AU657151B2 - Substituted pyrazolines - Google Patents

Description

657151 P/00/011 Regulation 3:2 Our Ref: 436723

AUSTRALIA

Patents Act 1990

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT *4 4 4. 0* 0* .4 .4 Applicant(s): Address for Service: Bayer Aktiengesellschaft D-5090 Leverkusen Bayerwerk

GERMANY

DAVIES COLLISON CAVE Patent Trade Mark Attorneys Level 10, 10 Barrack Street SYDNEY NSW 2000 Invention Title: Substituted pyrazolines The following statement is a full description of this invention, including the best method of performing it known to me:- 5020 4 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; US-A 4,174,393).

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

New substituted pyrazolines of the general formula (I) have been found, 2 3 R

N

R

2

R

3

N

1 64 S .i I (I) X

R

6 in which

R

I represents optionally substituted phenyl and either

R

2 represents a radical of the formula -CO-R 7

-COOR

7 or Le A 28 549 1 I I -S0 2

-R

7 and

R

3 represents hydrogen, alkyl or halogenoalkyl or

R

2 and R 3 together with the nitrogen atom to which they are bonded represent a heterocycle of the formula 0 0 0 0 ft. *t *o

S

S

0 0 01NQ

R

4 represents hydrogen, alkyl, halogenoalkyl, halogenoalkylthio, halogen, alkoxycarbonyl or in each case optionally substituted cycloalkyl or aryl,

R

5 represents hydrogen or alkyl,

R

6 represents, in each case optionally substituted alkyl, cycloalkyl or 3,4-disubstituted phenyl and Le A 28 549 2- X represents oxygen or sulphur, where R' represents hydrogen, alkyl, alkenyl, alkinyl, halogenoalkyl, halogenoalkenyl, halogenoalkinyl, alkoxyalkyl, alkylthioalkyl, nitroalkyl, cyanoalkyl, alkoxycarbonylalkyl, in each case optionally substituted cycloalkyl, aralkyl, aryl or heterocyclyl or a radical

"R

8

-N

R

9 in which either *0 0

R

8 represents hydrogen or alkyl and

R

9 represents alkyl or in each case optionally substituted aralkyl or aryl, or

R

8 and R 9 together with the nitrogen atom to which they are bonded represent an optionally substituted heterocycle which can, if appropriate, contain further hetero atoms.

0 Depending on the nature of the substituents, the compounds of the formula may optionally exist in the form of geometric and/or optical isomers or isomer mixtures of various compositions. The invention claims the pure isomers as well as the isomer mixtures.

Furthermore, it has been found that the new substituted Le A 28 549 3 pyrazolines of the general formula (I)

R

2 ~3 R1 N4

R

R1 represents optionally substituted phenyl, and either R 2 represents a radical of the f ormula -CO-R 7

-COOR

7 or -S0 2

-R

7 and !5 R 3 represents hydxogen, alkyl or halogenoalkyl or

R

2 and R 3 together with the nitrogen atom to which they are bonded represent a heterocycle of the formula 091 0 0 0

-NDN

0 0 Le A0859 9- R4 represents hydrogen, alkyl, halogenoalkyl, halogenoalkylthio, halogen, alkoxycarbonyl or in each case optionally substituted cycloalkyl or aryl,

R

5 represents hydrogen or alkyl,,

R

6 represents in each case optionally substituted alkyl, cycloalkyl or 3,4-disubstituted phenyl and X represents oxygen or sulphur, where

R

7 represents hydrogen, alkyl, alkenyl, alkinyl, halogenoalkyl, halogenoalkenyl, h;:kogenoalkinyl, alkoxyalkyl, alkylthioalkyl, nitroalkyl, cyanoalkyl, alkoxycarbonylalkyl, in each case optionally substituted cycloalkyl, aralkyl, aryl or heterocyclyl or a radical '_R8

R

9 in which either RI represents hydrogen or alkyl and Le A28 549 -5

R

9 represents alkyl or in each case optionally substituted aralkyl or aryl, or

R

8 and R 9 together with the nitrogen atom to which they are bonded represent an optionally substituted heterocycle which can, if appropriate, contain further hetero atoms, are obtained when pyrazoli-es of the formula (II) which are unsubstituted in the 1-position R2, R 3 RlVh 4 (I I

SII(II)|

1 in which

.R

I

R

2

R

3 and R 4 have the abovementioned meaning, o o:

H

S* *O Sa) with iso(thio)cyanates of the formula (III) R6-N=C=X (III) wi wh.

with iso(thio)cyanates of the formula (III) in which Le A 28 549 6 a

R

6 and X have the abovementioned meaning, or b) with (thio)carbamoyl chlorides of the formula (IV)

R

6

X

(IV)

in which

R

5

R

6 and X have 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 show a considerably better insecticidal activity compared with the compounds which are known from the prior art and which are similar chemically and/or from the point of view of their action.

Formula provides a general definition of the substituted pyrazolines according to the invention. Preferred compounds of the formula are those in which Le A 28 549 7as a a a t a.

R

1 represents phenyl which is optionally monosubstituted or polysubstituted by identical or different substituents, suitable substituents ng: halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl, each of which has 1 to 8 carbon atoms, in each case straight-chain or branched halogenoalkyl, halogenoalkcxy, halogenoalkylthio, halogenoalkylsulphinyl or halogenoalkylsulphonyl, each of which has 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, in each case straight-chain or branched alkenyl, alkinyl, alkenyloxy or alkinyloxy, each of which has 2 to 8 carbon atoms, in each case straight-chain or 15 branched alkoxycarbonyl or alkoximinoalkyl, each of which has 1 to 8 carbon atoms in the individual Salkyl moieties, straight-chain or branched halogenoalkoxycarbonyl having 1 to 9 carbon atoms and 1 to 17 identical or different halogen atoms, divalent dioxyalkylene which has 1 to 4 carbon atoms and which is optionally monosubstituted or polysubsti- *5 tuted by identical or different substituents from the series comprising halogen and/or straight-chain or branched alkyl having 1 to 4 carbon atoms, or 25 phenyl, phenoxy or phenylthio, each of which is O' optionally monosubstituted or polysubstituted by identical or different substituents from the series Scomprising halogen and/or straight-chain or branched S'alkyl having 1 to 4 carbon atoms; and either Le A 28 549 8 RL represents a radical of the formula -CO-R 7

-COOR

7 or -S0 2

-R

7 and

R

3 represents hydrogen, straight-chain or branched alkyl having 1 to 8 carbon atoms or straight-chain or branched halogenoalkyl having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, or

R

2 and R 3 together with the nitrogen atom to which they are bonded represent a heterocycle of the formula 0 .0 0or 1' o o R' represents hyrogen, straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or Sbranched alkoxycarbonyl having 1 to 9 carbon atoms, cycloalkyl which has 3 to 7 carbon atoms and which is optionally monosubstituted or polysubstituted by •N A eo Le A 28 549 9 identical or different alkyl substituents, straightchain or branched and having 1 to 4 carbon atoms, or represents phenyl which is optionally monosubstituted or polysubstituted by identical or different substituents, suitable substituents being those mentioned in the case of R, or represents straightchain or branched halogenoalkyl or halogenoalkylthio, each of which has 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, or represents fluorine, chlorine, bromine or iodine;

R

5 represents hydrogen or straight-chain or branched alkyl having 1 to 8 carbon atoms;

R

6 represents straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, cycloalkyl which has 3 to 7 carbon atoms and which is optionally monosubstituted or polysubstituted by identical or different substituents from the series comprising 20 halogen and/or in each case straight-chain or branched alkyl or halogenoalkyl, each of which has 1 to 6 carbon atoms and, in the case of the halogenoalkyl, 1 to 13 identical or different halogen atoms, or represents phenyl which is substituted in the 3,4-position, suitable phenyl substituents being those mentioned in the case of R 1 and X represents oxygen or sulphur, where Le A 28 549 10

R

7 represents hydrogen, in each case straight-chain or branched alkyl, alkenyl or alkinyl, each of which has up to 8 carbon atoms, in each case straightchain or branched halogenoalkyl, halogenoalkenyl or halogenoalkinyl, each of which has up to 8 carbon atoms and 1 to 17 identical or different halogen atoms, in each case straight-chain or branched alkoxyalkyl, alkylthioalkyl, nitroalkyl, cyanoalkyl or alkoxycarbonylalkyl, each of which has 1 to 6 carbon atoms in the individual alkyl moieties, or represents cycloalkyl which has 3 to 7 carbon atoms and which is optionally monosubstituted or polysubstituted by identical or different alkyl substituents, straight-chain or branched and having 1 to 4 carbon atoms, or represents aralkyl which has 1 to 6 carbon atoms in the straight-chain or branched alkyl moiety and 6 or 10 carbon atoms in the aryl moiety, aryl which has 6 or 10 carbon atoms or hetero-cyclyl which has 2 to 9 carbon atoms and 1 to S 20 5 identical or different hetero atoms (in particular nitrogen, oxygen and/or sulphur), each of which is optionally monosubstituted or polysubstituted in the aryl or heterocyclyl moiety by identical or different substituents, suitable aryl or t.eerocyclyl substituents being those mentioned in the case of R 1 or represents a radical of the formula and either and either i Le A 28 549 11

R

8 represents hydrogen or3 straight-chain or branched alkyl having 1 to 8 carbon atoms, and

R

9 represents straight-chain or branched alkyl having 1 to 8 carbon atoms or aralkyl which has 1 to 6 carbon atoms in the straight-chain or branched alkyl moiety and 6 or 10 carbon atoms in the aryl moiety or aryl which has 6 or 10 carbon atoms, each of which is optionally monosubstituted or polysubstituted in the aryl moiety by identical or different substituents, suitable aryl substituents in each case being those mentioned in the case of R 1 or

R

8 and R 9 r o

'I)

r together with the nitrogen atom to which they are bonded represent a saturated or unsaturated, optionally benzo-fused five- to sevenmembered heterocycle which can optionally contain 1 to 3 further hetero atoms (in particular nitrogen, oxygen and/or sulphur) and/or 1 to 3 keto groups and which is optionally monosubstituted or polysubstituted by identical or different s'lbstituents, suitable substituents being those mentioned in the case of R 1 Particularly preferred compounds of the formula are those in which R represents phenyl which is optionally monosubstituted to trisubstituted by identical or different substituents, suitable substituents being: Le A 28 549 12 halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl, each of which has 1 to 4 carbon atoms, in each case straight-chain or branched halogenoalkyl, halogenoalkoxy, halogenoalkylthio, halogenoalkylsulphinyl or halogenoalkylsulphonyl, each of which has 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, in each case straight-chain or branched alkenyl, alkinyl, alkenyloxy or alkinyloxy, each of which has 2 to 6 carbon atoms, in each case straight-chain or branched alkoxycarbonyl or alkoximinoalkyl, each of which has 1 to 4 carbon atoms in the individual alkyl moieties, straight-chain or branched halogenoalkoxycarbonyl having 1 to 5 carbon atoms and 1 to 9 identical or different halogen atoms, or divalent dioxyalkylene which has 1 to 3 carbon atoms and is optionally monosubstituted or polysubstituted by identical or different substituents from the series comprising halogen and/or straight-chain or branched alkyl having 1 to 3 carbon atoms, and phenyl, phenoxy or phenylthio, each of which is optionally monosubstituted or polysubstituted by identical or different substituents from the series comprising halogen and/or straight-chain or branched alkyl having 1 to 4 carbon atoms; and either

R

2 represents a radical of the formula -CO-R 7

-COOR

7 or

-SO

2

-R

7 and Le A 28 549 13

R

3 represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms or straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, or

R

2 and R 3 together with the nitrogen atom to which they are bonded represent a heterocycle of the formula 0 0 0

O

-N

0 or

S

5555

SS

5 5 S S or a six-membered heterocycle which can optionally contain 1 or 2 further hetero atoms (in particular nitrogen, oxygen and/or sulphur) and/or 1 to 3 keto groups, suitable substituents being those mentioned in the case of R 1

R

4 represents hydrogen, straight-chain or branched Le A 28 549 14 alkyl having 1 to 6 carbon atoms, straight-chain or branched alkoxycarbonyl having 1 to 5 carbon atoms, cycloalkyl which has 3 to 6 carbon atoms and which is optionally monosubstituted to tetrasubstituted by identical or different alkyl substituents, straightchain or branched and having 1 to 3 carbon atoms, or represents phenyl which is optionally monosubstituted to trisubstituted by identical or different substituents, suitable substituents being those mentioned in the case of R 1 or represents straightchain or branched halogenoalkyl or halogenoalkylthio, each of which has 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, or represents fluorine, chlorine or bromine;

R

5 reprsents hydrogen or straight-chain or branched alkyl having 1 to 6 carbon atoms;

R

6 represents straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 20 identical or different halogen atoms, cycloalkyl which has 3 to 6 carbon atoms and w'hich is optionally monosubstituted to tetrasubstituted by identical or different substituents from the series com- W prising halogen and/or in each case straight-chain or branched alkyl or halogenoalkyl, each of which has 1 to 3 carbon atoms and, in the case of the .0 halogenoalkyl, 1 to 7 identical or different halogen atoms, or represents 3,4-disubstituted phenyl, C C Le A 28 549 15 suitable phenyl substituents being those mentioned in the case of R 1 and X represents oxygen or sulphur, where

R

7 represents hydrogen, in each case straight-chain or branched alkyl, alkenyl or alkinyl, each of which has up to 6 carbon atoms, in each case straightchain or branched halogenoalkyl, halogenoalkenyl or halogenoalkinyl, each of which has up to 6 carbon atoms and 1 to 13 identical or different halogen atoms, in each case straight-chain or branched alkoxyalkyl, alkylthioalkyl, nitroalkyl, cyanoalkyl or alkoxycarbonylalkyl, each of which has 1 to 4 carbon atoms in the individual alkyl moieties, cycloalkyl which has 3 to 5 carbon atoms and which is optionally monosubstituted to tetrasubstituted by identical or d-fferent alkyl substituents, straight- S• chain or branched and having 1 to 3 carbon atoms, or represents aralkyl which has 1 to 4 carbon atoms in •the straight-chain or branched alkyl moiety and 6 or 20 10 carbon atoms in the aryl moiety, aryl which has 6 or 10 carbon atoms or heterocyclyl which has 2 to 9 carbon atoms and 1 to 4 identical or different hetero atoms (in particular nitrogen, oxygen and/or sulphur), each of which is optionally monosubstituted to trisubstituted in the aryl or heterocyclyl moiety by identical or different substituents, •g suitable aryl or heterocyclyl substituents being those mentioned in the case of R 1 Le A 28 549 16 or represents a radical of the formula nR 8 R9 and either '.15

R

e represents hydrogen or straight-chain or branched alkyl having 1 to 6 carbon atoms and

R

9 represents straight-chain or branched alkyl having 1 to 6 carbon atoms or aralkyl which has 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety and 6 or 10 carbon atoms in the aryl moiety or aryl which has 6 or 10 carbon atoms, each of which is optionally monosubstituted to trisubstituted in the aryl moiety by identical or different substituents, suitable aryl substituents in each case being those mentioned in the case of R 1 or

R

8 and R 9 20 together with the nitrogen atom to which they are bonded represent a saturated or unsaturated, optionally benzo-fused, five- or sixmembered heterocycle which can optionally contain 1 or 2 further hetero atoms (in particular nitrogen, oxygen and/or sulphur) and/or 1 to 3 keto groups and which is optionally monosubstituted to trisubstitued by identical or different substituents, suitable substituents being those mentioned in the case of R 1 99 9 9 9 0 o Le A 28 549 17 Very particularly preferred compounds of the formula (I) are those in which

R

1 represents phenyl which is optionally monosubstituted or disubistituted by identical or different substituents, especially suitable substituents being: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, s- or t-butyl, methoxy, ethoxy, n- or 1-propoxy, i-I s- or t-butoxy, methyithia, ethylthio, n- or i-propylthio, s- or t-butylthio, meth~ylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, trifluoromethyl, difluoLomethyl, trifluoromethoxy, difluoromethoxy, difluorochloromethoxy, dichiorofluoromethoxy, trichloromethoxy, tetrafluoroethoxy, pentafluoroethoxy, trichilorodiiluoroethoxy, dichlorotrif luoroethoxy, pentachioroethoxy, trif luoro- 9.methylthio, difluoromethylthio, dichlorofluoro- 0 methylthio, difluorochloromethylthio, trifluoromethylsuiphinyl, trifluoromethylsuiphonyl, allyl, propargyl, allyloxy, propargyloxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, sor t-butoxycarbonyl, trifluoromethoxycarbonyl, methoximinomethyl, methoxi4minoethyl, ethoximinomethyl, ethoximinoethyl, dioxymethylene, difluorodioxymethylene, dioxyethylene, tetrafluorodioxyethylene, tri'fluorodioxyethylene, difluorodioxyethylene, or phenyl, phenoxy or phenylthio, each of :which is optionally monosubstituted to Le A 28 549 18 trisubstituted by identical or different substituents from the series comprising fluorine, chlorine, bromine, methyl and/or athy.; and either R 2 represents a radical of the formula -CO-R 7

-COOR

7 or -S0 2 -R7 and

R

3 represents hydrogen, methyl, ethyl, n- or i-propyl or s- or t-butyl, or

R

2 and RI together with the carbon atom to which they are bonded represent a heterocycle of the formula efee **0V V S 9. 9 .9 9

S

SS S C S

S.

0Y 0 or 10 S S 9 05

S

S

S

*5 9 S o o p SFb0 55 S S 9 5 59 S 9.

R4 represents hydrogen, methyl or ethyl;

R

5 represents hydrogen, methyl or ethyl; Le A 28 549 19

R

6 represents s- or t-butyl, or represents cyclohexyl which is optionally monosubstituted or disubstituted by identical or different substituents from the series comprising methyl, ethyl, n- or i-propyl and/or trifluoromethyl, or represents 3,4-disubstituted phenyl, suitable substituents being those mentioned in the case of R 1 and X represents oxygen or sulphur, where

R

7 represents hydrogen, methyl, ethyl, n- or i-propyl, s- or t-butyl, allyl, propargyl, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, or represents alkoxyalkyl or alkylthioalkyl, each of which has 1 Sor 2 carbon atoms in th- individual alkyl moieties, S* 15 or represents cyclop_ l, cyclopentyl or cyclohexyl, each of which is optionally monosubstituted S: or disubstituted by identical or different substituents from the series comprising methyl, ethyl and/or n- or i-propyl, or represents phenyl, pyridyl or furanyl, each of which is optionally monosubstituted or disubstituted by identical or different S" substituents, suitable substituents in each case being those mentioned in the case of R 1 0: or represents a radical of the formula 25 Le A 28 549 and either

R

8 represents hydrogen, methyl, etiyl, n- or i-propyl or 8- or t-butyl and

R

9 represents methyl, ethyl, n- or i-propyl, sor t-butyl, or represents benzyl or phenyl, each of which is optionally monosubstituted or disubstituted by identical or different substituents, suitable substituents in each case being those mentioned in the case of R 1 or 4 10 R 8 and R 9 together with the carbon atom to which they are bonded represent a heterocycle of the formula -ND or -N 0 each of which is optionally monosubstituted or disubstituted by methyl.

Especially preferred compounds of the formula are those in which

R

1 represents phenyl which is optionally monosubstituted or disubstituted by identical or different substituents, especially suitable substituents 20 being: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, i-, or t-butoxy, methylthio, ethylthio, n- or i-propylthio, s- or t-butylthio, methylsulphinyl, Le A 28 549 21 ethylsuiphinyl, methylsuiphonylc ethylsuiphonyl, trifluoromethyl, difluoromethyl, trifluorornethoxy, di fluoromethoxy, di fluorochioromethoxy, dichioro fluoromethoxy, trichioromethoxy, tetrafluoroethoxy, pentafluoroethoxy, trichiorodifluoroethoxy, dichiorotrifluoroethoxy, pentachiorcethoxy, trifluoromethylthio, difluoromethylthio, dichiorofluoromethyithic, difluorochloromethylthio, trifluoromethylsuiphinyl, trifluoromethylsuiphonyl, allyl, propargyl, allyloxy, propargyloxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, s- or t-butoxycarbonyl,, trifluoromethoxycarbonyl, methoximinomethyl, methoximinoethyl, ethoximinomethyl, ethoximinoethyl,, dioxymethylena, difluorodio)ymethylene, dioxyethylene, tetrafluorodioxyethy'Lene, trifluorodioxyethylene, difluorodioxyethylene, or phenyl, phenoxy or phenylthio, each of which is optionally monosubstituted to trisubstituted by identical or different substituents from the series comprising fluorine, chlorine, bromine, methyl and/or ethyl; and either R 2 represents a radical -COR 7 and R 3 represents hydrogen or methyl or R 2 and R 3 together with the nitrogen atom to which they are bonded represent a heterocycle of the Le A 28 549 22 formula ;N or or 0 0 R' represents hydrogen,

R

5 represents hydrogen or methyl,

R

6 represents cyclohexyl which is optionally monosubr stituted or disubstituted by identical or different substituents from the series comprising methyl and/or trifluoromethyl, or represents 3,4-disubstituted phenyl, suitable substituents being those 10 mentioned in the case of and X represents oxygen, where

R

7 represents hydrogen, methyl, ethyl, n- or i-propyl, s- or t-butyl or cyclohexyl, or represents phenyl which is optionally monosubstituted or di- 15 substituted by identical or different substituents, suitable substituents being those mentioned in the B case of R 1 Reference may be made to the compounds mentioned individually in the preparation examples.

If, for example, 3-(4-chlorophenyl)-4-[(2-chlorophenyl)- If, for example, 3-(4-chlorophenyl)-4-[(2-chlorophenyl)- Le A 28 549 23 and 3-chloro-4-trifluoromethylphenyl isocyanate are used as starting materials, the course of process according to the invention can be represented by the following equation: C1 C1 C1 c O =N-4 F3 N-N 0

H

0 Cl Cl C1 I C If, for example, 3-(4-chlorophenyl)-4-[(2-chlorophenyl)carbonylamino]-4,5-dihydropyrazole and N-methyl-N-(3- ".chloro-4-trifluoromethylphenyl)-carbamoyl chloride are used as starting materials, the course of process (b) "b according to the invention can be represented by the 10 following equation: Le A 28 549 24 Cl 1 C1 CH 3 C1 f 7 7 H-C Cl'-- S 0 0

H

Cl Cl Base 00 CH3 Formula (II) provides a general definition of the pyrazolines which are unsubstituted in the 1-position, which :are required as starting materials for carrying out processes and according to the invention. In this formula R 1

R

2

R

3 and R 4 preferably represent those radicals which have already been mentioned in connection with the description of the compounds of the formula (I) according to the invention as being preferred for these .Q substituents.

10 The pyrazolines of the formula (II) which are unsubstituted in the 1-position were hitherto unknown and also a subject of the present invention. They are obtained, for example, when phenacylamine derivatives of the formula (V) Le A 28 549 25

R

1 -C-CH-N. 3(V 0 in which R1 R 2 R 3 and 11 4 have the abovementioned meaning are reacted with dimethylmethyleneiinmonium chloride, of the formula (VI), 2CNC3 c1 (VI) 5 if appropriate in the presence of a diluent such as, for example, acetonitrile, at temperatures between 30*C and S. *80*C, and, in a subsequent 2nd step, resulting phenacyldiamine derivatives of the formula (VII) 11 1 i R 3 :0 CH 2 x HC1 (VII)

N-CH

3 in which 10 R 2 RI and RW have the abovementioned meaning, Le A 28 549 26 are reacted with hydrazine hydrate at temperatures between 30"C and 80*C, if appropriate in the presence of a diluent such as, for example, acetonitrile.

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 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".

SPyrazolines of the formula (IIa) which are unsubstituted in the 1-position

R

2

R

3 N

"R

Hi H (IIa) N N H H in which

R

1

R

2 and R 3 have the abovementioned meaning, 15 are alternatively obtained when phenacylamine derivatives *of the formula (Va)

/R

2

R

1

-C-CH

2 -N3 (Va)

IIR

Le A 28 549 27 in which

R

1

R

2 and R 3 have the abovementioned meaning, are initially reacted, in a first step, with formaldehyde at temperatures between 30*C and 80°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 i 2R2 Rt-C-C-N,

(VIII)

II R 3 0 in which

R

1

R

2 and R 3 have the abovementioned meaning, *e 10 are subsequently reacted with hydrazine hydrate at temperatures between 30"C and 80*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".

Phenacylaine derivatives of the forulae and (Va) Phenacylamine derivatives of the formulae and (Va) Le A 28 549 28 are known or can be obtained in analogy to known processes for example, Chem. Ber. 122, 295-300 [1989]; J. Med. Chem. 29, 333-341 [1986); J. Amer. Chem. Soc. 98, 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. Chim. Fr. 1970, 2707-2711).

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

*t Phenacyl-enamine derivatives of the formula (VIII) are o* known or can be obtained in analogy to known processes 99 15 for example, Chem. Ber. 93, 387-391 [1960]; Sankyo 9 ;Kenkyusho Nemp 15, 36 [1963] or Chem. Abstr. 60: 11876d [1964]; J. Med. Chem. 30, 1497-1502 [1987]; JP 61- 053,239; US 4,277,420; Chem. Abstr. 87: 67 9 2 8y; Khim.- Farm. Zh. 9, 21-24 [1975] or CA 83: 58351v; Collect.

20 Czech. Commun. 19, 317-328 [1954]; Ann. Chim. 46, 267-269 [1956]; J. Chem. Soc. 1953, 4066-4073; Zh. Obshch. Khim.

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

Formula (III) provides a general definition of the iso(thio)cyanates required as starting materials for 25 carrying out process according to the invention. In this formula (III), R 8 and X preferably represent those Le A 28 549 29 radicals which have already been mentioned in connection with the description of the compounds of the formula (I) according to the invention as being preferred for these substituents. The iso(thio)cyanates of the formula (III) are generally known compounds of organic chemistry.

Formula (IV) provides a general definition of the (thio)carbamoyl chlorides required as starting materials for carrying out process according to the invention. In this formula R 5

R

6 and X preferably represent those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these substituents.

S

The (thio)carbamoyl chlorides of the formula (IV) are 15 generally known or can be obtained with the aid of known processes for example, JP 57-108,057 or Chem.

Abstr. 98: 53440y; JP-A 50-089,344 or Chem. Abstr. 83: 205987n; DE-A 2,429,523; AU-A 491,880 or Chem. Abstr. 89: 163572q).

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

These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons such as, for example, benzine, benzene, toluene, xylene, chloro- 25 benzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform or carbon tetrachloride; ethers such as diethyl ether, diisopropyl Le A 2u 549 30 ether, dioxane, tetrahydrofuran ,r 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,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, esters such as methyl acetate or ethyl acetate, or sulphoxides such as dimethyl sulphoxide.

Processes and according to the invention can preferably be carried out in the presence of a suitable reaction auxiliary. Suitable reaction auxiliaries are all customary inorganic or organic bases. These include, for example, alkaline earth metal hydroxides or alkali metal 15 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 carbonate or ammonium carbonate, alkali metal acetates or alkaline 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-dimethylaminopyri- .AN 25 dine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

When carrying out processes and according to the invention, the reaction temperatures can be varied within Le A 28 549 31 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 process under increased or reduced pressure.

To carry out process according to the invention, to 2.5 moles, preferably 1.0 to 1.5 moles, of iso(thio)- 10 cyanate of the formula (III) and, if appropriate, 0.01 to 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.

15 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).

To carry out process according to the invention, to 2.5 moles, preferably 1.0 to 1.5 moles, of (thio)- 20 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.

25 The reaction is carried out and the reaction products are worked up and isolated by generally customary methods Le A 28 549 32 The active compounds are suitable For combating animal pests, preferably arthropods 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, Oniscus asellus, Armadillidium vulgare and Porcellio scaber; from the order of the Diplopoda, for example, Blaniulus O guttulatus; from the order of the Chilopoda, for example, Geophilus carpophagus and Srctigera spec; from the order of the Symphyla, for example, Scutigerella immaculata; from the order of the Thysanura, for example, Lepisma saccharina; from the order of the Collembola, for example, Onychiurus armatus; from the order of the Oithoptera, for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, 20 Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistucerca 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 vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.; from the order of the Mallophaga, for example, Trichodectes spp. and Damalinea spp.; from the order of the Thysanoptera, for example, Le A 28 549 33 Herc.4nothrips f emoralis anO rips taba&-i; from the order of the Heteroptera, for axainple, Eurygaster spp., Dysdemc'.us intermedius, Piesma quadrata, Cimex lectula'-1.us, Rhodnius prolixus and Triatoma spp.; from the order of the Homoptera, for example, Aleurodes brassicee, Bemisita tabaci, Triaieturodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis f~.bae, Doralis pomi, Eriosoma lanigerum, Hyalopterus ariundinis, Macros iphum av-.enae, Myzus spp Phorodon humuli, Rhopalosiphinn padi, Empoasca spp., Euscelis bilobatus, Nephotettix. cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata IMP lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp.; from the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniariu.s, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosomt- neustria, Euproctis chrysorrhoea, Lymantria spp., Buccu.zatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia. spp., Earias insulana, Heliothis spp. Spodopteza exigue, Mamestra brassicae, Pariclis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, P ieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Ga±lleria mellonelia, Tineola bsse1liella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima and Tortrix vIridana; from the order of the Coleoptera, for example, Anobiun punctatun, Rhizopertha dominica, Acanthoscelides obtectus, Hylotrupes Le A 28 549 34 bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus app., Sitophilus spp Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus asajinilis, Hypoera postica, Dermestes app., Trogoderma app., Anthrenus app., Attagenus app., Lyctus app., Meligethes aenausr Ptinus app., Niptus hololeucus, Gibbium psyI,',Ii!.d!: n, Tribolium, app., Tenebrio molitor, Agriotes app., Ccnoderus app., Melolontha melolontha, Amphimallon solstitialis and Coatelytra zealandica; from the order of the Hymenoptera, for example, Diprion app., Hoplocampa app., Lasius app.,F Monomorium, phataonis and Vespa spp.; from the order of the Diptera, for example, Aedes app., Anopheles app., Culex app., Drosophila melanogaster, Musca spq., Fannia app., Callinhora erythrocephala, Lucilia app., Chrysomyia app., Cuterebra app., Gastrophilus app., Hypobosca app., Stomoxys app., :Oestrus app., Hypoderma app., Tabanus app., Tannia app., Bibio hortulanus, Oscinella frit, Phorbia app., Pegomyia :hyoscye-mi, Ceratitia capitata, Dacus oleae and Tipula paludosa; from the order of the Siphonaptera, for example, Xenopaylla cheopis anti Ceratophyllus app.; from :the order of the Arachnida, fox example, Scorpio maurus 25 and Latrodectus mactans; from the order of the Acarina, for example, Acarus siro, Argas spp., Ornithodoros app., Dermanyasus gallinae, Eriophyes ribis, Phyllocoptruta 00 oleivora, Boophilus spp., Rhipicephalus spp., Amblyornma spp., Hyalonima app., Ixodes app., Psoroptes app., Chorioptes app., Sarcoptes app., Tarsonemus app., Bryobia Le A 28 549 35 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 according to the invention can be employed with particularly good success for combating insects which are harmful to plants such as, for example, against the larvae of the mustard beetle S(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 15 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

S.

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 Le A 28 549 36 surface-active agents, that is, emulsifying agents and/or 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, such 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, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water; by liquefied gaseous extenders or carriers are meant liquids which are gaseous at ambient temperature and under atmospheric pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and 25 silicates; as solid carriers for granules there are suitable: for 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 30 sawdust, coconut shells, maize cobs and tobacco stalks; Le A 28 549 37 as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as albumen hydrolysis products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.

Adhesives 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 phospholipids such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other additives can be mineral and vegetable oils.

SIt is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and per cent by weight of active compound, preferably between 0.5 and The active compounds can exist, in their commercially available formulations and in the use forms prepared from 0* Le A 28 549 38 these formulations, in the form of a mixture with other active compounds such as insecticides, attractants, steriliants, acaricides, nematicides, fungicides, growthregulating substances or herbicides. The insecticides include, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, and the like.

The active compounds can furthermore exist, in their commercially available formulations and in their use forms prepared from these formulations, in the form of a mixture with synergists. Synergists are compounds by Swhich the action of the active compounds is increased without it being necessary for the synergist added to be active itself.

15 The active compound content of the use forms prepared from the commercially available formulations can vary within wide limits. The active compound concentration of the use forms can be between 0.0000001 to 95% by weight 20 of active compound, preferably between 0.0001 and 1% by weight.

They are used in a customary manner adapted to suit the use forms.

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

Le A 28 549 39 The preparation and use of the active compounds according to the invention can be seen from the examples which f ollow: Preparation Examples Example 1: Br HC1 (Process 1.52 g (0.00642 mol) of 3-chloro-4-trifluoromethoxy- 0*ee:phenyl isocyanate are added dropwise at room temperature with stirring to 2.26 g (0.00598 mol) of 3-(4-bromo- 10 phenyl) -4-f (4-chlorophenyl)-carbonylamino]-4 pyrazole in 50 ml of dichioromethane, and the mixture is ref luxed for one hour. For working-up, the reaction :mixture is cooled and precipitated solid is filtered off with suction and dried.

2.18 g (51% of theory) of 3-(4-bromophenyl)-4-[(4-chloro- 'Get. phenyl) -carbonylamino (3-chloro-4-trifluoromethoxy- 0*0.phenyl) -aminocarbonyl J-4, 5-dihydropyrazole of melting point >200 0 C are obtained.

Le A 28 549 -4 40 1 H NIIR (DISO-d/tetramethylsilane): 6 3.93; 4.26; 5.97; 9.54; 9.38 ppm The following substituted pyrazolines of the general formula (I)

R

2

,R

3

N

NJ

NxR are obtained in an analogous manner and following the general preparation instructions: 9 .9 9 9* *99*99 99 9 9* 99 99* 99 9 9 9.

9999 9 99 9 9 9 9 99 9 9 99 Le A 28 549 41 C. *C %0C C C C C* *C C C C

CC

C C

CC

Ex.

No.

R

3

R

4

R

5

R

6 X 1H NMR*) 1~ 7>C 0 0

H

H H H CF3 o 3.92; 4.25; 5.98; 9.37 9.39 o 3.96; 4.29 6.00; 9.39 9.90

-CQ-F

C'

0 H H H

CF

3 0 3.96; 4.30; 5.96; 9.31; 9.84 l K C 0 H H H

CF

3 1 0 3.94; 4.26; 5.99; 9.38; 9.44 -0-1.

Cl 0 H H H Cl

CF

3 0 3.95; 4.29; 5.95; 9.31; 9.65 O a *t 0 4 0* 0 *5*

V

59e a. a a.

a *a 0es Ex.

No.

R

3

R

4

R

5

R

6 X 1 H NMR" -0-Cl

-C>-F

-<D-F

0 cl 0 Cl 0

CN

H H H H H H H H H 0 3.94; 4.26; 5.98; 9.49; 9.63

CF

3 1 Cl o 3.94; 4.27; 5.95; 9.31; 9.58 o 3.93; 4.27; 5.95; 9.31; 9.48

DF

cl 0 cl 0k 0r Cl H H H

H

3 0 3.91; 4.25; 5.93; 9.21; 9.30

-F

H H H Cl /C CF 3 0 3.93; 4.26; 5.94; 9.31; 9.33 0 0 0 0 R 2 0%

R

3

R

4

R

5 X H MNR" Ex.

No.

-(3-F -(3-F

C

II

0 0

F

0 H H H H H H

F

-C

CF

3 H H H

CN

H H H <:J-F

F

H H H o 3.95; 4.28; 5.94; 9.41; 9.73 o 3.92; 4.25; 5.95; 9.30; 9.34 o 3.93; 4.26; 6.00; 9.32; 9.61 o 3.93; 4.26; 6.00; 9.33; 9.52 o 3.92; 4.25; 5.98; 9.36; 9.37 S S -AOL" W *5

O

e

O

0 ,lt R3 R4 R 5

R

6 X 1H NiwMY"' Ex.

No.

-(3D-F

-<D-F

CQ-F

0 -C-C3-F 0 -C-<Dl-l 11cI H H H Cl H H H H H H F o 3.92; 4.25; 5.99; 9.36; 9.40 o 3.91; 4.25; 5.99; 9.32; 9.44 o 3.77; 4.14; 5.94; 9.23; o 3.93; 4.27; 6.00; 9.53; if 3JU H H H

QCF

3

OCH

3 0 H H H CF 0 3.78; 4.15; 5.93; 9.20

R

2

S

r 4 X 1 H N414II Ex.

No.

-CJ-ci

OCH

3 0 -C cH3

C'

0l 0 H H H Cl ll-CF 3 H H H H H H C 3.94; 4.27; o 6.01; 9.53; 9.26 3.78; 4.14; o 5.93; 6.57; 6.96; 9.14 3.83; 4.15; o 5.86; 6.67; 6.95; 9.27 Cl Cl 0 0 H H H

C'

OCF

3 3.93; 4.28; 0 5.95; 9.52; 9.33 <D-r Cl H H H

OF

3.92; 4.30; 0 6.00; 9.50; 9.29 0 16 QC-6 .96 9 !Elt QS*'6 !L6*S 8Z'6 !zE6 iOO9g !TZ*V !C6*9 Ei16 £6*9 S6'S 'ET*V £9L*S oo\

TO

c ld To H H H H H H HH H H H R- H H H H H H 0 0 0 I 0 0 A0 0 log

ACQ-

ED

H

13o 0 s -1 K-I

CN

L.

ON

.xa 9N HT 9H1 SH vu £1 C C C C *if V. CC CCC C e r o r: ro c 9*r* 0* SO CS *S

OS..

S*

S*

R

3

R

4

R

5 e Ex.

No.

X 1 H NMR*' 3.93; 4.26; 0 5.97; 9.54; 9.38 r C/ -Br If 0

O

0 0

C'

H H H

CF

3 SHc H HI H H H H -D-F S H1 H H H

OF

3.90; 4.26; o 5.98; 9.18; 9.51 3.94; 4.26; o 5.98; 9.40; 9,53 3.80; 4.15; o 5.92; 6.68; 9.24 0Q 0 Cl H H oCI'g 3.90; 4.28; 0 6.01; 9.52; 9.20 S S S S SS 5 c S. S r R3 R4

S

*5* X 'H NMR*) Ex.

No.

K2F -C-Q-CH3 0 H H H 3H-CF 3 4.13; 5.93; 0 6.64; 6.92; 9.15 -0 Cl aC H H H CF3 4.14; 5.88; 0 6.62; 6.88; 9.26 Q11 Cl 0 H H H cl -C CF3 3.93; 4.28; 0 5.97; 9.32; 9.48 -0

CH

3 0 c 0 0 H H H -Ku-CF 3 H H H 3-C F 3 4.14; 5.97; 0 6.90; 9.20 3.82; 4.15; o 5.95 6.67; 9.32 a Ex.

No.

R3 R 4

R

5 R 6 X 'H NMR*) 43

<D-F

<D-F

/C

0 -CD F 0 H H H H H H

H

3.91; 4.24; 5.99; 9,24; 9.32 Cl

OCF

3 3.95; 4.27; 0 6. 00; 9.52; 9.39 Cl H H H O

H

Cl H H H 3.91; 4.24; 0 6. 00; 9.24; 9.34 3.92; 4.25; 0 5.99; 9.34; 9.37 46

D-

IC,- H H H

CN

F

3.93; 4.27; 0 6. 00; 9.30; 9.54

I

Ex.

No.

WT R 4

R

5

R

6 X 'H NMR*) cl~ 0 r 0 KD~c tKC-D-F

CF

3 H H H K1-F C1 H H H-CH 3 Cl H H H 3.97; 4.30; o 6.02; 9.31; 9.89 3.91; 4.24; o 5.98; 9.28; 9.32 3.93; 4.26; 0 5.99; 9.29; 9.47

F

C1 lI 0 Cl H H

HI

3.93; 4.26; 0 5.95; 9.31; 9.42

*S.

ft~ S S S S S *O S 0555 Ex.

No.

W

3 W RW R 6 X 'H NMR 0 52 Q7~~ 53 54

D-

56

F

0 (Cl-1 2 5

-C--CH

2

-CH

11 '-NCH 3 0 -C-CH 2 -CH

H

0 -C-CH 2

-CH,-H

11 "-CH 3 0 -C-CH2 -CH

H

11 -CH 3 0 H H 04F H H C

CF

H H H H Q

CF

3

CF

3

F

F

3.61; 4.02 3.86; 4.14; o 6.43; 9.54 o 5.69; 8.60 3.77; 4.15 o 5.78; 8.68 9.83 3.74; 4. 14 o 5.74; 8.67 9 .32 3.74; 4.16 o 5.76; 8.68 9.57 H H C 1

.CF

3 9.49

I

.a *.e

R

3

R

4

R

5

R

6 Li~ Ex.

No.

X 1H NiMiNR 57 -C -C 58 c 1 59

D-C

CH

3 -C CM II N.CH 3 0 o "CH 3 )---CH3 0 ,-H 3

-C-CH

II 'CH 3 0

/-CH

3 II '-CH 3 0

-CH

3 CH ,,-CH3 11 '-CH3 -C CM II \-CH 3 0 I H H p-CF 3 i H H -C -O-CF3 Cl H H H CF 3 Cl 3 61; 4.03 0 5.68; 7.78 8.55 3.74; o 5.76; 3.74; o 5.76; 9.59 4.17 8.63 4.17 8.61 H H H "-F

CN

3.74; 0 5.75; 9.50 4.17 8.61 61 /D 1C H H H 0-CHF 2 Cl 3.73; 5.75; 9.38 4.16 8.60 -<D-Cl H H F Cl 3.72; 4.15 0 5.74; 8.60 9.35 9.36 3.74; 4.15 C ft C C S .k2 W r R 3 C CC Ex.

No.

X 1H NM*i' -KD-ci Cl -UjBr -C CH II ~H 11 -CH:3 0 -C -CH

H

II 1.C H 3 0 H H H H H o 5.75; 8.60 9.23 3.73; 4.16 o 5.74; 8.61 0 .,CF2

-C-CH

3

I'

0 H H H F2 3.75; 0 5.71; 9.36 4.13 8.70 -Q-Br

-C-CH

Ii "*-CH 3 0

-C-(CH

2 3

II

0 HH H HH H 0-CF 2

CF

3 C1 3.75; o 5.75; 9.47 4.05; o 6.03; 8.06 4.18 8.62 4.11 C) The IH NMR spectra were recorded in hexadeuterodimethyl suiphoxide (DMSO-d6) with tetramethylsilane (TMS) as the internal standard. The data given is the chemical shift as 8 value in ppm.

ft ft ,ft ft..

ftftftftftft Ex.

No.

R 3 R 4

R

5

R

6 X Physical properties "D Br Br 0

(CH

2 3 11 0 H H Cl

CF

3 o 182*C o 220*C H H C I

-C-OCH

3 11 0 Cl H H H O3 0 200 0

C

71

(CH

2 3 11 0 Cl H H C

OCH-F~

2 0 194*C C -OC1] 0 H H H C I

-F

0 mfp.:>200*C e SOS 055 5 Ex.

No.

R 3 R 4 R-9 R 6 X Physical properties 1

-C-CH

3 11 0

-C-OCH

3 11 0 H H H H H H C I Cl1

-CF

3 Cl1 -C5-OCF 3 o >200*C o >200*C -K--ci

CH

3 0

CH

3 H H H 0 118*C

(CH

2 3 11 0 H H C1 0 l7OeC

-C-CH

3

II

0 H H H C1 -C5-OCHF 2 0 >200 0

C

0** 0 0 0 0 0 0 0 00 0 0 0 0 0 0 0 0 0000 0 0 0*e Ex.

No.

A

3 q 4

R

5 6 X Physical properties -GD-r

-C-C

2

H

5 11 0

-C-C

2

H

5 11 0 -C--C2 11 0 H H H H H H H H H Cl \CF3 Cl Cl o >200 0

C

o >200*C o rn.p.: >200 0

C

Preparation of the starting compounds Example II-1: Cl Cl

H-C--C)

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)-2g oxoethyl]-benzamide (preparation cf., for example, J.

Amer. Chem. Soc. 77, 1850 [1955]) in 100 ml of acetonitrile, and the mixture is refluxed for 3 to 5 hours.

When starting compound can no longer be detected in the 10 thin-layer chromatogram of the reaction 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 15 ether and subsequently with water, and dried.

a. 10.4 g (48% of theory) of 3-(4-chlorophenyl)-4-[(2are obtained as a brown solid which can be employed in the following reaction without further purification.

20 H NMR (DMSO-d 6 /tetramethylsilane): 8 5.68; 9.10 ppm a.

Le A 28 549 58 Example 11-2:

O

II CH3

H-C-CH

2

-CH

N IN CH 3

H

29 ml f 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, the mixture is stirred for a further hour at 50"C. For working-up, the reaction mixture is concentrated in vacuo, and the product which precipitates in this process is filtered off with suction and dried.

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

Example VIII-1: 0 FC-< -C-NH-

C

-CH

2

CH

*II II .0

CH

2

CH

3 50 ml of 37% strength aqueous formaldehyde solution, 1 ml 15 of piperidine and 1 ml of glacial acetic acid are added in succession at 60"C with stirring to 37.4 g (0.158 mol) Le A 28 549 59 of 2-isobutylcarbonylamino-4 I-f luoroacetophenone (preparatic"- comparek for example, DE 2,947,140; J. Heterocyci.

Chem. 24, 297-301 [1987], in 240 ml of methanol, the mixture is subsequently stirred at 60"C for a further hour, and the solvent is then removed in vacuo.

37.0 g (94% of theory) of 4'-fluoro-2-isobutylcarbonylamino-acrylophenone are obtained as a solid which can be directly reacted further wit4-hout additional purification.

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

S

*S C CC

R

2

_R

3

N

II Ex.

No.

R 3 R 4 1 H NMR*) *9

'S.C

Ot 0w C 11-3

-C

ociq 3 0 H H 5.80; 9.02

SC

S 5 9 o S S CC 0

-KD

11-4 0 H H 5. 82; 9. 09 Le A 28 549 60 Ex.

No.

R 3 R 4 1 H NMR*) -0ID 11-5 11-6

-<DI

11-7 too.

*0606 1. 6o 0 -Cl.

0 -C0 0 0

OCH

3 0 H H 5.70; 9.09 H H 5.75; 9.13 H H 5.84; 9.08 H H 5.77; 9.06 11-8 S S *6 6 6* 6 *566 *5 *0 0 0 56 5

S

11-9 11-10 H H 5.69; 9.08 H H 5.77; 9.01 Le A 28 549 61 Ex. R' No.

11-12 r 11-13 7-Br 11-14 11-15 R' R 4 IH NMR*)

U

CU U

CD

I I 0 0r -C-Cj>--1 11 0

'V

0 0I 0 0r H H 5.74; 9.03 H H 5.67; 9.07 H H 5.74; 9.09 H H 5.74; 9 11 H H 5.77; 9 01 H H 5.76; 9.&U' H H 5.75; 9.11 4C A

CA

cC

CRCU

CCi

C

U r C CC U C 10 C r 01 F 11-16 11-17 lF Le A 28 549 62 Ex.

No.

R 3 R4 'H NMR*) 11-18 11-19 11-20 11-21 11-22 11-23 10 11-24 B &Q<:-Br 0 0 -C-CQ-CH3 01 0 -C-:(CH3) H H 5.74; 9.12 H H 5.77; 8.96 H, H 5.78; 8.93 H H 5.76; 9.11 H H 5.75; 9.04 H H 5,75; 8.92 H 6.12; 7.68 00 0* Le A 28 549 63 Ex.

no.

R 3 R4' H NMR*) 11-25 0 -l C 2 C H H H 5.49; 8.40 0 1-26-KI~---1

-C-CH

2

-CH

3 H H 5.37; 8.37 9S~O

C*

C. C. 9.

C CC C9 9 S S CC *4

S*

C.

C 9 C9 C C C. C C. 4 CC

SC

11-27 J~B 11-28 11-29 0 11

(CH

2 )3

-C-CH

2 -CH C

CH

3 HI 5.86 H H 5.50; 8.40 R H 5.47; 8.35 11-30 10 11-31

-C-OCH

3 0 11

-C-CH

3 H H 5.23; 7.79 H H 5.44; 8.45 Le A 28 549 64 Ex.

No.

R 3 R4 IH NM~R*) 11-32 11-33 -ci- Br 0 0 11 -c--I H H 5.48; 8.67 H H 5.48; 8.64 11-34 0 11 CH 3

-C-CH

3 H H 5.49; 8.33 a.

to. S a.

0* 0 0 S 0* 00 Le A 28 549 65 Use Examples: In the use examples which f ollow, the compound listed below was employed as comparison substance: 0- (4-Methylthiophenyl) 0-ethyl S- (n-propyl) thionophosphate (disclosed in DE 2,111,414).

S

*5 50 S

S

S

S 55 S S 6* e S Se 9S Le A 28 549 66 Example A: Phaedon larvae test Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce 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 O 10 desired concentration.

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

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

*i In this test, for example the following compound of the 20 Preparation Examples shows superior activity compared with the prior art: 29.

0* Le A 28 549 67 Example B: Plutella test Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce 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 i 10 desired concentration.

Cabbage leaves (Brassica oleracea) are treated by dipping into the active compound preparation of the desired concentration and infested with caterpillars of the cabbage moth (Plutella maculipennis) while the leaves are 15 still moist.

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

In this test, for example the following compound of the Preparation Examples shows superior activity compared with the prior art: 33.

0 Le A 28 549 68

Claims (11)

1. Substituted pyrazolines of the general formula (I) R

2 ,R 3 I (I) in which R 1 represents optionally substituted phenyl, and either 5 R 2 represents a radical of the formula -CO-R 7 -COOR 7 or S" -S0 2 and R 3 represents hydrogen, alkyl or halogenoalkyl or R 2 and R 3 together with the nitrogen atom to which they are bonded represent a heterocycle of the formula 0 0 0 o *9 9 *9 9 Le A 28 549 69 0 0 0 0 0 o J or -N o 0 R 4 represents hydrogen, alkyl, halogenoalkyl, halogeno- Am alkylthio, halogen, alkoxycarbonyl or in each case optionally substituted cycloalkyl or aryl, 5 R 5 represents hydrogen or alkyl, *o 6 R 6 represents in each case optionally substituted i alkyl, cycloalkyl or 3,4-disubstituted phenyl and 9 X represents oxygen or sulphur, where R 7 represents hydrogen, alkyl, alkenyl, alkinyl, halogenoalkyl, halogenoalkenyl, halogenoalkinyl, alkoxyalkyl, alkylthioalkyl, nitroalkyl, cyanoalkyl, ~alkoxycarbonylalkyl, in each case optionally sub- stituted cycloalkyl, aralkyl, aryl or heterocyclyl or a radical R R9 159 Le A 28 549 70 in which either R 8 represents hydrogen or alkyl and R 9 represents alkyl or in each case optionally sub- stituted aralkyl or aryl, or R 8 and R 9 together with the nitrogen atom to which they are bonded represent an optionally substituted heterocycle which can, if appropriate, contain further hetero atoms. S2. Substituted pyrazolines of the general formula (I) according to Claim 1, in which •R 1 represents phenyl which is optionally monosub- stituted or polysubstituted by identical or different substituents, suitable substituents being: hr'ogen, cyano, nitro, in each case straight- chain or branched alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl, each of which has 1 to 8 carbon atoms, in each case straight- chain or branched halogenoalkyl, halogeno- alkoxy, halogenoalkylthio, halogfe alkyl- fO sulphinyl or halogenoalkylsulphonyl, each of "e which has 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, in each case straight-chain or branched alkenyl, o" 25 alkinyl, alkenyloxy or alkinyloxy, each of Le A 28 549 71 which has 2 to 8 carbon atoms, in each case straight-chain or branched alkoxycarbonyl or alkoximinoalkyl, each of which has 1 to 8 carbon atoms in the individual alkyl moieties, straight-chain or branched halogenoalkoxy- carbonyl having 1 to 9 carbon atoms and 1 to 17 identical or different halogen atoms, divalent dioxyalkylene which has 1 to 4 carbon atoms and which is optionally monosubstituted or polysub- stituted by identical or different substituents from the series comprising halogen and/or straight-chain or branched alkyl having 1 to 4 carbon atoms, or phenyl, phenoxy or phenylthio, each of which is optionally monosubstituted or 15 polysubstituted by identical Jr different substituents from the series comprising halogen and/or straight-chain or branched alkyl having O 1 to 4 carbon atoms; and either 0 R 2 represents a radical of the formula -CO-R 7 -COOR 7 or -S0 2 -R 7 and R 3 represents hydrogen, straight-chain or branched alkyl having 1 to 8 carbon atoms or straight- chain or branched halogenoalkyl having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, or ,goo 0* R 2 and R 3 together with the nitrogen atom to which they are bonded represent a heterocycle of the Le A 28 549 72 formula -M 0 0 0 0 0 0 0 00* oY I or 0 e R 4 represents hydrogen, straight-chain or branched alkyl having 1 to 8 carbon atoms, straight- chain or branched alkoxycarbonyl having 1 to 9 carbon atoms, cycloalkyl which has 3 to 7 carbon atoms and which is optionally monosub- stituted or polysubstituted by identical or different alkyl substituents, straight-chain or 10 branched and having 1 to 4 carbon atoms, or represents phenyl which is optionally monosub- stituted or polysubstituted by identical or different substituents, suitable substituents being those mentioned in the !ase of RI, or represents straight-chain or branched halogeno- alkyl or halogenoalkylthio, each of which has Le A 28 549 73 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, or represents fluor- ine, chlorine, bromine or iodine; R 5 represents hydrogen or straight-chain or branched alkyl having 1 to 8 carbon atoms; R 6 represents straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, cycloalkyl which has 3 to 7 carbon atoms and which is optionally monosub- stituted or polysubstituted by identical or o0. different substituents from the series compris- ing halogen and/or in each case straight-chain 15 or branched alkyl or halogenoalkyl, each of which has 1 to 6 carbon atoms and, in the case of the halogenoalkyl, 1 to 13 identical or different halogen atoms, or represents phenyl which is substituted in the 3,4-position, 20 suitable phenyl substituents being those men- tioned in the case of R 1 and SX represents oxygen or sul, ur, where R 7 represents hydrogen, in each case straight- chain or branched alkyl, alkenyl or alkinyl, each of which has up to 8 carbon atoms, in each case straight-chain or branched halogenoalkyl, Le A 28 549 74 halogenoalkenyl or halogenoalkinyl, each of which has up to 8 carbon atoms and 1 to 17 identical or different halogen atoms, in each case straight-chain or branched alkoxyalkyl, alkylthioalkyl, nitroalkyl, cyanoalkyl or alkoxycarbonylalkyl, each of which has 1 to 6 carbon atoms in the individual alkyl moieties, o: represents cycloalkyl which has 3 to 7 carbon atoms and which is optionally monosub- atituted or polysubstituted ny identical or different alkyl substituents, straight-chain or branched and having 1 to 4 carbon atoms, or represents aralkyl which has 1 to 6 carbon atoms in the straight-chain or branched alkyl 15 moiety and 6 or 10 carbon atoms in the aryl moiety, aryl which has 6 or 10 carbon atoms or heteroayclyl which has 2 to 9 carbon atoms and 1 to 5 identical or different hetero atoms, each of which is optionally monosubstituted or polysubstituted in the aryl or heterocyclyl moiety by identical or different substituents, suitable aryl or heterocyclyl substituents being those mentioned in the case of R 1 or represents a radical of the formula .AOL R 9 and either R 8 represents hydrogen or straight-chain or Le A 28 549 75 branched alkyl having 1 to 8 carbon atoms, and R 9 represents straight-chain or branched alkyl having 1 to 8 carbon atoms or aralkyl which has 1 to 6 carbon atoms in the straight-chain or branched alkyl moiety and 6 or 10 carbon atoms in the aryl moiety or aryl which has 6 or carbon atoms, each of which is optionally monosubstituted or polysubstituted in the aryl moiety by identical or different substituents, suitable aryl substituents in each case being those mentioned in the case of R 1 or R 8 and R 9 together with the nitrogen atom to which S.. they are bonded represent saturated or unsatur- ated, optionally benzo-fused five- to seven- 15 membered heterocycle which can optionally contain 1 to 3 further hetero atoms and/or 1 to 3 keto groups and which is optionally monosubstituted or polysubstituted by identical or different substituents, suitable substitu- 20 ents being those mentioned in the case of R'.

3. Substituted pyrazolines of the general formula (I) according to Claim 1 or 2, in which R 1 represents phenyl which is optionally monosub- stituted to trisubstituted by identical or different substituents, suitable substituents being: Le A 28 549 76 halogen, cyano, nitro, in each case straight- chain or branched alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl, each of which has 1 to 4 carbon atoms, in each case straight- chain or branched halogenoalkyl, halogeno- alkoxy, halogenoalkylthio, halogenoalkyl- sulphinyl or halogenoalky3sulphonyl, each of which has 1 to 4 carbon atoms and 1 to 9 iden- tical or different halogen atoms, in each caae straight-chain or branched alkenyl, alkinyl, alkenyloxy or alkinyloxy, each of which has 2 to 6 carbon atoms, in each case straight-chain O or branched alkoxycarbonyl or alkoximinoalkyl, each of which has 1 to 4 carbon atoms in the 15 individual alkyl moieties, straight-chain or branched halogenoalkoxycarbonyl having 1 to carbon atoms and 1 to 9 identical or different halogen atoms, or divalent dioxyalkylene which has 1 to 3 carbon atoms and is optionally monosubstituted or polysubstituted by identical or different substituents from the series comprising halogen and/or straight-chain or branched alkyl having 1 to 3 carbon atoms, and phenyl, phenoxy or phenylthio, each of which is 25 optionally monosubstituted or polysubstituted by identical or different substituents from the series comprising halogen and/or straight-chain or branched alkyl having 1 to 4 carbon atoms; and either Le A 28 549 77 R' represents a radical of the formula -CO-R 7 -COOR 7 or -S0 2 -R 7 and R 3 represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms or straight- chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, or R 2 and R 3 together with the nitrogen atom to which they are bonded represent a hetero- cycle of the formula C C. O0 0 0 -N 0 7; 0 0 0 OilD CCC. CC C. .3 CC C C C CE C C C. C C OYW R 4 represents hydrogen, straight-chain or branched Le A 28 549 78 alkyl having 1 to 6 carbon atoms, straight- chain or branched alkoxycarbonyl having 1 to carbon atoms, cycloalkyl which has 3 to 6 carbon atoms and which is optionally monosub- stituted to tetrasubstituted by identical or different alkyl substituents, straight-chain or branched and having 1 to 3 carbon atoms, or represents phenyl which is optionally monosub- stituted to trisubstituted by identical or different substituents, suitable substituents being those mentioned in the case of R I or represents straight-chain or branched halogeno- O alkyl or halogenoalkylthio, each of which has 1 to 6 carbon atoms and 1 to 13 identical or 15 different halogen atoms, or represents fluor- *o ine, chlorine or bromine; R 5 reprsents hydrogen or straight-chain or branched alkyl having 1 to 6 carbon atoms; S. R 6 :represents straight-chain or branched alkyl 20 having 1 to 6 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different o* halogen atoms, cycloalkyl which has 3 to 6 carbon atoms and which is optionally monosub- 25 stituted to ttrasubstituted by identical or different subst..tuents from the series compris- ing halogen and/or in each case straight-chain or branched alkyl or halogenoalkyl, each of Le A 28 549 79 which has 1 to 3 carbon atoms and, in the case of the halogenoalkyl, 1 to 7 identical or different halogen atoms, or represents 3,4- disubstituted phenyl, suitable phenyl substitu- ents being those mentioned in the case of R', and X represents oxygen or sulphur, where R 7 represents hydrogen, in each case straight- chain or branched alkyl, alkenyl or alkinyl, each of which has up to 6 carbon atoms, in each Scase straight-chain or branched halogenoalkyl, halogenoalkenyl or halogenoalkinyl, each of which has up to 6 carbon atoms and 1 to 13 identical or different halogen atoms, in each case straight-chain or branched alkoxyalkyl, alkylthioalkyl, nitroalkyl, cyanoalkyl or alkoxycarbonylalkyl, each of which has 1 to 4 carbon atoms in the individual alkyl moieties, cycloalkyl which has 3 to 6 carbon atoms and which is optionally monosubstituted to tetra- substituted by identical or different alkyl substituents, straight-chain or branched and having 1 to 3 carbon atoms, or represents 4 aralkyl which has 1 to 4 carbon atoms in the 25 straight-chain or branched alkyl moiety and 6 .i or 10 carbon atoms in the aryl moiety, aryl which has 6 or 10 carbon atoms or heterocyclyl which has 2 to 9 carbon atoms and 1 to 4 Le A 28 549 80 identical or different hetero atoms from the series comprising nitrogen, oxygen and sulphur, each of which is optionally monosubstituted to trisubstituted in the aryl or heterocyclyl moiety by identical or different substituents, suitable aryl or heterocyclyl substituents being those mentioned in the case of R' or represents a radical of the formula ,R 8 k R 9 and either 4 R 8 represents hydrogen or straight-chain or branched alkyl having 1 to 6 carbon atoms and R 9 represents straight-chain or branched alkyl having 1 to 6 carbon atoms or aralkyl which has 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety and 6 or 10 carbon atoms in the aryl moiety or aryl which has 6 or carbon atoms, each of which is optionally monosubstituted to trisubstituted in the aryl S 20 moiety by identical or different substituents, suitable aryl substituents in each case being those mentioned in the case of R 1 or R 8 and R 9 together with the nitrogen atom to which they are bonded represent a Le A 28 549 81 saturated or unsaturated, optionally benzo-fused, five- or six-membered heterocycle which can optionally contain 1 or 2 further hetero atoms from the series comprising oxygen and sulphur and/or 1 to 3 keto groups and which is optionally monosubstituted to trisub- stitued by identical or different substi- tuents, suitable substituents being those mentioned in the case of R'.

4. Substituted pyrazolines of the general formula (I) according to Claims 1 to 3, in which SR 1 represents phenyl which is optionally monosub- stituted or disubstituted by identical or different substituents, especially suitable substituents being: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, s- or t- S""2 butyl, methoxy, ethoxy, n- or i-propoxy, n-, 20 s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, s- or t-butylthio, methylsulphinyl, ethylsulphinyl, methyl- '4 sulphonyl, ethylsulphony, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluorometh- oxy, difluorochloromethoxy, dichlorofluorometh- oxy, trichloromethoxy, tetrafluoroethoxy, pentafluoroethoxy, trichlorodifluoroethoxy, dichlorotrifluoroethoxy, pentachloroethoxy, Le A 28 549 82 trifluoromethyithic, difluoromethyithic, dichlorofluoromethylthio, difluorochioromethyl- thio, trifluoromethylsuiphinyl, trifluoro- methylsuiphonyl, allyl, propargyl, allyloxy, propargyloxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, i-I s- or t- butoxycarbonyl, trifluoromethoxycarbonyl, methoximinomethyl, methoximinoethyl, ethox- iminomethyl, ethoximinoethyl, dioxymethylene, difluorodioxymethylene, dioxyethylene, tetra- fluorodioxyethylene, trifluorodioxyethylene, difluorodioxyethylene, or phenyl, phenoxy or 0 phenylthio, each of which is optionally mono- a.....substituted to trisubtituted by identical or ~:15 different substituents from the series compris- ing fluorine, chlorine, bromine, methyl and/or ethyl; and either R 2 represents a. radical of the formula -CO-R 1 -COOR 7 or -S0 2 -R 7 and 20 R 3 represents hydrogen, methyl, ethyl, n- or i- propyl or s- or t-butyl, or R 2 and R 3 together with the carbon atom to which they are bonded represent a hetero- a cycle of the formula Le A 28 549 83 0 0 0 0 0 N 7 *t b* a. r C C C 0C a 6 C CC C. R represents hydrogen, methyl or ethyl; R 5 represents hydrogen, methyl or ethyl; R 6 represents s- or t-butyl, or represents cyclohexyl which is optionally monosubstituted or disubstituted by identical or different substituents from the series comprising methyl, ethyl, n- or i-propyl and/or trifluoromethyl, or represents 3,4-disubstituted phenyl, suit- able substituents being those mentioned in the case of R i and X represents oxygen or sulphur, where Le A 28 549 84 15 4 4 2 2* *0 20 R 7 represents hydrogen, methyl, ethyl, n- or i- propyl, s- or t-butyl, allyl, propar- gyl, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 'entical or different halogen atoms, or represents alkoxyalkyl or alkylthio- alkyl, each of which has 1 or 2 carbon atoms in the individual alkyl moieties, or represents cyclopropyl, cyclopentyl or cyclohexyl, each of which is optionally monosubstituted or di- substituted by identical or different substi- tuents from the series comprising methyl, ethyl and/or n- or i-propyl, or represents phenyl, pyridyl or furanyl, each of which is optionally monosubstituted or disubstituted by identical or different substituents, suitable substitu- ents in each case being those mentioned in the case of R 1 or represents a radical of the formula R 8 and either nR9 and either R8 represents hydrogen, methyl, ethyl, i-propyl or s- or t-butyl and n- or R 9 represents methyl, ethyl, n- or i-propyl, n-, s- or t-butyl, or represents benzyl or phenyl, each of which is optionally Le A 28 549 85 monosubstituted or disubstituted by identical or different substituents, suitable substitu- ents in each case being those mentioned in the case of R 1 or R 8 and R 9 together with the carbon atom to which they are bonded represent a heterocycle of the formula -ND or -N o each of which is optionally monosub- 10 stituted or disubstituted by methyl.

5. Substituted pyrazolines of the general formula (I) according to Claims 1 to 4, in which R 1 represents phenyl which is optionally monosub- stituted or disubstituted by identical or different substituents, especially suitable substituents being: fluorine, chlorine, S" bromine, cyano, nitro, methyl, ethyl, n- or i- propyl, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, s- or t-butoxy, S. 20 methylthio, ethylthio, n- or i-propylthio, n-, s- or t-butylthio, methylsulphinyl, ethyl-

6. sulphinyl, methylsulphonyl, ethylsulphonyl, trifluoromethyl, difluoromethyl, trifluorometh- oxy, difluoromethoxy, difluorochloromethoxy, dichlorofluoromethoxy, trichloromethoxy, Le A 28 549 86 tetrafluoroethoxy, pentafluoroethoxy, tri- chiorodif luoroethoxy, dichiorotrif luoroethoxy, pentachioroethoxy, trifluoromethylthio, di- fluoromethylthio, dichlorofluoroniethylthio, difluorochloromet',,ylthio, trifluoromethyl- suiphinyl, trifluoromethylsuiphonyl, allyl, propargyl, allyloxy, propargyloxy, methoxy- carbonyl, ethoxycarnonyl, n- or i-propoxy- carkanyl, nl-, s- or t-butoxycarbonyl, trifluoromethoxycarbonyl, methoximinomethyl, methoximinoethyl, ethoximinomethyl, ethoximino- ethyl, dioxymethylene, difluorodioxymethylene, dioxyethylene, tetraf luorodioxyethylene, tri- fluorodioxyethylene, difluorodioxyethylene, or phenyl, phenoxy or phenyithic, each of which is optionally monosubstituted to trisubstituted by identical or different substituents from the series comprising fluorine, chlorine, bromine, methyl andior ethyl; and either R 2 represents a radical -CORI and R 3 represents hydrogen or methyl or 0 00-A R 2 and R 3 together with the nitrogen atom to which they are bonded represent a heterocycle of the formula .0 06 Le A 28 549 87 ;D or 0 0 RI represents hydrogen, R 5 represents hydrogen or methyl, R 6 represents cyclohexyl which is optionally mono- substituted or disubstituted by identical or a different substituents from the series compris- ing methyl and/or trifluoromethyl, or repre- sents 3,4-disubstituted phenyl, suitable sub- stituents being those mentioned in the case of S 10 R 1 and *fe 9 *0 X represents oxygen, where R 7 represents hydrogen, methyl, ethyl, n- or i-propyl, s- or t-butyl or cyclohexyl, or represents phenyl which is optionally mono- substituted or disubstituted by identical or di'-erent substituents, suitable substituents being those mentioned in the case of R 1 6. Process for the preparation of substituted pyr- azolines of the general formula (I) Le A 28 549 88 R 2 .,R 3 N I I N-Ft R 6 in which R1 represents optionally substituted phenyl, and eit',ier R 2 represents a radical of the formula -CO-R, -COOR 7 or -S0 2 -R 7 and R 3 represents hydrogen, alkyl or halogenoalkyl or R 2 and R 3 together with the nitrogen atom to which they are bonded represent a heterocycle of tha formula S 55 0 0 0 Le A 28 549 89 0 0 0 O o 0 or 0 1 R 4 represents hydrogen, alkyl, halogenoalkyl, halogenoalkylthio, halogen, alkoxycarbonyl or o. in each case optionally substituted cycloalkyl or aryl, R 5 represents hydrogen or alkyl, R 6 represents in each case optionally substituted alkyl, cycloalkyl or 3,4-disubstituted phenyl and S 10 X represents oxygen or alphur, where R 7 represents hydrogen, alkyl, alkenyl, alkinyl, halogenoalkyl, halcgenoalkenyl, halogeno- alkinyl, alkoxyalkyl; alkylthioalkyl, nitro- alkyl, cyanoalkyl, alkoxycarbonylalkyl, in each case optionally substituted cycloalkyl, aralkyl, aryl or heterocyclyl or a radical Le A 28 549 90 .R 8 NR 9 in Yhich either R' represents hydrogen or alkyl and R 9 represents alkyl or in each case optionally substituted aralkyl or aryl, or Re and R' together with the nitrogen atom to which they are bonded represent an optionally substituted heterocycle which *too can, if appropriate, contain further hetero atoms, characterised in that pyrazolines of the formula (II) which are unsub- stituted in the 1-position S...R 2 ,R RI N R4(II) H and in which R1, W 2 and R' have the abovementioned meaning, Le A 28 549 91 S *5S* S S .5 S SO S S. S. 5* *5 *5 S a *5 4* 5 S S 55 S. are reacted either a) with iso(thio)cyanates of the formula (111) R 6 -N=C=X Il in which RI and X have the abovementioned imeaning, or b) with (thio)carbamoyl chlorides of the formula (IV) RS C1(IV) in which R 5 R1 and X have the abovernentioned meaning, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary.

7. Pyrazolines of the general formula (II) Le A 28 549 92 R 2 R 3 H in which R1 represents optionally substituted phenyl, and either R 2 represents a radical of the formula -CO-R 7 0 5 -COOR' or -S0 2 -k 7 l fe.. *R PR 3 represents hydrogen, alkyl or halogenoalkyl, or R and R 3 together with the nitrogen atom to which they are bonded represent a hetero- cycle of the formula 0 0 0 0 Le A 28 549 93 or -N 0 R 4 represents hydrogen, alkyl, halogenoalkyl, halogenoalkylthio, halogen, alkoxycarbonyl or in each case optionally substituted cycloalkyl or aryl, R 7 represents hydrogen, alkyl, alkenyl, alkinyl, O halogenoalkyl, halogenoalkenyl, halogeno- alkinyl, alkoxyalkyl, alkylthioalkyl, nitro- alkyl, cyanoalkyl, alkoxycarbonylalkyl, in each case optionally substituted cycloalkyl, aralkyl, aryl or heterocyclyl, or represents a radical SR 8 R 9 in which either g. S R 8 represents hydrogen or alkyl and R 9 represents alkvl or in each case optionally substituted aralkyl or aryl, or R and R 9 together with the nitrogen atom to which they are bonded represent an optionally sub- stituted heterocycle which can, if appropriate, contain further hetero atoms. Le A 28 549 94

8. Pesticide, characterised in that it contains at least one substituted pyrazoline of the formula in admixture with an extender and/or surface active agent.

9. Method of combating animal pests, characterised in that substituted pyrazolines of the formula are allowed to act on animal pests and/or their environment.

Process for the preparation of pesticides, characterised in that substituted pyrazolines of the formula are mixed with extenders and/or surface active 10 agents.

11. A pyrazoline according to claim 1, substantially as herein described with reference to any one of the foregoing examples thereof. DATED this 13th day of December, 1994. BAYER AKTIENGESELLSCHAFf S. 20 By Its Patent Attorneys, DAVIES COLLISON CAVE p:\wpdoc~sgra\436723Vgs~