DD248272A5 - INSECTICIDES, ACARICIDES AND NEMATICIDES - Google Patents

Abstract

The invention relates to the use of partially known 5-aminopyrazole derivatives as pesticides, in particular as insecticides, acaricides and nematicides. It has been found that the partially known 5-aminopyrazoles of general formula (I) in which R 1 is hydrogen, alkyl or haloalkyl, R 2 is alkyl, haloalkyl, optionally substituted aralkyl or optionally substituted aryl, R 3 is hydrogen, XAr is in each case optionally substituted phenyl or pyridyl, and n is a number 0, 1 or 2, and where X is oxygen or sulfur and R4 has the meanings given in the application text, superior insecticidal, acaricidal and nematicidal Own properties. Formula (I)

Description

The invention relates to insecticidal, acaricidal and nematicidal agents containing 5-Aminopyrazoldarivaten, The erfindunosöemäßen means are anoewaridt for üekamofuna of animal pests, especially insects, arachnids and Nogmat odeη in aar agriculture and forestry, in stock and Ma.terialschutz and in the hygiene and veterinary sector.

characteristics oer known technical solutions

It is already known that pyrazole derivatives, such as, for example, 1,4-dimethyl-5-im, N- (dimethyl) -carbamoyloxy-3-methylthiomethyl-pyrazole-ol or the 5-10 n, N- (dimethyl) -ca rbamoy 1-oxyj-1-ms thy 1-3-met hylsulf inylmethy Ipy razol or 5 - fN _r N- (dimethyl) -ca rbamoy loxyj-l-isop Rooy 1-3-me thy lsulf ony Irpethy 1-pyrazole or the 5-n, N- (dimethyl-carbamoyloxy) -l-isobutyl-5-fN, N- (dimethyl) -carbamoyloxyJ-3-methylthiomethylpyrazole or the 1-cyclohexy-5-5-one N, N- (dimethyl) -ca-rbamoyloxy-3-methyl-1-sulfonyIpyrazole have insecticidal, nematocidal and fungicidal activity (cf., DE-OS 2 819 932, DE-OS 2 639 270 or Dc-03 2 912 494) ).

However, the Wirkhöhs or the duration of action of these compounds are "rat ion not always completely satisfactory, especially in certain insects or at low Anvvendungskonzent.

1117HR-

In addition, it is known that certain coumarinyl-phosphoric esters, such as 0, O-diethyl-O- (3-chloro-4-methylcoumarin-7-yl) -thionophosphorsäureester shows very good activity against certain ectoparasites (see, for. "Plant Protection and Pest Control" KH Büchel, G · Thieme Verlag, Stuttgart ^J JL y / /, b. Ύ ο j .

But also the efficacy of this class of compounds is not always completely satisfactory, especially at low levels and concentrations.

Finally, 5-amino-1-aryl-1-pyrazoles are best known (see, for example, Pharmacol., Ed., Pp. 25, 276-293, 1971, or Mycopathology, 74, 7-14, p £ 6: 1964 Hj and CA 95: 36257 q).

However, so far nothing is known about an 'effectiveness of this class of compounds against insects, mites or Neraatoden.

Object of the invention

The aim of the invention is the provision of new agents, in addition to good plant tolerance and favorable warm blood he toxicity at strong insecticidal, acaricidal and nematicidal activity.

Explanation of the essence of the invention

The invention has for its object to find new 5-Aminopyrazolderivat.e with the desired properties oeeiqnet as active ingredient in the inventive insecticidal, acaricidal and nematicidal agents.

it has been found that the partially known 5-aminopyrazoles of the general formula (I)

' ^vy n

I 'J I I <\

in which

R is hydrogen, alkyl or haloalkyl,

R is alkyl, haloalkyl, optionally substituted aralkyl or optionally substituted aryl,

 3 4

R is hydrogen, alkyl or a radical -C-R,

Ar is each optionally substituted phenyl or pyridyl, and

η is a number 0,1 or 2, where

X 'is oxygen or sulfur and

R is hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, alkoxyalkyl, alkylthioalkyl, optionally substituted cycloalkyl, optionally substituted aryl, alkoxy, alkylthio, optionally substituted aryloxy, optionally substituted arylthio, alkylamino, dialkyiamino or optionally substituted Arylamine stands,

possess insecticidal, acaricidal and nematicidal properties.

Surprisingly, the 5-aminopyrazoles of the general formula (I) to be used according to the invention show a significantly improved insecticidal, acaricidal and nematicidal activity than the pyrazole derivatives known from the prior art, for example the 1,4-dimethyl-5 - [N, N - (dimethyl) carbamoyloxyj-3-methylthiomethylpyrazole or the 5- [N, N- (dimethyl) carbamoyloxy] -1-methyl-3-methylsulfinylmethylpyrazole or the 5- [n, N- (dimethyl) carbamoyloxy] 1-isobutyl-3-methylsulfinylmethyl-pyrazole or the 5-one, N- (dimethyl) -carbamoyloxy] -1-isobutyl-3-methyl-su-imidinylmethyl-pyrazole or the 1-cyclohexyl-5- [N, N- (dimethyl) -carbamoyloxy] -3-methylthiomethyl-pyrazole or 1-cyclohexyl-5- ^ Ν, Ν- (dimethyl) -carbamoyloxyj -3-methylsulfinylpyrazole or 1-cyclohexyl-5 - [_ N, N- (dimethyl) carbamoyloxyj-3-methylsulfonyl-pyrazole or the coumarinyl phosphoric acid esters known in the art, such as 0, 0-diethyl-O- (3-chloro-4-methyl-coumarin-7-yl) -thionophosphorus Äureester, which are chemically and / or operatively obvious connections.

The 5-aminopyrazole derivatives to be used according to the invention are generally defined by the formula (I). Preference is given to those compounds of the formula (I),. at which

R represents in each case straight-chain or branched alkyl or halogenoalkyl having 1 to 4 carbon atoms and optionally 1 to 9 identical or different halogen atoms or represents hydrogen,

R is in each case straight-chain or branched alkyl or haloalkyl having in each case 1 to 8 carbon atoms and optionally 1 to 17 identical or different halogen atoms or represents optionally mono- or polysubstituted by identical or different substituents phenylalkyl or phenyl having optionally 1 to 4 carbon atoms in straight-chain or branched Alkyl part is, where as phenyl substituents in question: halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or halogenoalkylsulfonyl having in each case 1 to 4 carbon atoms in the individual alkyl moieties and optionally I to 9 identical or different halogen atoms,

R is hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms or for

4 is a radical -C-R,

X being

X is oxygen or sulfur, and

4 R is hydrogen, in each case straight-chain or branched alkyl, alkenyl, alkynyl, alkoxyalkyl, alkylthioalkyl, alkoxy, alkylthio, alkylamino, dialkylamino or haloalkyl having in each case up to 4 carbon atoms in the individual alkyl moieties and in the case of haloalkyl having up to 9 alike

or different halogen atoms, furthermore optionally mono- or polysubstituted, identically or differently by halogen, lower alkyl or lower halogenoalkyl-substituted cycloalkyl having 3 to 7 carbon atoms, and in each case optionally mono- or polysubstituted by identical or different substituents phenyl, phenoxy, phenylthio or phenylamino , where as Phenylsubs come into question,

where as phenyl substituent the ones mentioned at R

Ar is in each case optionally mono- or polysubstituted, identically or differently substituted phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl, suitable substituents being: cyano, nitro, halogen, in each case straight-chain or branched alkyl, alkoxy or alkoxycarbonyl in each case up to 4 carbon atoms, in each case also straight-chain or branched haloalkyl or halogenoalkoxy having in each case up to 4 carbon atoms and up to 9 identical or different halogen atoms;

or a residue -S (O) -R

R is amino, and in each case straight-chain or branched alkyl, alkylamino, dialkylamino or haloalkyl having in each case up to 4 carbon atoms in the individual alkyl moieties and in the case of haloalkyl having up to 9 identical or different halogen atoms, and

m stands for a number 0, 1 or 2 and

t 4 ö 'i / Ί

η is also a number 0,1 or 2.

Particular preference is given to those compounds of the formula (I) in which

R is hydrogen, methyl, ethyl, η- or i-propyl and trifluoromethyl,

R is methyl, ethyl, η- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, chloromethyl, difluoromethyl, difluorochloromethyl, fluorodichloromethyl , Trifluoromethyl, pentaf luroethyl, pentachloroethyl, fluorotetrachloroethyl, difluorotrichloroethyl, trifluorodichloroethyl, tetrafluorochloroethyl, heptafu luorpropyl, chloroethyl, brornethyl, chloropropyl or in each case optionally mono- to trisubstituted by identical or different substituted phenyl, benzyl or phenylethyl, being suitable as phenyl substituents: , Fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, methoxy, methylthio, trifluoromethyl, methylsurfinyl, methylsulfonyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl,

R is hydrogen, methyl, ethyl, n- or i-propyl

4 or is a radical -C-R,

II

in which

X is oxygen or sulfur and

2 4 δ Ί i ^L

R is hydrogen, methyl, ethyl, η- and i-propyl, allyl, propargyl, butenyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methylthiomethyl, methoxy, ethoxy, methylthio, ethylthio, methylamines ;, ethylamino, dimethylamines, diethylamino, trifluoromethyl, Trichloroethyl, dichlorofluoroethyl, difluorochloroethyl, chloromethyl, iodomethyl, bromomethyl, dichloromethyl, 1-chloroethyl, 2-chloroethyl, 2-bromomethyl, 3-chloropropyl, heptafluoro-n-propyl, in each case optionally one to four times, identical or different, by fluorine, Chloro, bromo, methyl or trifluoromethyl-substituted cyclopropyl, cyclopentyl or cyclohexyl, and in each case optionally mono- to trisubstituted by identical or different methyl, methoxy, chlorine or trifluoromethyl-substituted phenyl, phenoxy, phenylthio or phenylamino,

Ar is in each case optionally mono- to quintuple, identically or differently substituted phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl, suitable substituents being:

Cyano, nitro, fluorine, chlorine, bromine, iodine, methyl, ethyl, η- and i-propyl, n-, i-, s- and t-butyl, methoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, trifluoromethyl, trichloromethyl, difluorochloromethyl, difluorochloromethyl, chloromethyl, dichloromethyl, difluoromethyl, pentafluoroethyl, tetrafluoroethyl, Trifluorchlorpth.vl, Trif luorethyl, Dif luordichlorethyl, Trifluordichlorethyl, pentachloroethyl, trifluoromethoxy, trichloromethoxy, dichlorofluoromethoxy, difluorochloromethoxy, chloromethoxy, dichloromethoxy, difluoromethoxy, pentafluoroethoxy, tetrafluoroethoxy, trifluorochloroethoxy, trifluoroethoxy, Difluordichlorethoxy,

" M'J

Trifluorodichloroethoxy, pentachloroethoxy or a

Rest -S (O) -R ⁵ , where m

R is amino, methylamino, ethylamino, dimethylamino, diethylamino, fluorodichloromethyl, difluoromethyl, tetrafluoroethyl, trifluorochloroethyl, trifluoromethyl, methyl or ethyl,

m is a number 0, 1 or 2 and η is also a number 0,1 or 2.

In particular, the following 5-aminopyrazoles of the general formula (I) may be mentioned in addition to the compounds mentioned in the preparation examples:

R ¹ S (O) -R ²

ⁿ (D.

NH-R ^

Ar

R ¹ R ²

Ar

CH ₃ CH ₃

CH ₃ CH ₃ H

CH ₃ CH ₃ -CO-C ₂ H ₅ Cl

CF ₃ CH ₃ H CF ₃ CF ₃

CF ₃ ^CC1 2 ^FH CF ₃ ^CC1F 2 ^H CF ₃ C ₂ H ₅ H CF ₃ CH ₃ H CF ₃ CF ₃ H Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl

/ VS-CF.

t » ^CF 3

7 \ VCF.

CF

, - ^N > ^CF 3

V VS-CF.

_ ^ ^CF 3

R ¹ R ² R ³

Ar

CF.

C ₂ H ₅

CF. CH.

CH ₃ CH ₃

CF ₃ CF ₃ H

CF ₃ ^CC1 2 ^{FH 2}

CF ₃ CFCl ₂ H

CH ₃ CH ₃ - H 'O CH ₃ C ₂ H ₅ HO

Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

.cl

Cl

Cl Cl

CF.

VS-CF.

O VS-CF,

VS-CF.

CF.

Cl

Cl.

Cl Cl

Cl

'/ \ VCF.

R ¹ R ² R ³

Ar

CH ₃ CH ₃ H 2 CH ₃ C ₂ H ₅ H 1 CH ₃ C ₃ H ₅ H 2

CH ₃ ^CF 2 ^{Cl H}

CH ₃ CF ₂ Cl H

CH ₃ CF ₂ ClH 2

CH ₃ CF ₃ H 2

CH ₃ CCl ₂ FH

Cl.

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl

O \ VCF.

// VycF.

<L ^X > ^CF 3

CF

_ / ^CF 3

_7 ^CF 3

R ¹ R ²

Ar

H CF.

H CF.

H CF.

H CCI ₂ FH "OH ^CC1 2 ^FH

H CCl ₂ FH 2 H ^CF 2 ^{Cl H}

H CF ₂ Cl H 1 H CF ₂ Cl H 2 CH ₃ CF ₃ HO

F F

VS-CF.

VS-CF.

CF.

7 VVCF-

VS-CF.

CF.

VS-CF.

R ¹ R ² R ³

Ar

CH ₃ CF ₃

CH ₃ CF ₃

CH ₃ CCl ₂ FHO CH ₃ CCl ₂ FH 1

H CH ₃ HO

H CH ₃ HH CH ₃ H

HC ₂ H ₅ HO

F F

F F

F F

F F

CF.

CF,

CF.

7 Yy-CF.

7 YVcF.

CF.

V) -CF

V- /

H CF.

H CF.

H CF.

CCl ₂ F

CH-, CH.

CH.

CH "CH.

CH.

Ar

F Br

Cl

br

Cl

br

Cl Br

Cl

br

Cl

br

Cl Br

mm

Cl

, br

Cl Br

Cl

CF.

CF.

CF.

CF.

VS-CF.

NVCF.

\ VCF.

\ VCF.

£ £.

R ¹ R ² R ³

Ar

CH ₃ CCl ₂ FHO

CH ₃ ^CC1 2 ^FH

CH ₃ CCl ₂ FH CH ₃ CF ₃ HO

CH ₃ CF ₃

CH ₃ CF ₃

CH ₃ CF ₃

CH ₃ CF ₃ HO

Cl Br

Cl Cl

Cl Cl

Cl

OCF.

CH ₃ CF ₃ H 2

CH ₃ CCl ₂ FH 0 Cl, Cl

if \ V0CF ₃

R ¹ R ²

Ar

CH

CH ₃ CCl ₂ FH 2 H CH ₃ HO

H CH ₃ H

H CH ₃ H 2 HC ₂ H ₅ HO

HC ₃ H ₅ H 2 CH ₃ CH ₃ HOCH ₃ CH ₃ H 1

Cl Cl

Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl

OCF.

OCF.

OCF.

OCF.

OCF.

OCF.

OCF.

OCF.

OCF.

OCF.

R ¹ R ² R ³

Ar

CH ₃ CH- H 2

H CF.

H CF ₃ H

H CF ₃ H 2 H CCl ₂ F CH ₃ O

H ^CC1F 2 ^H H CClF ₂ HH ^CC1F 2 ^CH 3

H ^CC1F 2 ^{H 2} H CF ₃ -CH ₂ CH ₂ -OH 0

Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

Cl

OCF.

OCF.

OCF.

OCF.

Y VV-OCF.

// Vs OCF.

V VS-OCF.

\ V0CF.

OCF.

R ¹ R ² R ³

Ar

H CF ₃ -CH ₂ CH ₂ -OH

CF.

H ^CC1 2 ^F

CF.

CH ₃

Cl

Cl Cl

Cl Cl

Cl Cl

CF.

(' VS-CF.

CF

CF.

Cl

0 VVCF.

H CF.

CF.

CF.

CH, CF.

Cl

Cl

Cl Cl

CF.

CF.

CF.

CH, CClF,

Cl

CCIF.

CF ₃ CCl ₂ F

Cl Cl.

\ VCF.

(f VV-CF.

Ar

CF.

C ₂ H ₅ C ₂ H ₅ C ₂ H ₅ C ₂ H ₅

CH.

The 5-aminopyrazole derivatives of the formula (I) to be used according to the invention are known in some cases (cf., for example, Pharmaco, Ed., 2j5, 276-293 [101] or Mycopathologica 74, 7-14 [1981] see also CA. j) £ ^: 196411J or CA. 95: 36257q), in part they are the subject of a separate, previously unpublished patent application (see DE-P 3 402 308 of January 24, 1984) and can be obtained in analogy to the preparation processes described therein. Not yet known from the above literature are compounds of the formula (I) in which R is in each case hydrogen and

in the I.

a) R is optionally substituted benzyl (wherein R, η and Ar are as defined above) or

b) Ar is unsubstituted or monosubstituted

Phenyl (wherein R, R and η are as defined above) [except the compound: 5-amino-4- (4-chlorophenylsulfonyl) -1-phenyl-pyrazole; Cf. Khim.

Geterotsikl. Soedin. 1978 , 969-971 -bzw. CA. 8 ±:

17995Ox] or

c) Ar is polysubstituted phenyl, wherein

however, the 2 and 4 positions may not be substituted at the same time (and R, R and η are as defined above)

These compounds can be prepared analogously to the known or described herein (e.g., by reacting substituted aryl hydrazines with acrylonitrile derivatives to ring closure to 1-aryl-5-amino-pyrazoles and optionally subsequent further derivatization).

Also not known are 5-aminopyrazoles of the formula (Ia)

\ .S (O) -R ^Z N ^ η _(Ia)

ml

NH-R ³

Ar ¹

in which

ι · R is alkyl or haloalkyl

Ar ^{1 represents} substituted phenyl or optionally substituted pyridyl and

2 3

R, R and η are as defined above,

where R is s-butyl only if not simultaneously R is methyl, R is hydrogen, η is O and '. Ar is phenyl which is monosubstituted or disubstituted by chlorine.

Also not known are 5-amino-pyrazoles of the formula (Ib),

(Ib)

wel rather I 1 S (O) _n - * ² MR 3 in S-if I Ar "

R ^{1 is} hydrogen

Ar "represents optionally substituted 2-pyridyl,

- 3-pyridyl or 4-pyridyl and R, R and η have the meanings given above.

The not yet known aminopyrazoles of the formula (Ia) are obtained, for example, if

(a) (cO 4-thiocyanato-5-aininopyrazoles of the general formula (1Ia)

(Ha)

^NH

2 Ar ' ^Z

in which

1 <

R and Ar ^{1 have} the abovementioned meaning,

(a) (β) bis (pyrazolyl) disulfides of the formula (IIIa),

1 'R

(IIIa)

_N / _n

I NH HN, Ar ¹ Ar

in which

1 I

R and Ar 'are as defined above,

with halides of the formula (IV),

To - '* V <- 3 Λ,

R ² -hal (IV)

in which

R is as defined above and Hal is halogen,

if appropriate in the presence of a diluent and in the presence of a suitable reducing agent and in the presence of a base,

or when (b) 4-unsubstituted 5-amino-pyrazoles of the formula (Va)

(Va)

in which

1 "

R and Ar 'have the meanings given above, with sulfenyl halides of the formula (VI),

R ² -S-Hal '(VI)

in which

2 R has the meaning given above and Hai 'is halogen,

if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,

or if you are

(c) the 4-substituted 5-amino-pyrazoles of the formula (Ic) obtainable by processes (a - * 0, (a-β) or (b),

Ar '

in which

1 '2 R, R and Ar have the abovementioned meaning

in a generally customary manner with acylating agents or alkylating agents of the formula (VII)

R ⁶ -A (VII)

in which

6H 4

R is alkyl or a radical -C-R,

4 wherein X and R have the meaning given above

and A is an electron-withdrawing leaving group,

or with iso (thio) cyanates of the formula (VIII)

R ⁷ -N = C = X (VIII)

in which

R is alkyl or an optionally substituted aryl, and

X has the meaning given above,

optionally alkylated or acylated in the presence of a diluent and optionally in the presence of an acid binder on the nitrogen of the amino group in the 5-position of the pyrazole ring,

or if you are

(d) the 5-aminopyrazoles of the formula (Id) obtainable by processes (α-OL), (α-β), (b) or (c),

1 '2 RS r-SR

N ^

Ar

in which

1 '2 3

R, R, R and Ar ¹ are as defined above,

with oxidizing agents of the formula (IX), R-O-OH (IX)

- 27 in which

R is hydrogen or each optionally substituted alkanoyl or aroyl,

optionally oxidized in the presence of a diluent, optionally in the presence of a catalyst and optionally in the presence of an acid binder on the sulfur of the sulfenyl group in the 4-position of the pyrazole ring.

Analogously, the not yet known 5-aminopyrazoles of the formula (Ib) are obtained, for example, if

(e-dJ 4-thiocyanato-5-aminopyrazoles of the general formula (Hb)

SCN

NH '(lib)

Ar "

in which

1"

R and Ar "are as defined above,

or (e-β) bis (pyrazolyl) disulfides of the formula (IIIb),

1 "1"

^SS * (HIb)

I t

Ar "Ar"

i- 4 OI / - 28 -

in which

1"

R and Ar have the abovementioned meaning, with halides of the formula (IV) _;

R ² -hal (IV)

in which

R is as defined above and Hal is halogen,

if appropriate in the presence of a diluent and in the presence of a suitable reducing agent and in the presence of a base,

or if you are

(f) 4-unsubstituted 5-amino-pyrazoles of the formula (Vb),

(Vb)

in which

1"

R and Ar "have the abovementioned meaning, with sulphonyl halides of the formula (VI)

R ² -S-Hal '(VI)

in which

R has the meaning given above and Hai 'is halogen,

if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,

or if you are

(g) the 4-substituted 5-amino-pyrazoles of the formula (Ie) obtainable by processes (ε- <λ ·), (e-β) or (f),

1 "2

R ¹ SR ^

\ En)

2 ir »

in which

1 "2

R, R and Ar "are as defined above,

in a generally customary manner with acylating agents or alkylating agents of the formula (VII)

R ⁶ - A (VII)

in which

6 "4

R is alkyl or a radical -C-R,

4 ' wherein X and R have the meaning given above

and

A represents an electron-withdrawing leaving group, or with iso (thio) cyanates of the formula (VIII)

R ⁷ -N = C = X (VIII)

in which

7 ·

R is alkyl or optionally substituted

Aryl, and X has the meaning given above,

optionally alkylated or acylated in the presence of a diluent and optionally in the presence of an acid binder on the nitrogen of the amino group in the 5-position of the pyrazole ring,

or if you are

(h) the 5-aminopyrazoles of the formula (If) obtainable by processes (e- <x), (e-ß), (f) or (g),

I ¹ " qR ²

(If)

, _N. -NH-R ³ kr "

in which

1 "2 3

R, R, R and Ar "are as defined above

to have,

with oxidizing agents of the formula (IX),

R-O-OH

in which

R is hydrogen or each optionally substituted alkanoyl or aroyl,

optionally oxidized in the presence of a diluent, if appropriate in the presence of a catalyst and optionally in the presence of an acid binder on the sulfur of the sulfenyl group in the 4-position of the pyrazole ring.

If, for example, [5-amino-1- (2,4-dichlorophenyl) -methylpyrazol-4-yl-1-thiocyanate and methyl iodide are used as starting materials and sodium borohydride as the reducing agent, the course of the reaction of the preparation process (a-λ) can be followed represent the following equation scheme:

SCN

+ - CH ₃ I

NaBH ₄

KOH / CH ₃ OH

For example, using S, S'-bis-L5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -S-methylpyrazole-1-yl] -disulfide and 4-chlorobenzyl bromide as starting materials, and sodium dithionite as Reducing agent, the reaction sequence of the preparation process (a-ß) can be represented by the following equation:

Na ₂ S ₂ O ₄ NaOH

If, for example, S-amino-S-iriethyl-1- (2,4,6-trichlorophenyl) pyrazole and dichlorofluoromethanesulfenyl chloride are used as starting materials, the course of the reaction of preparation process (b) can be represented by the following formula scheme:

FCl ₂ CS-Cl

-HCl

(Base)

SCCl ₂ F

If, for example, 5-amino-3-methyl-4-trifluoromethylsulfenyl-1- (3,5-dichloropyrid-2-yl) -pyrazole and propionyl chloride are used as starting materials, the course of the reaction of preparation process (c) can be represented by the following formula scheme :

-HCl , (Basel

SCF.

NH-CC ₀ H ₁ . Cl 0

If, for example, "-methyl-S-methylthio-1- (2,6-dichloro-4-trifluoromethylphenyl) -5-propionamido-pyrazole and m-chloroperbenzoic acid are used as starting materials, the reaction sequence of the preparation process (d) can be used. represent by the following formula!

SCH.

Cl

C-O-OH

Cl

NH-CO-C ₂ H ₅

If, for example, L (5-amino-1-pyrid-2-yl) -pyrazol-4-yl-1-thiocyanate and methyl iodide are used as starting materials and sodium borohydride as the reducing agent, the course of the reaction of the preparation process (e-tyl) can be described by the following equation represent:

'V £ m

SCN

N ^NH 2

SCH.

NaBH

+ CH ₃ I

KOH / CH ₃ OH

For example, use is made of S, S'-bis-j_5-amino-1- (3-chloro-5-trifluoromethylthio-pyrid-2-yl) -pyrazol-4-yl] disulfide and 4-fluorobenzyl bromide as starting materials, and sodium dithionite as Reducing agent, the reaction sequence of the preparation process (e-ß) can be represented by the following equation:

S-S

+ 2 FV

Cl Cl ¹ Ti N

SCF.

CF.

Na ₂ S ₂ O ₄

-> 2

NaOH

If, for example, 5-amino-1- (5-chloropyrid-2-yl) pyrazole and trichloromethylsulfenyl chloride are used as starting materials, the course of the reaction of the preparation process (f) can be represented by the following formula scheme:

SCCl.

+ Cl ₃ C-SCI

HCl (base)

If, for example, 5-amino-4-ethylthio-1-pyrid-4-yl-pyrazole _and 3-propionyl chloride are used as starting materials, the course of the reaction of preparation process (g) can be represented by the following formula scheme:

+ C ₂ H ₅ -CO-Cl

-HCl

(Base)

If, for example, 4-ethylthio-1- (3,5-dichloropyrid-4-yl) -5-propionamido-pyrazole and hydrogen peroxide are used as starting materials, the course of the reaction of preparation process (h) can be represented by the following formula scheme:

Γ /

The 4-thiocyanato-5-aminopyrazoles required as starting materials for carrying out the preparation processes (a-oL) and (e-dO are generally defined by the formulas (Ha) and (lib). In the formula (Ha), R is preferably in each case straight-chain or branched alkyl or halogenoalkyl having 1 to 4 carbon atoms and optionally 1 to 9 halogen atoms, such as methyl, ethyl, ή- or i-propyl or trifluoromethyl, Ar ¹ is preferably monosubstituted or polysubstituted by identical or different substituents, or optionally simple or polysubstituted, identically or differently substituted 2- pyridyl, 3-pyridyl or 4-pyridyl, in each case being suitable as substituents:

Cyano, nitro, halogen, in each case straight-chain or branched alkyl, alkoxy or alkoxycarbonyl having in each case up to 4 carbon atoms, in each case also straight-chain or branched haloalkyl or haloalkoxy having in each case up to 4 carbon atoms and up to 9 identical or different halogen atoms or a radical -S (0 ) -R

R is amino, and in each case straight-chain or branched alkyl, alkylamino, dialkylamino or haloalkyl having in each case up to 4 carbon atoms in the individual alkyl moieties and in the case of haloalkyl having up to 9 identical or different halogen atoms, and

m stands for a number 0, 1 or 2.

1"

In the formula (lib) R is preferably hydrogen and Ar "preferably represents optionally mono- or polysubstituted by identical or different substituents 2-pyridyl, 3-pyridyl or 4-pyridyl as substituents mentioned in Ar 'in.Frage come.

The 4-thiocyanato-5-aminopyrazoles of the formulas (IIa) and (lib) are known in some cases (cf., for example, Farmaco Ed., 38 , 274-282 [1983]). They are obtained, for example, when 4-unsubstituted 5-aminopyrazoles of the formula (V)

R ¹

(V)

Ar in which

R is hydrogen, alkyl or haloalkyl and

Ar is substituted phenyl or each optionally substituted 2-pyridyl, 3-pyridyl or A- pyridyl,

with ammonium thiocyanate in the presence of bromine and acetic acid at temperatures between -20 ⁰ C and + 2O ⁰ C reacted.

The bis (pyrazolyl) disulfides required as starting materials for carrying out the preparation process (α-β) and (e-β) are generally defined by the formulas (IIIa) and (IIIb). In the formulas (IIIa) and (IHb) are the radicals

1 '1 "R and R and Ar' and Ar" preferably for those radicals which have already been mentioned in connection with the description of the precursors of the formulas (TIa) or (lib) as preferred for these substituents.

The bis (pyrazolyl) disulphides of the formulas (IIIa) and (IIIb) are not yet known. They are obtained when the above-described 4-thiocyanato-5-amino-pyrazoles of the formulas (Ha) or (Hb) with aqueous hydrochloric acid, optionally in the presence of a diluent, such as ethanol at temperatures between 2O ⁰ C and 12O ⁰ C implements.

The halides which are furthermore required as starting materials for carrying out the preparation processes (aOÜ, (a-β), (e- ^ 0 and (e-ß) are generally defined by the formula (IV).

In this formula (IV), R preferably represents those substituents which have already been mentioned in connection with the description of the inventively used 5-aminopyrazole derivatives of the formula (I) as being preferred for this radical. Hal preferably represents chlorine, bromine or iodine. The halides of the formula (IV) are generally known compounds of organic chemistry.

The 4-unsubstituted 5-aminopyrazoles required for carrying out the preparation processes (b) and (f) and for the synthesis of the precursors of the formulas (Ha) and (Hb) are generally defined by the formulas (Va) and (Vb). In the formulas (Va) and (Vb) are the 1 '1 "

Radicals R and R and Ar ¹ and Ar "preferably for those radicals which have already been mentioned as preferred for these substituents in connection with the description of the precursors of the formulas (Ha) and (Hb).

The 4-unsubstituted 5-aminopyrazoles of the formulas (Va) and (Vb) are known in some cases (cf., for example, J. Org. Chem., 36, 2972-2974 [1997] or J. Heterocyclic Chemistry , 345-349 [1970]; CA. £ 2: 13137c).

They are obtained, for example, when arylhydrazines of the formula (X)

Ar ¹ "-NH-NH- (X)

in which

Ar ^{111 is} substituted phenyl or each optionally substituted 2-pyridyl, 3-pyridyl or 4-pyridyl,

with acrylonitrile derivatives of the formula (XI),

R ¹ CN

c = c ^(XI)

R ² '

in which

R is hydrogen, alkyl or haloalkyl, _2 'is hydrogen or alkoxycarbonyl and

A is halogen, hydroxy, alkoxy, amino or dialkylamino,

either first in a l.Stufe, optionally in the presence of a diluent such as ethanol or glacial acetic acid and optionally in the presence of a reaction auxiliary such as sodium acetate at temperatures between -2O ⁰ C and +20 ⁰ C to the Arylhydrazinderivaten of formula (XII),

Ar

-NH-NH-C = C

^N R ²

(XII)

in which

1 2 '

Ar '' ', R and R have the abovementioned meaning,

and cyclized in a second stage, optionally in the presence of a diluent such as ethylene glycol monoethyl ether at temperatures between + 5O ⁰ C and + 15O ⁰ C, or in a reaction step without isolation of the intermediate of formula (XII), optionally in the presence of a diluent such For example, ethylene glycol monoethyl ether at temperatures between + 5O ⁰ C and +150 ⁰ C directly cyclized to the 5-aminopyrazoles of the formula (XIII)

Ar

in which

12 'R, R and Ar ^{111 have} the abovementioned meaning,

2 '

and in the case where R is alkoxycarbonyl, the compounds of formula (XIII) in a generally conventional manner, optionally in the presence of a diluent such as ethanol or isopropanol and optionally in the presence of a catalyst such as hydrobromic acid at temperatures between 5O ⁰ C and 15O ⁰ C saponified and decarboxylated.

The arylhydrazines of the formula (X) are known (cf., for example, US Pat. No. 4,127,575, US Pat. No. 3,609,158, DE-OS No. 2,558,399, J. Chem. Soc. C, 1971 , 167-174) can be prepared by methods which are known in principle in a simple analogous manner (cf., for example, Houben-Weyl "Methoden der organischen Chemie" Volume X, 2 p.203, Thieme Verlag Stuttgart 1967).

The acrylonitrile derivatives of the formula (XI) are generally known compounds of organic chemistry.

The sulfonyl halides which are furthermore required as starting materials for carrying out the preparation processes (b) and (f) are generally defined by the formula (VI). In this formula (VI), R preferably represents those substituents which have already been mentioned as preferred for this radical in connection with the description of the substances of the formula (I) which can be used according to the invention. Hai ¹ is preferably fluorine, chlorine, bromine or iodine.

The sulphonyl halides of the formula (VI) are generally known compounds of organic chemistry.

The 4-substituted 5-aminopyrazoles required as starting materials for carrying out the preparation processes (c) and (g) are generally defined by the formulas (Ic) and (Ie).

In these formulas (Ic) and (Ie), R and R and Ar ¹ and Ar "preferably represent those radicals which have already been described in connection with the description of the precursors of the formulas (Ha) and (lib) preferably mentioned for these substituents. R preferably represents those radicals which have already been mentioned in connection with the description of the substances of the formula (I) which can be used according to the invention as being preferred for this radical.

The 4-substituted 5-aminopyrazoles of the formulas (Ic) and (Ie) are compounds according to the invention and can be obtained by means of the preparation processes (a-dj, (a-β) or (b) or (e-dJ, (e) ß) or (f).

The acylating or alkylating agents further required as starting materials for carrying out the preparation processes (c) and (g) are generally defined by the formula (VII). In this formula (VII), R preferably represents straight-chain or branched alkyl having up to 4 carbon atoms.

and furthermore a radical -C-R,

Il

4 where X and R preferably represent those radicals which have already been mentioned in the description of the substances of the formula (I) which can be used according to the invention for these radicals.

A is preferably chlorine, bromine, iodine, p-toluenesulfonyloxy, alkoxysulfonyloxy or acyloxy. The alkylating and acylating agents of. Formula (VII) are well known compounds of organic chemistry.

The iso (thio) cyanates which can be used as starting materials as starting materials for carrying out the preparation processes (c) and (g) are generally defined by the formula (VIII). In this formula, X is preferably oxygen or sulfur and R is preferably straight-chain or branched alkyl having up to 4 carbon atoms, or phenyl optionally monosubstituted to trisubstituted by identical or different substituents: halogen, in each case straight-chain or branched alkyl, alkoxy or haloalkyl each having up to 4 carbon atoms and in the case of the haloalkyl having up to 9 identical or different halogen atoms.

R is in particular methyl, ethyl and optionally mono- to trisubstituted by identical or different phenyl, substituted by fluorine, chlorine, methyl, methoxy or trifluoromethyl.

The iso (thio) cyanates of the formula (VIII) are likewise generally known compounds of organic chemistry.

The 5-aminopyrazoles required as starting materials for carrying out the preparation processes (d) and (h) are generally defined by the formulas (Id) and (If). In these

1 '1 "formulas (Id) and (If) R and R and Ar ¹ and Ar" preferably represent those radicals which have already been described in connection with the description of the precursors of. Formulas (Ha) and (lib) are mentioned as being preferred for these substituents

2 3

were. R and R are preferably those radicals which have already been mentioned as preferred for these radicals in connection with the description of the substances of the formula (I) which can be used according to the invention.

The 5-aminopyrazoles of the formulas (Id) and (If) are compounds according to the invention and can be obtained by means of the preparation processes (a- <M, (a-β), (b) or (c) or (e-oil), ( e-ß), (f) or (g).

The oxidizing agents which are furthermore required as starting materials for carrying out the preparation processes (d) and (h) are generally defined by the formula (IX). In this formula (IX), R is preferably hydrogen, acetyl, propionyl, trifluoroacetyl or optionally substituted benzoyl, for example 3-chlorobenzoyl or 4-nitrobenzoyl. The oxidizing agents of the formula (IX) are generally known compounds of organic chemistry.

Suitable diluents for carrying out the preparation processes (a- ^ i.) And (a-ß) and (e-oO and (e-ß) are inert organic solvents.

These include.in particular aliphatic or aromatic, optionally halogenated hydrocarbons, such as gasoline, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, ethers, such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether or Alcohols, such as methanol, ethanol or propanol.

It is particularly advantageous to use as diluent the alcohol corresponding to the halide of the formula (IV) in the alkyl radical, ie. For example, when using methyl iodide as the halide of formula (IV) is particularly preferred methanol as a diluent in question.

As the reducing agent for carrying out the production processes (a-oU and (e-τθ), complex hydrides such as lithium aluminum hydride, lithium borohydride or sodium borohydride are preferably used, and sodium borohydride is particularly suitable.

Suitable reducing agents for carrying out the preparation processes (α-β) and (β-β) are all reducing agents which can usually be used for disulfide cleavings. Dithionites, such as sodium dithionite, are especially preferred.

The preparation processes (a-cO, (α-β), (e-: O and (e-β) are carried out in the presence of a suitable base, alkali metal hydroxides or carbonates, for example sodium or potassium hydroxide or sodium carbonate, are preferably used. or potassium carbonate.

The reaction temperatures in the implementation of the "manufacturing method - be varied within a substantial range, (a-ß), (e-dJ and (e-b) is generally carried out at temperatures between ⁰ ° C and (a i). + 12O ⁰ C, preferably at temperatures between + 2O ⁰ C and + 9O ⁰ C.

In order to carry out the preparation processes (a-jj or (e- * k) , in general 1.0 to 5.0 mol, preferably, are used per mole of 4-thiocyanato-5-aminopyrazole of the formula (Ha) or (lib) 1.8 to 2.5 moles of halide of formula (IV) and 1.0 to 5.0 moles, preferably 1.8 to 2.0 moles of reducing agent and 1.0 to 5.0 moles, preferably 1.5 up to 3.0 moles of base, in which case the 4-thiocyanato-5-aminopyrazole of the formula (Ha) or (lib) in .the respective diluent is reacted with the reducing agent using a nitrogen blanketing gas atmosphere and set after completion Reaction of the base and the halide of the formula (IV) The work-up and isolation of the reaction products of the formula (Ia) or (Ib) is carried out by customary processes.

To carry out the preparation processes (α-β) or (β-β), 1.0 to 5.0 mol, preferably 1.0 to 5.0 mol, are generally employed per mole of bis (pyrazolyl) disulphide of the formula (IIIa) or (IIIb) 1.8 to 2.5 moles of halide of formula (IV) and 1.0 to 5.0 moles, preferably 1.8 to 2.0 moles of reducing agent and 1.0 to 5.0 moles, preferably 1.5 to 3.0 moles of base. In this case, the bis (pyrazolyl) disulfide of the formula (IIIa) or (IIIb) in the appropriate diluent in the presence of the base at the corresponding reaction temperature with the reducing agent is first reacted, after a few hours the halide of the formula (IV ) and heat for an additional hour to the required reaction temperature. The processing and isolation of the

Action products of the formulas (Ia) or (Ib) is carried out by conventional methods.

Suitable diluents for carrying out the preparation process (b) and (f) are inert organic solvents.

These include, in particular, aliphatic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzene, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, ethers, such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether , Ketones, such as acetone or butanone, nitriles, such as acetonitrile or propionitrile, amides, such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, esters, such as ethyl acetate or sulfoxides, such as dimethyl sulfoxide.

The preparation processes (b) and (f) are optionally carried out in the presence of an acid binder. As such, all customary inorganic or organic bases are suitable. These include, for example, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate or Natri "umhydrogencarbonat, and tertiary amines such as triethylamine, N, N-dimethylaniline, pyridine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN ) or diazabicycloundecene (DBU).

The reaction temperatures can be varied within a substantial range when carrying out the production processes (b) and (f). In general, one works at temperatures between -20 ⁰ C and + 12O ⁰ C, preferably at temperatures between 0 ° C and + 50 ⁰ C.

For carrying out the preparation processes (b) and (f), in general 1.0 to 2.5 mol, preferably 1.0 to, are employed per mole of 4-unsubstituted 5-amino-pyrazole of the formula (Va) or (Vb) 1.5 moles of sulfonyl halide and 1.0 to 2.5 moles, preferably 1.0 to 1.5 moles, of acid binder. The reaction, workup and isolation of the reaction products of the formulas (Ia) and (Ib) is carried out according to generally customary procedures.

Suitable diluents for carrying out the preparation processes (c) and (g) are also inert organic solvents. Preferably, the organic solvents mentioned in the description of the preparation processes (b) and (f) are used as diluents.

The preparation processes (c) and (g) are optionally carried out in the presence of an acid binder. As such, the organic and inorganic bases mentioned in the description of the preparation processes (b) and (f) are suitable in particular.

The reaction temperatures can be varied within a wide range when carrying out the preparation processes (c) and (g). In general, one works at temperatures between -20 ⁰ C and + 8O ⁰ C, preferably at temperatures between -1O ⁰ C and + 40 ⁰ C.

For carrying out the preparation processes (c) and (g), in general 1.0 to 10.0 mol, preferably 1.0 to, are employed per mole of 4-substituted-5-amino-pyrazole of the formula (Ic) or (Ie) 5.0 mol of acylating or alkylating agent of the formula (VII) or iso (thio) cyanate of the formula (VIII) and optionally 1.0 to 5.0 mol of acid binder. The. Reaction, .Development and isolation of the reaction products of the formulas (Ia) or (Ib) is carried out according to general

- 48 known, conventional methods.

Suitable diluents for carrying out the preparation processes (d) and (h) are also inert organic solvents.

Preference is given to using hydrocarbons, such as benzine, benzene, toluene, hexane or petroleum ether; chlorinated hydrocarbons, such as dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride or chlorobenzene; Ethers, such as diethyl ether, dioxane or tetrahydrofuran; Carboxylic acids such as acetic acid or propionic acid, or dipolar aprotic solvents such as acetonitrile, acetone, ethyl acetate or dimethylformamide.

The preparation processes (d) and (h) may optionally be carried out in the presence of a drinking binder. As such, all commonly used organic and inorganic acid binders come into question. Preference is given to using alkaline earth metal or alkali metal hydroxides, acetates or carbonates, for example calcium hydroxide, sodium hydroxide, sodium acetate or sodium carbonate.

The preparation processes (d) and (h) can optionally be carried out in the presence of a suitable catalyst. As such, all commonly used for such sulfur oxidations customary catalysts come into question. As an example may be mentioned in this connection ammonium molybdate.

The reaction temperatures can be varied within a wide range when carrying out the production processes (d) and (h). In general, one works at temperatures between -2O ⁰ C and + 7O ⁰ C, preferably at temperatures between ^{0 0} C and + 5O ⁰ C.

To carry out the preparation processes (d) and (h) are generally used per mole of 5-aminopyrazole of the formula (Id) or (If) generally 0.8 to 1.2 mol, preferably equimolar amounts of oxidizing agent Forme-1 (IX ), if one wants to interrupt the oxidation of the sulfur at the sulfate stage. For the oxidation to sulfon are used per mole of 5-aminopyrazole of the formula (Id) or (If) is generally 1.8 to 3.0 mol, preferably twice molar amounts of oxidizing agent of the formula (IX). The reaction, workup and isolation of the end products of formula (Ia) or (Ib) is carried out by conventional methods.

The active ingredients are-with good plant tolerance and favorable toxicity to warm-blooded animals - for controlling animal pests, in particular insects, arachnids and nenatodes, which precontain in agriculture, in forestry, in the protection of stored products and in the hygiene sector. They are against normally sensitive and resistant Species as well as against all or individual stages of development. The above mentioned pests include:

From the order of isopods e.g. Oniscus asellus, Amadillidium vulgaris, Porcellio scaber.

From the order of diplopoda e.g. Blaniulus guttulatus.

From the order of Chilopoda e.g. Geophilus carpophagus, Scutigera spec.

From the order of Symphyla e.g. Scutigerella immaculata.

From the order of the Thysanura e.g. Lepisma saccharina.

From the order of Collembola e.g. Onychiurus armatus.

From the order of Orthoptera e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locustc.

Migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

From the order of deririptera, e.g. Forficula auricularia.

From the order of Isoptera e.g. Reticulitermes spp ..

From the order of the Anoplura e.g. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.

From the order of Mallophaga e.g. Trichodectes spp., Damalinea spp.

From the order of Thysanoptera e.g. Hercinothrips feinoralis, Thrips tabaci.

From the order of Heterop.tera 2.B. Eurygaster spp., Dysdercu-6 intermedius, Piesma quadrata, Cimex lectularius, Rhodnius pro-lixus, Triatoma spp.

From the order of Homoptera, for example, Aleurodes brassicae, BemLsia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Erev ^ coryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp. , Phorodonhurnuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psyila spp. From the order of Lepidoptera, for example, Pectinophora gossypiella, Bupalus'piniarius, Cheimatobia brumata, Lithocolletis bläncardella, Hyponomeuta _: padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lynantria spp. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma .exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp /, Trichoplusia ni, Carpocapsa pomohella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofr.annophila pseudospretelia, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambig'uella, - Kcmcna magnanina, Tortrix viridana.

From the order of Coleoptera e.g. Anobium punctatujn, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus ,. · ..- Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp.,

"'4 G ' ά /

Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus' Gibbiura psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica. From the order of Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp. From the order of Diptera e.g. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster ', Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp. , Oestrus spp., Hypoderraa spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitcta, Dacus oleae, Tipula paludosa.

From the order of siphonaptera e.g. Xenopsyllacheopii, Ceratophyllus spp.

From the order of the arachnids, e.g. Scorpio maurus, Latrodectus inactans.

From the order of Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribiE, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp , Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

Plant parasitic nematodes include Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.

The active compounds of the formula (I) which can be used according to the invention are distinguished by a high insecticidal, acaricidal and nematicidal activity. They can be used in particular against plant-damaging insects, such as against the caterpillars of the cabbage (Plutella maculipennis) or against the larvae of horseradish beetle (Phaedon coch'leariae), as well as against plant-damaging mites, such as against the common spider mite (Tetranychus urticae). They are also excellent for controlling soil insects and nematodes and can be used, for example, to combat Phorbia antiqua maggots or nematodes of the genus Meloidogyne incognita. Also a noteworthy root systemic effect, for example against Phaedon cochleariae larvae is to be emphasized. The nematicidal activity of the active compounds which can be used according to the invention can also be confirmed in the in vitro test, for example against endoparasitic nematodes of the genus Caenorhabditis elegans.

In addition, the active ingredients which can be used according to the invention have. substances of the formula (I) have a high activity against hygiene and storage pests and can be used, for example, to control the oriental cockroach (Blatta Orientalis) or to control the common grain beetle (Sitophilus granarius). In addition, the active compounds according to the invention can be used particularly successfully for controlling parasitic warm-blooded pests, (both ecto- and endaparasites), for example against the larvae of the gold fly (Lucilia cuprina), against bovine ticks (Boophilus microplus), against mange mites ( Psoroptes ovis), against stinging flies (Stomoxys calcitrans) or against the grazing livestock fly (Musca aututinalis).

In addition, the active compounds of the formula (I) which can be used according to the invention also have a good fungicidal activity and can be employed for controlling plant diseases such as, for example, against the pathogen of rice blotch disease (Pyricularia oryzae) or against scab and Botrytis pathogens.

In appropriate application rates, the active compounds of the formula (I) which can be used according to the invention moreover have a herbicidal activity.

The active compounds can be converted into the usual urethane thinners, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active substance-impregnated natural and synthetic substances, microencapsulations in polymeric substances and in seed coat lozenges, furthermore in formulations with Burning attachments, such as smoking cartridges, cans, spirals, etc., as well as ULV KaIt and warm mist formulations.

These formulations are prepared in a known manner / e.g. by mixing the active compounds with extenders, ie liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as an extender, e.g. also organic solvents can be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorothylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols, such as butarol or glycol, and their ethers and esters, ketor; "such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and di-methyl sulfoxide, and water; By liquefied gaseous diluents or carriers is meant those liquids which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers there are suitable: e.g. ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as fumed silica, alumina and silicates; suitable solid carriers for granules are: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic

see flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam formers are: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are: e.g. Lignin-sulphite liquors and methylcellulose.

Adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex polymers may be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90%. -

The active compounds which can be used according to the invention can be present in their commercially available formulations and in the forms of use prepared from these formulations in admixture with other active substances, such as insecticides, attractants, sterilants, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. The insecticides include, for example, phosphoric acid esters, carbamates, carboxylic esters, chlorinated hydrocarbons, phenylureas, microorganism-produced substances and the like.

The active compounds which can be used according to the invention can furthermore be present in their commercial formulations as well as in the formulations prepared from these formulations in admixture with synergists. Synergists are compounds which enhance the effect of the active ingredients without the added synergist itself having to be active.

The active substance content of the application forms prepared from the commercial formulations can be varied within wide ranges. The active ingredient concentration of the application forms may be from 0.0000001 to 95% by weight of active ingredient, preferably between 0.0001 and 1% by weight.

The application is done in a custom forms adapted to the application.

When used against hygiene and storage pests, the active ingredients are characterized by an excellent residual effect on wood and clay and by a good alkali stability on limed substrates.

-5G-

The erf indungsgernäß usable Wirkstoffs- are also suitable for combating insects, mites, ticks etc. in dsm area is animal husbandry and livestock, by combating the pests better results for. G. higher milk yields, higher weight, better animal coat, longer life, etc. can be achieved.

The application of the active ingredients used in the invention is done in these areas in well-known manner, such as by external application in the form of, for example, diving (Oippen), spraying (spraying), pouring (pour-on and spot-on) and Einpude rns.

Appli η d u η σ s b e i s ρ i e1

The invention will be described in more detail below with reference to some examples

V ι

explained.

Production Examples Example 1

8 g (0.023 mol) of 5-amino-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazol-4-yl-thiocyanate in 100 ml of absolute methanol are added in portions at room temperature in a nitrogen atmosphere with 1.6 g (0.042 mol) Sodium borohydride added. After completion of the addition, the mixture is stirred for 45 minutes at room temperature and then a solution of 2.4 g (0.042 mol) of potassium hydroxide in 40 ml of absolute methanol and then dropwise 6, o g (0.042 mol) of methyl iodide to. After complete addition, it is stirred for 3 0 minutes at room temperature, concentrated in vacuo, the residue is taken up in water, extracted several times with chloroform, dried over sodium sulfate, the solvent is removed in vacuo and the residual oil from petroleum ether.

6.1 g (78% of theory) of 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-methylthiopyrazole of melting point 106 ° C.-108 ° C. are obtained.

O Z 7?

Preparation of the starting compound

  SCN

NH,

ei 1 egg

To 20.5 g (0.07 mol) of 5-amino-l- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole and 10.7 g (0.14 mol) of amino thiocyanate in 300 ml of glacial acetic acid is added dropwise at 10 ^c C with stirring 11.2 g (0.07 mol) of bromine in 70 ml of glacial acetic acid and stirred for a further 10 minutes at +10 ⁰ C for work-up, the mixture is poured onto ice, prepared by adding concentrated aqueous ammonia solution pH 9, sucks the precipitated solid and dried it.

This gives 22.9 g (93% of theory) of 5-amino-l- (2,6-dichloro-4-trifluoromethylphenyl) -pyrazol-4-yl-thiocyanato a melting point of 137 ⁰ C.

24.5 g (0.1 mol) of 2,6-dichloro-4-trifluoromethylphenyl hydrazine are added dropwise with 20 ml of ethylenediaminetetraacetic acid disodium salt (= Titriplex III) in 150 ml of methanol at reflux temperature with 25 ml (27.6 g / 0.3 mol) of 2-chloroacrylonitrile. After the addition has ended, the mixture is refluxed for a further 8 hours, then 9 ml (0.16 mol) of 96% strength sulfuric acid are added dropwise and the mixture is refluxed for a further 6 hours. The cooled reaction mixture is mixed with 33.5 g (0.3 mol) of anhydrous sodium carbonate. After 4 hours, the solvent is removed in vacuo, the residue is taken up in 500 ml of water and stirred for 10 hours at room temperature. The mixture is filtered and the precipitate off, washed with water and dried in vacuo at 5O ⁰ C.

This gives 28.5 g (96% of theory) of 5-amino-l- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole of melting point '103 ⁰ C-105 ° C.

£. ί

4.35 g (6.6 mmol) of S, S'-bis-5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -pyrazol-4-yl]] - disulfide, 0.5 g (13 mmol) of sodium hydroxide and 2.3 g (13 mmol) of sodium dithionite are refluxed in a mixture of 80 ml of ethanol and 80 ml of water for 2 hours. Then, 2.45 g (13 mmol) of 4-fluorobenzyl bromide are added and refluxed for an additional hour. For working up, concentrate in vacuo to half the volume, extracted several times with chloroform, the combined organic phases are dried over magnesium sulfate and the solvent is removed in vacuo. The oily residue crystallizes on stirring with petroleum ether.

This gives 4.2 g (73% of theory) of 5-amino-l- (2,6-dichloro-4-trifluoromethylphenyl) - (4-f luorbenzyltbio) pyrazole of melting point 112 ° C-113 ° C.

Production of the Ausqangsverbindung

S- S.

11.9 g (0.04 mol) of 5-amino-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazol-4-yl-thiocyanate in a mixture of 300 ml of ethanol and 300 ml of water are added after addition of 80 ml 10 normal hydrochloric acid for 12 hours under reflux. For working up, concentrate in vacuo to half the volume and sucks off the precipitated solid.

This gives 10.4 g (80% of theory) of S, S'-bis - [5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazol-4-yl] disulfide of melting point 148 ° C-150 ° C.

BeispieJL_3

S-CCI-F

35.4 g (0.114 mol) of 5-amino-l- (2,6-dichloro-4-trifluoromethylphenyl) -3-methyl-pyrazole and 10 ml (0.125 mol) of anhydrous pyridine in 150 ml of dichloromethane are at 0 ⁰ C to 5 ° C while stirring dropwise with 12.6 ml (0.12 mol) dichlorofluoromethanesulfenyl chloride. After complete addition, it is stirred for a further 30 minutes at room temperature, 100 ml of dichloromethane are added and washed successively with dilute hydrochloric acid, water, sodium bicarbonate solution and aqueous sodium chloride solution, dried over magnesium sulfate and the solvent is removed in vacuo.

This gives 49.5 g (98% of theory) of 5-amino-l- (2, 6-dichloro-4-trifluoromethylphenyl) -4-dichlorfluormethylsulf enyl-3-methyl-pyrazole with a melting point of 131 ⁰ C.

Preparation of the starting compound

61.25 g (0.25 mol) of 2,6-dichloro-4-trifluoromethylphenylhydrazine and 21 g (0.25 mol) of diacetonitrile in 500 ml of ethanol are refluxed for 20 hours. 4 ml of concentrated sulfuric acid are added to the cooled reaction mixture and the mixture is heated for another 4 hours to 6O ⁰ C. For workup, the mixture is evaporated in vacuo, the residue taken up in chloroform and made alkaline with 25 percent aqueous ammonia solution. The organic phase is separated and the aqueous phase extracted with chloroform. The combined organic phases are dried over magnesium sulfate and freed from the solvent in vacuo.

This gives 62 g (80% of theory) of 5-amino-l- (2,6-dichloro-4-trifluoromethylphenyl) -3-methyl-pyrazole as a glassy substance.

¹ H-NMR (CDC1 ₃ / TMS) S = 2.23; 3.50; 5.49; 7.68 ppm

Beisgiel_4

2432

7 η

- 65 -

27.7 g (0.1 mol) .5 ^ _3-amino-methyl-l- (2, 4, 6-trichlorophenyl) pyrazole and 10 ml (0.125 mol) of anhydrous pyridine in 150 ml dichloromethane at 0 ⁰ C to 5 C. with stirring 12.6 ml (0.12 mol) of dichlorofluoromethanesulfenylchloride and stirred for 30 minutes. For working up, 100 ml of dichloromethane are added, the mixture is washed successively with dilute hydrochloric acid, water, sodium carbonate solution and brine, dried over magnesium sulfate and the solvent is removed in vacuo.

38.2 g (93% of theory) of 5-amino-4-dichlorofluoromethylsulfenyl-3-methyl-1- (2,4,6-trichlorophenyl) pyrazole are obtained

of melting point 125-127 ° C

Preparation of the starting compound

34.8 g (0.1 mol) of ethyl S-amino-S-methyl-1- (2,4,6-trichlorophenyl) pyrazol-4-ylcarboxylate are mixed in a mixture of 250 ml of 48 percent hydrobromic acid and 25 ml of isopropanol Heated to 12O ⁰ C hours. After completion of the reaction, 200 ml of water are added, adjusted with 10 percent sodium hydroxide solution to pH 7 to 8 and sucks off the precipitated solid.

This gives 18 g (65% of theory) of 5-amino-3-methyl-l- (2,4,6-trichlorophenyl) pyrazole of melting point 111 ° O113 ° C,

COOC ₉ H, /

A solution of 21.2 g (0.1 mol) of 2,4,6-trichlorophenylhydrazine and 18.3 g (0.1 mol) of ethyl 2-cyano-3-ethoxy-2-butenate in 250 ml of ethanol is 14 hours under Heated to reflux, then concentrated in vacuo, the residue taken up in dichloromethane, washed with water, dried over magnesium sulfate and freed from the solvent in vacuo.

This gives 22 g (63% of theory) of 5-amino-3-methyl-l- (2,4,6-trichlorophenyl) -pyrazol-4-ylcarbonsaureeethyIester of melting point 150 ° C.

CH

COOC-, Η-

^{2 5}

C = C ^C 2 ^H 5 ° ^CN

113 g (1 mol) of ethyl cyanoacetate, 162 g (1 mol) of triethyl orthoacetate and 204 g (2 mol) of acetic anhydride are heated under reflux, with ethyl acetate slowly distilled off and the reaction temperature rises to 14O ⁰ C. The Rücketand is distilled in a water jet vacuum.

This gives 57 g (32% of theory) of 2-cyano-3-ethoxy-2-butenoic acid ethyl ester of boiling point 15O ⁰ C at 24 mbar and a melting point of 70 ⁰ C (Umkristal! Isation of isopropanol).

Beisgiel_5

S-CCl ₂ F

30 g (0.114 mol) of 5-amino-1- (2,4,6-trichlorophenyl) pyrazole and 10 ml (0.125 mol) of anhydrous pyridine in 150 ml of methyl.

Are lenchlorid at 0 ⁰ C to 5 ⁰ C with 12.6 ml (0.12 mol) Dichlorfluormethansulfenylchlorid and stirred for 30 minutes. For workup, 100 ml of methylene chloride and washed successively with dilute hydrochloric acid,

Water, sodium bicarbonate solution and brine, dry over magnesium sulfate and remove the solvent in vacuo.

This gives 44.5 g (98.7% of theory) of 5-amino-4-dichlorfluormethansulfenyl-1- {2,4,6-trichlorophenyl) pyrazole of melting point 101 ⁰ C to 106 ⁰ C.

Beispiel_6

SCCl-F

NH-CCH ₁

 Il 2 5

Cl O

13.0 g (0.029 mol) of 5-amino-4-dichlorofluoromethylsulfenyl-1- (2,4,6-trichlorophenyl) pyrazole are stirred for 10 hours at room temperature with 50 ml of propionic anhydride and 1 ml of concentrated sulfuric acid. The reaction mixture is then added dropwise to 100 ml of ice-cold methanol, stirred for one hour and then evaporated to dryness. The residue is taken up in dichloromethane, washed successively with water, sodium bicarbonate solution and brine, dried over magnesium sulfate and freed from the solvent in vacuo.

This gives 8.9 g (68% of theory) of 4-enyl Dichlorfluormethansulf 5-do- propionami I- (2,4,6-trichlorpyhenyl) -pyrazole of melting point 129 ⁰ C.

O Il

S-CCl ₂ F

N NH-CO-C ₇ H Cl JL Cl ^

3 g (6.6 mmol) of 4-dichlorofluoromethanesulfenyl-5-propionamido-1- (2,4,6-trichlorophenyl) pyrazole and 1.5 g (8.7 mmol) of m-chloroperbenzoic acid in 10 ml of dichloromethane are allowed to stand for 16 hours stirred at room temperature, filtered, the Fütrat successively with sodium bicarbonate, sodium thiosulfate, again with. Sodium bicarbonate and then washed with sodium chloride solution, dried over magnesium sulfate and freed from the solvent in vacuo.

To give 2.8 g (90.2% of theory) of 4-Dichlorfluormethylsulfinyl-5-proplonamido-l- (2,4,6-trichlorophenyl) -pyrazole of melting point 146 ⁰ C.

In a corresponding manner and in accordance with the general preparation information, the following 5-aminopyrazole derivatives of the general formula (I) are obtained:

R ¹ S (O) -R ²

ⁿ Vnh-r ³

Ar

..... 'OZ / 2

physical properties

10 H

11 h

12 H

13 H

8 H

9H CF.

CCl ₂ F

CCl ₂ F

CCl ₂ F

CCl ₂ F

CH ₃ -CH ₂ -CO

CH ₃ -CO

Mp 139 ⁰ C

Mp 131-138 ⁰ C

Mp 99-105 ⁰ C

Mp 55-62 ⁰ C

Mp 135-138 ° C

Mp 60-65 ⁰ C

14 H

CCl ₂ F

Cl Cl

Mp 55-62 ⁰ C

15 H CCl ₂ FH

16 H ^CC1 2 ^FH

NMR (3-H, Pyr.) 7.57 ppm (s, 1H) (CDCl ₃ / TMS)

Mp 81-87 ⁰ C

17 H ^CC1 2 ^FH

Mp 77 ⁰ C

18 H

CCl ₂ FH

NMR

"äl, (3-H, Pyr.) 7.61 ppm (s, lH) (CDCl / TMS)

Ex.

No. R R

physical properties

19 H

20 H ^CC1 2 ^FH

Cl Cl

Mp 112-121 ⁰ C

Mp 55-61 ° C

21 H ^CC1 2 ^FH

22 H ^CC1 2 ^{F CH} 3

23 H ^CC1 2 ^FH

CF ₃ O

CF ₃ 0

NMR

OI (3-H, Pyr.)

7.58 ppm (s, lH)

(CDC1 ₃ / TMS)

Mp 107-110 ⁰ C

O Fp 148-153 '

24 H CCl-

26 H

CF.

25 H CF ₃ H

27 H ^CC1 2 ^FH

28 H ^CC1 2 ^FH

29 H ^CC1 2 ^FH

Mp 75-88 ⁰ C ·

Mp 86-94 ⁰ C

Oil (3-H, Pyr.) 7.64 ppm (s, IH) (CDCl ₃ TMS)

Mp 104-107 ⁰ C

Öi (3-H, Pyr.) 7.64 (s, IH) (CDCI ₃ / TMS)

Cl 1 mp 69-75 ° C

Ex.

No. R

Ar

Physiatic features

30 H ^CC , ¹ 2 ^FH

31 H CCl ₂ FH

32 H ^CC1 2 ^FH

33 H ^CC1 2 ^FH

34 H ^CC1 2 ^FH

Cl

(/ \\ - Cl 2 mp 63-69 ° C

O mp 101-107 ⁰ C

CI Cl

Cl 0

CHO OC ₉ H CF ₃ 0

F 'F

F ₃ C NMR:

Oil (3-H, Pyr

7.67 ppm (s, l

(CDC1 ₃ / TMS)

NMR:

Oil (3-H, Pyr

7.70 ppm (s, l

(CDC1 ₃ / TMS)

Ü ^X Vci 2 mp 61-65 ⁰ C

3 5 H ^CC1 2 ^FH

Cl

Mp 117-124 ° C

36 H ^CC1 2 ^FH

Cl Fp 132-137 ⁰ C

37 H CF ₃ H

38 H QY

39 H CCl ₂ FH

CF ₃ 2

he

Cl

CF ₃ 1

Mp 57-63 ° C

Mp 86-92 ° C

Mp 45-55 ° C

4 0 H -CF ₂ -CCl ₂ FH

Cl

O mp 117-119 ° C

Cl

Le A 23 753

Ex.

No. R

physical properties

41 H

42 CH ₃ CCl ₂ F

NIIR:

Oil (3-H, Pyr.)

7.73 (s, lH)

(CDC1 ₃ / TMS)

O mp 69-7O ⁰ C

43 CH ₀ CCl-F C _o H _c C0

\\ 0 Fp 194 ⁰ C

4 4 CH

, _r Fp 94-95 ⁰ C

45 CH

Mp 108-110 ⁰ C

46 CH ₃ CCl ₂ FC ₂ H ₅ CO

Ep 174 ° C

47 CH ₃ CCl ₃ FC ₃ H ₅ CO

Mp 208 ⁰ C

48 CH 49 CH

C ₂ H ₅ CO

NMR: oil

3-CH ₃ (pyr.), S, 2.2 7 ppm (CDCI ₃ / TMS)

O mp 128-13O ⁰ C

50 CH ₃ CCl ₂ FC ₂ H ₅ CO

Mp 179 ° C

51 CH ₃ CCl ₂ FH

51a H

Le A 2 3 75

Mp 63-64 ⁰ C

^ Ä. Q O? "ϊ

1 .

No. R: R

Ar

physical properties

52 (CH ₃ ) ₃ C CCl ₂ FH

53 CH ₃ CCl ₃ H

54 CH ₃ CF ₃ H

5 5 CH ₃ J /

CF.

CF., O mp 140-144 ⁰ C

0 mp 150-152 ⁰ C

0 Fp 147 ^U C

.0 'Fp 58-82 ⁰ C

56 CH ₃ CCl ₂ FH

57 CH ₃ ^CC1 2 ^FH

58 H CH ₃ H

O Fp 58-61 C

O mp 78-80 ° C

U \ Vci 0 Fp 114 ⁰ C

59 H

60 H

62 H

CH

CH

61 H CH ₃ . , H

CH ₃ H

\ Vci 0

Mp 92-95 ⁰ C (Zers.)

2 mp 146-15O ⁰ C

2 mp 60-65 ⁰ C

Cl 2 FP 170-171 ⁰ C

Le A 23 753

4 ö ü; 2

Ex.

No. R

Ar

physical properties

63 H · C ₃ H ₅ H

O Fp 81-82 ⁰ C

64 H (CH ₃ ) ₂ CH- H

O mp 77-79 ° C

65 H

O mp 124-127 ⁰ C

66 CH ₃ CH ₃

67 CH ₃ C ₃ H ₅ H

68 H ^CC1 2 ^FH

O Fp 54-57 ⁰ C

CF, O mp 109-110 ⁰ C

E'p 92-94 ° C

69 H ^CC1 2 ^FH

0 mp 85-89 ° C

70 H ^CC1 2 ^FH

0 Fp 70 ° C

71 H ^CC1 2 ^FH

Cl

V-COOCH ₃ 0 mp 140-144 ⁰ C

Cl

72 H ^CC1 2 ^FH

2 mp 107-110 ⁰ C

73 H

Le A 23 753

1 fp 75-77 ° C

Example

 No.

Ar

phys ika1i see η characteristics

74 H

O Fp 88-80 ° C

75 H ^CC1 2 ^FH

76 H ^CC1 2 ^FH

Br Cl.

M-CF-O Fp 80-83 ⁰ C

0 Fp 68-72 ⁰ C

77 H ^CC1 2 ^FH

78 H CCl ₂ FH

79 H ^CC1 2 ^FH

\ VCF.

2 bp 104-106 ° C

0 NMR:

7.60 ppm (s, 1H) 4.36 ppm (s, 2H) (CDCl ₃ / TMS)

(/ \ VcF- 2 mp 128-132 ⁰ C

ΥΥ-ci

Cl CF

80 H ^CC1 2 ^F * ^H

81 H

83 H

84 H

^CC1 2 ^FH

12 H ^CC1 2 ^FH

CF ₃ CH ₃

CF ₃ H

// \ VBr

F ₃ CO

Ni! [R:

7.61 ppm (s _f IH) 4.26 ppm (s, 2H) (CDCl ₃ / TMS) mp 100-101 ⁰ C.

NMR:

7.57 ppm (s, lH)

4.31 ppm (s, 2H)

I ₀ / TMS)

5§-60 ° C

0 Fp

'/ \ VOCF, 0 mp 112-113 ° C

85 H

Le A 23 753

CF.

0 mp 90-91 ° C

Ex.

No. R

Ar

physical properties

86 H, CH ₃ H

87 CH ₃ CH ₃ H

88 CH ₃ C ₂ H ₅ H

89 CH ₃ (CH ₃ ) ₂ CH- H

^CF

(f vS-ci ο

Mp 179-182 ⁰ C

Mp 128-131 ⁰ C

Cl 'Cl

V V) -Cl 0 mp 121-123 ⁰ C

he

' ₃ O Fp 100-101 ⁰ C

90 H ^CC1 2 ^FH

91 CH ₃ CF ₃ H

OCF

NMR:

7/7 ppm (s, IH) O S, 2 ppm (IH)

8.6 ppm (IH) (CDC1 ₃ / TMS)

3. O Fp 67-70 ⁰ C

92 CH ₃ CF ₃ H

VV " ^C1

122-125 ° C

93 H CCl ₂ FH

2 mp 102-110 ⁰ C

94 H CCl ₂ FH

95 H CCl ₂ FH

\ / ^CF

Mp 68-7 4 ⁰ C

( ⁷ _y-CF ₃ 0 Fp 60-70 ⁰ C

CH ₃ CF ₃ COC ₂ H ₅

H CF ₃ η

Le A 23 753

\ VCF

3

Mp 138 C

Mp 67-68 ° C

Ex. R ¹ R ² No.

R ³ Ar

η physical properties

98 CH ₃ CCl ₂ FH

99 CH ₃ CClF ₂ H

100 CH

CF ₃ H

101 CH ₃ CCl ₂ FH

egg ·

Cl Cl

Cl Cl

br

Cl

0 fp. 133-134

r 0 mp 132-134 ⁰ C

F ₃ 2 mp. 150-152 ⁰ C

F ₃ 1 mp 135-138 ⁰ C

102 CH ₃ CCl ₂ FH

Cl

2 mp. 58-61 ⁰ C

103 CH ₃ CF ₃ H

104 CH ₃ CF ₃ H

105 CH ₃ CClF ₂ H

Cl

Cl

br

1 m.p. 147 ⁰ C

2 mp 103-105 ⁰ C

0 mp 114-116 ⁰ C

Le A 23 753

Ex. R ¹ R ² R ³ Ar

No.

η physical properties

106 CH ₃ CF ₃ H

1 fd. 157-159 °

107 CH ₃ CClF ₂ H

108 CH ₃ CClF ₂ H

NMR: 0 oil 3-CH., (Pyr.)

(CDCl ₃ / TMS)

1 mp. 118-122 ⁰ C

109 CH ₃ CClF ₂ H

2 fd. 59-61 ° C

110

CClF ₂ H

III CH ₃ CClF ₂ H

112 CH ₃ CCl ₂ FH

113 CH

CF ₃ H

1 Fd. 76-80 ⁰ C

2 Fd. 143-144 ⁰ C

Br_ 2 Fd. 184-185 ⁰ C

Br 2 Fd. 135-138 ⁰ C

Le A 23 753

'f 4 ö Ί / ' a

Ex. R no.

R ^J Ar

η physical properties

Cl

CH-

CClF ₂ H

Cl Cl CH-

CCl ₂ FH

Cl

CH-

CF ₃ H

Cl

CH ₃

CClF ₂ H

Cl

Cl

CH ₃ CCl ₂ F CO-C ₂ H ₅

Cl

CH ₃ CCl ₂ FH

CH-

CF ₃ H

Cl

Cl

Cl /

CF

Cl

Cl Cl CH ₃ CCl ₂ FH

CF

Cl 2 mp 154-155 ⁰ C

Br 1 mp. 168-170 ⁰ C Br 1 mp. 170 ⁰ C

Br 1 mp. 82-85 ⁰ C

1 Fa. 174 ⁰ C

2 m.p. 145 ⁰ C

3 P mp 144-149 ° C

Mp.

Le A 23 753

£ _ -TW in J n>

Ex. R ¹ H ²

No.

Ar Cl _ / η see physical J> -SCF ₃ properties Cl V- / Z Cl O Mp 80-96 ° C ) Cl Cl

122 CH ₃ CCT ₂ FH

123 CH ₃ CF ₃ H

SCF

₃ 0 mp 118-121 ° C

124 CH ₃ CCl ₂ FH

F ₃ 0 mp 75-77 ° C

125 CH ₃ CF ₃ H

F ₃ 0 mp. 83 ° C

126 CH ₃ CCl ₂ FH

V-OCF ₃ 0 mp. 95-97 ⁰ C

127 CH ₃ CF ₃ H

128 C ₂ H ₅ CCl ₂ FH

0 mp 100-101 ⁰ C

0 Mp. 105-108 ⁰ C

Le A 23 753

Ex. R ¹ R ² No.

η physical properties

C ₂ H ₅ CF ₃ H

F ₃ O mp 113-116 C

C ₂ H ₅ CCl ₂ FH

0 mp 89-93 ⁰ C

C ₂ H ₅ CF ₃ H

0 mp, .. 76-78 ⁰ C

CH ₃

CF ₃ H -C

SO ₂ CF ₃ 0 _NMR .

01, 3-CH ₃ (pyr.) S, 2.30 ppm (CDCI ₃ / TMS)

CH ₃

CF ₃ COC ₂ H ₅

^F 3 ¹ mp 135-137 ° C

CH-

CF ₃ COC ₂ H ₅

Mp 132-133 ^U C

CH ₃

CFo H

SO ₂ CF ₃ 0 mp 160-169 ° C

Le A 23 753

C - '* OC

Ex. R ¹ R ² No.

Ar

η physical properties

Cl

136 CHo CFo 'H

Cl Cl

137 CH ₃ CF ₂ Cl H 138 CH ₃ CF ₃ COCH ₃

Cl

Cl

139 CH ₃ CF ₃

br

Cl

2 mp. 147-148 C

0 mp. 63-65 ⁰ C

CFo 0 mp 157-15 9 ⁰ C Br - 0 mp I43 ^u c

140 C ₂ H ₅ CCl ₂ F COCH ₃ -Cl 0 mp 158-160 ° C

Cl

141 C ₂ H ₅ CF ₃ COCH ₃

0 m.p. 178-180 ⁰ C

Cl

142 CH ₃ CCl ₂ FH

143 CH ₃ CF ₃ H

Br Cl

br

0 mp 105-107 ⁰ C

0 Mp. 136-137 ⁰ C

Le A 23

- f '· * Zm a jar

Ex. R no.

R ^J Ar

η physical properties

Cl

144 CH ₃ CF ₃ H

Cl

145 C ₂ H ₅ CF ₃ COCH ₃

146 C ₂ H ₅ CF ₃ COCH ₃

0 mp. 137-138 ⁰ C 1 mp. 62-64 ⁰ C 2 mp. 140-141 ⁰ C

147 C ₂ H ₅ CCl ₂ F COC ₂ H ₅

148 C ₂ H ₅ CCl ₂ F COC ₂ H ₅

Cl 149 C ₂ H ₅ CCl ₂ F COC ₂ H ₅ - ^ / -Cl 0 mp 120-121 ⁰ C 1 NMR:

Oil, 3-CH- (Pye.) (T, 1.07 " ³ PPm)

.) (q, 2.26)

₇ (CDC ₃ / TMS)

2 m.p. 91-93 ⁰ C

Cl

150 C ₂ H ₅ CF ₃ H

151 C ₂ H ₅ CF ₃ H

1 m.p. 146-147 ⁰ C 2 m.p. 91-92 ° C

Le A 23

2482

Ex. R • No.

R ^J Ar η physical properties

Cl C ₂ H ₅ COl ₂ FH - \ V ~ Cl

Cl Cl

C ₂ H ₅ CCl ₂ FH - <'> - C1

Cl Cl

CH ₃ CClF ₂ H - (- Cl

Cl Cl '

CH ₃ CClF ₂ COC ₂ H ₅ - \ 7-CF

Cl

CH ₃ CClF ₂ COC ₂ H ₅

Cl

Cl

CH ₃ CClF ₂ COC ₂ H ₅

Cl 1 mp. 138-140 ⁰ C.

2 Fd. 60-61 ⁰ C

0 Mp. 130-131 ⁰ C 0 Mp. 135 C

1 mp. 144-145 ° C

2 Fd. 144 ⁰ C

158 CH ₃ CF ₃ COC ₂ H ₅ - <> - Cl 0 mp. 164 ^° C

CHo CCl ₇ -F COCoH

<J Cj, Ct

Cl

Cl /

0 fp. 144-146 ⁰ C

Cl

Le A 23 75 3

Ex. R ¹ R ² No.

Ar

η physical properties:

Cl

CH ₃ CClF ₂ * COC ₂ H ₅ -C> -Cl

Cl

OP ¹ P. 131 ° C

CH ₃ CClF ₂ H

Cl

f X

1 mp. 63-67 ⁰ C

Cl Cl CH ₃ CClF ₂ H

^ ₃ 2 Fp-. 120-128 ⁰ C

Cl Cl

CH ₃ "CF ₃ COC ₂ H ₅

0 fd. 128-130 ⁰ C

Cl

CH ₃ CCl ₂ F COC ₂ H ₅ -C 7 OCF ^

Cl Cl

-OCFo Cl 0 mp 10 2 C

CH ₃ CClF ₂ H

0 m.p., 111-112 ⁰ C.

CH ₃ CF ₃ COC ₂ H ₅ - <'> ~C1

Cl Cl CH ₃ CF ₃ COC ₂ H ₅ - \> ~ C1

Cl 0 Fd. 118-124 ⁰ C

2 m.p. 100-102 ⁰ C

Le A 23 753

Ex. R ¹ R ² .No,

R ^J Ar

η physical properties

Cl

168 CH ₃ CCl ₂ F COC ₂ H ₅

Cl Cl

169 CH ₃ CCl ₂ F COC ₂ H ₅

Cl Cl

170 CH ₃ CClF ₂ COC ₂ H ₅

171 CH ₃ CClF ₂ COC ₂ H ₅

Cl Cl

> χ

Cl Cl

172 CH ₃ CClF ₂ COC ₂ H ₅

1 p. 102-103 ⁰ C

1 2 mp. 168-169 ⁰ C

1 1 mp. 161-16 3 ⁰ C

1 2 mp. 111-113 ⁰ C

CF ₃ 0 mp 108-109 ⁰ C

Cl Cl

173 CH ₃ CF ₃ H

'V-Cl 1 m.p. 178-180 ⁰ C

Cl Cl

174 CH ₃ CF ₃ H

1 2 mp. 145-147 ⁰ C

Cl Cl

175 CH ₃ CCl ₂ FH

1 1 mp. 180-181 ⁰ C

Cl

Le A 23

2 " P f) "9> Λ ^ i ^ d ί £

Ex. R no.

R ^J Ar

η physical properties

Cl

CHo CCIoF H - <"> ~ C1

, y

Cl

Cl CH ₃ CClF ₂ H

Cl

Cl CH ₃ CClF ₂ H

Cl

Cl

CH ₃ CF ₃ COC ₂ H ₅

Cl

Cl

CH ₃ CF ₃ COC ₂ H ₅

Cl

Cl

Cl Cl CH ₃ CCl ₂ F COC ₂ H ₅

Cl

Cl CH ₃ CClF ₂ COC ₂ H ₅

Cl 2, mp. 162-178 ⁰ C.

1 mp 155-156 °

2 fd. 128-134 ° C

OCFo 1 mp. 60-65 ° C

CF ₃ 2 mp, 122-123 ⁰ C.

181 CH ₃ CCl ₂ F COC ₂ H ₅ - <) - OCF ₃ 2 m.p. 146-147

CFo 2 mp 172 C

CFo 1 mp 129-130 ⁰ C

Le A 23 753

Ex. R ¹ R ² R ³ Ar

No η physical properties

184 CH ₃ CClF ₂ COC ₂ H ₅ 2 m.p. 151 ^W C

185 CH ₃ CF ₃ H

1 mp. 65-70 ⁰ C

186 CH ₃ CF ₃ H

OCF ₃ 2 mp. 121-123 ⁰ C

187 CH ₃ CCl ₂ FH

OCF ₃ 1 mp. 72-76 ⁰ C

188 CH ₃ CCl ₂ FH

-OCF ₃ 2 m.p. 72-76 ⁰ C

189 CH ₃ CClF ₂ H

OCF ₃ 1 mp. 63-67 ⁰ C

190 CH ₃ CClF ₂ H

CF ₃ 2 mp. 114-115 ⁰ C

191

CH ₂ -CH ₂ -C ^v> H

) V ₁

CF ₃ 0 mp 108-110 ⁰ C

Le A 23

Ex. R ¹ R ² No.

Ar

η physical properties

192 CH ₃ CH ₃ 'H

Cl Cl

193 CH ₃ CH ₃ H

'Cl Cl

194 CH ₃ . C ₂ H ₅ H Cl Cl

195 CH ₃ C ₂ H ₅ H

196 (CH ₃ ) ₃ C CH ₃ H 'VCF, Cl Cl

Cl Cl

197 CH ₃ - <> - Cl H

// ν

198 CH-, - <> - € 1 H

199 HC ₂ H ₅ H

1 mp. 56-60 ⁰ C

2 Fd. 179-181 ⁰ C

1 Fd. 62-66 ⁰ C

2 mp 140-156 ⁰ C

0 FP 81 ° C

OFd. 72 ° C

Cl Cl

^ V-CF ₃ 2 mp. 73-78 ⁰ C

Cl

Cl - { ^X V-C1 O Fd. 61 ° C

Le A 23

e. a

Ex. R ^J no.

Ar

η physical properties

200 CH ₃ CGl ₂ FH

201 CHo CFo H

Cl

N =

Cl Cl ) Λ

NMR:

2 oil, 7.8 (s, lH) 8.2 (IH) 8.6 (IH) (CDCI ₃ / TMS)

CF ₃ 0 mp 119-123 ° C

Cl

202 H CF ₂ Cl H

2 mp. 148-150 ⁰ C

203 H H 0 CFcCl mp. 96-98 ⁰ C

204 H CF ₀ Cl H

1 p. 110-115 ⁰ C

205 H CF ₃ H

0 mp, 126 ⁰ C

206 H CFo H 2 Fp. 144 ^C

207 H CCIoF H NMR: 0 7.63 ppm (S ₇

4.35 ppm (s wide, 2H]

Le A 23 753

Ex. R ¹ R ² R ³ Ar no.

η physical properties

H CF ₃ H br \ Y, mf * TT ^1/3 208 ) Cl Cl J H CF ₃ H Cl \ ^V > -SCF ₃ 209 } Cl br

1 mp. 82-88 ⁰ C

0 mp HO-Hl ⁰ C

H CCl ₂ FH - C

0 for 110-115 ⁰ C

H . CCl ₂ FH

H

CCl ₂ FH

Cl Br

OCF _:

Cl

br

Cl

V-Br 0 Fd. 73 ⁰ C

2 m.p. 145 ⁰ C

213 H CCl ₂ FH - (VCF ₃ 1 Fp '99-112 ⁰ C

Br Br

OCF '

H CCl ₂ FH

-Br 2 mp. 132 ° C

Le A 23 753

• I. -VV * m I

Ex. R ¹ R ² R ³ Ar

No.

η physical properties

H CCl ₂ FH

Cl

Br Cl

V-F O Fp. 119 ° C

H CF ₂ Cl H

0 mp 116-118 ⁰ C

Br Cl

217 H CFpCl. H ~ < VCF ₃ 1 mp 117-118 ⁰ C

H

CCl ₂ FH

Br Br

-ζ

Cl Cl

-Br 0 mp 84-86 ⁰ C

H

CF ₂ Cl H

Br 0 mp 87-88 ⁰ C

Cl Cl H

: ι η

0 fp. 150-156 ⁰ C

Br Cl H

CCl ₂ FH

> -F 2 mp. 80-85 ° C

br

Le A 23 753

ti / c.

Ex. R ¹ R ² . No.

Ar

η physical properties

222 H

223 H

225 H

226 H

CCl ₂ FH

224 H CCl ₂ FH

CCl ₂ FH

CCl ₂ FH

Cl

Br Cl

br

vBr

CH-

Cl

Br Cl

'V-B

Cl

2 mp 165-168 ⁰ C

2 mp 170-175 ⁰ C

0 mp 125-133 ⁰ C

'V-Br 1 mp. 102-107 ⁰ C

1 p. 70-77 ⁰ C

227 H

228. H

CCl ₂ FH

CCl ₂ FH

0 mp 134-136 ° C

0 'Mp. 70 ⁰ C

Le A 23 753

- 95 -

 ~ · - mm I Sm

Ex. R ¹ R ²

No.

Ar

η physical properties

229 H

230 h

231 H

CF ₂ Cl H

CCl ₂ FH

CClF ₂ H

br

Cl

OCF

2 mp, 112-120 ⁰ C.

NMR 0 oil,

7.62 ppm (s, 1H) 4.24 ppm (s, 2H) (CDCl ₃ / TiMS)

0 Mp. 103-108 ⁰ C

232 H

CClF ₂ H

0 mp 119-122 ⁰ C

233 H CClF ₂ H

CF.

2 mp 128-133 ⁰ C

234 H CClF ₂ H

OCF ^

1 mp. 78-98 ⁰ C

235 H CClF ₂ H

) CF

2 mp. 98-103 ⁰ C

Le A 23 753

Eg no.

R ² R ³

Ar

η physical properties

236. H CCT ₂ FH

237 H CCl ₂ FH

238 H CCl ₂ FH

239 H

241 H

242 H

CCl ₂ FH

240 H CCl ₂ FH

CCl ₂ FH

br

br

Cl )

br

br

br

Br Cl

br

Cl

Cl

0 fp. 88-90 ⁰ C

Br 0 mp. 80-85 ⁰ C

1 Fd. 106-111 ⁰ C

0 fp. 1-09-113 ⁰ C

Cl O mp. 113-116 ⁰ C

Br 2 mp 80 ^° C

SCF ₃ 0 mp 114-118

Le A 23 753

Ex. R ¹ R ² R ³ Ar

η physical properties

br

H CClF ₂ H

F ₃ 1 mp. 63-70 ⁰ C

Br Br H

CF ₃ H

F ₃ 0 mp 94 ⁰ C

Cl

H CCl ₂ F CH ₃

Cl

H

CCl ₂ FH

F ₃ 2 mp. 144-150 ⁰ C

F ₃ 1 mp. 70-72 ⁰ C

Cl Cl H

CCl ₂ F CH ₃

F ₃ 1 mp 141-146 ⁰ C

Cl Cl

H CF ₃ COCH ₃

F ₃ 1 mp 103 ⁰ C

Cl Cl H

CF ₃ H

CF ₃ 0 mp 131-132 ⁰ C

Cl

Le A 23 753

Ex. R ¹ R ² No.

Ar

η physical properties

250 H CF, H

0 fp. 82-83 ⁰ C

Cl Cl

251 H

CCl ₂ FH

NO ₂ 0 mp. 137-139 ⁰ C

Cl

252 H

CF ₃ H

CF, 1 mp 55-57 ⁰ C

Cl Cl

253 H CCl ₂ FH

Cl

254 H

CF ₃ H ·

CF ₃ 1 mp 59-66 ° C

F ₃ 1 mp 133 ° C

Cl Cl

255 H

CCl ₂ FH

CF ₃ 2 mp. 107-112 ° C

Cl

256 H

CF ₃ H

CF ₃ 2 mp. 110-116 ⁰ C.

Cl

257 H CF ₃ H

F ₃ 2 mp. 108-111 ° C

Cl

Le A 23 753

£ L h CZ ί?

Ex. R ¹ R ² R ³

No.

Ar

η physical properties

258 H CCl ₂ FH

H ₃ O mp. 116-118 ⁰ C

259 H

CCl ₂ F

Cl

F Cl

F Cl

0 mp 95-97 ⁰ C

Cl

260 H

/ CH ₃ CCl H

F ₃ 0 mp 121 ⁰ C

Cl

Cl

'S ν

261 H CCl ₂ FH

(CH ₃ ) ₃ 0 mp, 150-152 ⁰ C

Cl

262 H

CCl ₂ FH

F ₃ 0 m.p. 81-83 ⁰ C

CF *

CH-

263 H

CCl ₂ FH

H ₃ 0 mp 154-156 ⁰ C

CH-

Cl

264 H CClF ₂ H

F ₃ 1 mp. 92-99 ⁰ C

Cl

Le A 23 753

Z 4 O Z ft

Ex. R ' No.

Ar

η physical properties

265 H

266 H

CF ₃ 'H

CF ₃ H

Cl Cl

0 mp 122-124 ⁰ C

0 mp 109-114 ⁰ C

267 H CClF ₂ H

268 H

270 H CCl ₂ F CH (CH ₃ ) ₂

269 H

271 H 2 mp, 125-132 ° C

1 mp. 125-127 ⁰ C.

1 mp. 208-210 ⁰ C

NiMR: 2 oil,

7.88 ppm (s, 1H) 1.07 ppm (d, 6H) (CDC 1- / TiMS)

0 fp. 166-16 9 ⁰ C

Le A 23

Ex. R ¹ R ² No.

R ^d Ar

η physical properties

Cl

272 H CF ₃ H

Br Cl

273 H CCl ₂ F COCH ₃

274 H

CF ₃ H

275 H CH (CH ₃ J ₂ H

Cl Br

Cl Cl

Cl

0 mp 127-128 ⁰ C 2 mp 164-165 ⁰ C 2 mp 135-136 ⁰ C 1 mp 60-65 ⁰ C

276 H CH ₃ Ή

0 fp. 92 ⁰ C

277 HC ₂ H ₅ H

278 H CH (CH ₃ ) ₂ H

Cl

Cl

0 m.p. 67-68 ⁰ C

0 fp. 82-83 ⁰ C

Le A 23 753

- 102 -

Ex. R No.,

Ar

η physical relations

279 H

^C 2 ^H 5

1 mp. 57-61 ⁰ C

280 H

^C 2 ^H 5

Mp 130 ⁰ C

281 H CH (CH ₃ ) ₂ H 2 mp 142 ⁰ C

282 H CH ₃ H

0 fd. 105 ⁰ C

283 H

C ₂ H ₅ H 0 Fd. 85 ° C

284 H

CH ₃ H

0 mp, 110 ° C

285 H

OHC

0 Fd. 72-73 ⁰ C

Le A 23

Ex. R ¹ R ² R no.

Ar

η physical properties

286H CH (CH ₃ ') 2H

287 H - \ / -Cl H

288 H - <f V-Cl H

289 H CH ₃ H

Cl

Cl

Cl Cl

> χ

Cl Cl

NMR:

2.24 ppm (d, 6H) 3.9 5 ppm (s, IH) 7.57 ppm (s, 1H) 7.6 6 ppm (s, 2H) (CDC1 ₃ / TMS)

Mp 155 ⁰ C

CF ₃ · 2 mp 178 ⁰ C

OCF ₃ 0 mp. 90 C ⁰

Cl

290 H

^C 2 ^H 5

Cl

H - / V - 0CF _: Cl

Mp. 79 ° C

291 H CHo H

Cl

Cl

OCFo 1 mp. 146 ⁰ C

292H CH-3H

OCF ₃ 2 mp. 124 ⁰ C

Cl

Le A 23 753

Ex. R ¹ . R ² R ^: No.

Ar η physical relations

Cl

HC ₂ H ' ₅ ^h .

Cl Cl

HC ₂ H ₅ H -C > -0CF ₃

Cl Cl

₃ ) O;

Cl Cl

H CFpCHFCl H -C

Ct \

Cl

Cl f

H CH ₂ -CH ₂ - ^ ^v > H - <"

Cl

Cl Cl

> - <

H CCl ₂ FH -C ^N > -OCF

Cl

Cl Cl

H CF ₃ H

Cl 1 Fd. 108-110 ⁰ C 2 mp 129 ⁰ C

295 H CH (CH ₃ ) O; H - <"V-OCF ₃ 0 Fp ₍ 80 ° C

0 Fd. 73 ° C

0 Fd. 68-69 ⁰ C

O,

0 m.p. 106-110 C 0 m.p. 84-87 C

Le A 23 75 3

Ex. No. Ar

η physical relations

300 h

301 H

C ₉ H ₁ .

CF,

F F

(3 -K, Pyr.) 7.75 (S / IH) (CDC1 ₃ / 1MS)

(3-H, Pyr.) 7.71 (s, 1H) (CDC1 ₃ / TMS)

302 H

303H - CCl ₉ FH

0 Fp ,. 81-87 C

CH (CH ₂ ) ₂ O mp. 130-135 ° C

304 H CF ₃ H

- <V-CF- 2 mp. 145-147 ° C

305 H CF ₃ H

-C V- CF_ 1 m.p. 66-75 ° C

306 CE ^ CF ₃ CH ₃

CF-0 mp. 64-65 ° C

♦ Le A 23

- 106 -

r * 'β ij ·? ft i -ν -J £ / £

Ex. R ^J no.

Ar

η physical relations

307 Oi ₃ CF ₃ CH ₃

Cl

* W

Cl Cl

cF ₃

1st fp. 250 "C

308 CH ₃ ^CC1F 2 ⁰ ^ * ⁹⁵ ~ ⁹⁷ ° ^α

309 CH ₃ CF CH

Cl

Cl

OCF

0 fp. 80-82 ⁰ C

310 CH-, CF CH -C ^N V-CF_ 0 m.p. 68-69 ° C

Cl

311 CH ₃ CCl ₂ F CH ₃

Cl

0 oil

^>>:; Le A 23 75 3

Application Examples

In the following application examples, the following compounds are used as comparative compounds:

CH ₃ SCH

CH.

-CH

3 '(A)

CH

CH.

1,4-Dimethy1-5-LN, N- (dimethyl) -carbamoyloxyj-3-methylthiomethylpyrazole (known from DE-OS 2 912 494)

0 M

CH ₃ -S-CH

^N W ^ 1

CH-

CH. CH.

(B)

5- [n, N- (dimethyl) carbamoyloxy] -1-methyl-3-methylsulfinylmethyl-pyrazole (known from DE-OS 2,819,932)

0 11

CH ₃ -S-CH ₂

^Nv N 0-CO-N '1C ₃ H ₇

CH. CH.

(C)

5 - [N, N- (dimethyl) -carbamoyloxy)] -1-isopropyltriphenyl-3-methylsulfinylmethylpyrazole (known from DE-OS 2,819,932), Le A 23 753

Il

CH ₃ -S-CH ₂

t i

^K N O-CO-N 'IC ₄ H ₉

CH.

CH.

5-Qn, N- (dimethyl) -carbamoyloxyj-1-isobutyl-3-methylsulfinylmethyl-pyrazole

(known from DE-OS 2 819 932)

CH ₃ -S-CH ₂

^N ¥ O-CO-N

(E]

-S-FNjN- (dimethyl) -carbamoyloxyj-3-methylthiomethyl-1-pyrazole (known from DE-OS 2 839 270)

O II

I ₃ -S-CH ₂

N O -CO-N H

CH. CH.

(F)

1-Cyclohexyl-5 - [N, N- (dimethyl) -carbamoyloxy] -3-methylsulfamoylpyrazole (known from DE-OS 2 839 270)

Le A 23 753

O Il

CH ^ -S-CH ^J II

CH.

CH.

(G)

1-Cyclohexyl-5-QN, N- (dimethyl) -carbamoyloxy] [-3-methylsulfonylmethyl-pyrazole (known from DE-OS 2,839,270)

 0.0-diethyl-O- (3-chloro-4-methyl-coumarin-7-yl) thionophosphoric acid ester (known from "Pflanzenschutz und Schädlingsbekämpfung", K.H. Buche 1, G. Thieme Verlag Stuttgart 1967, p.

Le A 23

Be i SD i e1 A 5

Phaedon larvae test

Solvent:*? Parts by weight of dimethylformamide emulsifier: * 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable active ingredient preparation, 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 being dipped into the preparation of active compound of the desired concentration and are populated with horseradish leaf beetle larvae (Phaedon cochleariae) while the leaves are still moist.

After the desired time the kill is determined in % . 100% means that all beetle larvae have been killed; 0 '/, means that no beetle larvae were killed.

In this test, for example, the following compounds of the preparation examples show superior effectiveness over the prior art: 1, 5, 7, 10, 11, 13, 14, 15, 16, 17, 18, 24, 25, 29, 31, 49, 61, 62, 78, 70, 66, 63, 90, 22, 51a, 83, 92, 38, 37, 36, 77, 247.

Le A 23, 753

LI * υ LI

- Ill - '"

Example B 5

- Plutella test,

Solvent; 7 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable active ingredient preparation, 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 being dipped into the preparation of active compound of the desired concentration and with caterpillars of the cabbage (Plutella maculipennis)

occupied as long as the leaves are still wet.

After the desired time the kill is determined in%. 100 Ά means that all caterpillars have been killed .:

0% means that no caterpillars have been killed. 25

In this test, for example, the following compounds of the preparation examples show superior effectiveness over the prior art: 3, 5, 10, 11, 12, 13, 16, 17, 21, 23, 25, 27, 29, 30, 31, 61, 68, 70, 90, 22, 51a, 83, 92, 38, 36, 77. 247.

Le A 23

- 112 -

At game C

Tetranychus test (resistant)

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 with the stated amount of solvent and the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Bean plants (Phaseolus vulgaris) which are heavily infested by all stages of development of the common spider mite or bean spider mite (Tetranychus urticae) are treated by being dipped into the preparation of active compound of the desired concentration.

After the desired time, the kill is determined in % . 100 Ά means that all spider mites are killed

were; 0 Ά means that no spider mites have been killed.

In this test, e.g. the following compounds of preparation examples superior efficiency over the prior art: 10, 11, 17, 21, 70, 66, 63, 90, 51a, 37.

Le A 23 753

Be ids iel D 5

Boundary Concentration Test / Soil Insects

Insect Insect: Phorbia antiqua Maggots in soil Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound with the stated amount of solvent _t is the indicated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

The preparation of active compound is intimately mixed with the soil. It plays the concentration of the active ingredient

in the preparation practically irrelevant, the only decisive factor is the weight of active substance per unit volume of soil, which is stated in ppm (= mg / 1). You fill the bottom in pots and leave them at room temperature

stand

 25

After 24 hours, the test animals are placed in the treated soil and, after a further 2 to 7 days, the effectiveness of the active ingredient is determined by paying out the dead and living test insects in%.

grad is 100 % . if all test insects have been killed, it is 0% if there are as many test insects as in the untreated control.

In this test, e.g. the following compounds Te

the production examples superior effect

in the prior art: 3, 10, 12, 11, 9, 66. Le A 23 753

Example E 5

Grenzkonzentra, tion test / root systemi see effect

Insect Insect: Phaedon cochleariae Solvent: 3 parts by weight of acetone 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, the indicated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

The preparation of the active compound is intimately mixed with soil. The concentration of the active substance in the additive

The decisive factor is solely the amount of active substance per unit volume of soil, which is stated in ppm (= mg / l). Fill the treated soil in pots and plant them with cabbage (Brassica oleracea). The active substance can thus be removed from the plant

roots are picked up from the ground and transported into the leaves.

/ For the proof of the root systemic effect will be

after 7 days only the leaves with the above

called test animals occupied. After another 2 days, the evaluation is done by counting or estimating the dead animals, From the killing numbers, the root systemisehe effect of the drug is derived. She is 100 %, if all

Le A 23 753

Test animals are killed and O%. if just as many test insects live as in the untreated control.

In this te's-t show 2.B. the following compounds of the preparation examples superior action over the prior art: 1, 3, 10, 12, 11, 9,

Le A 23

At saiel F 5

Limit concentration test

Test nematode: Meloidogyne incognita Solvent: 3 parts by weight of acetone 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, the indicated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

The preparation of active compound is intimately mixed with soil which is heavily contaminated with the test nematodes. It plays

· ...

the concentration of the active ingredient in the preparation practically irrelevant, the only decisive factor is the amount of active ingredient per unit volume of soil, which is given in ppm. Pour the treated soil into pots, plant potatoes and keep the pots at a greenhouse temperature of 18 ^° C.

After six weeks, the potato roots are examined for cysts-and the effectiveness of the active ingredient is determined in%. The efficiency is 100% if the infestation is completely

...

is consistently 0 'λ, when the infestation is as high as in the control plants in untreated, but equally contaminated soil.

In this test, 2.B. the following compounds the

Production examples superior effect over the

State of the art: 12

 Le A 23 753

At game G 5

LD ₁₀₀ -TeSt

Test animals: * Blatta orientalis

Solvent *: acetone 10

2 parts by weight of active compound are taken up in 1000 parts by volume of solvent. The resulting solution is diluted with further solvent to the desired concentration 'ions

 15

2.5 ml of active ingredient solution are pipetted into a Petri dish. On the bottom of the Petri dish is a filter paper with a. Diameter of about 9.5 cm. The Petri dish will remain open until the

on,

Solvent has completely evaporated. Depending on the concentration of the active ingredient solution, the amount of active ingredient per m 2 of filter paper varies. Then add the indicated number of test animals to the Petri dish and cover with a glass lid. 25

The condition of the test animals is checked 3 days after preparation of the experiments. The kill is determined in%. This means 100 '/., That all test animals were killed; 0 % means that no test animals were killed

In this test, e.g. the following compounds of Preparation Examples superior effect over the prior art: 3, 10, 11, 16, 25.

Le

At game H

Test animals; Sitophilus granarius

Solvent: acetone 10

2 parts by weight of active compound are taken up in 1000 parts by volume of solvent. The resulting solution is diluted with additional solvent to the desired concentrations

 15

2.5 ml of drug solution are pipetted into a Petri dish. On the bottom of the Petri dish is a filter paper with a diameter of about 9.5 cm. The Petri dish will remain open until the

Solvent has completely evaporated. Depending on the concentration of the drug solution, the amount of active ingredient per m ^ filter paper is different levels. Then add the indicated number of test animals to the Petri dish and cover with a glass cap. 25

The condition of the test animals is checked 3 days after preparation of the experiments. The death in V is determined. 100% means that all test animals were killed; 0 Vt means that no test animals were killed. 30

In this test, e.g. the following compounds of Preparation Examples superior effect over the prior art; 3, 10, 11, 12, 16, 17, 18, 24, 25,

27, 28, 29, 30, 31, 49, 61

 35

Le A 23 753

Example I 5

Test with Lucilia cuprina larvae (QP res. Goondiwindi strain)

Emulsifier: 35 parts by weight of ethylene glycol monomethyl ether

35 parts by weight of nonylphenol polyglycol ether

To prepare a suitable active ingredient preparation, three parts by weight of active compound are mixed with seven parts by weight of the abovementioned solvent mixture, and the concentrate thus obtained is diluted with water to the particular desired concentration.

Approximately 20 Lucilia cuprina res.-larvae are placed in a test tube containing approximately 1 cm ³ horse meat and 0.5 ml of the active ingredient preparation. After 24 hours, the kill rate is determined.

In this test, e.g. the following compounds of the preparation examples superior effect over the prior art. 5, 10, 11, 12, 22, 23, 25, 27, 29, 30, 35, 36, 37, 38, 39, 66, 67.

Le A 23 753

• ü. ^ " ^» 4Sm M

With so much K 5

Test with Boophilus microplus resistant / QP-resistant Biarra strain

Solvent *: 35 parts by weight of ethylene glycol monomethyl ether

35 parts by weight of nonylphenol polyglycol ether

To prepare a suitable preparation of active compound, three parts by weight of active compound are mixed with seven parts by weight of the abovementioned solvent mixture, and the concentrate thus obtained is diluted with water to the desired concentration.

10 adult Boophilus microplus res. are immersed in the test drug preparation for 1 minute. After conversion into plastic cups and storage in an air-conditioned room, the degree of kill is determined.

In this test, e.g. the following compounds of the preparation examples superior effect over the prior art: 5 »10, 11» 12, 23, 25, 27, 36, 37, 38, 39, 66, 67.

Le A 23 753

Let's play L 5

Facefly test (Musca autumnalis)

Solvent: 35 parts by weight ethylene glycol monomethyl

ether 35 parts by weight Nonylphenolpolyglykolether

In order to prepare a suitable formulation, three parts by weight of active compound are mixed with seven parts of the abovementioned mixture, and the emulsion concentrate thus obtained is diluted with water to the particular desired concentration.

Ten adult faceflies (Musca autumnalis) are placed in petri dishes, the filter paper discs corresponding

Contain large quantities soaked in 1 ml of the active compound preparation to be tested one day before the start of the test. After 3 hours, the degree of kill is determined in percent. where 100% mean that all and 0% mean that no flies

have been killed

 25

In this test, e.g. the following compounds of the preparation examples superior effect over the prior art: 22, 25, 35, 36, 38.

Le A 23 753

At saiel M 5

Test with PsoroDtes ovis

Solvent: 35 parts by weight ethylene glycol monomethyl

ether

* ^ 35 parts by weight of nonylphenolpolyglycol

ether

To produce a suitable preparation of active compound, three parts by weight of active compound are mixed with seven parts by weight of the abovementioned solvent mixture, and the concentrate thus obtained is diluted with water to the desired concentration.

Approximately 10-25 Psoroptes ovis are made up into 1 ml of the active ingredient to be tested, which have been pipetted into a low-density tablet nests. After 24 hours, the degree of destruction is determined. _; ,

In this test, e.g. the following compounds of the preparation examples superior effect over the prior art: 25,. 35, 38, 66, 67.

Le A 23 753

Example N 5

Test with parasitic adult biting flies (Stomoxys calcitrans)

Solvent ": Cremophor 10

To prepare a suitable preparation of the active ingredient, the active substance in question is mixed with the specified solvent. in the ratio 1: 2 and the resulting concentrate is diluted with water to the desired concentration.

10 adult lentils (Stomoxys calcitrans) are grown in Petri dishes containing sandwiches containing 1 ml of the active substance to be tested one day before the start of the experiment.

, After 3 hours, the percent kill rate is determined, where 100 X means that all and 0 % means that no fly has been killed.

· ·

In this test, e.g. the following compounds of the preparation examples superior effect over the prior art: 66,

Le A 23753

At game P

Nematodes in vitro test

The killing and inhibition of the proliferation of the nematode Caenorhabditis elegans in liquid medium in the presence of bacteria (E. coli), which nourish the nematodes, is tested.

The substances to be tested are added to the cultures and the resulting impairment of reproduction as

nematocidal effect evaluated. Indicated is the concentration t which prevents the propagation. -

In this test, e.g. the following compounds of the preparation examples an at least 95% inhibition of the multiplication of the nematode C. elegans

at a concentration of <100 μg / ml: 5, 7, 8, 10, 12, 13, 14, 15, 16, 17, 18, 19, 23, 25, 27, 28, 29,

at a concentration of ± 10 μg / ml: 30, 36,

Le A 23

Claims (5)

Experience san spruc.h 1. insecticidal, acaricidal and nematicidal agents, characterized by a content of at least one S-aminopyrazole of the general formula - (I). IT ι. " ' N ...> - HH-R ³ A r in which -1 ' K is hydrogen, alkyl or haloalky1, R 1 is alkyl, haloalkyl, optionally substituted aralkyl or optionally substituted aryl, "" for hydrogen, alkyl or a kost stands, jl Ar is each optionally substituted phenyl or pyridyl, and π is a number 0, 1 or 2, in which X is oxygen or sulfur and - 125 - R is hydrogen, AlIo / 1, alkenyl, alkynyl, Halogenalky1, alkoxalkyl, alkylthioalkyl, optionally substituted cycloalkyl, optionally substituted aryl, alkoxy, alkylthio, optionally substituted AryJLoxy, optionally substituted Ärylthio, for alkylarnino, for dialkylamino or for optionally substituted arylamino in addition to extenders and / or surface-active agents. , 2. Insecticidal, acaricidal and nematicidal agents according to item 1, characterized in that in the general formula 1 R ~ is in each case straight-chain or branched alkyl or halogenoalkyl having 1 to 4 carbon atoms and optionally 1 to 9 identical or different halo atoms or hydrogen, R * "is in each case straight-chain or branched alkyl or haloalkyl having in each case 1 to 8 carbon atoms and optionally 1 to 17 identical or different halogen atoms, or in each case optionally mono- or polysubstituted is identical or different or substituted phenylalkyl or phenyl having optionally 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety, suitable phenyl substituents being in each case: halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl, Alkylsulfonyl, haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl having in each case 1 to 4 carbon atoms in the individual alkyl moieties and optionally 1 to 9 identical or different halogen atoms, R is hydrogen, straight or branched Is alkyl having 1 to 4 carbon atoms or is a radical -CR ⁴ , in which
25 X is oxygen or sulfur, and R ^{4 is} hydrogen, for each straight-chain or branched alkyl, alkenyl, alkynyl. alkoxy alkyl, alkylthioalkyl, alkoxy, alkylthio, alkyl amino, dialkylamino or Haloqenalkyl each having up to 4 carbon atoms in the individual alkyl moieties and in the case of the haloalkyl having up to 9 identical or different Halogen atoms, in addition to Le A 23 753 or phenyl, phenoxy, phenylthio or phenylamino which is monosubstituted, polysubstituted or disubstituted by halogen, lower alkyl or lower haloalkyl, and each optionally mono- or polysubstituted, identically or differently substituted phenyl, phenoxy, phenylthio or phenylamino, where as phenyl substituents at R ^ mentioned in question, Ar is in each case optionally monosubstituted or polysubstituted, identically or differently substituted phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl, suitable substituents being: cyano, nitro, halogen, in each case straight-chain or branched alkyl, alkoxy or Alkoxycarbonyl having in each case up to 4 carbon atoms also each straight-chain or branched haloalkyl or halogenoalkoxy having in each case up to 4 carbon atoms and up to 9 identical or different halogen atoms or a radical -S (O) _m -R ⁵ in which R for amino, as well as for each straight-chain or branched alkyl, alkylamino, dialkylammo or Haloalkyl having in each case up to 4 carbon atoms in the individual alkyl moieties and in the case of the haloalkyl having up to 9 identical or different halogen atoms, 35 Le A 23 753 rn is a number O ₁ i or 2 and η is also a number 0, 1 or 2r . 3. A method for controlling insects, arachnids and nematodes, characterized in that 5-aminopyrazoles of the formula (I) act on insects, arachnids and nematodes and / or their habitat IaBt. 4. Use of 5-Arninopyrazolen the general formula- (Ϊ) according to item 1, characterized in that they. used for controlling insects, arachnids and nematodes. · "" - 5. A process for the preparation of insecticides, okarizidsn and nematizicisn means, characterized in that ma, η 5-aminopyrazoles according to formula (I) mixed with extenders and / or surface-active agents.