyrrolidine derivative of the general formula I What is claimed is: 1. A composition according to claim 1, wherein the active ingredient is a compound of formula (I): R ³ ® znxmená xtom Volik Guoru or chlorine mmtihoxyskupinu dinormmetnop ^one group trifbuormetOoxyskfpinf · 2 · 1propinplooptkupinu or trrflbУrmettylb1 group being not ^{b, R 3 Pla d} stxvuje radical of formula R ² of formula znxmená sub ^ t Substituent at position 4 or 5, wherein 20 ~ ^OTR R is hydrogen, fluorine or chlorine, methyl, methyl, trifluoromethyl or difluoromethoxy or R is as defined below R ³ předstrvuje radical of formula wherein R represents a hydrogen atom or an ethyl group, R @ 5 represents a C1-4 alkyl group, a fluorine atom, a chlorine atom, a C1-3 alkyl group, a 1-fluoromethyl group, a trifluoromethyl group, a trifluoromethyl group, a trifluoromethyl group, R ³ represents a radical of formula (I), or a methyl group or a methylmethylamino-β-1, or R ³ represents a radical of formula Z represents a bridge of the formula [o- (cr ³¹ r ³² ) _c -o _c -] wherein c is a number of 1 to 2, c is a number of 0 or 1, the sum of c + c 'being at least 2, 31 32 R @ 1 and R @ 5 are in each case hydrogen, fluorine or methyl, provided that if c has a value of 1 and has a value of 1.3132 then R and R @ they do not simultaneously denote hydrogen atoms, Q R represents a hydrogen atom or a methyl group and, independently of one another, is an oxygen or sulfur atom, in admixture with a brownish carrier. 2. A compound according to claim 1, wherein said compound is of the formula (I '). that it contains, as active ingredient, a compound of the formula hydrogen, fluorine or chlorine, lilboromethyl, phenyl, or trifluoromethyl, 252497 'is bonded at the 4-position of 5 and represents a radical of formula _R 20 wherein ЭЛ '· R (2) represents a hydrogen, fluorine or C 1-6 atom or a trifluoromethyl group or a radical of formula R ³ represents a radical of formula wherein R ^ is perceived as having a hydrogen oebo skupiou methyl and ^R5 z ^ Me ^ ^f lulof hydrogen ^atom cdoru ^ o ^ ^ огтеОЬу УШ skupiou. Rebo the rest of the formula V and W are as described in point 1. 3. The composition of claim 1 wherein the active ingredient comprises a compound of formula (I) wherein: ^Lj R represents hydrogen, fluorine or chlorine, trifluoromethyl, difluoromethoxy or trifluormehhoxyskupinu, R is attached at the 4 or 5 position and represents a radical of the formula wherein R ² represents hydrogen, fluorine or chlorine or triíluormehhylovou radical, or the radical represents a radical of formula -O— \ r ^{4 R} where 4 ·· R is R ⁵ represents a hydrogen atom or a methyl group and a fluorine or chlorine atom or a trifluoromethyl group or a radical of formula CH3 or a O-CH ₂ ; h ₃ V and W are as defined in 1. 4. The composition of claim 1, wherein the active ingredient is a compound of formula (I) wherein W is O and the remaining moieties are as in 1. 5. A composition according to claim 1, wherein the active ingredient is a compound of the formula (I) in which the general formula (I) is one. meaning as defined in claim 1 with the R ^{1 G Z} e represents a ^ ^b of uoau not chloau, ^components oaemnthoxys ^to r ^pi ir Neto three luoemeУhfx ^u ^ group. 6. The composition of claim 1, wherein the active ingredient is a compound of formula (I), wherein the general formula (I) is as defined in (1), wherein the R 1 substituent is attached at the 4-position. 7. A composition according to claim 3, characterized her ^ ^ said compound being 3- (4-dillformttУfxyftnnl) 5N- ^{(2,3-dihydro-2,2-d} imettylbrtioforalji 51) --- íennypyfajofin-l -kkrrfO5 amide. 8. A composition according to claim 2, wherein the active ingredient is 3,4-diis-4-fluoro-4- (2,3-dihydro-2,2,3,3-tetrophenylbenzofuran-5-). (11) plaqueszin-1-kroffoimide. 9. The composition according to clause 3, characterized in that the composition is as follows: 3. A method according to claim 1, wherein the active ingredient is 3,4-Ois (4-fluorophenyl) -N- (2,3-dihydoo-2,2-dimethyleneburofuran-5-yl) pyrzofi-1-carfoxamide. 10. A composition according to item 2 characterized ^ čujcí in that it contains as active ingredient N- (2,3-dihydro ^^, 3,3-tttrkfjuorbtnzofurani5 "yl) -3- (4-difjufrmethhfolunyl) -5" ^to 5enilfylrjolirily kr0fOkmi ^d . 11. A composition according to claim 1, wherein the active ingredient is N- (2,2-difluorophenol-1-yl) -3- (4-difluoromethylphenyl) -N-ethyl-4-phenylpyazzolin-1-one. -krrfχy amid. 12. The composition of claim 2, wherein the active ingredient is 3,4-Ois (4-chlorophen-4-yl) -N- (2,. Alpha.-dimethyl-, 3-reniophiophof-1 -). yl) pyrsololine-1-kaofoxamide. 13. A composition according to claim 2, wherein the active ingredient is N- (2,25-difluoro-1,3-reniophiophof-1-yl) -3,4-bis (4-fluoro-phenyl) -capasphliyl-1. -kaofokamid. 14. A composition according to claim 2, wherein the active ingredient is 3 (45Chlfkutynyl) - N - (2,2-difluoro-1,3-O-thiophiophol-1-yl) -4- (4fphosphinyl) pyrimidine-1-carfoxamide. 15. A composition according to claim 1, wherein the active ingredient is 3- (4-di-methoxyphenyl) 5N- {2,3-dihydro-2,2,3,3-tetrahydro-benzo-furan-5-yl. 14-Methyl-14-enenilpyrazoline-1k robookmid. 16. The composition according to item 3, characterized by: 3. A method as claimed in claim 3, characterized in that it contains 3- (4-chlorophenyl) -N- [44- (4-difluorophenylphenooyl) uranyl] -4- (4-phenylpiperazin-1-yl) -caphoxoxide. 17. A composition according to claim 3, wherein the active ingredient is N - [* 4 (4-difluoromethoxy-oxo-phenyl) -phenyl] -3- (4-difluoromethoxyphenyl) -4- (4-fluorophenyl) -pyrrzoline-1-carbfxamide. 18. The composition of claim 2, wherein the active ingredient is 3- (4-hydroxyphenylphenylphenyl) -4- (4-fluorophenyl) -N52,3-dihydrof-2,2,3,3-thetaalphiobenzene-5- yl) pyrkzf5. fin-1-carfocaeid. 19. A composition according to claim 2, which comprises: - (4-difluoromethoxyphenyl) -4- (4-fluorophenyl) -N- (1,2-dihydro-2,2-dihydroxyphenyl) -4- (4-difluoromethoxyphenyl) -4-, - (1-fluorophenofuran-Gy) 1) pyrazoline-1-carboxamide. 20. A composition according to claim 1, wherein the active ingredient is 4- (4-chlorophenyl) -N- (2'-dihydro-2,2-dimethylbenzofuran-5-yl) -3-. phenylpytazoline-1-carboxamide. . 21. A composition according to claim 3, wherein the active ingredient is 3- (4-chlorophenyl) -4- (4-fluorophenyl) -N- (2,2-dihydro-2,2-dimethylbenzofuran-5). -y1) pyrazole mb-catboxamide. 22. The composition of claim 3, wherein the active ingredient is 3- (4-difluoromethoxyphenyl) -4- (4-fluorophenyl) -N- (2,3-dihydto-2,2). 1-methylbenzofuran-5-yl) pyrazoline-1-carboxamide. 23. The composition of clause 3, wherein the active ingredient is 4- (4- -chlorophenyl) -3- (4-difluoromethoxyphenyl) -N- (2'-dihydro-2,2-dimethoxyfluoro-5-fluoro-1-carboxamide). 24. A process for the preparation of the active compounds according to claim 1, characterized in that the compound is of the general formula R ³ -N = C = W in which it is as in 1, reacts with a compound of the general formula r 1 in which it is as in 1, and the resulting product is optionally methylated to introduce a methyl group in the meaning of the symbol