AU657344B2 - Substituted pyrazolines - Google Patents

Description

Our Ref: 436963 P/00/011 Regulati~on 3:2 5734

AUSTRALIA

Patents Act 1990

ORIGINAL

COMPLETE SPZ~CIFICATION STANDARD PATENT *5 S S S S 5* Applicant(s): Address for Servi7.'I: Bayer Aktiengesellschaft D-5090 Leverkusen Bayerwerk

GERMANY

DAVIES COLLISON CAVE Patent Trade Mark Attorneys Level 10, 10 Barrack Street SYDNEY NSW 2000 substituted pyrazolines Invention Title: The following statement is a full description of this invention, including the best method of performing it known to me:- 5020 The invention relates to new substituted pyrazolines, to a plurality of processes for their preparation, and to their use as pesticides.

It has been disclosed that certain substituted pyrazolines have insecticidal properties for example, DE-A 2,700,258; DE-A 2,529,689 and US-A 4,174,393).

However, the level, or duration, of action of these previously known compounds is not entirely satisfactory in all fields of application, in particular in the case k 10 of certain insects or when low concentrations are applied.

New substituted pyrazolines of the general formula (I) have been found RZ 3 NN H

I

x N-R 6

H

in which X, R R' R' and R' can in each case assume the 15 following combinations of meanings: 9 9.* Le A 29 065 1 R2 cl 0 cl -kD 0 cl 0 cl 0 cl cl

D

cl -c- 11 0 R3 R6 x H -<D-CF3 H -<D-SCF3 H CHF2 CF3

H

cl H -<D-CF3 H -<D-F Le A 29 065 2

S.

-<D-F

-<D-Br -<D-Br

-<D-F

-<D-F

-<D-F

0c I D~ 0 H -ICF 0 -C-<iJD-F H

-CF

3 0 -C-D H j(DOCZHS 0

CF

3 CfDjB r H 0 S S

S.

S S 5 5* Le A 29 065-3 3

RIR

2 R R6x H 0 0 99 9 9.

*9 9

S

9 9 9. 9 9.

K c 1

OCH

3 0 TO-D- H 0 0CH 3 0 0CH 3 0 0 0 -Q<-CHF2 -C>,0.CF3 -<D0CiF 2 -JDj0CHF2 Le A 29 065-4 4

C

**qC C. C

C

CC

C.

C

C. C

CC

CC

C-C

I

-Jc

I

Cl 0 Cl

H

0 c 1 0 c 1 0 0 0 -<D-OCF3

I

-<D-Br

-F

-G(J-OCHF2 0 C.

C

C.

0*CC

CC

C. C

C

C C C C C. C C C C K-<D'3 Le A 29 065- 5 -0

-F

0 0' Jj 0 0D- 0 0 0 R3R 6 H -c<J-F H c9 0CFI 0 0 0 0 0 0 0 0

S

S S

S.

0 *0 S

S

S.

S. S St

S.

*3.

Si S a S 3 '3 -<D-Br

-<D-F

Le A29 065 -6 RC-c -0 r 9 0* 0 0 0

-C.

-c 0 -cI 0 0 -oD H -(jc 1 H -K<i-CF 3 H Br -0o H -&3-F H QBr 5* 9 .9 9.

9 e5 9 5 9 9 Si S 95 -o

-KD

Le A 29 065-- 7 -Q-c 1

S

S. S S. S

S*

-C-0 H 0 -jC- Q-C 1 H 0

H

0 0 C<JjBr H CfJ2>Br H 0 -c~Qjr H 0 -Q:-CF3 -K1-OCHF 2 S. S S S 555.

S

S S S. S S. S S SS Le A 29 065-- 8 JJ>-Br K-Ci1

H

0 -C-<7j-H 3

H

0 -C-CQ>-CH3 H 0

H

01 0 C-0 H 0 -C-0jc H 0 c H 0 -C-F3 i.

C

*8

*CC.

C.

C C

C

*0 -<Dj--C4F 2 0 1>F 0 Le A 29 065-9 9 -0- 0 0 0

H

0 -CG?0H H 0 -<D-cFz 3

BCF

S

S*

5*

S.

*5 5 a 55 S S S S S S S 5 *5 Le A29 065 10 ER 1 Q-B r KCjB r IfR 0 0 0 -CQ(:-cH1 H 0 -C-Q0 H H 0

R

6 -QD-CF3 -C}-OCF 2 -cDl-OCiF 0*00*0 S S

S

S S *S S 0

S

5 S S Le A 29 065 11 KR1 -0DB To .b *t) 4~ -C0 0 0

-C-QD-F

0 0 0 0 0 H Br Hi 7j -CF 3 H -Q-F H 4

J--CF

3 H -KD/2-CF 3 H -DC H C-r H -i-c 4* 5

S

S. S S S Le A29 065 1 R3 R 6 x 14 H r 0 0 -0 -0 -k7 0 Cl -k 0 0

CH

3 0 CH0

C-

3 0 H -KID--O

CHF

2 H/ F

H

H

>OCFJ

I

I.

I

*1

I

In.

I I I I

I.

II I I I *I II I I

I

*I**II

I

-0 -0 Le A 29 065 -1 13

-KD

-KD

500***

S

SS

S. S S. S

SS

S.

a S. S -0

-<D-F

-F

-<D-F

CH

3 0 0

CH

3 0 CH0

CH

3 0 -C H 0 0 0 0

R

6 x -<D-CF 3 -YQO-CF3 5, 5 S S a Sn.

55 .5

'S

S

5.5.

55 Sb S S S SS S S S S 55 Le A29O065 14

-<D-F

0 C-F H 0 -C F H 0 CC >B r H 0 -CC3>" BrH 0 -C-<CjF* H 0 -(DQ-jOCHF 2

CF

3

/F

Br c I -o

*O

S

.555

S*

S*

S. S

SS

S

S. 5

S

S

.5 55

S

Le A A~ 065 -1 15 -Q-Sr 1

R

2 3

R

6 x S S* S *0 S S S

S.

S

S

S S 0C~- 0 0 0C D- 0 .c-CD1 0 0 0 H

>-F

CF

3 c 1

CF

3

CF

3 n-Gj3 S S

S.

S S S. S

SSS*

SS&*

S.

S S S S SQ S

S.

Le A29O065 16 ~-Cj-zi 0 0 Cl H

-JC

C

C C C. C C. C Ce

C.

C

C. S

CS

*b -BJ r 0 11

-C-(CHZ

0 11 C25 0

(CH

2 5 0 11 -C (CM 2 5 -c&-c 1 0

IIDCF

*5 C C C

CC

C C CC C

S.C.

C

C#

e C C C Ci C C S C C CS Le-A 29 065 17 R1R 3 R6X 1 1 Q-ci1 0 11

(CM

2 )5- 11 '-CH 3

-C-CH

2

-CH

-C-CH 2 -CH

,-H

11'-

H

0

,,-CH

3

-C-CH

2

-CH

11--C4 0 -C-CH 2 -CH

,-H

II

'-CH

3 0

-C-CH

0 -C-CH2 3 I I 0 >cF 3 0 H -(-0OCF 3 0 H -K<i-CF 3 0 H cio1 H 0 H 0 H 2 0 H DF 0 H -f-0CF 3 0 S. S S 8S

S

S S *5 S S.

S

S.

S S S S 55 S S Le A 29 065 1 18 K-Ci- -C-CHZ1-CH 3 ti 0

-C-CH

2

-CH

3 11 0

R

6 H OCl H -<Q7Br H -Q-F -C-0CH3 11 0 S. S

-KISF

(CH

2 3 It 0i -0 -CF3

,-CH-

3

-C-CH-

2

-CH

IlCH 0

S

0S

SW

S

S. S

S

S

S S *S S S 11 I-CH 3 0

,--CH

3

-C--CH

11 '-Cfl 3 0

-C-CH

2

CH

II

-CH

3 0

C-CH-

2 -CH ,-H 0 H 0

-F

CF3 H I-D C 0 -<D--Br Le A 29 065 -1 19 Rl 1

I

1 1 R2 R 3 -C-cH 2 -CHi 0 C -CH- 0

-C-CH

11

CH

0

-H

11 '-CH 3 0 It 'CH3 0 II CH 3 0 Ii,-CH 3 0 H ~-0--OCHF 2 H 3 0 H CE 3 0 H -<D2 -F3 a H -II ci 0 H Br 0

S.

C. SW S. S

S

OS S 0@

S.

55S* S S 5 S S

S

55 5*

S*

0-

-CHF*

Le A 29 065 20 f2 c -0j-r 11 C H 3 0 3 -C CH H 0

-C-(CH

2 3 0

C-(CH

2 3 0 -C--CI4 3

H

11 0

-C-CH

3

H

0 -C0CH 3 0 0

R

6 Cl KDCF3 I

I*

'ewe..

S S 9* 9 59 9 S C Sq 9.99,5

S

S. 9* 9* 9@ C e *5 5@ Ce 9 9* 99 we..

99 9 9* Le A29 065 21 ER 1 r r

I

-C-(CH2) 3- 11 0 C-(CH2) 3 11 0 r

CHF-,

-C 1 -C--Cf'2-CH ,-CH3 I I '-'CH3 0 -c-c2HS It 0 0 0 0 0 r i

-<D-F

-<D-F

C--l 11 0 0 C-CH CH3 11 '---CH3 0

-C-CH

11 H 3 0 H -C CHF2 H -<D-F H -C CF3 H -<D-F H -O-CF3 r 0 H -CF3 Le A 29 065 22 'K~Br #2-F R 2 0c- 0 0 -C-CH

"-H

11 "-CH3 0 11 3 0 11 '-CH 3

C-CH

III 'N.CH 3 0 H c1 H

CF

3 H 1

H

H B

S*

S.

S

Furthermore, it has been found that the new substituted pyrazolines of the general formula (I) Le-A 29 065 23

-"H

H

in which the substituents X, R 2 R' and R 6 have the abovementioned meaning are obtained when pyrazolines of the formula (II) which are unsubstituted in the 1-position,

R

2 INt

H

5 in which R1, R2 and RI have the abovementioned meaning, are reacted either a) with isocyanates of the formula (III) in which R' have the abovementioned meaning, or with carbamoyl chlorides of the formula (IV) ,N-C ,(IV) H C1 Le A 29 065.-2 24 in which

R

6 has the abovementioned meaning, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary.

Finally, it has been found that the new substituted pyrazolines of the general formula have a good activity against animal pests.

Surprisingly, the substituted pyrazolines of the general formula according to the invention have a considerably better insecticidal activity compared with compounds which are known from the prior art and related chemically and/or from the point of view of their action.

Specific reference may be made to the compounds mentioned in the preparation examples.

15 If, f r example, 3-(4-chlorophenyl)-4-[(2-chlorophenyl)carbo lylamino]-4,5-dihydropyrazole and 4-trifluoromethylpheny isocyanate are used as starting material, the course of the reaction of process according to the invention can be represented by the following equation: 0* 0 0 O=CN-D-F3 Le A 29 065 25 Cl C- N N 0 0UNH/C F 3 If, for example, 3-(4-chlorophenyl)-4-[(2-chlorophenyl)and N-methyl-N-(4trifluoromethylphenyl)-carbamoyl chloride are used as starting materials, the course of the reaction of process according to the invention can be represented by the following equation: 0* *5 S *5 Cl CH3 Cl-C-N-( ii base

S

*O *i S S C1-s C1

II

0N.F

CH

3 Formula (II) provides a general definition of the pyrazolines which are unsubstituted in the 1-position and which are required as starting materials for carrying out process and according to the invention. In this formula R 1

R

2 and R 3 represent those radicals which Le A 29 065 26 have already been mentioned in connection with the description of the compounds of the formula according to the invention.

The pyrazolines of the formula (II) which are unsubstituted in the 1-position are not yet known. They are obtained, for example, when phenacylamine derivatives of the formula (V)

H

I /R 2 R-C-CH-N,

(V)

I R 3 0 in which R' R 2 and R 3 have the abovementioned meaning, are reacted with dimethylmethyleneimmonium chloride of the formula (VI) +,CH3 2C=N Cl (VI) CH3 if appropriate in the presence of a diluent such as, for example, acetonitrile, at temperatures between 30°C and and, in a subsequent 2nd step, the resulting phenacyldiamine derivatives of the formula (VII)

H

S R2

R

I

-C-C-Ne- II I R 3 0 CH2 x HCI (VII)

N-CH

3

CH

3 in which Le A 29 065 27 R R 2 and R 3 have the abovementioned meaning, are reacted with hydrazine hydrate, if appropriate in the presence of a diluent such as, for example, acetonitrile, at temperatures between 30 0 C and 80 0

C.

In this context, it is also possible and may be advantageous to carry out the reaction of the phenacylamine derivatives of the formula with dimethylmethyleneimmonium chloride of the formula (VI) and the subsequent reaction of the resulting phenacyldiamine derivatives of the formula (VII) with hydrazine hydrate in one reaction step in a so-called "one-pot process".

Alternatively, the pyrazolines of the formula (II) are also obtained when phenacylamine derivatives of the formula (Va) R2 1-C-CH 2 -N3 (Va) 0 15 in which

R

2 and R 3 have the abovementioned meaning, are initially reacted, in a first step, with formaldehyde at temperatures between 30 0 C and 80 0 C, if appropriate in the presence of a diluent such as, for example, ethanol, and the resulting phenacyl-enamine derivatives of the formula (VIII)

CH

2 11 R2 R-C-C-C-N% (VIII) S: II R in which in which Le A 29 065 28

R

2 and R 3 have the abovementioned meaning, are subsequently reacted with hydrazine hydrate at temperatures between 30°C and 80 0 C, if appropriate in the presence of a diluent such as, for example, ethanol.

In this context, it is also possible and may be advantageous to carry out the reaction of the phenacylamine derivatives of the formula (Va) with formaldehyde and the subsequent reaction of the resulting phenacyl-enamine derivatives of the formula (VIII) with hydrazine hydrate in one reaction step, in a so-called "one-pot process".

Phenacylamine derivatives of the formulae or (Va) are known or can be obtained analogously to known processes for example, Chem. Ber. 122, 295-300 [1989]; J.

Med. Chem. 29, 333-341 [1986]; J. Amer. Chem. Soc. 98, 15 3621-3627 [1976]; Tetrahedron 31, 2145-2149 [1975]; Zh.

Org. Khim. 10, 2429-2436 [1974]; J. Org. Chem. 55, 3658- 3660 [1990]; Chem. Ind. 1975, 177; Synthesis 1990, 520).

Dimethylmethyleneimmonium chloride of the formula (VI) is known for example, J. Org. Chem. 47, 2940-2944 [1982]; Bull. Soc. Chime Fr. 1970, 2707-2711).

.e Some of the phenacyldiamine derivatives of the formula (VII) are known for example, US 2,980,674 [1957] and CA 56: 3419 [1962]).

Phenacyl-enamine derivatives of the formula (VIII) are S 25 known or can be obtained analogously to known processes for example, Chem. Ber. 93, 387-391 [1960]; Sankyo Kenkyusho Nempo 15, 36 [1963] and Chem. Abstr. 60: 11876d (1964]; J. Med. Chem. 30, 1497-1502 [1987]; Le A 29 065 29 JP 61-053,239; US 4,277,420; Chem. Abstr. 87: 67928y; Khim.-Farm. Zh. 9, 21-24 [1975] and CA 83: 58351v; Collect. Czech. Commun. 19, 317-328 [1954]; Ann. Chim.

46, 267-269 [1956]; J. Chem. Soc. 1953, 4066-4073; Zh.

Obshch. Khim. 30, 3714 [1960]; Pharm. Chem. J. 9, 301-304 [1975]).

Formula (III) provides a general definition of the isocyanates required as starting materials for carrying out process according to the invention. In this formula (III), R 6 preferably represents those radicals which have already been mentioned in connection with the description of the compounds of the formula according to the invention. The isocyanates of the formula (III) are generally known compounds of organic chemistry.

Formula (IV) provides a general definition of the carbamoyl chlorides required as starting materials for carrying out process according to the invention. In this formula R 6 represents those radicals which have already been mentioned for these substituents in connection with the description of the substances of the <ormula according to the invention.

The carbamoyl chlorides of the formula (IV) are generally known or can be obtained with the aid of known processes for example, JP 57-108,057 and Chem. Abstr. 98; 53440y; JP-A 50-089,344 and Chem. Abstr. 83: 205987n; DE-A 2,429,523; AU-A 491,880 and Chem. Abstr. 89; 163572q).

Suitable diluents for carrying out processes and (b) according to the invention are inert organic solvents.

Le A 29 065 30 These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons such as, for example, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform or carbon tetrachloride; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether; ketones such as acetone or butanone or methyl isobutyl ketone; nitriles such as acetonitrile, propionitrile or benzonitrile; amides such as N,N-dimethylformamide, N,Ndimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, esters such as methyl acetate or ethyl acetate, or sulphoxides such as dimethyl sulphoxide.

SProcesses and according to the invention can Spreferably be carried out in the presence of a suitable i reaction auxiliary. Suitable reaction auxiliaries are all customary inorganic or organic bases. These include, for example, alkaline earth metal hydroxides or alkali metal hydroxides such as sodium hydroxide, calcium hydroxide, potassium hydroxide or else ammonium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen 25 carbonate or ammonium carbonate, alkali metal acetates or Salkaline earth metal acetates such as sodium acetate, potassium acetate, calcium acetate or ammonium acetate, and also tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, pyridine, piperidine, N-methylpiperidine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicycl.ononene (DBN) or diazabicycloundecene (DBU).

Le A 29 065 31 When carrying out processes and according to the invention, the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0°C and 120°C, preferably at temperatures between 20°C and Processes and according to the invention are customarily carried out under atmospheric pressure. However, it is also possible to carry out the processes under increased or reduced pressure.

For carrying out process according to the invention, to 2.5 moles, preferably 1.0 to 1.5 moles, of isocyanate of the formula (III) and, if appropriate, 0.01 to moles, preferably 0.1 to 1.2 moles, of base used as a reaction auxiliary are generally employed per mole of pyrazoline of the formula (II) which is unsubstituted in the 1-position.

The reaction is carried out and the reaction products are worked up and isolated by generally customary methods (cf. in this context the Preparation Examples).

For carrying out process according to the invention, 1.0 to 2.5 moles, preferably 1.0 to 1.5 moles, of carbamoyl chloride of the formula (IV) and, if appropriate, 0.01 to 2.0 moles, preferably 0.1 to 1.2 moles, of base used as reaction auxiliary are generally employed per mole of pyrazoline of the formula (II) which is unsubstituted in the 1-position.

The reaction is carried out and the reaction products are worked up and isolated by generally customary methods.

The active compounds are suitable for controlling animal Le A 29 065 32 pests, preferably arthropodes and nematodes, in particular insects and arachnida, which are encountered in agriculture, in forestry, in the protection of stored products and of materials, and in the hygiene field. They are active against normally sensitive and resistant species and against all or some stages of development.

The abovementioned pests include: From the order of the Isopoda, for example, Oni,scus asellus, Armadillidium vulgare and Porcellio scaber; from the order of the Diplopoda, for example, Blaniulus guttulatus; from the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spec; from the order of the Symphyla, for example, Scutigerella immaculata; :from the order of the Thysanura, for example, Lepisma saccharina; Cfrom the order of the Collembola, for example, Onychiurus armatus; 20 from the order of the Orthoptera, for example, 9latta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria; from the order of the Dermaptera, for example, Forficula auricularia; from the order of the Isoptera, for example, Reticulitermes spp.; from the order of the Anoplura, for example, Phylloxera 30 vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. and Linognathus spp; from the order of the Mallophaga, for example, Le A 29 065 33 Trichodectes spp. and Damalinea spp.; from the or~der of the Thysanoptera, for example, Hercinothrips femoralis and Thrips tabaci; from the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma guadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.; from the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, ?4acrosiphum wenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, SaissetI a oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp.; from the order of the Lepidoptera, for example, Pectino- *phora gossypiella, Bupalus piniarius, Cheimatobia :brumata,, Lithocolletis blancardella, Hypornomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis too. chrysorrhoea, Lymantria spp. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spr-, Euxoa spp.., Feltia spp., Earias insulana, Heliothis spp., 9podoptera exigua, Mamestra brassicae, Panolis flanimea, Prodenia litura, 25 Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp-., Chilo spp., Pyrausta nubilalis, Ephestia ON. kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ainbiguella, Homona magnlanima and Tortrix imidana; from the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Acanthoscelides Le A 29 065 34 obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica app., Psy..liodes chrysocephala, Epilachna varive stia, Atomaria app., Oryzaephilua surinamensia, Antho nomus app., Sitophilus app., Otiorrhynchus aulcatus, Co5mopolites sotdidus, Ceuthorrhynchus assimilis, Hypera poatica, Dermestes app., Trogoderma app., Anthrenus app., Attagenus app., Lyctus app., MIeligathes aeneus, Ptinus spp., Niptus hololeucus, Gibbium paylloides, Tribolium app., Tenebrio molitor, Agriotes spp., Cono derus app., Melolontha melolontha, Amphimallon soisti tialis and Costelytra zealandica; from the order of the Hymenoptera, for example, Diprion app., Hoplocainpa app., Lasius app., Monomorium pharaonis and Veapa spp.; from the order of the Diptera, for example, Aedes app., Anopheles app., Culex app., Drosophila melanogaster, Muaca app., Fannia spp., Calliphora erythrocephala, :Lucilia app., Chryaomyia app., Cuterebra app., :20 Gastrophilus app., Hyppobosca app., Stomoxys app., Oestrus app., Hypoderma app., Tabanus app., Tannia app., Bibio hortulanus, Oscinella frit, Phorbia app., Pegomyia hyoscyami, Ceratitis capitatal Dacus oleae and Tipula paludosa; from the order of the Siphonaptera, for example, Xenopsylla cheopis and Ceratophyllus app..

From the order of the Arachnida, for example, Scorpio maurus and Latrodectus mactans; ~:from the order of the Acarina, for example, Acarus airo, :30 Argas app., Ornithodoros app., Dermanyasus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus app., Rhipicephalus app., Axublyomma app., Hyalommna app., Ixodes Le A 29 065 35 spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp..

The phytoparasitic nematodes include Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp. and Trichodorus spp..

In this context, the active compounds can be employed with particularly good success for combatting insects which are harmful to plants such as, for example, against the larvae of the mustard beetles (Phaedon cochleariae) or against the caterpillars of the cabbage moth (Plutella maculipennis).

Depending on their particular physical and/or chemical :properties, the active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances and in coating compositions for seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans, fumigating coils and the like, as well as ULV cold mist and warm mist formulations.

These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or Le A 29 065 36 dispersing agents, and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, iuch as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, miethyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as wel. as water; by liquefied gaseous extenders or carriers are meant liquids which are gaseous at ambient tempe-rature and under atmospheric pressure, for example aarosol propellants, such as halogenohydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers there are suitable: 20 for example ground natural minerals, such as kaolins, S.i clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates; as solid carriers for granules there are suitable: for 25 example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying 30 and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, auch as polyoxyethylene fatty acid esters, polyoxyathylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, Le A 29 065 37 alkylsulphonates, alkyl sulphates, arylsulphonates as well, as albumen hydrolysi products; as dispersing agents there are suitable: foi ,ample lignin-sulphite waste liqaors and methylcellulosu.

.dhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phosphol,pids, such as cephalins and lecithins, can be used in the formulations.

Other additives can be mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Vol Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, 7zo dyestuffs and metal phthalocyanine dye- 15 stuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The foni..lations in general contain between 0.1 and per cent by weight of active compound, preferably between and 20 Tha active compounds can exist in their commercially available formulations and in the use forms prepared from these formulations in the form of a mixture with other active compounds such as insecticides, attractants, sterilants, acaricides, nematicides, fungicides, growthregulating substances or herbicide, The insecticides include, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms and the like.

Le A 29 065 38 The active compounds can furthermore exist in their commercially available formulations and in the use forms prepared from these formulations in the form of a mixture with synergistics. Synergistics are compounds by which the action of the active compounds is increased without it being necessary for the synergistic added to be active itself.

The active compound content of the use forms prepared from the cose-acially available formulations can vary within wide .limt. The active compound concentration of the use forms can be from 0.0000001 to 95 by weight of active compound, preferably between 0.0001 and 1 by weight.

They are used in a customary manner adapted to suit one 15 of these forms.

When used against hygiene pests and stored-product pests, the active compounds are distinguished by an outstanding residual action on wood and clay and by a good stability to alkali on limed substrates.

20 The preparation and use of the active compounds according to the invention can be seen from the examples which follow: S f.

Le A 29 065 39 Preparation Examples Example 1 0 NH-0--CF 3 (Process 1.2 g (0.00642 mol) of 4-trifluoromethylphenyl isocyanate are added dropwise with stirring at room temperature to 2 g (0.00598 mol) of 3-(4-chlorophenyl)-4-((2-chloroin 50 ml of :dichioromethane,, and the mixture is ref luxed for one hour.

:10 For working-up, the reaction mixture is cooled, and solid which has precipitated is filtered off with suction and dried.

1.6 g (51 of theory) of 3-(4-chlorophenyl)-4-[(2chlorophenyl) -carbonylamino]-l-( (4-trifluoromethylphenyl)-aminocarbonylJ-4,5-dihydropyrazole of melting point 200 0 C are obtained.

:1H-NM (DMSO-d 6 /tetramethylsilane): *8 3.96(dd); 4.29(t); 5.95(m); 9.33(d); 9.53(s) ppm.

The following substituted pyrazolines of the general Le~ A 29 n65 40 formula are obtained in an analogous manner and following the general preparation instructions: R2.

R

3 o N-R 6

H

Ex.

a a 4

S

**aa 5* *5 e C1 0 C1 0 C1 0 C1 0 i 0 0 -<D-SCF3 2

CF

3 -0 C1 -0-c 1Q-CF3

-CJ-F

a S5 S a.

a* 6 V<D-B Le A 29 065 41 Ex.

SS S

A*

A.

A

*5 A

A*

AA

-DB

11 12 13 F 14 cl 0 0 Cl 0 Cl 0 0 0 0 0 H H -r -§3-F .K73-Br -0CQCF3 A. A

A.

A.

0* A.

A.

A

A

A.

C A A A AA A A S

A.

H

-CF

3 H -<Qj-C 2

HS

Le A 29 065 42 Ex.

C -C4<:>Br 0

CF

3 H -b 0. 0: 0. 1.: 16 0C-C 0 0CM 3 171 0 0

OCH

3 0

OCR

3 21 0 22 K~~ciOCH 3 2 1 1 -C-0 H i B H H -<Jj--OCHF2 H l-OF 0 0* *0 000 *0 0 *0 0 0 0000 0 0 0 e 0 0 -63-F3 H -<-OCHF 2 Le A 29 065 43 Ex. RR3& 24 -Z~-i 1 ii 0 D-CHF 2

F

251 c 0 26 0 27 0 ii I 0 29 1Q c H

CF

3 0~ o 0* S. S So 0500 S S S S 50 S0 *0555*

S

C I Br

>--CHF

2 30 D- 0 H

F

44 0 0* 0 *0 0 0* *0 000000 00 o *0 Ex. R 31 -D 32 33 -KD-F 34 F 35 36 37Q 38 K R 2 -c-CJ>F 0

-C-Q:-F

0 0 a -CQ>Br 0 R3 R6 H

F

H C:>-ci1 H -D B H

CHF

2 H -DI

F

H <liEF H- -CI-OF 3 H 0* ~0 00 0 S 0 0 o 0 0005 5* 0 0 0 0 0 50 00 Le A 29 065 45 Ex.

41 42 43 441

D

jC<-QCH3 0 iKC<DH3 01 0 0 H -C -r H H -KID;>-CF 3 H 7>B S9000 0 0.0* a a 00 a 00 a 0 a 0 0000 00 00 a 00 0 0000 00 0 0 0 00 0 0* Oa 46 47Q Cl 0 Cl 0 H H -ci1 Le A 29 065 46 Ex.

*9*SB* 9 .4.

9* 9. 9 9. 9 9* 99 999@@9 9 .9 9e 9* 48 49 52 53 1.

54 55 r 56r C 1 0 0 C0 11K 0

C-KD-.

01 0 0 0 H KD-B r H I H (J3-Br~ H <>B

S

9.

99 9 9 0 9. 9 99 Le A 29 065 -4 47 .00.

0S 57 :>B 58 59r 61 62>-1 63 -1 645 0 -CQ<:-Br 0 -CQ-Br 0 0 0 0 0

HR

H H K-0CF2 H -C:>,ci1 H :,Br H >I-B r H I H

C"CF

H 3 H

>-CF

OS

.5.5 5, *5 S 55 a. 555.

S.

S S S S S *5 S 9O 55 Le A29 065 48

E

6 X. R 66 DBr 67 -0 -B r 68 DBr 69 B

C-

71 -r 72 -D r 73 74Q 0 0 0 H R/

H

H rC-C H <>B H

-CF

H F H

CF

6* 6 9

S.

Le A 29 065 49 S. S

SS

S. S 5~ Ex. R 1 76 1 77 -C 1 78 D-1 79 -D C D -I 81 -D C 82 KOD-Br 83 B 0

~-C>-CH

3 0 ~-KD-CH 3 0 0 0 toc 0 0 0

R

6 H F H -D

OF

H K<Dc F 3

H-K-

H -C H 3 H 2 H 0-F H -D-C1

S.

S S

S

S S 55 S S

S.

Le A 29 065 50

E

0~~Saa a a.

a.

a a, a a x. R 84 86r 87 88 89 91 92 -C-7J-CH 3 0 0 -C0 0

C-Q-F

01 0 0 0 H -KQ- z-

H

H -Q-F H C:-F 3 H H 0. 0.

Le A 29 065 51 Ex.

93D 96 98 99l0o -C0 0 0 cl 0 Cl

CH

3 0

CH

3 0 0 H Br H -0CHF 2 H -C-F H- -c;j-'0CF 3 0 00 0 00 0 0* 4 00 Le A29O065 52 Ex.

1.01 102 103

-K)

104 105 7>- 106 107 108 XF **44 4* .4

CH

3 0 0

CH

3 0 CH0

-C

0

CH

3 0 -C-DCi 01 0 0 H -C:>-OCHF 2

H

H .4 .4 4* 4 4 0 Le A29O065 53 Ex.

S

109 F 110 1 112 D F 113 F 114 C F 1 16 0 ,r 117 z-B 0

-C-QD-F

01 0 -C<DBr 0 -C-C3-F 01 0 0F 0 R -C-OCHF 2 H 1C

CF

3 H -CJz H -C

CF

3 H F

S*

S.

555.

S S S. 0. 0.

Le A29 065 -54- Ex.

0 0 Cl

CF

3

H

CF

3

CF

3

CF

3 H Cl K-b1 bo*..

C S

C

C.

124 D- 0 0 Le A29O065 55 Ex.

e, a 126 B 127 -D s 128 j B 129 -D B 130 -D B 131 -D B 132 -D B 133 134 CI 0

-C-(CT-

2 5 0 -C-(CH-1)S- 0 11

C-(CH

2 0 11)5

(CH

2 0

IL

-C-(CH

2 5 0 11 C2CH)) -<D-Fv -QCF3 *0 00 a 0 OOea 0 0 SO 0

[I

0 H

F

H

-DOF

-C-CH2 H I -cl Le A29 065 56 Ex.

9. 9 9O 9S**99 .9 135 -C 136 -C 137 -KD-ci 138 -DC 139 -c 140 -DC 142 -DC 143 l-1

-CH

I NI.-CH3 0

,,CH

3

-C-CH

2

-CH

I I 'N%H 0 -C-CHZ-CH

I.IH

0 C CH2

,-CM

3 0

C-CH-C

0

-C-CH

2

-CH

3 I I 0

H-D-F'

H -Kil j-o-CF 3 H -<Qjj--C I

S.

9 9 9* 99 9 9 *9

-C-CH

2

-CH

3 1t 0

-C-CH-

2

-CH

3 11 0 Le A 29 065 57 Ex.

144 145 146 147 148 149 iso 151 152

-C-OCR

3 0 H <DB r x-C

H

3

-C-CH

2 -CH- H 11

"'CH

3 0

(CH)

0 -C-CI4 2 -CH H 0 -C-CR H I~ I -cRli 0

-C-CR

2 -CH R H H 0

C-CH

2 -CR -H H 0

C-CH

2 -C 3

H

-CHM ,-H 3 I C -R -CH 3

H

CM

F

3 -<>CF 3 a *0 a. a a a a. a a a a.

a *aaa a a a a a. a a a a.

a a. *a a a a -C -Br -C HF -0 0- CF Le A 29 065 -5 58 153 KDc 154 KIIc 155 156 K0 -C 1 157 158 159 C H 3

-C-CH

11

H

0 I, '-CH3 0

~-CH

3

N--H

3 0 H3

-C-CH

II Nz"H3 If '-CH3

"-CH

3

-CH

3 0 0 H

F

~QcF3 H f c I H Br 9* 9 9.

99 99 9 9* *9 9 99.999 9 9. 9 .9 99 9 .9.9 99 99 .9 99 9 9 9 9 99 .9 99 9 9 9 9 9 9 OclHw 2 -O -S-CF 3 161 -D II ~NCH3 0 cl Le A 29 065 59

E

S SO SO S* C 0*

C

*045CS S S x. R 163 -D B 164 Br 165 166 D Br 167 Br 168 D -1 169 -D B 170 -D B 0 -C-CH2 0 0

-C--.CH

3

H

11 0

-C--CH

3

H

11 0 0 -C-C CH 0 11 0 K11>o

C:

I

f~B r >--CHF 2

C.

*C

55 C

S

S

OS..

S 55 S C S C C S

CC

Le A29 065 60 Ex. R 171 172 -1 173r 174 B 175 D

F

17 6 C -C--CH 2 -CH ,-H 11 '-CH 3 0 c 2

H

I i 0

II-

0 0

-C-CH,-H

0 H f-Ci H

F

'no S* S

SO

050505 0e 55 0~ 0 55 S S S S S S

S.

177 C -r 1.78 -D B 179 C Br 0t 0 0 H

-F

H-2~c

H

Le A29 065 61 Ex.

F

3 18 0 I18I1 182 -CH3i CH 3 0 -C--CH

-'H

I I '-CH 3 0 C--C H -I I I 'CH 3 0 H C

-F

H 1

HHF

0. 9.

0. 9 o0 0 0.09.

Le A 29 065.

62 Preparation of the starting compounds: Example II-1: Cl -v "H Cl NMN 0

H

g (0.0856 mol) of N,N-dimethylmethyleneimmonium chloride are added at room temperature with stirring to 20 g (0.065 mol) of 2-chloro-N-[2-(4-chlorophenyl)-2oxoethyl]-benzamide (preparation cf., for example, J.

Amer. Chem. Soc. 77, 1850 r1955]) in 100 ml of acetonitrile, and the mixture is refluxed for 3 to hours. When the starting compound can no longer be 10 detected in the thin-layer chromatogram of the r.action mixture, 6.5 ml of hydrazine hydrate are added, and the mixture is refluxed for a further 4 to 6 hours. For working-up, the reaction mixture is cooled and precipitated solid is filtered off with suction, washed first with diethyl ether and then with water, and dried.

•10.4 g (48% of theory) of 3-(4-chlorophenyl)-4-[(2chlorophenyl)-carbonylamino]-4,5-dihydropyrazole are obtained as a brown solid which can be used in the subsequent reaction without further purification.

20 'H-NMR (DMSO-ds/tetramethylsilane) 8 5.68; 9.10 ppm Le A 29 065 63 Example 11-2: 0 1II /-CH3

H-C-CH

2

-CH

NN- cH3

H

29 ml of hydrazine hydrate are added at 40-50°C with stirring to 37.0 g (0.149 mol) of 4'-fluoro-2-isobutylcarbonylaminoacrylophenone in 150 ml of ethanol, and the mixture is stirred for a further hour at 50 0 °C For working-up, the reaction mixture is concentrated in vacuo, and the product which precipitates during this process is filtered off with suction and dried.

37.0 g (95% of theory) and 3-(4-fluorophenyl)-4-isobutyl- 10 carbonylamino-4,5-dihydropyrazole are obtained as a yellow solid which can be reacted further directly without additional purification.

Example VIII-1: 0 II 3/CH F-..>.-C-NH-C-CH2-CH 11 II

'CH

0 CH 2 3 :4 50 ml of 37% strength aqueous formaldehyde solution, 1 ml of piperidine and 1 ml of glacial acetic acid are added in succession with stirring at 60°C to 37.4 g (0.158 mol) S: of 2-isobutylcarbonylamino-4'-fluoroacetophenone (preparation cf., for example, DE 2,947,140; J. Heterocycl.

Chem. 24, 297-301 [1987]) in 240 ml of methanol, the mixture is subsequently stirred for a further hour at Le A 29 065 64 0 C, and the solvent is then removed in vacuc.

37.0 g (94% of theoryl of 4'-fluoro-2-isobutylcarbonylaminoacrylophenone are obtained as a solid which can be reacted further directly, without additional purificati n.

The following pyrazolines of the general formula (II) which are unsubstituted in the 1-position are obtained in an analogous manner:

R

2

,R

3 R'j

NN

(I I) 0 000000 0 0000 00 00 0 0 00 00 000000 0 *0 9 00 00 Ex.

No.

R 3 R 4

'H-NMR*)

11-3

-KD

0CH 3 '0

-C-Q:-F

0 H H 5.80; 9.02 11-4 00 0 0 0 0 0 0000 O *0 00 0 00 0 00 0 0 00 0 00 H H 5.82; 9.V~ H H 5.77; 9.06 11-5-0ID Le A 29 065 65 Ex. R' P2 R3 R4 'H-NMRO) No.

116

-OX

11-8 11-9 >F Cl 0 I I 0 -C0 0 0

OCH

Cl

O

0 c I 0 H H 5.70; 9.09 H H 5.75; 9.13 H H 5.69; 9.08 i H 5.69; 9.08 H H 5.77; 9.01 c o o r a CC

CC

C

CC

'CC.

10

C

11-11 11-12 H H 5.74; 9.03 H H 5.67; 9.07 Le A 29 065 66 Ex. Rl R2 No.

11-13r 11-14 r 11- 15r 11- 16 -C )II-F 11-17 11-18 0 0 0 -C 7j-Br 11 0 R3 R 4

'H-NMR*)

H H 5.74; 9.09 H H 5.74; 9.11 H H 5.77; 9.01 H H 5.76; 9.06 H H 5.75; 9.11 H H 5.74; 9.12 e S 10 0 11-19 1!-2 0

H

0 Ir-KD CH3 H 0 H 5.77; 8.96 H 5.78; 8.93 Le A 29 065 67 Ex.

No.

R

3 R4 'H-NMR*) II- 21 1 11-22 -C1( -cI H 0 0 0

II

11 -C-(CH2)5- H 5.76; 9.11 H 5.75; 9.04 H 5.75; 8.92 H 6.12; 7.68 11-23 11-24 S/Br S S S S

S

0 11-25 \711~C -I*.-CH 3

H

-C-CH

2 _CH CH

~CH

3 0 11-26 11 H 1-C-CH 2

-CH

3 H 5.49; 8.40 H 5.37; 8.37 11-28 0

'I

(CM

2 3 0 11

,-CH

3

H

C-C H CH 'IH -c-cN 0 cr H 5.86 H 5.50; 8.40 Le A 29 065 68 Ex.

No.

R3 R 4

'H-NMR

1 11-29 -0 -cl 0 H 3 H H 5.47; 8.35 11-30 11-31 11--32 0 11 C-C C- 3 0 H H 5.23; 7.79 H H 5.44; 8.45 H H 5.48;- 8.67 O 1-3D B 11-34 0 11 -c-I 0 11 3

-C-CH

,-NCH

3 H H 5.48; 8.64 H H 5.49; 8.33 *5 S S S S e .5 55.5 S S S S 55

S

Le A 29 065 69 Use Examples In the use examples which follow, the compound listed below was employed as comparison substance:

S

CH

3 S-(9 0 -O-c 2

H

0- (4-Methyithiophenyl) 0-ethyl S- (n-propyl) thionophosphate (disclosed in DR 4 2,111,414) a.

o 0* 00 0 0 0* *0 a a 0R ~0 a.

a. a a a a.

*0 0 a a.

Oa*a a 0* Le A 29 065 70 Example A: Phaedon larvae test Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by dipping Sinto the preparation of active compound of the desired concentration and infested with mustard beetle larvae (Phaedon cochleariae) while the leaves are still moist.

After the specified time, the destruction is determined in percent. 100% means that all beetle larvae have been destroyed; 0% means that no beetle larvae have been destroyed.

In this test, a superior activity compared with the prior art is shown, for example, by the following compounds of S: the preparation examples: 36, 52, 63.

o *&o S0 o* Le A 29 065 71 Example B: Plutella test Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, 1 part by weight of active compov 1 is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by dipping into the preparation of active compound of the desired concentration and infested with cabbage moth caterpillars (Plutella maculipennis) while the leaves are still moist.

15 After the specified time, the destruction is determined in percent. 100% means that all caterpillars have been destroyed; 0% means that no caterpillars have been destroyed.

In this test, a superior activity compared with the prior 20 art is shown, for example, by the following compounds of the preparation example: 106.

.oo9 .9 Le A 29 065 72

Claims (2)

1. Substituted pyrazolines of the general f ormula (I) R 2 N .R H H __EtH (1) X N -R 6 H in which X, R 2 RI and R' can in each case assume the following combinations of meanings: e* e Le A 29 065,-7 73 -Q-F Cl 0 Cl 0 Cl 0 Cl 0 0 R 3 R 6 x H SCF 3 CF 3 Cl H -0: 4 4e a a a a a C a. a a a. Le A~ 29 065 74 Q<DBr a a a. a a. H 0 TO 1 0 H 0 0 C I 0 -C Br H I I 0 c BrH 0 -c H 0 -c 3 -<D-Br -CD-F -o-oc 2 HS 0 0 0 0 0 0 0 0 0 a a a a *a a a *0 -KD-B r -GD-F Le A 29 065 75 9L S90 6Z V r 0 LAHDO T ID )E 0 .400-0 0 0 LHOO 0 14I 0 H 3 H 3 H 3 .H.O 0 H H D/ HR3 I I I 4 44*44@ I 4 4 44 44 44 4 4 44 0 4 4 44 44 4 0 4

444. .444 4444 4 44 4 94 4 44 4 444444 4 44 4 44 4 44 4 I, 44 4 0 4444f~4 13 L a- 0 /0 A a x98 E aI -cici KDci KD~ci a a. a a a a. -Q-F Q<DF R 2 R 0 0 Cl Cl 0 0 0 0 H F a H -<Qj-CF 3 0 H (7j- 1 0 H C> r 0 H -§3---OCHF2 H F 0 H- -K<7--OCF 3 a H- jCF 3 3 R 6 a. a a. a a. a a Le A 29 065 77 BL 990 6Z'V gr Ts-D-- 0 c 43 ES 0 1-I1 14 CH o0 0 0- 0 0~ Ot 00 9 0 00 0 0 000 0 000000 00 0 0 0 K 7DciF -0>C S. S a. -0 0 0 0 -C- 0 c 0 Cl 0 0 H H H -F H C-I H <>B S. S S S S S. S e S. -0 -0 Le A29 065 79 S. S* -C1j -r -<jjBr -QDBr R 2 R 3 H 0 0 -C-0 H 0 -C-Q-c H 0 H 0 0 0 0 R6j-a -B ri x 0 0 *S S S S S S CF 3 -<QCF3 Le A29O065 80 J~j-Br R2R 3 IR 6 x 9 *9*9 9* 99 9 9. 9 9 9 9 9* 9 *9 .9 0 0 0 0 1 H -7 -F H -OF H -<:j-CFF 2 H4J(D-F H -DOF HJ-D-C1 H B 99 9. 99 99 99 S 9 9. 99 5 99 9. 9 9. 9 9. Le A 29 065 81 R1 -C -Br -C -Br Q-Br -C -Br -<D-Br 0 0 0 0 0 0 H -KID.--CF1 H OCF 9*O* 0* -0 6~ -oCi -C-QD-CH3 H 0 0 I C3 Le A29 065 82 -Q-c I K<D C I R 2 R3 R 6 x -CH3 H 0 0 0 0 0 -C C HF 2 F e..s 9 S. .9 9* 9. 9 9 9 9 9 9 .4 9 9. S. Le A 29 -065 83 -Q-i -0DS -0DB R2R 6 X 0 H H 0 -C-CD--F H 0 -C4D H 0 -c-Ql H 0 0 3 -Q-CF 9* 9 9. I Le A29 065 84 F? 2 R 3 R6 x 0H K a j r 0 0 -0 -0 -o Cl 0 C- 0 0 CH 3 0 -C. 0 CH 3 0 -c 0 t o 4.S .00. 5* 06 S S 5* *5 S *55 0*S9 5*55 to 6 0 S C S H H /F H 0CF 3 -0D -KD Le A 29 065 -KD -o -0 -0 R2 6 3 CH 3 0 0 CH 3 0 -C H 0 CH 3 0 -C H 0 CH 3 0 0 0 -c 1 H. -C<DCL I 0 R 6 x S S S *5 SS S .5.55. 4* 9 *5 S. -K:I-oc F 3 -69-CF3 0* S. *5 S S S S 5* 5* S *5 Le A29 065 86 LB S90 6Z 0- 9 4 9 9 S S @9 @4 0 C C S. 9 C CC 9. 9 C C4 0 C SOCC 9 9 9. S 90 9 '49 C S 0 Co C 9 C 09 0* 0. 9 SC 4 S CAD I .18 (74- ID 1D~Q~ 0 0 0 11 I H J 0 H4 0 11I H <I3 ID~KD~ A A 14 J-'II1 ID~Q~ 0 ZR0 x H- Ii r <jj~r 4Jj~r <Qj~r RZ R 3 R 6 X 0 ~C-QD-F 0 H -F H D- CF 3 H -C a C SC C C* C. S. S C Ct CC S C. C CS S. K<D-C 1 -C-C3D-F 0 0C< -H CC CC .RC. Re CC C CR CO C CC C C C. C C CR H -7 CF 3 H -C/ CF 3 H -CJ-c 1 -Dcic1 0 Le A29 065 88 KDci 0 0 CF 3 H <:b H-KbI 0 a #POO. -<D-Br r -C -Br r -<D-Br -<D-Br 0 11 (CH 2 5 0 (CM 2 5 0 (CM 2 5 0 11 -C-C CH 2 5 (CH 2 5 -(Q--OCF3 K<Dc 1 -CJ jar -<D-OHF 2 O 00 0* 0 0 0 4* 0 0. 0 00 Le A29065 -89 r -C -c 1 I 1 I -C I -C I 0 11 (CHZ) -C-CHZ-CH CH3 11 '--'CH3 0 -c-CH2-CH ,--CH3 11 C- H 3 0 -c-cli2-CH 11 CH3 0 ",-CH3 -c-CH2-CH -C-CH2-CH ,--CH3 I I -CH3 0 -C-CH2-CH 3 -c-CH:3 -c-CH2-cj13 I I 0 -o-CF3 H -C-3--.oCF3 H -<D-CF3 H -0 -C I H r CHF2 H H -<D-0-CF3 06 0 04 be Le A 29 065 90 1 -C-CH- 2 -CH 3 11 0 -C-CH 2 -CH 3 11 0 H -Ga-F -C-OC- 3 'II 0 *0e 0. 0 S* 0 0* 0* 0000*0 0 09 0 o *0 -KD-i ~ciir (CH2 3 -C F3 -C-CHZ-CH 11-C1 *0 i 00 00* 04 00 0 -C-CZH,-3 CH 2 -C H3 ,-CH 3 -C-CK 11 'N"-CH 3 0 -C-CHZ-CH-CH 11 '-CH 3 0 0 H I D CF H 2 CF F3 Oak 00IV 0 0 00 0 00 0 00 0 09 -C -Br Le A29 065 91 RI -C -F -<D-F I -0--Cl -c-CHCH--H H II H-CH3 0 -CC.,-CH H -C-CH H 11 '"-CH 3 0 -C CH H 0 -CHFZ 3 CF 3 0 9 S 9 9 4. 4 A. .4 4 9449*4 4 .9 0 4* -0-cl "-CH 3 0 .4 4 9, 44 *499 9* 94 4 CH 3 C -CH 0 0 ".-CH 3 0 11IIH 0,l1 H I 4. 9 4* 4 4 9 9 44 4 94 Ki<'o CHF -0-CF 3 Le A29 065 92 ~O~-Br YJDBr 0 -C -CH H 0 -C-(CHC 2 3 0 Ii I 0 I I 0 -C--OCH 3 I I 0 -Qa cl -KIY-c o 0 CF3 0 S *S5S 5* S S S S. 0e S S S 55 S. S. 5* S S. S S S S S. S .5 0 H C Br Le A29O065 93 K~sr QaD-r 0 -0-(CH 2 3 11 0 CHF 2 0-C I -CC2C ,-CH 3 H 2 -CH 3 0 S S 55 5 S S K<Dci -0-B 0 0 0 H H C CF SS S S -C-CH -f H 0 C-CH-CH '-,Cfl 3 H F H F 5 5 5 0 5* S SO Q0 Br 0 H -D -F Le A29 065 94 -<O-Br K~cr Y -C I 0 4***eS S 4.-n 0* 4* 4. S 4 49 4 4. I S S 4* -C-CH 0 C-CM 0 -C-CH M-H CH 3 0 C-CH ,-H 11 CH 3 0 C-CM 'H 11 -'CH 3 0 H 1 H -<DBr H -F H >-I H D0-CF H -Q-C I H r 4. 5 49 5* I 5* I .4 4 4 o 4 m 44 4* 4 4 9. 4. *4 Le A29 065 95 Process for the preparation of substituted pyrazo- lines of the general formula (I) NNX X N -R 6 H in which the substituents X, R 2 R 3 and R 6 can assume the combinations of meanings which are listed in Claim 1, characterised in that pyrazolines of the formula (II) which are unsubstituted in the 1-position *0000K a)S wihioyn so h oml (III) adin which has ndR hv the abovementionedgo A 10b) with ic myanat ries of the formula (I V)) Le A 29 065 -996 -97- 6 R N- (IV) H Cl in which R 6 has the abovementioned meaning, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary. 3. Pesticide, characterised in that it contains at least one substituted pyrazoline of the formula in admixture with an extender and/or surface active agent. 15 4. Method of combating animal pests, characterised in that substituted pyrazolines of the formula are allowed to act on animal pests and/or their environment. 5. Process for the preparation of pesticides, characterised in that substituted pyrazolines of the formula are mixed with extenders and/or surface-active agents. 6. A pyrazoline according to claim 1, substantially as herein described with reference to any one of the foregoing examples thereof. *ee S DATED this 13th day of December, 1994 BAYER AKTIENGESELLSCHAFT By Its Patent Attorneys, DAVIES COLLISON CAVE p:\wpdoc\grs\436963\Jgs Substituted pyrazolines Abstract There are described new pyrazolines of the formula (I) R 2 R 3 R 1 N H (I) X N-R 6 H in which X, R 1 R 2 R 3 and R 6 have the meaning given in the description, and the process for their preparation. The new pyrazolines are used as pesticides. Le A 29 065