DE3537884A1 - PYRAZOLINE COMPOUNDS, METHOD FOR THEIR PRODUCTION AND THEIR USE IN FIGHTING PAD INSECTS - Google Patents

Description

- ΛΟ --- -:: .: -. ';; ο E ο 7 QQ

3537882

The invention relates to new pyrazoline compounds, methods for their preparation and intermediates, as well as the use of the pyrazoline compounds in combating Insect pests.

Pyrazolines are 5-membered heterocyclic compounds following formula

It is known that certain 1-carbamoylpyrazoline derivatives have an insecticidal effect. For example, TJS-PS 4,174,393 describes 1-carbamoylpyrazolines, which in the 3- "and Α-positions of the pyrazoline ring carry phenyl groups * and - which have an insecticidal effect.

The invention is based on the object of new pyrazoline compounds to make available, which are characterized by a pronounced insecticidal effect. The solution to this The problem arises from patent claims 1 to 27 and the description below.

The pyrazoline compounds of the invention have the general 3-shape
R *

^R B

C7

^r - ^ - ■ - ^{; ; :} 3537885

The substituents have the meaning given in claims 1 to 9.

The term "halogen" or "halogen atom" means a fluorine, chlorine or bromine atom. The term "down" in context with, for example, "alkyl", "alkoxy" or "alkynyloxy" means an unbranched or branched radical with 1 to 6, preferably 1 to 4 carbon atoms · The term "halogen" in connection with another term means that one or more hydrogen atoms have been replaced by one or more halogen atoms.

Of the pyrazoline compounds of the invention, those compounds are generally preferred in which W is an oxygen atom, especially when E ^{1 is} in the 4-position, preferably a halogen atom, for example a chlorine or fluorine atom, or a lower haloalkoxy radical, e.g. is a difluoromethoxy. The pyrazoline compounds in which the radical R- is in the 4-position are generally more active than the corresponding 5-substituted pyrazolines. Compounds in which the radical Rn is a phenyl group which bears a substituent R'-n are particularly preferred. In this connection it is preferred that the remainder

E ^ is in the 4-position, and preferably a halogen-25

atom, for example a chlorine or fluorine atom.

rest
In connection with the / R _G , the preferred pyrazoline compounds are derived from those compounds which are either 2,3-dihydro-2,2-dimethylbenzofuran-5-y1-, 2,3-dihydro-2,2,3 , 3-tetrafluorobenzofuran-5-yl-, 2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-6-yl-, 2,2-difluoro-1,3-benzodioxol-5-yl- or have a 2,2-dimethyl-1,3-benzodioxol-5-yl group or a 4-phenoxyphenyl group. In the latter case, the group Rp ₁ is preferably a hydrogen atom and the remainder

R-g is in position 4 and is preferably a lower haloalkoxy radical.

L J

^Γ -12-- - yYY : ": 3537883

Examples of preferred pyrazoline compounds of the invention are 3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide, 3,4-bis - (4 ~ luophenyl) -ΪΓ-2,3-dihydr o-2,2,3,3-tetrafluorobenz of uran-5-yl) pyrazoline-1-carboxamide, 3,4-bis - (4- -: i? luophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -pyrazoline-1-carboxamide, N- (2,3-dihydro-2,2,3,3- tetrafluorobenzofuran-5-yl) -3- (4 ~ difluoromethoxyphenyl) -4-phenylpyrazoline-1-carboxamide, N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- ( ¹ ^ - <üi luormethoxyphenyl) -U-methyl-4-phenylpyrazoline-1-carboxamide, 3, ² ^ -bis- ( ² ^ -chlorophenyl) -N- (2,2-dimethyl-1,3-benzodioxol-5-yl) -pyrazoline-1-carboxamide, N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3,4-bis- (4-fluorophenyl) -pyrazoline-1-carboxamide, 3- (4- Chlorophenyl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) -4- (A-- fluorophenyl) -pyrazoline-1 -carboxamide, 3- (4-difluoromethoxyphenyl) - N- (2,3-dihydro-2,2,3,3-tetrafluorobenz of uran-5-yl) -N-methyl- ^ - phenylpyrazoline-1-carb oxamid, 3_ (4-chlorophenyl) -1- / ² TC 4-difluoromethoxyphenoxy) -phenyl / - ^ - phenylpyrazoline-1-carboxamide, N - ^^ - C ^ -Mfluoromethoxyphenoxy) -phenyl7-3- (4-difluoromethoxyphenyl ) -4- (4-fluorophenyl) -pyrazoline-1-carboxamide, 3- (4-difluoromethoxyphenyl) -4- (4-fluorophenyl) -H- (2,3-dihydr0-2,2,3,3- tetrafluorobenzofuran-5-yl) -pyrazoline-1-carboxamide, 3- (4-difluoromethoxyphenyl) -4- (4-fluorophenyl) -H_ (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-6- yl) -pyrazoline-1-carboxamide, 4- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -3-phenyl-pyrazoline- ^/ l-carboxamide, 3- (4 ~ chlorophenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -pyrazoline-1-carboxamide, 3- (4-difluoromethoxyphenyl) _4 ~ ( 4_fluorphenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5_yl) _py _ra Zolin-1-carboxamide and 4- (4-chlorophenyl) -3- (4-difIuormethoxyphenyl) -N- (2,3 -dihydr0-2,2-dimethylbenzofuran-5-yl) -pyrazoline-1-carboxamide

For use in controlling insect pests, the pyrazoline compounds of the invention become insecticides Processed agents that contain at least one pyrazoline compound of the invention in a mixture with conventional carriers

3537887t

1 and / or diluents included.

The pyrazoline compounds of the invention can by reaction a corresponding aromatic isocyanate or isothiocyanate with an appropriately substituted pyrazoline be prepared according to the following reaction scheme:

N-C =

The product can be formed in a manner known per se the corresponding N-alkylated pyrazoline compounds be alkylated.

The pyrazolines used according to the process are in general known. The isocyanates and isothiocyanates used according to the process can be obtained from the corresponding amines be prepared by conventional methods. Some of the amines are commercial products. Other amines can affect the in the manner described in the following examples.

example 1

3- (4-chlorophenyl) -K- / ³ ? - (4-chlorophenoxy) -pheny 17-4-phenylpyrazoline-1-carboxamide

Under dry nitrogen as a protective gas, a mixture of 10.9 g (0.17 mol) of 4-liter luornitrobenzene, 9.95 g (0.077 mol) of 4-chlorophenol and 11.8 g (0.085 mol) of potassium carbonate in 175 ml of dimethyl sulfoxide is used for 2 days heated to 70 ⁰ C and stirred. the reaction mixture is cooled and filtered. the Piltrat is diluted with water to 1 liter. After

^r - ^ - .UJ JZ ' 353788Ϊ

the mixture is extracted three times with 200 ml of methyl ether each time. The ether extracts are combined and washed with water and saturated aqueous sodium chloride solution. The washed ether extract is then dried over sodium sulfate and filtered. The filtrate is evaporated under reduced pressure. There are obtained 13.5 g of 4- (4-chlorophenoxy) nitrobenzene from P. 67 to 70 ⁰ C.

In the hydrogenation of 13.5 g (0.054 mol) of 4- (4-chlorophenoxy) nitrobenzene in the presence of 0.15 S platinum oxide in 250 ml of tetrahydrofuran, 4- (4-chlorophenoxy) aniline is obtained in quantitative yield obtain.

A solution of 0.75 S (0.0034 mol) of 4- (4-chlorophenoxy) aniline in 25 ml of toluene is added dropwise with stirring to a solution of 0.43 ml (0.0036 mol) of trichloromethyl chloroformate in 20 ml of toluene. After the addition has ended, the mixture is heated to 85 ° C. for 3 hours. The mixture is then cooled to room temperature and the solvent is distilled off under reduced pressure. The residue obtained is dissolved in 25 ml of diethyl ether. This solution is added dropwise to a slurry of 1.0 g (0.0034 mol) of 3- (4-chlorophenyl) -4-phenylpyrazoline in diethyl ether with stirring. After adding three drops of triethylamine, the mixture is stirred for 2 days at room temperature. The solvent is then distilled off. 0.92 g of 3- (4-chlorophenyl) -N- / 5- (4-chlorophenoxy) -phenyl7-4-phenylpyrazoline-1-carboxamide from P. 158 to 161 ⁰ G are obtained. Calc .: C 66.92 4.22

Found: C 66.06 H 4.95.

Nuclear Magnetic Resonance Spectrum: 8.06 ppm (CDCI,).

r. - 15 -

3537882

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

100.0 g (0.67 Hol) of 2,3 ~ dihydro-2,2-dimethylbenzofuran are ^{added dropwise at a temperature of 5 °} C. within 1 hour with an ice-cold mixture of 43 ml of concentrated nitric acid and 50 ml of concentrated sulfuric acid and stirred · After the addition is complete, the mixture is ^{stirred for a further 2 1/2 hours at 0} ° C. · The reaction mixture is then poured into ice water and extracted with diethyl ether. The ether extract is dried over anhydrous magnesium chloride and filtered. The 3? Filtrate is evaporated under reduced pressure. A black oil remains, which is purified by column chromatography on silica gel. It is eluted with a 9: 1 mixture of toluene and η-hexane. 50.0 g of 2,3-dihydro-2,2-dimethyl-5-nitrobenzofuran are obtained as a pesticide.

20.0 g (0.1 mole) 2,3 ~ dihydro-2,2-dimethyl-5-nitrobenzofuran are hydrogenated in the presence of 0.2 g of platinum oxide in 250 ml of methanol. There are 16.6 g of 5-amino-2,3-dihydro-2,2-dimethylbenzofuran obtain.

A solution of 0.56 g (0.0034 moles) of 5-amino-2,3-dihydro-2,2-dimethylbenzofuran in 20 ml of toluene is added dropwise with stirring to a solution of 0.43 ml (0.0036 mol) of trichloromethyl chloroformate added in 20 ml of toluene. When the addition is complete, the mixture is refluxed for 3 hours heated. The mixture is then cooled to room temperature and the solvent is distilled off under reduced pressure. The residue obtained is taken up in 25 ml of anhydrous diethyl ether and the solution is added dropwise and with stirring to a mixture of 1.0 g (0.0034 mol) of 3- (4-chlorophenyl) -4-phenylpyrazoline and three drops of triethylamine given in 25 ml of diethyl ether. The mixture is stirred for about 18 hours at room temperature. After that, the

the resulting solid was filtered off from the mixture. The filter cake is suspended in ethanol and filtered off again. There are 0.47 g of 3- (4-chlorophenyl) -] i- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) - ⁱ '-phenylpyrazolin-1 -carboxamide from

F. 160 to 162 ⁰ C obtained. Calc .: C 70.00 H 5.4-3 Found: C 69.50 E 3.36 MR spectrum: 9.00 ppm (DMSO-dg).

Other compounds in this series are made in a similar manner manufactured. The NMR singlet corresponding to the = HH proton and that which is characteristic of these compounds is also indicated in some cases. Unless otherwise is indicated, is used as the solvent for the NMR spectrum CDCl ^. In some cases the elemental analyzes specified.

Example 3

3,4-diphenyl-N- (4-phenoxyphenyl) -pyr azoline-1-carb oxamide, F. 184 to 188.9.17 ppm (DMSO-dg)

Example 4

Nv / 4- (4-chlorophenoxy) -phenyl7-3,4-diphenylpyrazoline-1 carboxamide, m.p. 146 to 149, 8.83 ppm (DMSO-de). 25th

Example 5

3- (4-chlorophenyl) -H- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide, 163 to 166, 8.03 ppm.

Example '6

N- (4-phenoxyphenyl) -4-phenyl-3- (4-tr if luormethylphenyl) pyrazoline-1-carboxamide, M.p. 188-190. 8.10 ppm.

Example 7 3,4-bis (4-chlorophenyl) -N- (4-phenoxyphenyl) -pyrazoline-1-carboxamide, 189 to 193. 8.20 ppm

L J

Example 8 3- (4-chlorophenyl) -Ν- (3-methyl-4-phenoxyphenyl) -4-phenylpyrazolia-1-carboxamide, F. 15I to 157. 9.13 ppm (DMSO-dg).

Example 9 3- (4-Glilorp] ienyl) -3! T- ^ 5- (2-fluoropheiLOxy) -phenyl7-4-piienylpyrazoline-1-carboxamide, 153 to 155, 8.16 ppm.

Example 10 3- (4-GtLloΓp] lenyl) -H - / [ ^z l · - (3-fluorophelloxy) -pllenyl7-4-pb.enylpyrazoline-1-carboxamide, mp 173 to 175 · 9.33 ppm. ( DMS0-d ₆ ).

Example 11

Ή - /% - ~ (3-chlorophenoxy) -phenyl7-3- (4-chlorophenyl) -4-phenylpyrazoline-1-carboxamide, m.p. 169 to 174. 9.30 ppm (DMSO-dg).

B e i s ρ i e -1 12

3- (4-chloroplienyl) -N- / 5- (4-fluorophenoxy) -phenyiy ^ -phenylpyrazoline-1-carboxamide, m.p. 164 to 167, 8.13 ppm. 20th

Example 13

phenylpyrazoline-1-carboxamide, m.p. 161 to 164, 8.03 ppm.

Example 14 H _ ^ _ (4-Gb.lorplieiioxy) -phenyl7-3- (4-difluoromethoxyphenyl) -4-phenylpyrazoline-1-carboxamide, F. 103 to IO7. 8.00 ppm.

Example 15 3,4-bis (4-chlorophenyl) -N- (3-methyl-4-phenoxyph .enyl) -pyrazoline-1-carboxamide, m.p. 188-190, 9.23 ppm. (DMS0-d ₆ ).

Example 16

3,4-bis- (4-Cb.lorophenyl) -N- ^ (2-fluorophenoxy) -phenyl7-pyτazolin-1-carboxamide, 160 to 162, 8.10 ppm.

L J

Γ - 18 -

Example 17 3,4-bis- (4-chlorophenyl) -N- ^ f- (3-f luophenoxy) -pheny ^ -pyrazoline-1-carboxamide, F. 144 to 146, 9.20 ppm (DMSO-dg).

Example 18 N- / 4 "- (3-chlorophenoxy) -phenyl7-3, 4-bis- (4-chlorophenyl) -pyrazoline-1-carboxamide, F. 135 to 140, 9.30 ppm (DMSO-dg).

Example 19 3,4-bis- (4-chlorophenyl) -N- ^ f- (4-f Iuophenoxy) -phenyl7-pyrazoline-1-carboxamide,! ^1st 168 to 170, 9.23 ppm (DMSO-dg).

Example 20

Ν_ / Ζμ_ (4-chlorophenoxy) -phenyl7-3,4-bis- (4-chlorophenyl) -pyrazoline-i-carboxamide, Ϊ. 154 to 156. 9.30 ppm (DMSO-dg).

Example 21

3,4-bis- (4-chlorophenyl) -N- ^ t- (4-trifluoromethylphenoxy) -phenyl ^ -pyrazoline-i-carboxamide, E. 191 to 194. 9.30 ppm (DMS0-d ₆ ).

Example 22

3- (4-Chlorophenyl) -4-phenyl-W- (4-phenylthiophenyl) -pyrazoline-1-carboxamide, Έ. 157 to 162, 8.20 ppm. 25th

Example 23

3,4-bis- (4-chlorophenyl) -N- (4-phenylthiophenyl) -pyrazoline-1-carboxamide, Έ ¹ . 169 to 171, 8.20 ppm.

Example 24 3,5-bis- (4-chlorophenyl) -N- (4-phenoxyphenyl) -pyrazoline-1-carboxamide, M.p. 168 to 170. 8.30 ppm

Example 25 3_ (4_chlorophenyl) -5- (4-trifluorme thy lphenyl) -N- (4-phenoxyphenyl) -pyrazoline-1-carboxamide, P. 164 to 167. 8.00 ppm.

L J

^Γ - * ¹⁹ - 353788?

Example 26 3,5-bis- (4-Clilorpiienyl) -II- ₍ / 4- (2-f-fluorophenoxy) -pheny-1-pyrazoline-1-carboxamide, E. 174 to 178, 8.50 ppm.

Example 27 3,5-bis (4-chlorophenyl) -I ^; r- / ^z f- (3-fluoropheiioxy) -piienyl7-pyrazoline-1-carboxamide, Έ. 164 to 168.9.00 ppm (DMSO-dg).

Example 28 3,5-bis- (4-chlorophenyl) -N- / ^z £ - (4-f iuophenoxy) -phenyl7-pyi * azoline-1-carboxamide, Έ. 165 to 167. 9.16 ppm (DMSO-dg).

Example 29

N- / 4 ^ - (4-chlorophenoxy) -phenyl7-3,5-bis ~ (4-chloropnenyl) -pyrazoline-1-carboxamide, F, 142 to 144, 9.20 ppm (DMSO-dg).

Example 30

3,5-bis- (4-0nlorophenyl) -N- / 5- (4-trifltiormethylpiienoxy) -phenyl-7-pyrazole: bi-1-carboxamide, E ¹ . 155 to 158. 8.43 ppm (CDCl ^ / DMSO-dg).

Example 31

3_ (4-Chlorophenyl) -E-ZJi- (4-trifloromethylphenoxy) -phenyl7-5- (4-trifluoromethylphenyl) -pyrazoline-1-carboxamide, J, to 146, 8.06 ppm.

Example 32

N- ^ 5- (4-chlorophenoxy) -phenyl7-5- (4-chlorophenyl) -3- (4-difluoromethoxyphenyl) -pyrazoline-1-carboxamide, I. 66 to 7 ° x 8.60 ppm (DMSO-dg).

Example- 33 5_ (1 _T 3-Benzodioxol-5-yl) -3- (4-chlorophenyl) -N- (4-phenoxyphenyl) -pyrazoline-1-carboxamide, 5 ¹ . 125 to 128, 8.36 ppm

L J

^Γ -20- - 3537885

Example 34 5- (1,3-Benzodioxol-5-yl) -N- ^ 4 ^ (4-chlorophenoxy) -phenyl7-3 · - (4-chlorophenyl) -p; 7razoline-1-carboxamide, 3 ?. 174 to 175,

8.06 ppm.
5

Example 35

N- (2,3-Dih.ydr 0-2,2-dimetb.ylbenz of ur an-5-yl) -3, 4-dipb.enylpyrazoline-1-carboxamide, 3 ?. 139 "to 143.7" 96 ppm.

Example 36 3- (4-Mfluoromethoxyplienyl) -N- (2,3- <Ühydro-2,2-dimethylbe3izofTiran-5-yl) -4-plienylpyrazoline-1-carboxamide, 3 ?. 75 "to 7.96 ppm.

¹ S example 37

(+) - 3, ^ -bis- (4-Chlorpheiiyl) -N- (2,3-dihydro-2,2-dimethylbenzofTiran-5-yl) -pyrazoline-1-carboxamide, 3 ?. 134 to 137, 7.93 ppm.

Example 38 3,5-bis- (4-chloroplienyl) -N- (2,3-dihydro-2,2-dimethylbeiizofuran-5-yl) -pyrazoline-1-carboxamide, 1 ?. 175 to 180, 8.86 ppm (DMS0-d ₆ ).

Example 39 N- (1,4-Benzodioxan-6-yl) -3- (4-chlorophenyl) -4-phenylpyrazoline-1-carboxamide, E. 112 to 115- 7.96 ppm.

Example 40 JSf _- (I _i 4-Benzodioxan-6-yl) -3,4-bis- (4-chloroplieiiyl) -pyrazoline-1-carboxamide, 3 ?. 140 to 145, 7.96 ppm.

Example 41

3- (4-chlorophenyl) -N- (4-ph.enoxyphenyl) -4-pb.enylpyrazoline-1-carbothioamide, 3 ?. 105 to 110, 10.30 ppm (DMSO-dg).

Γ - 21 -

Example 42 5,4-bis (4-chlorophenyl) -N- (4-pheno2cyphenyl) -pyrazoline-1 carbothioamide, P. 151 to 153- 9.26 ppm (DMSO-dg).

Example 43

Ef- ^ 4 * - (4-chlorophenoxy) -phenylj - ^, 4-bis- (4-chlorophenyl) -pyrazoline-1-carbothioamide, P. 179 to 183. 9.10 ppm.

Example 44 3- (4-Chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzoftiran-5-yl) -4-phenylpyrazoline-1-carbot] aioamide, 3 ?. 92 to 95, 10.12 ppm (DMS0-d ₆ ).

Example 45 3,4-bis (4-chlorophenyl) -N- (2,3-dib.ydro-2,2-dimethylbenzofuran-5-yl) -pyrazoline-1-carbot32ioamide, i ¹ . 149 to 154, 9.00 ppm (DMS0-d ₆ ).

Example46

N- (1,4-Benzodioxan-6-yl) -3,5 ~ bis (4-chloropienyl) -pyrazoline-1-carboxamide, P. 83 to 85- 9.33 ppm (DMSO-dg).

Example 47

5- (4-Clilorphenyl-3- (4-trif luorme thylphenyl) -H - / ^ - (4-trifluoromethylphenoxy) -phenylj-pyrazoline-1-carboxamide, P. 183 to 185. 8.77 ppm

Example 48 H- (2,3-Diiiydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -3- (4-difluoromethoxyphenyl) -4-phenylpyrazoline-1-carboxamide , 0 g (0.086 mol) 2-chloro-4-nitrophenol, 11.9 S (0.086 mol) potassium carbonate, 1.5 g (0.02 mol) propanethiol, 33.7 S (0.13 mol) 1.2 -Dibrometrafluoroethane and 115 ml of N, H-Dimethy! Formamide submitted. The pressure vessel is closed and the mixture is ^{stirred at 50 °} C. for 48 hours. Then the pressure vessel is brought to room temperature.

L J

^Γ -22- - 3537883

cooled, opened and poured the contents into a separatory funnel. 200 ml of a 2 η sodium hydroxide solution are then placed in the separating funnel. The mixture obtained is extracted four times with 300 ml of diethyl ether each time. The ether extracts are combined and washed twice with 100 ml of 2 η sodium hydroxide solution each time. The washed ether extract is dried over magnesium sulfate and filtered. The filtrate is evaporated under reduced pressure. An oil is left behind. The reaction described above is repeated three more times. The oily residues obtained from the four experiments are combined and purified by column chromatography on silica gel. It is eluted with a 95: 5 mixture of n-heptane and toluene. There are 57, 6 g 3-chloro-4- (2-bromo-1,1,2,2-tetrafluoräthoxy) nitrobenzene as an oil.

In a pressure vessel, 10.0 g (0.028 mol) of 3-chloro-4- (2-bromo-1,1,2,2-tetrafluoroethoxy) nitrobenzene, 9.0 g (0.14 mol) of copper powder (75 micron ), 0.45 g (0.0028 mol) of 2,2'-dipyridyl and 40 ml of dimethyl sulfoxide. The pressure vessel is sealed and the mixture was heated 190-195 for 2 hours to ⁰ G and stirred. The pressure vessel is then cooled to room temperature, opened and the contents poured into a separating funnel. About 200 ml of 2 η hydrochloric acid solution are then poured into the separating funnel. The mixture is extracted three times with 150 ml of diethyl ether each time. The ether extracts are combined and washed successively with 200 ml of 2 η hydrochloric acid, 200 ml of saturated aqueous sodium chloride solution and 200 ml of 2 η sodium hydroxide solution.

The washed ether extract is dried over magnesium sulfate and filtered. The solvent is evaporated under reduced pressure. An oil remains. the The above-described reaction is repeated six more times. The oily residue of the seven attempts will be combined and purified by column chromatography on silica gel. It is eluted with toluene. The eluate is

L J

^Γ -23- "3537883

steams. A yellow oil remains. The oil is in 125 ml Dissolved methylcyclohexane and placed the solution in a refrigerator for about 18 hours. The resulting crystals will be filtered off. Yield 20.7 S 2,2,3,3-tetrafluoro-5-nitrobenzofuran. The piltrate is evaporated under reduced pressure. What remains is an oil that under reduced pressure is distilled. There are another 3.0 g of boiling point product 75 ° C / 0.2 torr obtained.

The hydrogenation of 2.15 g (0.011 mol) of 2,2,3,3-tetrafluoro-5-nitr © benzene in the presence of 0.25 g of platinum oxide in 150 ml Methanol provides 2.15 g of 5-amino-2,2,3,3-tetrafluorobenzofuran.

A solution of 0.75 S (0.0036 moles) of 5-amino-2,2,3,3-tetrafluorobenzofuran in 109 ml of toluene is added dropwise and with stirring to 8.0 ml of a 20 percent solution of phosgene given in toluene. When the addition is complete, the mixture is refluxed for 2 hours. After that, the mixture cooled and the solvent was distilled off under reduced pressure. The residue obtained is in 15 ml Dissolved diethyl ether and, with stirring, to a solution of 1.04 g (0.0036 mol) of 3- (4-difluoromethoxyphenyl) -4-phenylpyrazoline and three drops of triethylamine in 100 ml of diethyl ether. When the addition is complete, the mixture becomes Heated under reflux for 1 hour, then cooled to room temperature and stirred for about 18 hours. Thereupon the solvent distilled off under reduced pressure. The solid residue obtained is recrystallized from ethanol.

There are 0.99 g of N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -3- (4-difluoromethoxyphenyl) -4-phenylpyrazoline-1-carboxamide from P. 155 "up to 159 ° C. Calc .: C 58.58 H 3.29
Found: C 57.81 H 3.75.

Nuclear Magnetic Resonance Spectrum: 8.16 ppm.

^r - ² ^ - 3537883

3537883

Example 4-9 3,4-bis (4-chlorophenyl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) -pyrazoline-1-carboxamide

A solution of 1.18 g (0.0068 mol) of 5-amino-2,2-difluoro-1,3-benzodioxole (prepared by a method described in the literature) in 80 ml of tetrahydrofuran is added dropwise to 24 ml of a 5 bis 10 ⁰ C cold, 20 percent solution of phosgene in toluene. When the addition is complete, the mixture is stirred at 2 ° C. for 1 hour and then refluxed for 2 hours. The solvent is then distilled off under reduced pressure. 1.4 g of a liquid residue remain.

0.68 g of the residue obtained are slowly and with stirring to a solution of 0.93 g (0.0032 mol) of 3,4-bis (4- Chlorophenyl) pyrazoline and three drops of triethylamine in Given 20 ml of diethyl ether. When the addition is complete, the mixture is stirred at room temperature for about 18 hours. A minor one The amount of solid in the reaction mixture is filtered off. The 3? Filtrate is evaporated under reduced pressure. Of the The residue obtained is purified by column chromatography on silica gel. It is made with a 1: 1 mixture of n-heptane and ethyl acetate eluted. The eluate is evaporated. It 1.3 g of the title compound with a melting point of 150 ° to 155 ° C. are obtained.

Calcd .: C 56.34 H 3.08
Found: C 57.16 H 2.89
Nuclear Magnetic Resonance Spectrum: 8.10 ppm.

The compound of Example 50 is prepared in a similar manner.

Example 50

N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) - ⁱ i-phenylpyrazolin-1-carboxamide, Έ. 135 to 138, 8.10 ppm.

Example 51 3- (4-Fluorophenyl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide, F. 187 "to 191. 8.10 ppm.

Example 52

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

Example 53

3- (4-chlorophenyl) -N- / 5- (4-chlorophenoxy) -phenyl7-4-phenylpyrazoline-1-carboxamide, F. I70 to 174-. 8.10 ppm.

Example 54-

3- (4-chlorophenyl) -N- / 5- (4-nitrophenoxy) -phenyl7-4 ~ phenylpyrazoline-1-carboxamide, F. 187 to 189. 8.30 ppm.

Example 55

3- (4-Chlorophenyl) ~ - /% - (4-methoxyphenoxy) -phenyl7-4-phenylpyrazoline-1-carboxamide, m.p. 159 to 160, 8.07 ppm. 20th

Example 56

3- (4-chlorophenyl) -N- / 5- (4-difluoromethoxyphenoxy) -phenyl7-4-phenylpyrazoline-1-carboxamide, 181-184-8.07 ppm.

B e- "i s ρ i e 1 57 N- / 4- (4-chlorophenoxy) -phenyl7-3- (4-trifluoromethoxyphenyl) 4-phenylpyrazoline-1-carboxamide, F. I32 to 134-. 8.16 ppm.

Example 58 N- / 5-C 4-Chlorophenoxy) -phsnyl7-4-phenyl-3- / 4 "- (2-pr opinyloxyphenyl7-pyrazoline-1 -carboxamid, F. 160 to 164-. 8.13 ppm.

Example 59

3- (1,3-Benzodioxol-5-yl) -N- (4 ~ phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide, F. 220 to 223, 8.06 ppm.

L J

-26 - 3537883

Example 60 4- (4-chlorophenyl) -N- (4-phenoxyphenyl) -3-phenylpyrazoline-1-carboxamide, P. 153 "to 155 x 8.16 ppm.

Example 61 3,4-bis (4-fluorophenyl) -N- (4-phenoxyphenyl) -pyrazoline-1-carboxamide, F. 194 to 198. 8.16 ppm.

Example 62 N- / 4 "- (2-Chlorophenoxy) -phenyl7-3,4-bis- (4-chlorophenyl) -pyrazoline-1-carboxamide, M.p. 182 to 186. 8.10 ppm.

Example 63

3,4-bis- (4-chlorophenyl) -N-A-C 4-methoxyphenoxy) -phenyl-7-pyrazoline-1-carboxamide. 8.20 ppm.

Example 64 3- (4-Chlorophenyl) -4- (4-fluorophenyl) -N- (4-phenoxyphenyl) -

pyrazoline-1-carboxamide, m.p. 178 to 179. 8.10 ppm. 20th

Example 65

N- / 5- (4-chlorophenoxy) -phenyl7-3- (4-chlorophenyl) -4- (4-fluorophenyl) -pyrazoline-1-carboxamide, P. 143 to 145. 8.03 ppm.

Example 66

3 _ (4_chlorphenyl) -4- (4-methylpheny1) -N- (4-phenoxyphenyl) -pyrazoline-1-carboxamide, P. 165 to 168. 8.10 ppm.

Example 67

n_ / Z £ - (4-chlorophenoxy) -phenyl7-3- (4-chlorophenyl) -4- (4-methoxyphenyl) -pyrazoline-1-carboxamide, P. 169 to 173- 8.07 ppm.

Example 68

4- (4-5 ¹ Iu orphenyl) -3- (4-methoxyphenyl) -N- (4-phenoxyphenyl) pyrazoline-1-carboxamide, mp 184 ppm to 187. 8.17.

L J

^Γ -27- '3537882

Example 69 N- ^ 5- (4-Difluoromethoxyphenox7) -ph.enyl7-3- ( ^z f-d.ifluoromethoxyphenyl) -4- (4-fluorophenyl) -pyrazoline-1-carboxamide. 8.10 ppm.

Example 70 Ny / 5- (4-Ghlorplienoxy) -pheiiyl7-3- (l ^z ~ chlorplienyl) - ⁱ i-phenylpyrazolin-1-thiocarboxamide, F. 179 to 183. 9.10 ppm.

Example 71 3- (4-DifluoromettLOxyphenyl) -N- (4-phenoxyph.en.yl) -4-phenylpyrazoline-1-thiocarboxamide, M.p. 132 to 136. 9.13 ppm.

Example 72

4- (4-chlorophenyl) -N- (4-- phenoxyphenyl) -3-phenylpyrazoline-1-thiocarboxamide, F. I31 to 133. 9.16 ppm.

Example 73

N - /% - (4-Chlorophenylthio) -phenyl7-3,4-diphenylpyrazoline-1-carboxamide, P. 186-190, 8.20 ppm. 20th

Example 7 ^

3- (4-chlorophenyl) -N- / 5- (4-chlorophenylthio) -phenyl7- ^£ l-phenylpyrazoline-1-carboxamide, m.p. 178 to 181, 8.23 ppm.

Example 75 3_ (4-dif luorme thoxyphenyl ^ -phenyl-N- (4-phenylthiophenyl) pyrazoline-1-carboxamide, F. 135 to 14-0. 8.13 ppm.

Example 76 3 _i 4 - bis (4-chlorophenyl) -N- / 5- (4 ~ f Iuophenylthio) -phenyl-7-pyrazoline-1-carboxamide, m.p. 171 to 175-8.20 ppm.

Example 77

3,4 - bis (4-chlorophenyl) -Ν-7Ή- (4-chlorophenylthio) -phenyl7-pyrazoline-1-carboxamide, F. 15I to 156. 8.13 ppm.

- ²⁸ - '■ "3'5" 3788i

Example 78 3,4-bis (4-chlorophenyl) -N- ^ 4 "- (3-chlorophenoxy) -phenyl7-pyrazoline-1-carboxainide, F. 135 to 14-0. 9.20 ppm (DMSO-dg)

Example 79 3- (4-Methoxyphenyl) -N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide, P. 188 to 192. 8.46 ppm (CDCWDMSO-dg).

Example 80

ο 3- / 4 "- (2-pr opinyloxy) -phenylZ-N- (4-phenoxyphenyl) -4-phenylpyrazoline-1-carboxamide, ] ?. 121 to 126, 8.10 ppm.

Example 81

3- (4-Chlorophenyl) -N- (2,3-dihydrobenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide, 3 ?. 155 to 158 7 _? 93 ppm.

Example 82

3- (4-Bif luormethoxyphenyl) -N- (2 ^ -dihydxobenzofizran ^ -yl) - ⁴ ~ phenylpyrazolin-1-carboxamide. 7.93 ppm. 20th

Example 83

3,4-bis- (4-chlorophenyl) -lii- (2,3-dihydrobenzofuran-5-yl) -pyrazoline-1-carboxamide, i ¹ . 214 to 216, 7-93 ppm.

B is ρ ie 1 84 3- (4-iluophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide, Ϊ ¹ . 156 to 160, 7.93 ppm.

Example 85

3- (4-methoxyphenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide, F. 164 to 169-8.00 ppm.

Example 86 3 _ (4-Trifluoromethoxyphenyl) -N- (2,3-dihydro-2,2-dimethylbenzofTiran-5-yl) -4-phenylpyrazoline-1-carboxamide, ΊΡ. 81 to 83, 7.98 ppm.

L J

^r - ² ^ "3537883

Example 87

Ν- (2,3-üihydro-2,2-dimethylbenzoftiran-5-yl) -4 ~ phenyl-3- ^ 4- (propinyloxy) -phenyl7-pyrazoline-1-carboxamide, F. 175 "to 179.8, 00 ppm.
5

Example 88

3-O, 3-Benzodioxol-5-yl) -H- (2,3-diydro-2,2-dimethyl'benzofuran-5-yl) - ^ phenylpyrazoline-1-carboxamide, F. 223 to 227.8, 90 ppm (DMSO-dg).
10

Example 89

4- (4-Chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenz of uran-5-yl) -3-phenylpyrazoline-1-carboxamide. 8.00 ppm.

Example 90

3,4-bis- (4-5 ^l luophenyl) -N- (2,3-dih.ydro-2,2-dimethylbenzofiran-5-yl) -pyrazoline-1-carboxamide, Έ. 161 to 166. 7 »93 ppm.

Example 91 3- (4-Chlorophenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -pyrazoline-1-carboxamide, P. 169 to 171. 7.96 ppm.

Example 92 3_ (4_Glorophenyl) -4- (4-methylphenyl) -N- (2,3-diliydr o-2,2-dimethylbenzofuran-5-yl) -pyi ^> azoline-1-carboxamide, P. to 139-7 , 96 ppm.

Example 93 3_ (ζμ-chlorophenyl) -4- (4-methoxyphenyl) -N- (2,3-dihydr 0-2,2-dimethylbenzofurarL-5-yl) -pyrazoline-1-carboxamide, P. to 186.7.93 ppm.

Example 94-4- (4-Pluophenyl) -N- (2,3-dihydr0-2,2-dimethylbenzofuran 5-yl) -3- (4-methoxyphenyl) -pyrazoline-1-carboxamide, P. to 182, 7.93 ppm.

L J

^Γ - 50 - - -. 3537889

Example 95 4- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -3- (4-methoxyphenyl) -pyrazoline-1-carboxamide, F. 157 to 160, 7.96 ppm.

Example 96

3- (4-Difluoromethoxyphenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofTiran-5-yl) -pyrazoline-1-carboxami.d, I ¹ .

to 172.7.93 ppm.
10

Example 97

4- (4-chlorophenyl) -3- (4-difluoromethoxyphenyl) -N- (2,3-dihydr o-2,2-dimetb.ylbenzof-uran-5-yl) -pyrazoline-1-carboxamide, i ¹ .

to 95-7.93 ppm.
15th

Example 98

3_ (4-difluorometiioxyphenyl) -l! T- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-6-yl) -4-piienylpyrazoline-1-carboxamide, I *.

152 to 157, 8.33 ppm.
20th

Example 99

3- (4-Lifluorometlioxyphenyl) -4- (4-fluorophenyl) -N- (2,3-dihydr o-2,2,3,3-tetraf luorbenzof Tiran-6-yl) -pyrazolin-1-carboxamide,

S ¹ . 110 to 114, 8.33 ppm. 25th

Example 100

3_ (4-Difluoromethoxyphenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -pyrazoline-1-carboxamide,

1. 155 to 159. 8.20 ppm. 30th

Example 101

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

Example 102 3- (4-Difluoromethoxyphenyl) -N- (2,2-dimethyl-1,3-benzodioxol-5-yl) -4-phenylpyrazoline-1-carboxamide, P. 48 to 150, 7.93 ppm.

L _l

^Γ -51- 353788?

T example ΙΟ3

3,4-bis- (4-ciaorphenyl) -N- (2,2-dimethyl-1,3-benzodioxol-5-yl) -pyrazoline-1-carboxamide, M.p. 168 to 169, 7.93 ppm.

. Example 104

N- (1,4-Benzodioxan-5-yl) -3- (4-difluoromethoxyphenyl) -4-phenylpyrazoline-1-carboxamide, 7 »93 ppm.

Example 105 IT- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) -N-methyl-4-phenylpyrazoline-1-carboxamide, F. 110 to 114-,

Example 106 4- (1,3-Benzodioxol-5-yl) -N- (4-phenoxyphenyl) -3-phenylpyrazoline-1-carboxamide, P. 195 to 197- S, 03 ppm.

Example 107

3- (4-Clilorplienyl) -N- / 5- / 5- (1,1-dimethylethyl) -phenoxy / -phenylZ - ^ - phenylpyrazoline-i-carboxamide, E ¹ . 192.5 to 194, 8.03 ppm.

Example 108

3 _ (4-chlorophenyl) -4- (4-fluorophenyl) -N- / 4 "- (4-methylphenoxy) phenylj-pyrazoline-i-carboxamide, 162 to 164, 8.03 ppm.

Example 109

3_ (4-Chlorpiienyl) -4- (4-fluorophenyl) -W-ß-ß- (1,1 -dimethylethyl) -phenoxy _< 7-phenyl7-pyrazoline-1-carboxamide, m.p. 188 to 198. 8, 03 ppm.

Example 110

3- (4-chlorophenyl) -] $ - ß-ß- (1 -methylethyl) -phenoxy.7-phenyl7-4-phenylpyrazoline-1-carboxamide, m.p. 181 to 182.5- 8.06 ppm. 35

-32- 3537883

example

3- (4-chlorophenyl) -4 ~ (4 ~ fluorophenyl) -N- / 4 "- / $ - (1-methylethyl) -phenox ^ -pheny ^ -pyrazoline-i-carboxamide, F. 186 to 187. 8.60 ppm (CDCWDMSO-dg).

Example 112

3 - (4 ™ chlorophenyl) -N- / 4-- (4 ~ metliy! Phenoxy) -phenyJ ^ -A-phenylpyrazoline-1-carboxamide, J ¹ . 150 to 151 x 8.06 ppm.

Example 113 3- (4-chlorophenyl) -N- / 5- / 5- (1-methyl ethoxy) -phenoxjZ-phenyl / -4-phenylpyrazoline-i-carboxamide, I ¹ . 158 to 160.5 x 8.06 ppm.

Example 114-3- (4-chlorophenyl) -4 ~ (4 ~ fluorophenyl) -N- / 5- / 5- (1 -methylethoxy) phenox27-phenyl7-pyra2olin-1-caΓboxamide, F. 213 to 216. 8.66 ppm

Example 115 3,4-bis (4-fluorophenyl) -H - /;? - / 5- (1-methylethoxy) -phenox27 " phenylZ-pyrazoline-i-carboxamide, m.p. 134-136, 8.06 ppm.

Example 116

3,4 bis (4-fluorophenyl) -N-Z5- (4-chlorophenoxy) -phenyl7-pyrazoline-1-carboxamide, m.p. 197 to 198.5- 8.70 ppm (CUCl ₅ / DMS0-d ₆ ).

Example 117

3,4-bis- (4 ~ fluorophenyl) -N - ^ - ^ - (1,1 -dime thy Iäthyl) -phenoxy7-phenylZ-pyrazoline-i-carboxamide, 189 to 192, 8.70 ppm (CDCWDMSO-Dg).

Example 118

3,4 bis (4-fluorophenyl) -N- ^ i-C ^ -cyanophenoxy) -phenyl7 ~ pyrazoline-1-carboxamide, m.p. 198-200, 8.13 ppm.

L J

^Γ -33 - 3537885

Example 119

phenyl7-pyTazolin-1-carboxamide, m.p. 146 to 150. 8.02 ppm.

Example 120 3- (4-Chlorophenyl) -N - / 4 "- (4 - cyaiiophenoxy) -phenyl7- ⁱ t-plienylpyrazoline-1-carboxamide, m.p. 170 to 172, 8.16 ppm.

Example 121 F- (1,4-Benzodioxan-6-yl) -4- (4-chlorophenyl) -3- (4-difluoromethoxyphenyl) -pyrazoline-1-carboxamide, 1. 124 to 128. 7.93 ppm.

Example 122

3 _t 4-bis (4-chloroplienyl) -N- (2,3-di] aydro-2,2-dimethylbenzofuran-5-yl) -N-methylpyrazOlin-1-carboxamide, F. 150 to 155 ·

Example 123 N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3,4-diphenylpyrazoline-

1-carboxamide, m.p. 214-216. 8.83 ppm (CDCl ^ / DMSO-dg). 20th

Example 124

H- (2 _{liters of} 2-difluoro-1,3-benzodioxol-5-yl) -3,4-bis (4-fluorophenyl) -pyrazoline-1-carboxamide, m.p. 178 to 18P. 8.10 ppm.

B is ρ ie 1 125 3_ (4-chlorophenyl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) -4- (4-fluorophenyl) -pyrazoline-1-carboxamide, i ^1st 147 to 15I. 8.06 ppm.

Example 126 3- (4-difluorometb.oxyplienyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenz of uran-5-yl) -IT-methyl-4-pheny Ipyrazoline-1-carboxamide.

Example 127 3_ (4-Cb.lorphenyl) ~ 4- (4-difluorometb.oxyplieiiyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -pyrazolin-1-carboxamide, P. to 159. 7.96 ppm.

L J

3537885

Example 128 3- (4-Difluoromethoxyphenyl) -N- (2,3-dihydro-2,2-difluorobenz of uran-5-yl) -N-methyl-4-phenylpyrazoline-1-carboxamide.

Example 129 4 ~ (4 ~ Chlorophenyl) -H- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4 - difluoromethoxyphenyl) -pyrazoline-1-carboxamide. 8.06 ppm.

Example 130 4_ (i _? 3-Benzodioxol-5-yl) -3- ( ^/ i-chloropheiiyl) -N - ^ - (4-fluoromethoxyph. Enoxy) -piierLyl7-pyrazoliii-1-carboxamide.

Example 131

Z} ._ (1 ^ 3-Benzodioxol-5-yl) -I- / 5- (4-clilorphenoxy) -phenyl7-3_ ( 4_ch.l orphenyl) pyrazoline-1-carboxamide.

Example 132

4- (1,3-benzodioxol-5-yl) -3- (4-cb.l or phenyl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) -pyrazoline- 1-carboxamide.

Example 133

4- (1,3-benzodioxol-5-yl) -3- ^(Z '-chlorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorbenzofuran-5-yl) pyrazoline-1 -carboxamide.

B, -e i s ρ i e 1 13 ^ A - (1,3-Benzodioxol-5-yl) -3- (4-chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -pyrazoline-1-carboxamide .

Example 135

4_ (ι, 3-Benzodioxol-5-yl) -N - ^ - (A - dif luormethoxyphenoxy) -phenyl7-3- ( 4-difluoromethoxyphenyl) pyrazoline-1-carboxamide.

Example 136

4 ~ (1,3-Benzodioxol-5-yl) -W ^z f- (4-chloroplaenoxy) -phenyl7-3- (4-difluoromethox; 7phenyl) -pyrazoline-1-carboxamide.

^Γ - ³⁵ ~ 3537885

Example 137

4- (1,3-Benzodioxol-5-yl) -H- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) pyraz olin-1-carb oxamide.

Example 138

4- (1,3-Benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) -N- (2,3-dihydr0-2,2,3,3-tetrafluorobenzofuran-5-yl) -pyrazolin-1- carboxamide.

Example 139 4- (1,3-Benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) -N- ( 2,3- <iinydr 0-2,2-dimethylbenz of ur an-5-yl) -pyrazole-1 carboxamide.

Example 140 4- (1,5-Benzodioxol-5-yl) -N- (2,3-dihydro-2,2-dimethylbenzofur an-5-yl) -3-pb.enylpyrazoline-1-carboxamide.

example

4_ (1,3-benzodioxol-5-yl) -N- (2.3-diliydro-2,2,3,3-tetraf luorbenzof • iiran-5-yl) -3-plienylpyi ^l quinazolin-1 -earboxamid.

Example 142

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

Example 14-3

4- (1,3-Benzodioxol-5-yl) -N- / 4- (4-difluoromethoxyphenoxy) -plienyl7-3-plienylpyrazoline-1-carboxamide. 30th

Example 144-

4- (1,3-Benzodioxol-5-yl) -N- / 5- (4-chlorophenoxy) -phenyl7-3-phenylpyrazoline-1-carb oxamide.

Example 145 4- (2,2-DiflTior-1,3-benzodioxol-5-yl) -N-Z4- (4-difluorometlioxyphenoxy ) -phenyl7-3- (4-f ltiorphenyl) -pyrazoline-1-carboxamide.

L J

^Γ -36- ■ - "■ '353788?

Example 146 Ny {4 "- (4-Chlorophenoxy) -phenyl7-4- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4-fluorophenyl) -pyrazole: ha-1-carboxamide .

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

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

Example 149 4- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3- (4-fluorophenyl) -N- ( 2,3-dihydr O-2,2-dimethylbenz of ur an-5-yl) -pyrazoline-1 carboxamide.

Example 150 4- (2,2-difluoro-1,3-benzodioxol-5-yl) -N- / ^z f- (4-difluoromethiioxyphenoxy) -pheny ^^ - pkenylpyrazoline-1-carboxamide.

Example 151

N- / 4 * - (4-Culophenoxy) -phenyl7-4- (2,2-difluoro-1,3-benzodioxol-5-yl) -3-phenylpyrazoline-1-carboxamide.

Example 152 4, N-bis- (2,2-difluoro-1,3-benzodioxol-5-yl) -3-phenylpyraz o-

lin-1-carboxamide.
30th

Example 153

4- (2,2-Difluoro-1,3-benzodioxol-5-yl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -3-phenylpyrazolin-1- carboxamide.

Example 151 4- (2,2-difluoro-1,3-benzodioxol-5-yl) -N- (2,3-di3aydro-2,3-dimethylbenzofuran-5-yl) -3-phenylpyrazoline-1-carboxamide.

L J

^Γ - 37 - ■■ "■■ _ 3537885

Example 155

4- (2,2-Difluoro-1,3-benzodioxol-5-yl) -N- <fl • - (4-difluoromethoxyphenoxy) -phenyl7-3- (4-difluoromethoxyphenyl) -pyrazoline-1-carboxamide.
5

Example 156

4-chlorophenoxy) -phenyl? - ² ! - (2,2-difluoro-1,3-benzodioxol- -3- (4-- difluoromethoxyphenyl) -pyrazoline-1-carboxamide.

Example 157 4, N-bis (2,2-difluoro-1,3-benzodioxol-5-yl) -3- ( ^z 1-difluoromethoxyphenyl) -pyrazoline-1-carboxamide.

Example 158

4- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3 - (^ - difluoromethoxyphenyl) -N- (2,3-dihydr0-2,2,3,3-tetrafluorobenzofuran-5-yl ) -pyrazoline-1-carboxamide.

Example 159

4 ~ (2,2-difluoro-1,3-benzodioxol-5-yl) -3- ( ^z l-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) - pyrazoline-1 carbon oxamide.

Example 160

4- (i, 4-Benzodioxan-6-yl) -3- (4-chlorophenyl) -N- / 5- (4-difluoromethoxyphenoxy) -phenyl-7-pyraz olin-1-carboxamide.

Example 161

4- (1,4-Benzodioxan-6-yl) -N- ^ f- (4-chlorophenoxy) -phenyl7-3- (4-chlorophenyl) -pyrazoline-1-carboxamide.

Example 162 4- (1 _f 4-Benzodioxan-6-yl) -3- (4 ~ chlorophenyl) -H- (2,2-difluoro-

1,3-benzodioxol-5-yl) pyrazoline-1-carboxamide. 35

L J

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

Example 164-4- (1,4-Benzodioxan-6-yl) -3 - (^ - clilorph.enyl) -N- (2,3-dihydio-2,2-dime thylbenz of ur an-5-yl) -pyr az olin-1 -carboxamid.

Example 165 4— (1, ^ - Benzodioxan-6-yl) -N- / 5- (4-difluoroniethoxypheiioxy) -

Example 166

4- (1,4-Benzodioxan-6-yl) -N- ^ 5- (A-chlorophenoxy) -phenyl7-3- (4-difl-uormetiioxyphenyl) -pyrazoline-1-carboxamide.

Example 167

, 4-benzodioxan-6-yl) -H- (2,2-difluoro-1,3-benzodioxol-5- -3- (2f-dif luormethoxyphenyl) pyr az ol-i-carb oxamide. 20

Example 168

A- (1,4-Benzodioxan-6-yl) -3- (4-difl \ iomethoxyphenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) - pyrazoline

1-carboxainide.
25th

Example 169

4 - (1,4-Benz odioxan-6-yl) -3- (4-difluoromethoxyphenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -pyrazolin-1-

carboxamide.
30th

Example 170

4- (1,4-Benzodioxan-6-yl) -N / 4 * - (4-difluoromethoxyphenoxy) phenyl7-3-phenylpyrazoline-1-carboxamide.

B e i s ρ i e 1 4 - (1,4-Benzodioxan-6-yl) -N- / 5- (4-chlorophenoxy) -phenyl7- 3-phenylpyrazoline-1-carboxamide.

L J

Γ _ 39 - ^: "π.

Example 172 4- (1,4-Benzodioxan-6-yl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3-phenylpyraz olin-1-c arboxamide.

Example 175 4- (1,4-Benzodioxan-6-yl) -H- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl ) -3-phenylpyrazoline-1-carboxamide.

Example 174-4- (1,4-Benzodioxan-6-yl) -N- (2,3-diliydro-2,2-dimethylbenzo- for an-5 ~ 7l) -3-pb-enylpyrazoline-1-carboxamide.

Example 175

3- (1ί 3-Benzodioxol-5-yl) -N- ^ i- (4-difluoromethoxyphenoxy) -phenyl7-4— (4-fluoroplienyl) -N-methylpyrazoline-1-carboxamide.

Example 176

3- (1 ί 3-Benz odi oxol-5-yl) -ΪΓ- / ί- (4-cnlorphenoxy) -phenyl7- · ^ - (4-fluorophenyl) -pyrazoline-1 -carboxamide. 20th

Example 177

3- (1,3-Benzodioxol-5-yl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl ) -4- (4-fluoroplienyl) -pyr azoline-1-carboxamide.

Example 178 3- (1,3-Benzodioxol-5-yl) -4- (4-fluorophenyl) -H- (2,3-dihydro-2,2,3,3-tetrafluorobenz ofuran-5-yl) pyrazoline-1-carboxamide.

Example 179

3- (1,3-Benzodioxol-5-yl) - ⁱ l- ( ^z l-fluoropb.enyl) -Ii- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -pyrazolin-1- carboxamide.

Example 180

3- (2,2-Difluoro-1,3-benzodioxol-5-yl) -N - ^ - C4-difluoromethoxyphenoxy) -phenyl7-4- (4-fluorophenyl) -pyrazoline-1-carbox amide.

Example 181

N -, / 5- (4-Chlorophenoxy) -phenyl7-3- (2,2-difluoro-1,3-benzodioxol-5-y 1) -4- (4-fluoropheny1) -N-methylpyrazoline-1-carboxamide.

Example 182

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

Example 183

3- (2,2-Difluoro-1,3-benzodioxol-5-yl) -4- (4-fluorophenyl) -N- (2,3-dihydro ~ 2,2,3,3-tetraf luorbenzofuran-5-yl) pyrazoline-1-carboxamide.

Example 184 3- (2,2-Difluoro-1,3-benzodioxol-5-yl) -4- (4-fluorophenyl) -N- (2,3-dihydr0-2,2-dimethylbenzofuran-5-yl) - pyraz olin-1-carboxamide.

Example 185 3- (Ί, A-Benzodioxan-G-yl) -IT ^ -C 4-difluoromethoxyphenoxy) - ph.enylpyrazoline-1-carboxamide.

Example 186

3- (1,4-Benzodioxan-6-yl) -N- ^ 5- (4-chlorophenoxy) -phenyl7- 4-phenylpyrazoline-1-carboxamide.

Example 187 3_ (1,4-Benzodioxan-6-yl) -N- (2,2-difluoro-1,3-benzodioxole-

5-yl) -N-methyl-4-phenylpyrazoline-1-carboxamide. 30th

Example 188

3_ (1,4-Benzodioxan-6-yl) -N- (2,3-dihydro-2 _i 2 _r 3,3-tetrafluoro-benzofuran-5-yl) -4-phenylpyrazolin-1-carboxamide.

Example 189 3- (1,4-Benzodioxan-6-yl) -N- (2,3-dihydro-2,2-dimethylbenzof uran-5-yl) -A-- pheny lpyrazolin-1-carbon oxamide.

Example 190

N- / ¥ - (4-dif luo: rmethoxyphenoxy) -phenyl7-3- (2,3-dihydro-2,2-dimethylbenzof iiran-5-yl) -4 ~ phenylpyrazoline-1-carboxamide.

Example 191

N-A-C ^ -chlorophenoxy) -phenyl7-3- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyr azoline-1-carbon oxamide.

For ρ ie 1 192 N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-pb. enylpyraz olin-1 carboxamide.

Example 193

N- (2,3-Dihydr 0-2 ₁ 2,3,3-tetrafluorobenz ofuran-5-yl) -3- (2,3-dihydr0-2,2-dimethylbenz öf "uran-5-yl) - H-methyl-4-phenylpyrazoline-1-carbon oxamide.

Example 3, N-bis- (2,3-Dinydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carb oxamide.

Example 195 Ν- / ί- (4-Dif luorme thoxyphenoscy) -pheny ^ - ^ - (A-- fluorophenyl) -

3- (4-methylphenyl) pyrazoline-1-carboxamide. 25th

Example 196

N- / Zf_ (Z {._ chlorophenoxy) -phenyl7-4- (4-fluorophenyl) -3- (4-methyl phenyl) -pyr azoline-1-carboxamide.

For example, 1,197 N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -4- (4-fluorophenyl) -3- (4-methylphenyl) -pyrazoline-1-carboxamide.

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

L J

Example 199 4- (4-j? Luophenyl) -N- (2,3-clihydr ο-2,2-dimethylbenz ofuran-5-yl) -N-methyl-3- ( 4-methylphenyl) pyrazoline-1-carboxamide.

Example 200 Ν- / Ά- (4-M-fluoromethoxyphenoxy) -phenyl7-4- (3-fluorophenyl) -N-methyl-3- (4-methylphenyl) -pyrazoline-1-carboxamide.

Example 201 o S- / TL- (4-chlorophenoxy) -phenyl7-4- (3-fluorophenyl) -3- (4-methylphenyl) -pyrazoline-1-carboxamide.

Example 202

N- (2,2-difl-uor-1,3-benzodioxol-5-yl) -4- (3-fluorophenyl) -3- (ζµ-me ethylphenyl) -pyr azoline-1-carboxamide.

Example 203

4- (3-Pluophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenz of-or an-5-yl) -3- (1-methylphenyl) -pyrazoline-1 -carb oxamid. 20th

Example 204

4- (3-fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenz of • uran-5- ' yl) -3- (4-methylphenyl) pyrazoline-1-carboxamide.

B e i s ρ i e 1 205 N- / ZJL · (4-difluoromethoxyphenoxy) -phenyl7-4- (2-fluorophenyl) 3- (4-methylphenyl) -pyrazoline-1-carboxamide.

Example 206 N- / 4- (4-Chlorophenoxy) -phenyl / -4- (3-fluorophenyl) -N-methyl-3_ (iL_ _m ethylphenyl) -pyrazoline-1-carboxamide.

Example 207

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

L j

Γ. 43 - - Π

Example 208 4- (2-1IuOrPlIeIIyI) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzof uran-5-yl) -3- (4-methylphenyl) -pyrazole-1-carboxamide.

Example 209 4- (2-Iluophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -3- (4-methylphenyl) -pyraz olin-1-carb oxamide.

Example 210 N- / i- (4-Difluorme1: hoxyphenoxy) -phenyl7-3- (3-i ^> luophenyl) -4- (4-fluorophenyl) -pyrazoline-1-carboxamide.

Example 211

N- / 5- (4-chlorophenoxy) phenyl 7-3- (3-fluorophenyl) -4- (4-fluorophenyl) pyrazoline-1-carboxamide.

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

(4-fluorophenyl) -N-methylpyrazoline-1-carboxamide. 20th

Example 213

3_ (3_Fl _UO rphenyl) -4- (4-fluorophenyl) -U- (2,3-dihydro-2,2,3,3-tetrafluorobenzene-5-yl) -pyrazoline-1-carboxamide.

Example 214 3- (3-fluorophenyl) -4- (4-fluorophenyl). -N- (2,3-dihydro-2,2-dimethylbenz ofuran-5-yl) pyrazoline-1-carboxamide.

Example 215

ff_ / ZjL · (4-difluoromethoxyphenoxy) -phenyl7-3- (2-fluorophenyl) 4- (4-fluorophenyl) -pyrazoline-1-carboxamide.

Example 216

N- ^ f- (4-Chlorophenoxy) -phenyl7-3- (2-fluorophenyl) -4- (4-fluorophenyl) -pyrazoline-1-carboxamide.

L J

Example 217

Ν- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3- (2-fluorophenyl) ~ 4- (4-f luophenyl) pyrazoline-1-carboxamide.

Example 218

3- (2-Fluorophenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzof-araxL-5-yl) -N-methylpyrazoline-1-carboxamide.

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

Example 220

3,4-bis- (4-i ^1- luophenyl) -IT- (2,3-dihydro-2,2,3,3 _f 7-pentafluorobenzofuraix-5-yl) pyrazoline-1-carboxamide.

Example 221 4- (4-chlorophenyl) -Ii- (2,3-dihydro-2,2,3,3,7-pentaf luorbenzo-

furan-5-yl) -3- (4-methylphenyl) pyrazoline-1-carboxamide. 20th

Example 222

H- (2,3-dihydro-2,2,3,3,7-pentafluorobenzofuran-5-yl) -3,4-diphenylpyrazoline-1-carboxamide.

B eis ρ ie 1 223 3- (4-Difluoromethoxyphenyl) -N- (2,3-dihydro-2,2,3,3,7-pentafluorbenz of uran-5-yl) - ⁱ i-phenylpyrazolin-1- carboxamide.

Example 224

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

Example 225

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

L J

r _ 45 - '■ "' ■ - π

Example 226 4- (4-Chlorophenyl) -N- (2,2,6-trimethyl-1,3-'benzodioxol-5-yl) -3- ( 4-methylphenyl) pyrazoline-1-carbon oxamide.

Example 227 N- (2,2,6-Trimethyl-1,3-benzodioxol-5-yl) -3,4-dipnenylpyrazoline-1-carboxamide.

Example 228 3- (4-Difluoromethoxyplienyl) -W- (2,2,6-trimethyl-1,3-benzodi oxol-5-yl) - ^ Hplienylpyrazolin-1 -carboxamid.

Example 229

3- (4_ci _l iorplienyl) -N- (2,2,6-trimethyl-1,3-benzodioxol-5-yl) -4-phenylpyrazoline-1-carboxamide.

Example 230

3,4-bis (4-fluorophenyl) -N- (7-methoxy-2,2-dimethyl-1,3-benzodioxol-5-yl) -pyrazoline-1-carboxamide. 20th

Example 231

4- (chlorophenyl) -W- (7-methoxy-2,2-dimethyl-1,3-benzodioxol-5 »yl) _3_ (4-methylphenyl) pyraz olin-1-carb oxamide.

For example, 1,232 H- (7-Metlioxy-2,2-dimethyl-1,3-benzodioxol-5-yl) -3,4-diphenylpyrazoline-1-carboxamide.

Example 233 3- (4-difluoromethoxyphenyl) -N- (7-methoxy-2,2-dimethyl-1,3-benzodioxol-5-yl) - ⁱ l · -phenylpyrazolin-1-carboxamide.

Example 3_ (Z | _Chlorophenyl) -N- (7-methoxy-2,2-dimethyl-1,3-benzodioxol-5-yl) -4-phenylpyrazoline-1-carboxamide.

L J

Example 235 3,4 bis (4: E ¹ luophenyl) -Ή- / 2,2 -dimethyl-7- (1-methylethyl) -1,3-benzodioxol-5-yl7-pyrazoline-1-carboxamide.

Example 236 4- (4-Chlorophenyl) -N- / 2,2-dimethyl-7- (1-methylethyl) -1,3-benzodioxol-5-yl7-3 - (^ - niethy IPhBUyI) -PyTaZOUn-I-carboxamide.

Example 237 N- / 2,2-Dimethyl-7- (1 -metb.ylatb.yl) -1,3-benz odioxol-5-yl7-3, A - diphenylpyrazoline-i -carboxamide.

Example 238

3- (A ~ difluorometb.oxypb.enyl) -N- / 2,2-dimethyl-7- (1-methylethyl) 1,3-benzodioxol-5-yl7- ⁱ l -pb.eIlylpyrazoline-1-carboxamide .

Example 239

3_ (4-Chloropb.enyl) -N- / 2,2-dimethyl-7- (1-methylethyl) -1,3-benzodioxol-5-yl7-4-phenylpyrazolin-1 -carboxamide. 20th

Example 2A-0

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

For ρ ie 1 24-1 4- (4-chlorophenyl) -N- (2,3-dihydro-7-ethyl-2,2,3,3-tetrafluorobenzofuran-5-yl) -3- (4-methylphenyl ) -pyrazoline-1-carboxamide.

Example 24-2 H-C 2,3-Dihydro-7-ethyl-2,2,3,3-tetrafluorobenzof uran-5-yl) 3,4-diphenylpyrazoline-1-carboxamide.

Example 24-3

3- (4-Difluoromethoxyphenyl) -H- (2,3-dihydro-7-ethyl-2,2,3,3-tetrafluorobenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide.

L J

Example 244-3- (4-Chlorophenyl) -lf- (2 ₁ 3-dihydro-7-ethyl-2,2,3,3-tetrafluorobenzofuran-5-yl) -4-phenylpyrazoline-1 -c type oxamide .

Example 24-5 3- (4-Chlorophenyl) -N ~ / 5- (4 -> methylsulfonylplienoxy) -pIienyl7- ^z ! - · phenylpyrazoline-1-carboxamide.

Example 24-6 3,4-bis (4-3? Luophenyl) -N- / 5- (4-methylsulfonylphenoxy) -phenyl7-py3? Az olin-1 -c type »oxamide.

Example 24-7

3- (4-difluoromethoxyphenyl) -N- / 5- (4-methylsulfonylphenoxy) phenyl7-4-phenylpyraz olin-1 -c art) oxamide.

Example 24-8

3- (4-Chlorophenyl) -4- (4-fluorophenyl) -N- / 5- (4-methylsulfonylphenoxy) -phenyl-7-pyrazoline-1-carboxamide. 20th

B e i s ρ i e 1 24-9

U- ^ 4 ~ - (4-methylsulfonylphenoxy) -phenyl7-3,4-diphenylpyr az oz olin-1-carboxamide.

B is ρ ie 1,250 3.4 ~ t> is- (^ -Fluorophenyl) -N- (2 _} 3-dihydr o-7-difluoromethoxy-2,2-dimethylbenzofuran-5-yl) -pyrazoline -1 -carb oxamide.

Example 251

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

Example 252

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

L J

Example 253 3- (4-Difluoromethoxyphenyl) -N- (2,3- <uhydr o-7-difluoromethoxy-2,2-dimethylb enz ofuran-5-yl) -4-phenylpyrazoline-1-carbon oxamide.

Example 254 3- (4-Ghlorphenyl) -N- (2,3-dihydro-7-difluoromethoxy-2,2-dimethylbenzofuran-5-yl) - 5 ~ ⁱ phenylpyrazolin-1-carboxamide.

Example 255 N- (7-Chloromethyl-2,2-dimethyl-1,3-benzodioxol-5-yl) -3,4-bis (4-fluorophenyl) pyraz olin-1-carb oxamide.

Example 256

H_ (7_ Chloromethyl-2,2-dimethyl-1,3-benzodioxol-5-yl) -4- (4-chlorophenyl) -3- (4-methylphenyl) -pyrazoline-1-carboxamide.

Example 257

N- (7-Chloromethyl-2,2-dimethyl-1,3-benzodioxol-5-yl) -3,4-diphenylpyrazoline-1-carboxamide. 20th

Example 258

N- (7-Chloromethyl-2,2-dimethyl-1,3-benzodioxol-5-yl) -3- (4-difluoromethoxyphenyl) -4-phenylpyrazoline-1-carboxamide.

B is ρ ie 1 259 N- (7-chloromethyl-2,2-dimethyl-1,3-benzodioxol-5-yl) -3- ( ^z ichiorphenyl) -4-phenylpyrazoline-1-carboxamide.

Example 260 N- (2,3-Dihydro-2,2-dimethylbenzofuran-5-yl) -3- ^ 7- (1-methylethyl) -2,2-dimethyl-1,3-benzodioxol-5-yl7- ^z l-phenylpyrazoline-1-carboxamide.

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

L J

Example 262

N- (2,3-Dihydr0-2,2-dimethylbenzofuran-5-yl) -3- (7-fluoro-2,2-dimethyl-1,3-benz odioxol-5-yl) -4-phenylpyrazoline-1-carboxamide.

Example 263

N- (2,3-Dihydro-2,2-dimethylbenz of uran-5-yl) -3- (7-difluoromethoxy-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-fluorophenyl) -4- (2,3-dihydr0-2,2-dimethylbenzofuran-5-yl) -pyxaz olin-1-carboxamide.

For example, 1 265 N- (2,2-difluoro-1,3-benzodioxol-5-yl) -3- (4-fluorophenyl) -4-. (2,3-dihydr0-2,2,3,3-tetrafluorobenzofuran-5-yl) -pyrazoline-1-carboxamide.

Example 266 N- / 3- (4-trifluoromethylphenoxy) -phenyl7-3,4-bis- (4-fluorophenyl ) -pyrazoline-1-carboxamide.

Example 267

N- / 5- (4-i ^1- luophenoxy) -phenyl7-3,4-bis- (4-fluorophenyl) -pyrazoline-1-carboxamide.

Example 268

N - / "- (4-Difluoromethoxyphenoxy) -phenyl7-3, ^z l - 'bis- (4-fluorophenyl) -pyrazoline-1-carboxamide.

Example 269

3,4-bis- (4-i'luorophenyl) -N - / ^ - (4-methylphenoxy) -phenyl-7-pyrazoline-1-carboxamide.

L J

Example 270 3- (7-Chloromethyl-2,2-dimeth7l-1,3-benzodioxole-5-7l) - ^z ! -, li-bis- (4-fluorophenyl) -pyrazoline-1-carboxamide.

Example 271 N- (2,3-Dihydro-2,2-dimethylbenzof Tiran-5-yl) -4- / 7- (1-Met3aylethyl) -2,2-dimethyl-i ^ -benzodioxol ^ -ylZ ^ -pkenylpyrazoline-1-carboxamide.

Example 2? 2 N- (2,3-Dihydr o-2,2-dimethylbenz oftenu? An-5-yl) -4- (7-methoxy-2,2-dimethyl-i , 3-benzodioxol-5-yl) -3 ~ pb-enylpyrazoline-'1-carboxamide.

Example 273 N- (2,3-Diliydro-2,2-dimethylbenzof uran-5-yl) - ² '- (7-f luor-2,2-dimethyl-1,3-benzodioxol-5-yl) -3 -piienylpyrazoline-1-carboxamide.

example

N- (2 _i 3-dihydro-2,2-dimethylbenzofuran-5-yl) - ^z '- (7- <iiilnormethoxy-2 _T 2-dimethyl-1,3-benzodioxol-5-yl) -3-pb- enylpyrazoline-1-carboxamide.

For example, 1,275 4- (7-chloromethyl-2,2-dimethyl-1,3-benzodioxol-5-yl) -3, H-bis (4-fluorophenyl) -pyrazoline-1-carboxamide.

Usually the pyrazoline bonds are found processed into insecticidal agents that contain the active ingredient in sufficient quantities. These funds can be common contain surface-active compounds and carriers to facilitate the distribution of the active ingredients. The active ingredients can, for example, in the form of sprays, dusts or granules for the control of harmful insects can be used. The type of application depends

L J

of course on the type of insect pests to be controlled and the environment. Examples of insecticidal agents are coarse granules, dusts, wettable powders, emulsifiable concentrates and solutions.
5

Granules can contain porous or non-porous particles, for example attapulgite clay or sand, which act as carriers serve for the pyrazoline compounds. The particle size of the Granules are relatively large, generally about 400 to 25ΟΟ microns. The particles are either with the pyrazoline compound impregnated from a solution or coated with the pyrazoline compound. Sometimes too Adhesives used. Granules generally contain 0.05 to 10 percent by weight, preferably 0.5 to 5 percent by weight Active ingredient.

Dusts are mixtures of pyrazoline compounds with finely divided solids, such as talc, attapulgite clay, kieselguhr, Pyrophyllite, chalk, diatomaceous earth, calcium phosphate, Calcium and magnesium carbonates, sulfur, flour and others organic and inorganic solids that serve as carriers for the active ingredient. These finely divided solids have an average particle size of less than about 50 microns. A typical dust for control from insect pests contains 1 part pyrazoline compound, such as 3- (4-chlorophenyl) -N- / 5- (4-chlorophenoxy) -phenylZ - ^ - phenylpyrazoline-1-carboxamide, and 99 parts of talc.

The pyrazoline compounds of the invention can also be made into liquid concentrates. To this end the active ingredients are dissolved in suitable liquids or emulsified or processed into solid concentrates by adding talc, clays and other known solid carriers. The concentrates usually contain about 5 to 50 percent by weight of active ingredient, e.g. 3-C ^ - Chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -

L J

4- phenylpyrazoline-1-carboxamide, and 95 to 50% inert substances, which include surfactants dispersants, emulsifiers and wetting agents. However, it can also even higher concentrations of active ingredient can be used.

The concentrates are diluted with water or other liquids before use and used as a spray or used with other solid carriers as a dusting agent.

Typical carriers for solid concentrates (also known as wettable powders) are puller earth, clays, and silicas and other highly absorbent, easily wettable inorganic diluents. A solid concentrate to combat of harmful insects each contains 1.5 parts by weight of sodium lignosulfonate and sodium lauryl sulfate as a wetting agent, 25 parts 3- (4-ChIorphenyi) -N- (2,3-dihydro-2,2-dimethythy Ibenzofuran-5-yl) -4- (4-chlorophenyl) -pyrazoline-1-carboxamide and 72 parts of attapulgite clay.

The preparation of concentrates is useful for transporting the low melting point pyrazoline compounds of the invention. These concentrates are made by melting the active ingredient together with Λ% or more of a solvent to form a concentrate that does not solidify on cooling to or below the freezing point of the pure product.

Examples of suitable liquid concentrates are emulsifiable concentrates, the homogeneous liquids or pasty Represent masses that can be easily dispersed in water or other liquid carriers. These liquid Concentrates may or may consist of the pyrazoline compound and a liquid or solid emulsifier can also use a liquid carrier such as xylene, high-boiling aromatic hydrocarbons, isophorone and others relatively poorly volatile organic solvents

keep. These concentrates are used in water or other liquid carriers and normally used as a spray.

Typical surfactants, dispersants and emulsifiers for pesticidal agents are, for example Alkyl and alkylarylsulfonates and sulfates and their sodium salts, Alkyl amide sulfonates, including "fatty acid methyl taurides, Alkylaryl polyether alcohols, sulfated higher alcohols, polyvinyl alcohols, polyethylene oxides, sulfonated animal and vegetable oils, sulfonated petroleum oils, fatty acid esters of polyhydric alcohols and ethylene oxide adducts these esters and adducts of long-chain mercaptans and ethylene oxide. There are numerous other types of suitable ones available surfactants available. When using a surfactant, it usually lies in an amount of 1 to 15 percent by weight im Insecticidal agents.

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

The pyrazoline compound resides in the insecticidal agents that are diluted for use, usually in one Amount from about 0.001 to about 8 weight percent.

The insecticidal compositions containing a pyrazoline compound of the invention may also contain other active ingredients, e.g. other insecticides, nematicides, acaricides, fungicides, Plant growth regulators and fertilizers. To combat insect pests, the pyrazoline compounds must be on the areas to be combated are applied in an effective amount. For example, the funds can act on the insects themselves or on the plants attacked by the insect pests

L · J

be applied. When applying to agricultural used areas, the active ingredient is either applied to the soil or worked into the soil. For the most For purposes of application, quantities of around 75 to 4000 g / ha are sufficient, preferably 150 to 3000 g / ha.

The effectiveness of the pyrazoline compounds was determined as follows.

The compounds were applied to leaves in various concentrations in aqueous solutions containing 10% acetone and 0.25% octylphenoxypolyethoxyethanol. Pinto bean plants were placed on a turntable in a hood. The test solutions were applied by means of a syringe. The test solutions were sprayed onto the top and bottom of the leaves. The plants were then allowed to dry and the end of the stem was cut off. Each stem was placed in water through a paper cup. Ten insects of one kind were placed in each cup, which was covered on it. Southern army worms (Spodoptera eridania), Mexican bean beetles (Epilachna varivestis), beetroot army worms (Spodoptera exigua) and cabbage caterpillars (Trichoplusia ni) were used for the evaluation. After 4 days at 26 ^° C. and 50% relative humidity, the mortality is determined. The test results are summarized in Table I. The mortality of the insects is usually lower when the experiments are carried out for a shorter period of time.

A number of the pyrazoline compounds are also active against southern corn rootworm larvae (Diabrotica undecimpunctata howardi Barber) when applied to the floor. The compounds studied are also very effective against the Colorado potato beetle (Leptinotara decemlineata Say).

To whom Table I. SAW Mortification) manic
lot .Sheet evaluation 100 BAW CL (ppm) 100 Connect 500 100 manure 500 Insects (% 100 1 500 MBB 8.7 2 500 100 65 100 3 250 100 50 90 4th 500 100 85 90 5 500 100 70 6th 500 100 35 7th 500 70 15th 8th 500 100 100 9 500 100 50 10 500 90 100 90 11th 500 100 90 12th 500 85 13th 500 100 35 14th 500 93 55 15th 500 100 100 16 500 100 40 17th 500 100 15th ■ 18th 500 100. 100 19th 500 90 20th 500 100 21 80 22nd 70 100

Table I (! PlaceSetting)

To whom
manic
lot Sheet evaluation SAW Abortion) Connect
manure (ppm) Insects (% 30th BAW CL 500 MBB 23 250 40 75 100 24 500 95 65 25th 500 30th 95 26th 500 80 90 27 500 75 90 28 500 95 64 29 500 10 65 60 30th 500 5 50 70 31 500 5 80 32 500 100 75 33 500 100 100 34 500 10 98 35 8th 100 98 45 90 36 32 100 80 97 100 37 500 98 25th 38 500 95 100 39 500 100 70 40 128 100 100 41 128 95 42 95

Table I (continued)

To whom
manic
lot
(ppm) Sheet evaluation. SAW Mortification) Connect
manure 500 Insects (% 100 BAW CL - 43 500 MBB 100 44 32 100 100 45 500 100 40 100 100 46 500 100 10 4? 8th 30th 100 48 500 5 100 100 95 49 500 100 100 50 100 100 60 51 500 100 95 • 52 500 40 10 53 500 100 85 54 500 100 80 5 5 500 100 100 56 250 100 100 57 500 100 40 58 500 100 100 59 200 100 60 60 32 100 100 61 500 100 95 55 9i 62 500 45 95 63 500 95 100 64 100 100

Table I (continued)

To whom-
manic Sheet evaluation ■ SAW Dept.ötune;) Connect ΐηεηκβ
(ppnu Insects ( % 100 BAW CL manure 500 MBB 100 65 500 100 95 66 500 100 0 67 500 85 60 68 8th 100 100 5 IOC 69 500 100 10 70 200 100 30th 71 200 60 90 72 500 100 80 73 500 100 45 74 200 100 100 75 200 100 76 500 95 95 77 200 80 5 5 500 0 60 78 200 90 100 79 500 95 100 80 250 100. 90 81 128 100 100 82 250 100 90 83 100 85 100 84 200 100 «Σ 100

Table I (continued)

; MBB SAW (% Kill) LL Connecting Sheet evaluation: 95 95 BAlV 100 manure To whom-
amount of _insects 100 100 40 86 (ppm) 100 25th 85 87 16 100 100 10 88 500 100 100 90 89 100 100 100 100 100 90 200 100 100 100 91 16 100 100 92 32 100 100 · 93 500 100 90 94 500 100 100 95 95 500 100 100 85 96 200 100 40 83 80 97 32 100 100 33 85 98 8th 100 100 90 100 99 16 100 100 100 100 16 100 100 101 32 90 95 100 102 1000 100 100 13th 103 128 100 70 105 16 45 0 106 16 100 75 107 256 108 1000 ro oo

ORIGINAL BATHROOM

Table I (continued)

Sheet evaluation MBB kten (% kill) Connect To whom-
application amount x _nse 0 "'SAW BAW_ _ ± ± manure (ppm) 70 0 109 1000 0 0 110 1000 100 0 111 1000 100 90 112 1000 100 10 113 1000 100 30th 114 1000 100 15th 115 1000 55 100 116 500 100 0 117 500 100 100 118 500 100 95 119 500 95 100 120 500 100 100 121 500 15th 100 122 64 100 0 123 64 100 100 124 64 100 125 64

MBB = Mexican bean beetle

saw = southern army worm

BAW = 'Beetroot Army Worm

CL = cabbage caterpillar,

Claims (30)

VOSSIUS · VOSSIUS -TAU C H-r \ i IF.-P HEU N EiviAN N RAUH PATENT LAWYERS SIEBERTSTRASSE A- ■ SOOO MUNICH 86 · PHONE: (O89) 4-7 4O 75 CABLE: BENZOLPATENT MDNCHEN · TELEX 5-29 4-53 VOPAT D 5 ET: ü 092 October 24, 1985 Case: 4-575 FMC Corporation. Philadelphia, PA., USA 10 "Pyrazoline compounds, process for their preparation and their use in the control of insect pests " 15 claims Pyrazoline compounds of the general formula R, ^R B 20 W ^ R _c 25 in the R. a group of the formula 30, in which R ' _{A is} a hydrogen or halogen atom, a lower alkyl, lower alkoxy, lower haloalkoxy, lower alkynyloxy or lower haloalkyl radical, or a group of the formula R ¹ ORIGINAL INSPECTED is where X is a bridge of the formula in which a has a value from 1 to 3, a ^{1 has} the value 0 or 1, a + a ^{1 has} a value of at least 2 but at most 3, R'jy ^ and E ¹ ^ g each hydrogen or halo Genatome or lower alkyl radicals and R'j ^ q is a hydrogen or halogen atom, a lower alkyl, lower alkoxy, lower haloalkoxy or lower halogen alkyl radical, Eg is in the 4- or 5-position and a group of the formula 20th ^R B
15th in which H'-g is a hydrogen or halogen atom lower alkyl, lower alkoxy or lower haloalkyl radical is or a group of the formula where Y is a bridge of the formula is, in which b has a value from 1 to 3, b ^{1 has} the value 0 or 1, b + b ^{1 has} a value of at least 2 but at most 3, R'j. and R'-no is in each case hydrogen or halogen atoms or lower alkyl radicals and R'-nn is a hydrogen or halogen atom, a lower alkyl, lower alkoxy, lower haloalkoxy or lower haloalkyl radical, Rq is a group of the formula 35 - 3- ■ - · "· ' ^: ' 353788Φ in which Rq is a hydrogen atom or a lower alkyl radical, Rg is a lower alkyl radical, a halogen atom, a lower alkoxy radical, a lower haloalkoxy radical, a lower haloalkyl radical, a cyano or nitro group or a group of the formula -NR-pR ,, in which R ™ and Rn are each a lower alkyl radical or a group of the formula -SO _n R ₁ J, in which Rg is a lower alkyl radical and η is 0, 1 or 2, or a group of the formula is where Z is a bridge of the formula is, in which c has a value from 1 to 3, c 'has the value 0 or 1, c + c ^{1 has} a value of at least 2 but at most 3, R'qa and R'q-d each have a hydrogen or Is a halogen atom or a lower alkyl radical, with the proviso that R ¹ QA UE-d- ^ ¹ es ⁿ ^ ^c ^ * simultaneously denote hydrogen atoms if c is 1 and c'. is 1, and R ' _C Q is hydrogen or halogen, lower alkyl, lower alkoxy, lower haloalkoxy or lower haloalkyl, R ^ is hydrogen or lower alkyl, and V and W each represent oxygen or sulfur. 2. Compounds according to claim 1, characterized in that W is an oxygen atom. 3. Compounds according to claim 1, characterized in that R ¹ . is halogen or lower haloalkoxy. ^Γ - * ^ ^: Υ IÜ "O"> 3537883 4. Compounds according to claim 1, characterized in that that R-n is in the 4 ~ position. 5. Compounds according to claim 1, characterized in that that Rg is a group of the formula is. 6. Compounds according to claim 3-, characterized in that E'g is a halogen atom. 7. Compounds according to claim 1, characterized in that that R _{G is} a group of the formula
15th or a 2,3-dihydro-2,2-dimethylbenzofuran-5-yl--, 2,3-dihy dro-2,2,3,3-tetrafluorobenzofuran-5-yl, 2,3-dihydro-2,2,3 ^ -tetrafluorobenzofuran-ö-yl-, 2,2-di- or
is fluoro-1,3-benzodioxol-5-yl / 2,2-dimethyl-1,3-benzodioxol-5-yl group. 8. Compounds according to claim 1, characterized in that Rq is a group of the formula is. 9. Compounds according to claim 8, characterized in that R _{E is} a lower haloalkoxy radical. 10. 3- (4-Difluoromethox7-phenyl) -H- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -4-phenylpyrazoline-1-carboxamide · ^L J ^Γ - 5: V. ^: "3537885 11. 3,4-bis (4-iauophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -pyrazoline-1-carboxamide. 12. 3 _i ^ -bis- (4-5 ¹ luorphen7l) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) pyrazoline-1-carb oxamide. 13. N- (2,3-Dihydro-2,2,3,3-tetrafluorobenzofuran-5-71) -3- (4-difluoromethoxyphenyl) -4-phenylpyrazoline-1-carboxamide. 14. N- (2,2-Difluoro-1 ^ -benzodioxol ^ -yl ^ -C ^ -difluoromethoxyphen7l) -N-metli7l-4-phen7lp7razoline-1-carboxamide. 15. 3,4-bis (4-chlorophenyl) -N- (2,2-dimethyl-i, 3-benzodioxole- 5-7I) -pyrazoline-1-carboxamide.
15th 16. N- (2,2-Difluoro-1,3-benzodioxol-5-yl) -3,4-bis- (4-fluorophen7l) -pTraz olin-1-carboxamide. I ?. 3- (4-0hlopphenyl) -N- (2,2-difluoro-1,3-benzodioxol-5-yl) -4- (4-fluorophenyl) -pyrazoline-1-carboxamide. 18. 3- (4-Difluoromethoxyphenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzene ofuran-5-yl) -N-methyl-4-phenyl-pyrazoline-1- carboxamide.
25th 19. 3_ (4-Chlorophenyl) -N- ₍ /5-(4-difluorometiioxyph.enoxy) -phenyl7-4-phenylpyrazoline-1-carboxamide. 20. N- / 5-C4-Difluoromethoxyphenoxy) -phenyl7-3 - (^ - difluoromethoxyphenyl) -A- (4-fluorophenyl) -pyraz olin-1-carb oxamide. 21. 3- (4-Difluoromethoxyphenyl) -4- (4-fluorophenyl) -N- (2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl) -pyrazolin-1- carboxamide.
35 L J ^Γ - ⁶ T ^: Υ "I = J" Ο "> 3537882 3537882 22. 3- (4-Difluoromethoxyphenyl) -4- (4-fluorophenyl) -N- (2,3-dihydr o-2,2,3,3-t s met luorbenz ofuran-6-yl) -pyrazole-1-carboxamide. 23. 4- (4-Chlorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran 5-yl) -3-phenylpyrazoline-1-carboxamide. - (4-Fluorophenyl) -N- (2,3-dihydro-2,2-dimethylbenzofuran-5-yl) -pyrazoline-i-carboxamide. 10 25. 3- (4-Difluoromethoxyphenyl) -4- (4-fluorophenyl) -N- (2,3-dihydr 0-2,2-dimethylbenz ofuran-5-yl) pyrazoline-1-carboxamide. 26. 4- (4-Chlorophenyl) -3- (4-difluoromethoxyphenyl) -N- (2,3-dihydr0-2,2-dimethylbenz ofuran-5-yl) pyrazoline-1-carboxamide. 27. Process for the preparation of the compounds according to claim 1, characterized in that a compound of the general formula R-H = C = W with a compound of the general formula R, reacts and optionally the product obtained to form a pyrazoline compound of the formula ^R A L _n L J ^r -7-V ' ^: 3537885 alkylated, in which R. is a group of the formula is in which R ¹ ^ is a hydrogen or halogen atom, a lower alkyl, lower alkoxy, lower haloalkoxy, lower alkynyloxy or lower haloalkyl radical, or a group of the formula is where X is a bridge of the formula [O-CCR ' _AA R' _AB ) _a -O _a J is, in which a has a value from Λ to 3, a ^{1 has} the value O or 1, a + a 'has a value of at least 2 but at most 3, E ¹ ^. and R'a-r is both hydrogen or halogen atoms or a lower alkyl radical and R'aq is a hydrogen or halogen atom, a lower alkyl, lower alkoxy, lower haloalkoxy or lower haloalkyl radical, R "in the 4- or 5 Position and a group of the formula is »in the R'-n a hydrogen or halogen atom is lower alkyl, lower alkoxy or lower haloalkyl radical, or a group of the formula RV L J ^Γ - ⁸ - \ / - J - ^: \ .C ^: 3537883 where Y is a bridge of the formula [O- (CR ' _BA R' _BB ) _b -O _b , l is, in which b has a value from 1 to 3, b ^{1 has} the value O or 1, b + b ^{1 has} a value of at least 2 but at most 3, R ¹ B, and R'-nn each a hydrogen or Is a halogen atom or a lower alkyl radical, and R ¹ ^ q is a hydrogen or halogen atom, a lower alkyl, lower alkoxy, lower haloalkoxy or lower haloalkyl radical, Rq is a group of the formula R. in which R ^ is a hydrogen atom or a lower alkyl radical, EU is a lower alkyl radical, a halogen atom, a lower alkoxy, lower haloalkoxy or lower haloalkyl radical, a cyano or nitro group, or a group of the formula -HR-pRo , in which R ™ and R ~ are each a lower alkyl radical or a group of the formula -S0 _n % ^ ¹³ ** ^ ^der % ^e ^ ^{a n} ^ ^ed - is a ^lower alkyl radical and η has the value 0, Λ or 2, or a group of the formula is where Z is a bridge of the formula tO - ^ 'cA ¹¹ ' CB ³ C- ⁰ C ³ is, in which c has the value Λ to 3, c ^{1 has} the value 0 or 1, c + c ^{1 has} a value of at least 2 but at most 3, R'qa UE-ä ^r 'cb in ^{each case a} hydrogen or Is a halogen atom or a lower alkyl radical, with the proviso that R'qa and ^r 'cb ¹¹ ^ k * at the same time a hydrogen atom ^L J ^Γ - ⁹ - ^: Ξ: -; 353788Ä ¹ 1, when c is 1 and c ¹ is 1, and Η ' _{σσ is} a hydrogen or halogen atom, a lower alkyl, lower alkoxy, lower haloalkoxy or lower haloalkyl radical, R «is a hydrogen atom or lower 5 is an alkyl radical and V and W are each an oxygen or Mean sulfur atom. 28. Use of the compounds according to one of the claims to 26 in the control of insect pests. 10 L J