DE1940032B - Substituted N phenyl succimmides, process for their preparation and their use as fungicides - Google Patents

Description

The invention relates to new substituted N-phenylsuccinimides of the general formula I.

R ₁

K ₂ LC \

in which R ₁ and R _{2 are} identical or different and represent a hydrogen atom, an alkyl radical having 1 to 3 carbon atoms, a benzyl group, a phenyl group or a chlorophyllium group, R _{3 represents} a hydrogen or halogen atom or a methyl group and X a halogen atom with the proviso that X is a fluorine, bromine or iodine atom when R ₁ , R ₂ and R _{3 are} hydrogen atoms.

The following compounds, the structural formulas of which are given in Table I, are preferred:

have cyclized to succinimide by heating with elimination of water.
Preferred starting compounds are, for. B.

M - (3 ', 5' -DichlorophenylH-methyl- (I I)

succinimide
N- (3 ', 5'-dichlorophenyl) -3,3-dimethyl- (III) succinimide

N- (3,4,5-trichlorophenyl) succinimide .. (IV) N- (3 ', 5'-dichloro-4'-methyl-phenyl) - "(V)

succinimide
N- (3 ', 5'-pichlorophenyl) -3-phenyl- (Vl)

succinimide
N- (3 ', 5'-dichlorophynyl) -3- (2 "-chlor- (VII)

phenyl) succinimide
N- (3 ', 5' -dibromophenyl) -3-phenyl- (VJ JI)

succinimide
N- (3 ', 5' -Dichlorophenyl) -3-benzyl- (IX)

succinimide
N- (3 ', 5' -DichlorphenyO-S-methyl- (X)

• ^ -phenylsuccinimide
N- (3,5-dibromophenyl) succinimide (Xl)

and
N- (3 ', 4', 5 '-Trichlorophenyl) - (Xl I)

3,3-dimethyl succinimide

The invention also relates to a process for the preparation of the substituted N-phenylsuccinimides of the general formula I. The process is characterized in that substituted amber » acid monoanilides of the general formulas XIII or XIV

N- (3 ', 5'-dichlorophenyl) - (Ha)

2 (or 3) methyl succinic monoamide

N- (3 ', 5'-dichlorophenyl) - (UIa)

2,2 (or 3,3) dimethyl succinic monoamide

N- (3,4,5-trichlorophenyl) - (IVa)

succin monoamide

N- (3,5-dichloro-4'-methyl-phenyl) - (Va)

succin monoamide

N- (3 ', 5'-dichlorophenyl) - (VIa)

2 (or 3) -phenylsuccinic monoamide

N- (3 ', 5'-dichlorophenyl) - (VIIa)

2 (or 3) - (2 "-chlorophenyl) succinic monoamide

N- (3 ', 5'-dibromophenyl) - (Villa)

2 (or 3) -phenylsuccinic monoamide

N- (3 ', 5'-dichlorophenyl) - (JXa)

2 (or 3) benzyl succinic monoamide

N- (3'.5'-dichlorophenyl) -2-methyl- (Xa)

2-phenylsuccinic monoamide

N- (3 ', 5'-dichlorophenyl) -3-methyl- (X a)

3-phenylsuccinic monoamide

N- (3,5-dibromophenyl) -succin- (XJ a)

monoamid

and

N- (3 ', 4', 5'-Trichlorophenyl) - (XIl a)

2,2 (or 3,3) -dimethyl-

succin monoamide

R ₁ -C-COOH
CH, CONH

R ₁ -C-CONH
CHXOOH

(XIII)

(XIV)

in which R ₁ , R ₂ , R ₃ and X have the abovementioned meaning. In the process according to the invention, the substituted N-phenylsuccinimides can be prepared from the corresponding succinic acid monoanilides by simply heating to about 170 ^° C. However, the reaction at 10O ⁰ C of a dehydrating agent such as acetic anhydride, acetyl chloride, phosphorus pentachloride or phosphorus oxychloride, preferably acetic anhydride is carried out to give the desired substituted N-phenylsuccinimide is obtained in high yield preferably with stirring in the presence of. The reaction time in this case is about 1 hour.

The invention also relates to the use of the substituted N-phenylsuccinimides of the general Formula I as a fungicide or in fungicidal agents.

They can either be in pure form or together with an inert carrier in any conventional manner Type of application, e.g. B. in the form of dusts, wettable powders, oil sprays, sprays, tablets, emulsifiable concentrates or in the form of granules. Furthermore, the substituted N-phenylsuccinimides of the invention in combination with other compounds, e.g. B. together with blasticidin-S, kasugamycin, polyoxin, Pentachlorobenzaldoxime, 7-1,2,3,4,5,6-hexachlorocyclohexane, 3,5-dichlorophenyl maleic acid imide, 3,5-dichlorophenyl succinimide ^^ - dichlorophenylitaconic acid imide, Ο, Ο-diethyl-S-benzyl-thiophosphoric acid ester, O - ethyl - S, S - diphenyl - dithiophosphoric acid ester, O - butyl - S - benzyl - S - ethyl - dithiophosphoric acid ester, O, O - dimethyl - O - (3 - methyl - 4 - nitrophenyl) - thiophosphoric acid ester, S - [1,2 - bis - (ethoxycarbonyl) ethyl] - O, O - dimethyl - dithiophosphoric acid ester, 0.0 - dimethyl -S- (N- methyl - carbamoylmethyl) -dithiophosphoric acid ester, O, O - diethyl - O - (2 - isopropyl - 6 · methyl - 4 - pyrimidinyl) thiophosphate, 3,4 - Dimethylphenyl - N - methyl - carbamate, zinc - ethylene - bis - dithiocarbamate, N - trichloromethylthio-4 - cyclohexene -1,2 - dicarboxyimide, N - (1,1,2,2 - tetrachloroethylthio) -4-cyclohexene-1,2-dicarboxyimide and iron methyl arsonate can be used. In all combinations, the effectiveness of each one Connections not deteriorated. As a result, it is possible to have multiple diseases and infestations to combat harmful insects at the same time, being synergistic depending on the combination Could expect effects. In addition, the substituted N-phenylsuccinimides in combination ~ nation with others, especially agricultural = ■ lent chemicals, e.g. B. Herbiciden, Netnatoeiden 35 ■ § and miticides, or together with fertilizers H be used.

The substituted N-phenylsuccinimides show excellent effectiveness z. B. against Piricularia oryzae, Pellicularia sasakii, Cochliobolus miyabeanus, Sclerothinia sclerotiorum and Sphaerotheca fuliginea, which attack arable and horticultural crops. In addition, they are well suited for combating Aspergillus niger. The connections are but hardly harmful to animals and plants.

So far there are no fungicides with a similarly broad biocidal spectrum and with such activity known.

The examples illustrate the invention.

Examples 1 to 11

Production of substituted N-phenylsuccinimides

55

A mixture of 0.1 mol of a substituted succinic acid monoanilide of the general formulas XIII or XIV, 50 g of acetic anhydride and 1.0 g of anhydrous sodium acetate are ^{stirred at 90 to 100 °} C. for 1 hour in a 100 ml four-necked flask. Acetic acid and acetic anhydride are then distilled off under reduced pressure; the residue is washed with water and dried, and the desired substituted N-phenylsuccinimide is obtained in relatively pure form and in high yield. The pure product is obtained by recrystallization from alcohol.

An overview of the examples is given in Table I.

T? (N SS Ig Tf ro _ ζ
Il 6. ' - co >' Ce "
1 ^ ro ro entai

'- (N <N

1 <N

B δ

I) C C <u

4 = -O U C

as

CN (N

continuation

example

Output compound

Substituted N-phenyl succinimide Structural formula (no.)

F (T) Bulge
<%> 186 to 187.5 95 161 to 162 91 100 to 101 94 152.5 to 153.5 98 124.5 to 127.5 92

Elemental analysis (X = halogen)

H (%) N (%) 2.17
2.07 5.03
4.81 3.51
3.36 5.43
5.45 3.46
3.28 4.37
4.12 2.84
'3.00 3.95
3.80 2.71
2.58 3.42
3.31

IVa

Va

VIa VIIa

villa

Br

(5V)

(V)

(VI)

(VII)

(VIII)

calculated: 43.12
found: 43.25

calculated: 51.18
found: 51.24

calculated: 60.02
found: 60.50

calculated: 54.19
found: 54.36

calculated: 46.97
found: 47.04

(Cl)

38.19

37.80

(Cl)

27.47 27.66

(Cl)

22.15

21.99

(Cl) 29.99

29.77

(Br)

39.07

38.93

continuation

Starting
connection Substituted N-phenyl succinimide Structural formula (no.) N ^^^ Cl (XII) F (C) yield Elen »
C (% | : ntarana! yse O
H <%> : = Halogen)
N (%) X (%) example O CH ₃ / II Cl a - \ Il ^cl IXa O 112 to 113.5 90 calculated: 61.10
found: 61.68 3.92
4.04 4.19
4.19 (Cl)
21.22
20.87 8th ^{2 C} \ f \
N ^> (K) H ₂ CC / I Il ci O HjC O Xa / —V_ '" ^C1 111 to 112.5 93 calculated: 61.09
found: 60.81 3.92
3.91 4.19
4.05 (Cl)
21.22
21.04 9 H ( - <- / ι Il α O O (Br) XIa Il Br 158.5 to 159.5 96 calculated: 36.07
found: 36.21 2.12
2.18 4.21
4.35 48.00
48.11 10 H ₂ CC _x _i N ^> (XI) H ₂ CC / I Il Br O (Cl) XIIa O 181 to 182 94 calculated: 47.01
found: 46.74 3.29
3.15 4.57
4.58 34.69
34.60 11th Il ei H ₂ CC _x _J CH _3x

Production of biocidal agents

The compounds marked with a number in the examples can be seen in Table I. will.

Example 12
Dust

3 parts of compound IV and 97 parts of clay are carefully mixed and powdered. The dust contains 3% of the active compound and can be used directly.

Example 13
Dust

4 parts of compound VIII and 96 parts of talc are carefully mixed and powdered. The dust contains 4% of the active compound and can can be used directly.

Example 14
Wettable powder

50 parts of compound V, 5 parts of an alkylbenzenesulfonate type wetting agent and 45 parts Diatomaceous earth is carefully mixed and powdered. The powder is used with water diluted and sprayed.

Example 15
Emulsifiable concentrate

10 parts of compound IX, 60 parts of dimethylformamide, 20 parts of dioxane and 10 parts of an emulsifier of the polyoxyethylene-alkylphenol type are mixed to form an emulsifiable concentrate. To the Application, the concentrate is diluted with water and sprayed.

example
granules

16

35

40

5 parts of compound X, 93.5 parts of clay and 1.5 parts of a binder based on polyvinyl

alcohol are carefully powdered and mixed together. After kneading with water it becomes the mixture granulated and dried. The granules are used directly for application.

Example 17
Combined dust

2 parts of the compound III, 1.5 parts of pentachlorobenzaldoxime, 1.5 parts of O-n-butyl-S-ethyl-S-benzyldithiophosphoric acid ester and 95 parts of clay are carefully mixed and powdered. The dust center] contains 5% active compounds and can directly be used.

Example 18
Combined dust

2 parts of compound VIl, 1.5 parts of O-n-butyl-S-ethyl-S-benzyl-dithiophosphoric acid ester, 2 parts of O, O - dimethyl - O - (3 - methyl - 4nitrophenyl) - thiophosphoric acid ester, 1.5 parts of 3,4-dimethylphenyl-N-methyl-carbamate and 93 parts of clay are used carefully mixed and powdered. The dust contains 7% active compounds and can be used directly will.

The following test examples show the excellent biocidal effect of the substituted according to the invention N-phenyl succinimide.

Test example 1
Control of Piricularia oryzae

Rice plants of the Waseasahi variety are grown in flower pots 9 cm in diameter to the 3-leaf stage drawn and then with 100 mg / pot of the compounds listed in Table II each dusted in 3.0% concentration. After a day, the plants will be with a Spore suspension of Piricularia oryzae inoculated and sprayed, after 5 days the number of Infested sites counted. As can be seen from Table U, the substituted N-phenyl succinimides are of the invention much more effective than the known comparison compounds.

Table II

connection

C-CH ₂

CH - CHiCH -

') Well-known comparisons.

Number of infestation sites
per 10 sheets

0
7th
2
9
11

194

11th

Continued 12

connection

Number of infestations per 10 leaves

213

Not dealt with *) Known comparison compound.

167

289

Test Example 2 Control of Cochliobolus miyabeanus

Rice plants of the Waseasahi variety are grown in flower pots 9 cm in diameter to the 4-leaf stage drawn and with 10 ml / pot of an aqueous suspension of those listed in Table II Compounds each sprayed at a concentration of ppm. After a day, the Plants with a spore suspension of Cochh'obulus miyabeanus inoculated and sprayed. 3 days later, the number of infestation sites is counted. As can be seen from Table III, the new substituted N-phenyl succinimides are much more effective than the known comparison compounds.

Table III

II ...

III ..

VI ..

VII. VIII.

IX ..

XI ..

connection

*) Known comparison compound.

Number of infestations per leaf

0 0 4 15 8 2 3 6

84

Continued 14

connection

Number of infestations per leaf

103

Not treated
Known comparison compound.

Test Example 3 Control of Pellicularia sasakii

Kinmaze rice plants are grown in porcelain Wagner pots up to a height of 50 to 60 cm drawn. The leaves of the individual plant stems are inoculated with Pellicularia sasakii. To one day, the plants with 10 ml / pot of an aqueous emulsion of those listed in Table IV Compounds each sprayed at a concentration of 200 ppm. After 7 days it will measured the size of each infested site, using the following procedure for the evaluation comes:

The extent of damage is determined by the relationship between the infestation index 0:

No spots on the leaf surface.

Infestation index 1:

Shadows as signs of staining are observed on the leaf surface.

Infestation index 2:

Spots less than 3 cm in size (length) are observed on the leaf surface.

Infestation index 3:

Spots larger than 3 cm in size are observed on the leaf surface.

Extent of damage =

Σ (infestation index number of stems)
Number of stems examined x 3

100

definitely.

As can be seen from Table IV, the new substituted N-phenyl succinimides are significantly more effective than the known comparison compounds.

Table IV

connection

*) Known comparison compound.

Extent of damage

4.2 22.7

2.9 18.6 17.4 18.8 19.3

6.2 11.7

78.5

Continued 16

connection Extent of damage

NHCOOC ₂ H

Cl

C-CH-CH ₅ CH =

71.7

100

100

100

Cl

TUZ *) **)

Not treated 100

15.5
100

·) Known comparison compound. ■ * ·) Trade name for an 80% wettable powder

Monomethylarsine-bis-dimethyl-dithiocarbamate

Zinc dimethyl dithiocarbamai

Tetramethyhhiuram disulfide

Test Example 4 Control of Sphaerotheca fuliginea

Pumpkin plants of the Heian Kogiku variety are grown in flower pots from 12 cm in diameter to 3 to 4-leaf stage drawn and each with 7 ml / pot of a suspension of the specified in Table V. Compounds each sprayed at a concentration of 500 ppm. One day later the plants are inoculated and sprayed with a spore suspension of Sphaerotheca fuliginea.

After 10 days, the extent of damage is measured on four upper leaves of each plant the stain determined.

For each compound, the value in the last column of Table V represents the result of a series of tests with 7 pots. As can be seen from Table V, those according to the invention are substituted N-phenylsuccinimide is much more effective than the known comparison compounds.

109 526/394

17th

Table V

18th

connection

Cl

Not treated.
·) Known comparison compound.

Cl

Extent of harm

7.4 10.3

5.7

4.6 11.2

4.3

37.5

33.7

38.9

50.1

42.7

55.6

Test Example 5 Bioeides Spectrum

The waxy Aspergillus niger is examined according to the dilution method. The information > 200

delaying influence of the and > 1000 means that at a concentration

given compounds on various plant - from 200 or 1000 ppm no effect observed

pathogenic fungi and bacteria as well can be watched out for.

Table VI connection Test organism

Pincularia oryzae

Cochliobolus miyabeanus

Alternaria kikuchiana

Pellicularia sasakii

Pythium aphanidermatum
Pellicularia filamentosa ..

Corticium rolfsii

Botrytis cinerea

Sclerotinia sclerotiorum ..

Alternaria mali

Glomerella cingulata ....
Xanthomonas oryzae ....
Aspergillus niger

C!

Cl

20th

Minimum inhibitory concentration (ppm)

—CH-CHj

Il O

(H)

40

40

40

200

200

40

200

40 40 40 40

C-CH ₂

Il
O

(Comparison connection)

> 200

> 200

200

> 200

200

200

200

200

200

> 200

> 200

> 200

> 1000

example connection Phytotoxicities

Rice plants (Waseasahi) Pumpkin plants (Hcian Kogiku)

Acute oral toxicity

in rats LD ₅₀ (mg / kg)

> 1500

> 1500

> 1500

> 1500

21

continuation

22nd

example connection Phytotoxicities

Rice plants (Waseasahi)

Pumpkin plants (Heian Kogiku)

Acute oral toxicity

in rats LD ₅₀ (mg / kg)

10

Cl

-N

-N

QH ₅

Cl

QH ₅

/ VCH ₂ QH ₅

-N> 1500

> 1500

> 1500

1500

> 1500

> 1500

> 1500

2300

continuation

example connection Phytotoxicities

Rice plants (Waseasahi) Pumpkin plants (Heian Kogiku)

Acute oral toxicity

in rats

LD ₅₀ (mg / kg)

Cl

control

> 1500

1500

(Farmaco Ed.Sience, Vol. 22 (1967), pp. 781 to 785)

Remarks:

- = No phytotoxicity.

± = Very low phytotoxicity.

+ = Slight phytotoxicity. -H- = moderate phytotoxicity -Ht- = strong phytotoxicity.

The compounds according to the invention show little or no phytotoxicity.

Claims (7)

Patent claims: 1. Substituted N-phenyl succinimides of the general Formula I, R ₁ O I Il x R ₂ -CC _n χ / y vx (I) in which R ₁ or R _{2 are} identical or different and represent a hydrogen atom, an alkyl radical having 1 to 3 carbon atoms, a benzyl group, a phenyl group or a chlorophenyl group, R _{3 represents} a hydrogen or halogen atom or a methyl group and X a halogen atom is, with the proviso that X is a fluorine, bromine or iodine atom when R ₁ , R ₂ and R _{3 are} hydrogen atoms. 2. N-ß'.S'-dichlorophenylJ-S-methylsuccinimide. 3. NK3 ', 5'-dichl (jrphenyl) -3,3-dimethylsuccinimide. 4. N- (3,5-dibromophenyl) succinimide. 5. N-βAS-trichlorophenyosuccinimide. 55 6. Process for the preparation of the compounds according to claim I, characterized in that substituted succinic acid monoanilides of the general formulas XIIl or XlV R ₂ -C- COOH
CH ₇ CONH R ₂ -C - CONH ^^ ^
CH ₂ COOH in which R ₁ , R ₂ , R ₃ and X have the aforementioned meaning, cyclized to the succinimide by heating with elimination of water. 7. Use of the compounds according to claim 1 as fungicides. 109 526/394