DE1668025C3 - Phenylhydrazones of 1,2-dicarbonyl compounds - Google Patents

Description

<f> -N - N = C (V)

C-Y

Ii

in which Y, Z and m have the meaning given above and Hal stands for halogen, optionally in the presence of solvents with alkali metal salts of the general formula

MeX '

(VI)

in which Me stands for an alkali metal and X 'for cyano.

3. Use of phenylhydrazones according to claim 1 for combating insects and Acarina.

On

(ID

in which Z and m have the meaning given above and An for a at the 3; Anion that occurs diazotization is, if appropriate in the presence of diluents, with active methylene compounds of the general formula

H, C

(UI) The present invention relates to the subject matter characterized in the patent claims.

It has already become known that certain phenylhydrazones of dicyanoketone, eg. B. "A-Dicyano carbonyl-ZS-dichlorophenylhydrazone, to combat of insects and mites can use (see FIG. US Pat. No. 3,157,569).

It has been found that the new phenylhydrazones of the general formula

C-Y

Il

in which X and Y are as defined above, or b) diazotization products of amines according to Formula II with 2-halo-1,3-dicarbonyl compounds of the formula

fS — N — N = c '

C-Y

CH ₃ CO

Shark

\
CY

Il

in which X stands for chlorine, cyano or nitro, Y for alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 3 carbon atoms, Z for alkyl with 1 to 4 carbon atoms, chlorine, nitro, trifluoromethyl or trifluoromeate 50 thylmercapto and m a whole Number from 1 to 4 means, both as free compounds and in the form of their alkali salts, alkaline earth salts and amine salts, have strong insecticidal and acaricidal properties.

ss It has also been found that the phenylhydrazones of the formula (I) are obtained if a) diazotized amines of the general formula

(IV)

On

(Π)

in which Y has the meaning given above and Hal stands for halogen, optionally in The presence of diluents or converts

in which Z and m have the meaning given above and An stands for an anion occurring in the diazotization, given

if in the presence of diluents, with active methylene compounds of the general formula

H, C

(111)

CH ₃ CO shark

/ \
H CY

Il ο

(IV)

c) Phenylhydrazone compounds of the general formula

Hal

/ ~ Vn-n = i

(V)

C-Y O

in which X and Y have the meaning given above, converts or

b) diazotized amines of the general formula II with 2-halogen-1,3-dicarbonyl compounds d-sr in general formula

C-Y

Il
ο

in which Y, Z and / n have the meaning given above and Hai stands for halogen, optionally in the presence of solvents with alkali salts of the formula

MeX '

(VI)

in which Y has the meaning given above and Hal stands for halogen, optionally in Reacts presence of diluents or in which Me for an alkali metal and X 'for Cyano stands, implements.

It should be noted that the starting materials (V) of process fc) according to processes (a) and (b) can be produced.

It can be described as extremely surprising that the phenylhydrazones according to the invention are a have stronger insecticidal and acaricidal effectiveness than the chemically very similar prior art Phenylhydrazones.

If one uses 3,5-bistrifluoromethylaniline, which in Phosphoric acid was diazotized with nitrosylsulfuric acid at 0 to 10 °, and methyl cyanoacetate as Starting materials, the course of the reaction in process (a) can be carried out by the following reaction scheme be reproduced:

IF ₃ C

CN

To + CH,

CO ₂ CH ₃

N-N = C

CN

CO ₂ CH ₃

(VI)

If you use 2-chloro-5-trifluoromethyl-aniline, which can vary further phenylhydrazone,

was diazotized in concentrated hydrochloric acid with NaNO2 The course of the reaction according to method (b) and (c]

and (X-chloroacetylacetone as starting materials, 45 is given by the following equation:
one a hydrazone, which z. B. with KCN to one

N-N =

Cl

COCH,

COCH ₃

(VIII)

The starting material used for the process (a) and (b) used for the process (c) 0

Starting materials (II), (III) and (IV) as well as those for the 65 is obtained according to processes (a) and (b).

Process (c) used starting materials (VI) are Processes (a) and (b) are practically under d <

already known and can be carried out according to the same reaction conditions known per se.

Process can be produced in a simple manner. The diluents are water and rr

Water-miscible organic solvents in question. These include alcohols such as methanol and ethanol as well as acetic acid. The organic diluents serve as solubilizers for the methylene component. The implementation itself is preferably in carried out in a pH range of 4 to 8 To buffer the mineral acids, bases such as Sodium acetate, sodium carbonate or sodium hydroxide added

The reaction temperatures are generally between -20 and + 30 °, preferably between -10 and + 20 °.

When carrying out the reaction, it is expedient to use equimolar amounts of the starting materials Ratios, optionally the methylene component in a slight excess. The reaction is in generally ended after 2 to 6 hours, in which case it is expedient in some cases to continue for a few hours to stir at room temperature. The phenylhydrazones are generally obtained in crystalline form and can be isolated by filtering off from the reaction mixture.

The procedure (c) is carried out in a similar manner. The same solvents and solvent mixtures are used. However, the pH value does not play a role here. The temperatures are in general between 0 and 80 ° C, preferably between 20 and 7O ⁰ C.

The phenylhydrazones obtained by the three processes can be converted into their alkali metal salts in the usual way, Alkaline earth salts and amine salts are transferred. The sodium, potassium, calcium, Magnesium, triethylamine and ethylaniline salts.

The preparation of these solutions is carried out in the usual way, for. B. by dissolving the phenylhydrazones in organic solvents such as alcohols and addition of the bases. The salts are usually sparingly soluble and precipitate, but they can also be mixed with ether be precipitated. It is also possible to evaporate the solvent.

The active compounds according to the invention have strong insecticidal and acaricidal properties with low phytotoxicity Effects on. The active ingredients can therefore be used with good success in combating harmful sucking and biting insects, dipteras and mites (Acarina) can be used.

The sucking insects mainly included aphids, such as the peach aphid (Myzus persicae), the black bean aphid (Doralis fabae); Scale insects such as Aspidiotus hederae, Lecanium hesperidum, Pseudococcus maritimus; Thysanoptera such as Hercinothrips femoralis, and bed bugs such as the beet bug (Piesma quadrata) and the bed bug (Cimex! ectularius).

The biting insects essentially include caterpillars such as Plutella maculipennis, Lymantria dispar; Beetles, such as grain beetles (Sitophilus granarius), the Colorado potato beetle (Leptinotarsa decemlineata, but also species living in the ground such as the Wireworms (Agriotes sp.) And white grubs (Melolontha melolontha); Cockroaches, like the German one Cockroach (Blattella germanica); Orthoptera such as the cricket (Gryllus domesticus); Termites, such as Reticul - termes; Hymenoptera, like ants.

The Diptera include in particular the flies, such as the deaf fly (Drosophila melanogaster), the Mediterranean fruit fly (Ceratitis capitata), the housefly (Musca domestica) and mosquitoes such as the mosquito (Aedes aegypti).

Among the mites, the spider mites (Tetranychidae), like the common spider mite, are particularly important (Tetranychus urticae), the fruit tree spider mite (Paratetranychus pilosus); Gall mites, such as the currant gall mite (Eriophyes ribis) and tarsonemids, the Tarsonemus pallidus, and ticks. The effects set in quickly and last a long time.

If the phenylhydrazones are used in the form of their salts, their effectiveness changes

ι ο general only extremely slightly.

The active compounds according to the invention can be converted into the customary formulations, such as Solutions, emulsions, suspensions, powders, pastes and granulates. These are done in a well known manner manufactured, e.g. B. by mixing the active ingredients with extenders, so liquid solvents and / or solid carriers, optionally with the use of surface-active agents, that is to say emulsifiers and / or dispersants. In the case of use of water as an extender can be, for. Stomach organic solvents can be used as auxiliary solvents. The liquid solvents are im essential in question: aromatics, such as xylene and benzene, chlorinated aromatics, such as chlorobenzenes, paraffins, such as Petroleum fractions, alcohols such as methanol and butanol, sfjrk polar solvents such as dimethylformamide and Dimethyl sulfoxide, as well as water; as solid carrier materials: natural stone powder, such as kaolins, clays, Talc and chalk, and synthetic rock flour, such as finely divided silica and silicates; as emulsifiers: non-ionic and anionic emulsifiers, such as Polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ether. Alkyl sulfonates and aryl sulfonates; as a dispersant: e.g. B.

Lignin, sulfite peeling, and methyl cellulose.

The active compounds according to the invention can be used in the formulations as a mixture with other known ones Active ingredients are present. The formulations generally contain between see 0.1 and 95 percent by weight of active ingredient, preferably wise between 0.5 and 90.

The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsions ns, suspensions, powders, pastes and granulates be applied. The application happens in usual way, e.g. B. by pouring, spraying,

Dust, scatter or mist. The active ingredient concentration in the ready-to-use

gen preparations can vary over a larger area. Generally it is between 0.001 and 5%. When applying according to certain modern methods, however, it can also be very concentrated Active ingredient preparations are used. With these is the active ingredient content ζ. Β. between 20 and 80%.

Example A. Plutella test

Solvent:

3 parts by weight of dimethylformamide.

Emulsifier:

1 part by weight of alkylaryl polyglycol ether.

For the production of an appropriate drug additive

1 part by weight of active ingredient is mixed with the preparation specified amount of solvent that the specified

Contains amount of emulsifier and dilutes the concentrate

with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation of active compound and are filled with dew Cabbage moth caterpillars (Plutella maculipennis).

After the specified times, the degree of destruction is determined in%. 100% means that all Caterpillars were killed while 0% indicates that no caterpillars were killed.

Active ingredients, active ingredient concentrations, evaluation times and results are based on the following Table shows:

table

(phytosanitary insects) Active ingredients

Active ingredients

Active ingredient oil concentration tralion in "., in".;. according to .V

"5

Cl

(known)

CN

CN

0.2
0.02

100 0

Cl

CN

-NN = C
I.
H

Cl

Ci

° 2 ^ \ / -NN = I

Cl

0.2 100 C-OC ₂ H,
Il 0.2 100 Il
O CN 0.2 KM) C-OC ₂ H ₅ 0.02 100 Il
O

Cl

C.

F ₃ C

CN

N-N = C 0.2

!, V-OCH, ° ⁰²

CN

J-N = C 0.2

V-OC ₂ H ₅ ° - ⁰²

Il ο

100 HX)

KX) 100

CN

-NN = C ^X 0.2 HH)

"0.02 100

H. 0 ^{a (X) 2 I0} °

.15

40

45

F ₁ C

JNN = C
i
H

J-N = C

egg

^C1

J-N = C

Cl -

CN
V-OC ₁ H,

Il "' ο

Cl
C-CH,

Il ' ο

egg

C-CH,

Il ο

Cl
COC ₂ H,

ti

Effective

sloff- lot ul

con / en- urad

nation in%

in "n after

0.2 K) O 0.02 K) O O. (X) 2 80

0.2 HX) 0.02 HX) O. (X) 2 50

0.2
0.02

0.2
0.02

KX) HX)

HX) HX)

Cl N- CN N-C CCH,
i | N = C ^ C-C (CH,), N = C C-CH .. N = C ⁷ 0.2 HX) I. Il
O Il O CC (CH,),
I! 0.02 HX) H O ■ o O. (X) 2 60 CN CN CN Γ
C \ N = C
VC (CH,),
Il O Cl N- CN 0.2 100 L. H 0.02 HX) <V r Cl N- 0.2 KX) I.
H 0.02 KX) Cl Cl I.
H 0.2
0.02 J (X)
HX) J- Cl N CD KX) H 0.02 100 J ~. CF,

609

Fnrlsct / ung

Effective Ah- MofT- UiIlIIlL ¹ S- lialion III ",, in "ii after 3 ^y

F ₁ C

Cl

NN = C

CN

C C (CH,),

il
O

0.2 0.02

100 KK)

CN

F ₁ C Ss

NN = C
I.
H

0.2

0.02

O. (X) 2

KK)

K) O

90

Example B Phaedon larvae test ^2S

Solvent:

3 parts by weight of dimethylformamide.

Emulsifier:

I part by weight of alkylaryl polyglycol ether.

To produce a suitable active compound preparation, 1 part by weight of the relevant compound is mixed more active. Substance with the specified amount of the respective solvent, which is the above Amount of emulsifier contains, and dilute the concentrate obtained with water to the desired concentration.

With this active ingredient preparation, cabbage leaves are made (Brassica oleracea) sprayed to runoff and then with mustard beetle larvae (Phaedon cochleariae) occupied.

The degree of destruction of the pests is determined after the times given in the table below and expressed in% where 100 means that all and 0% means that none of the beetle larvae have been killed became.

Tested active ingredients, applied active ingredient concentrations, evaluation times and obtained test results are shown in the following table:

table

(plant damaging insects)

Active ingredients

Effective

substance killing

concentration *

tration in%

in% after ¥

55

60

CN

0.2 0.02

100 0

(known)

10

', -N-N = C

Cl

<f V

Cl

CN

COCH,
O

CN

Effective

MMfT-

kon / cn
iration
in "ι.

0.2
0.02

0.2
0.02

CN

o ₂ -CH ₃

CN

0.2

0.02

0.002

0.2
0.02

0.2
0.02

0.2
0.02

0.2
0.02

N-N = C

CO ₂ -C ₂ H ₅

0.2
0.02

sirail in '11 after.'

1Ö0 JtX) ₁

Example C Tetranychus test

Solvent:

3 parts by weight of dimethylformamide.

Emulsifier:

1 part by weight of alkylaryl polyglycol ether.

To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the ro specified amount of solvent that contains the specified amount of emulsifier and dilutes the concentrate with water to the desired concentration.

With the preparation of the active substance bean plants (Phaseolus vulgaris), which are approximately 10 up to 30 cm, sprayed dripping wet. These bean plants are strong at all stages of development Bean spider mite (Tetranychus telarius) infested.

After the times given, the effectiveness of the active compound preparation is determined by the counts dead animals. The degree of destruction obtained in this way is given in%. 100% means all Spider mites have been killed, 0% means that no spider mites have been killed.

Active ingredients, active ingredient concentrations, evaluation times and results are based on the following Table shows:

Active ingredients

12th

N-N-C

N-N = C

N-N = C

Effective
sloff-
con / en-
(ration
in % away
killing
Degree
in %
after 3 ^y CN C-OCH ₃
Il 0.2
0.02 98
90 Il
O CN C-OC ₂ H ₅ 0.2
0.02 100
100 Il
O CI 0.2
0.02 100
60

table
(plant-damaging mites)

Active ingredients

Cl

CN

Cl

(known)

N-N = C

CN

" ¹ C-OCH ₃ O

Active Abstoff- kill concentrated degrees concentration in% in% after 8 ^J

0.2 0.02

0.2 0.02

70 0

90 60

40

45 -N-N = C

C-CH ₃

VN-N =

C-CH ₃

-N-N = C

0.2
0.02

0.2
0.02

0.2
0.02

0.2
0.02

100 60

100 98

100 98

98 70

0.2 0.02

98 80

0.2 100

° ^{'02 10} ° 0.002 50

55

60

N-N = C

N-N = C

Cl

0.2

0.02

0.002

0.2
0.02

100

100

50

100 60

13th

continuation

Active ingredients

Effective substance / cn- (ration
in %

Cl

0.2
0.02

Away-

loluiigsgrad in% after 8 ''

100 60

Active ingredients, active ingredient concentrations, evaluation times and results are based on the following! Table shows:

0.2

100

0.02 70

0.2 100 0.02 98

0.2 100 0.02 80

CN

F ₃ CS

N-N = C

CO ₂ -CH ₃

0.2
0.02

100 90

Example D Tetranychus test (resistant)

Solvent: Parts by weight of dimethylformamide.

Emulsifier:

Part by weight of alkylaryl polyglycol ether.

To prepare an appropriate preparation of active ingredient, 1 part by weight of active ingredient 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.

With the preparation of the active substance bean plants (Phaseolus vulgaris), which are approximately 10 to 30 cm, sprayed until dripping wet. These bean plants are strong with all stages of development common spider mite or bean spider mite (Tetranychus urticae).

After the specified times, the killing is carried out in % determined 100% means that all spider mites have been killed; 0% means that none Spider mites have been killed.

table Mites) Effective Away- (plant damaging sloff- soldering Tetranychus test kon / cn- urad WiikslolTc iraiion in % in "u after S days

NH-N = C

^ ^ NH-N = C ⁷

NH-N = C

CN

Vn

NO ₂
COCH ₃
NO ₂
COCH ₃

0.2
0.02

0.2
0.02

0.2
0.02

100
70

100
60

example 1

115 g of 3,5-di-trifluoromethylaniline are dissolved in 400 m of 85% H ₃ PO ₄ with 157.5 g of 41 o / cent Nitrosylschwefel acid at 5 to 10 ⁰ C diazotized. After the diazotization has taken place, the mixture is diluted with 1 liter of water and filtered. This diazonium salt solution is poured into a «

Mixture of 49.5 g of cyanoacetic acid methyl ester in 1 50% acetic acid and 1.1 kg of sodium acetate unte stirring at 0 to 10 ⁰ C is added dropwise through the addition of aqueous wide Natriumacetatiösung maintaining a pH of 5 in the mixture. After completion *

the addition of the diazonium salt solution is stirred for a further 1 hour, the precipitated product is filtered off with suction and unc washed with several liters of water. The residue is taken up in methylene chloride over sodium dried sulfate and after distilling off;

Methylene chloride residue obtained from wash basins Zin recrystallized. 136 g (80% of theory) are obtained. Cyano-carbomethoxy-carbonyl ^^ - bisttrinuormethyl) -phenylhydrazone as light yellow needles with a melting point of 155 °.

Example 2

Cl

CN

Cl

/ Y-N-N-c '

COC ₂ H ₅

Il

98.5 g of 2,4,5-trichloroaniline are diazotized in 400 ml of concentrated H2SO4 (</ = 1.84) with 157.5 parts of 41% nitrosylsulfuric acid at 5 to 10 ^{° C.} After diazotization, the mixture is diluted with chopped ice and filtered. This diazonium salt solution is then added dropwise at 0 to 15 ° C with stirring to a mixture of 57 g of ethyl cyanoacetate, 250 ml of acetic acid, 1.5 l of ice water and 2 kg of sodium acetate. A pH of 4 to 5 is maintained in the mixture by further addition of sodium acetate. Then it is diluted with 1 liter of water and stirred for 1 hour. The precipitated product is filtered off with suction and the reaction product is separated from inorganic salts by taking up with methylene chloride. After drying and distilling off the methylene chloride, 122 g (76% of theory) of cyano-carboethoxy-carbonyl ^ AS-trichloro-phenylhydrazone are obtained. Recrystallized from ethanol, yellow needles with a melting point of 133 ° to 134 °.

amide and dissolved in a solution of 7.1 g (0.11 mol) KCN and 5.6 g (0.1 mol) of KOH in 750 ml of water were added dropwise at room temperature with vigorous stirring. After the addition has ended, the mixture is stirred for 15

After 5 minutes, activated charcoal is added, the filtrate is filtered and acidified with glacial acetic acid. The precipitate is sucked off, washed with water and dried. 41.0 (85%) <x -cyano-α-acetylcarbonyl-2-chloro-5-trifluoromethylphenylhydrazone are obtained in the form of a light yellow powder,

which can be recrystallized from ethanol for purification. 114 to 118 °.

In a manner analogous to that described in Examples 1 to 4, the following! links can be produced according to formula (I):

Example 3

NH-N = C _n

Cl

CCH ₁

195.5 g (1 mole) of ^ -chloro-S-trifluoromethylaniline dissolved in 560 g of concentrated hydrochloric acid. The hydrochloride partially precipitates. The suspension is added 1.8 kg of ice and 1.21 of water and diazotized rapidly at 0 ° with 72 g (1.05 mol) of sodium nitrite in 160 ml of water.

The solution of the diazonium salt is filtered and added dropwise to 5 ⁰ C to a mixture of 134.5 g (1 mol) "-Chloracetylaceton in 600 ml of ethanol and 500 g of potassium acetate in 800 ml of water from 0. During the coupling, the pH was kept at about 6 by adding more potassium acetate. The cooling is removed and the mixture is stirred for 4 hours, filtered off with suction, washed thoroughly with water and recrystallized from ethanol. 183 g (61%) of a- (chloro - «- acety'carbonyl-2-chloro-5-trifluoromethyo-phenylhydrazone are obtained as light-colored crystals with a melting point of 151 to 153.degree.

Example 4

NH-N = C

CN

COCH,

29.9g (0.1 mole) α-acetyl-α-chlorocarbonyl ^ -chlor-S-trifluoromethylphenylhydrazone (shown as described in Example 3) are in 300 ml of dimethylform-

No. X Y Z M.p. "C 5 CN -OC2H5 2-CI. 5-CFi 120 to 124 20th 6th CN -OCH 3 2-CI. 5-CFi 143 7th CN -OCH3 2.4,5-CI i 197 8th CN -OC2H5 3.5- (CFi) :; 154 9 CN -UC2H5 2.6-CI2, 4-NO: 14t) to 147 10 CN -OCH3 2.6-CI2, 4-NO. ' 159 to 160 25th 11th CN -OC2H5 2.5-C12. 4-NO> 157 12th CN -OCH3 2.5-CI2, 4-NO: 168 13th CN -OC2H5 2,4-NO2 183 to 184 14th CN -OC2H5 2-CHi. 6-NO2 142 to 146 15th CN -OC2H5 2-CI. 4-CFi 146 30th 16 CN -OC2H5 2.6-O2. 4-CFi 116 to 117 17th CN -OCH3 2,6-Cl2. 4-CFi 122 18th CN -OC2H5 2.3.4.5-CI4 139 19th CN -OC2H5 2-CFi 117 to 118 20th CN -OCH3 2-CFi 156 to 157 35- 21 CN -OC2H5 3-CF. 126 22nd CN -OCH3 3-CFi 103 23 CN -OC2H5 4-CFi 135 to 136 24 CN -OCH3 4-CFi 115 25th CN -OC2C5 3-CFi, 4-CI 151 40 26th CN -OCH3 3-CFi. 4-CI 149 27 CN -OCH3 2-CFi, 4-CI 173 to 174 28 CN -OC2H5 2-NO2, 4-CFi 141 29 CN -OCH3 2-NO2, 4-CFi 172 30th CN -OCH3 2-CN, 5-CI 169 45 31 NO2 -OCH3 3,5- (CF3) 2 133 to 134 32 NO2 -OC2H5 3,5- (CFi) 2 ; 07 to 109 33 CN -CHs 3,5- (CFi) ₂ 154 to 158 34 CN -CHs 2.6-CI2. 4-NO2 106 to 111 35 Cl -CH ₃ 2-CI 135 to 136 50 36 Cl -OC2H5 2-CI 92 to 94 37 Cl -CHi 4-CI 160 to 172 38 Cl -CH3 3,4-Cl ₂ 224 to 225 39 Cl -OC2H5 3,4-Cl2 158 to! 59 40 Cl -OC2H5 2-CI, 5-CF3 114 to 115 55 41 Cl -CHi 2.4,5-Ch 145 42 Cl -CH3 3,5- (CFi) ₂ 184 to 187 43 Cl -OC2H5 3,5- (CFi) ₂ 122 to 124 44 Cl -CH3 2,6- (CH3) 2 72 to 74 45 Cl -OC2H5 2,6- (CH 3) 2 42 to 43 60 46 CN -OCH3 3,5- (CFi) 2 235 dec. K-SaIz 47 NO2 CHi 2-CI 118 48 NO2 CHi 4-CI 172 to 174 49 NO2 CHi 2-CI, 5-CFi 138 to 140 65 50 NO2 CHi 2,6- (CH 1) 2 107 to 110 51 NO2 -OCH) 2-CI, 5-CFi 149 to 151 52 NO2 -OC2H5 , 2,4,5-Oi 117 to 119 53 CN CHi 2-CI. 5-CFi 114 to 118

continuation X Y Z M.p. C. 5 No. X Y Z M.p. "C No. CN CH3 H 172 to 175 72 CN CH3 2,6- (CH 3) 2 125 to 129 54 CN CH3 4-Cl 228 to 231 73 CN CH 3 2,4,6- (CH 3) 3 86 to 88 55 CN CH3 2-CI 117 to 119 74 CN CH3 2.6 (C2H5) 2 72 to 73 56 CN CH3 3-Cl 188 to 190 IO 75 CN QCH ₃ ) S. 3-Cl 156 to 157 57 CN CH3 3,4-Cb 202 to 203 76 CN C (CHs) ₃ 3.5 Ch 227 to 228.5 58 CN CH3 3,5-Cb 218 to 223 77 CN QCHj) ₃ 3,4-Ch 216 to 218 59 CN CH3 2,4,5-Ch 138 to 140 78 CN QCHs) ₃ 2-CFs, 4-Cl 145 to 147 60 CN CH3 2-Cl, 6-CHs 115 to 118 79 CN QCHs) ₃ 2-CI, 5-CF3 Iü3 to 164 61 CN CH3 2-CHs, 4-Cl 145 to 147 15th 80 CN QCH 3) 3 2-CH3, 4-Cl 173 to 176 62 CN CH3 2-CFs, 4-Cl 109 to 110 81 CN QCH3) 3 (CFs) ₂ 124 to 128 63 CN CH3 2-NO2 199 to 201 82 CN QCHs) 3 2,4,5-Ch 158 to 161 64 CN CHs 4-NO2 268 to 269 83 CN CH ₃ 4 SCFs 155 to 159 65 CN CH3 3-Cl, 4-NO2 222 to 223 84 CN CH3 2 SCFs 78 to 83 66 CN CH3 3-NO2, 4-Cl 247 to 248 20th 85 CN OC2H5 2-CF ₃ , 4-Cl 98 to 100 67 CN CH3 2-NO2, 4,6-Cb 95 to 96 86 CN OC2H5 3.5-CJ2 131 to 135 68 CN CH3 2,5-Cb, 4-NO2 176 to 178 87 CN OCH 3 3.5 Ch 195 to 197 69 CN CH3 2,4- (NO2) 2 150 to 151 88 CN OCH 3 4-SCF ₃ 128 70 CN CHj 2-CHj, 3-NO2 149 to 150 89 CN OCH 3 2-S-CFs 99 to 100 71 90 CN C (CH 3) 3 4-S-CFs 88 to 99

Claims (2)

Claims: c) Phenylhydrazone compounds of the formula 1. Phenylhydrazones of 1 ^ -dicarbonyl compounds of the general 5 formula "* (D in which X is chlorine, cyano or nitro, Y is alkyl with 1 to 4 carbon atoms or alkoxy with up to 3 carbon atoms, Z is alkyl with 1 to 4 carbon atoms, chlorine, nitro, trifluoromethyl or trifluoromethylmercapto and m is an integer from 1 to 4 means 2. Process for the preparation of phenylhydrazones of 1,2-dicarbonyl compounds, characterized in that one
a) diazotized amines of the general formula Shark