DE2354873C3 - 11/30/72 Japan 120437-72 Fungicidal agents based on bicyclic dicarboxylic acid derivatives Sumitomo Chemical Co, Ltd, Osaka (Japan) - Google Patents

Description

CONH

COOR

CONH

b) a hydrogen, chlorine or bromine atom, a methyl or nitro group,

c) a hydrogen, chlorine or bromine atom or a nitro group and R a hydrogen atom or a methyl group,

means. One example is an active ingredient of the formula

CO

15th

described. It is also stated that this ver (I-b) bindings to combat worms, spider mites, insects, bacteria, fungi and protozoa, im Plant protection, as well as to suppress cramps in small rodents can serve. From the FR-PS 20 35 073 are N- (3,5-dihalophenyl) imide derivatives of the general type that act against phytopathogenic fungi Formula III

or

1-c)

in which R is a hydrogen atom or an alkali metal atom means.

2. Use of 3,5-dichlorophynyl compounds of the general formula I for combating fungi of the genus Sclerotinia and Botrytis.

US Pat. No. 3,261,845 discloses a large group of N - phenyl - 7 - oxabicyclo [2.2.1] heptane - 2,3 - dicarboximide derivatives of the general formula II

(H)

well known in the

a) a fluorine, chlorine or bromine atom, a trifluoromethyl, Methyl, ethyl, nitro, methyl mercapto, methoxy, ethoxy or acetyl group,

(III)

* CO

described in which X and X 'are a haloalom and A including a 1,2-cyclohexylene, 1,2-cyclohexadienylene or is o-phenylene radical.

The invention is based on the surprising finding that the compounds of the specified in claim 1 general formula I-a, 1-b and I-c a contrast superior fungicidal activity against phytopathogenic fungi, for example Sclerotinia

4> sclerotiorum, Rhizoctonia solani, Botrytis cinerea, Piricularia oryzae, Cochliobolus miyabeanus or Pellicularia sasakii, but do not develop any phytotoxicity towards the useful plants if they are applied in amounts that are sufficient

so are to ensure fungicidal activity. In addition to being well tolerated by plants, they have Compounds of the general formulas I-a, I-b and I-c have an extremely low toxicity Mammals and fish.

The subject matter of the invention is characterized in the claims. The alkali metal can in particular Be sodium or potassium.

For example, in the form of dusts, the fungicidal agents of the invention may be wettable

bo powders, emulsifiable concentrates, sprays, Aerosols, incense, pellets or granules are present that contain at least one compound of the general Formula I, either alone or in conjunction with one or more gaseous, solid or

b5 liquid carriers, commonly used in fungicidal Funds used are included. In addition to the 3,5-dichlorophenyl compounds, the general Formula I can include the fungicidal agents of the invention

contain one or more known fungicides. Fungicides suitable for this purpose are, for example

Bluslicidin S, Kasugamycin, Polyoxin, Cellocidin,

Chloramphenicol, validamycin, streptomycin, griseofulvin, cycloheximide, pentachloronitrobenzene, Pentachlorophenol and its salts, 2,6-dichloro-4-nitroaniline, Zinc ethylene bis (dithiocarbamate), zinc di methy idithiocarbamate, Manganese ethylene bis (dithiocarbamate), bis (dimethylthiocarbamoyl) disulfide, 2,4,5,6-Tetrachloroisophthalonitrile, 2,3-dichloro-1,4-naphthoquinone, Tetrachloro-p-benzoquinone, tetrachlorophthalide,

p-DimethylaminobenzoldiazonatrJumsulfonat, 2- (1 -MethylheptylHMi-dinitrophenylcrotonal, 2-heptadecylimidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -S-triazine, dodecylguanidine acetate, 6-methyl-2,3-quinoxalinedithiol-cycIo-S, S-dithiocarbonate,

N-trichloromethylthio ^ -cyclohexene-1,2-dicarboximide,

N- (1,1,2,2-tetrachloroethylthioH-cyclohexene-1,2-dicarboximide,

3- (3,5-dichlorophenyl) -5,5-dimethyloxazolide-

indion-2,4,

N- (3,5-dichlorophenyl) -maleimide, N-O.S-dichlorophenylJ-succinimide, N- (3,5-dichlorophenyl) itaconimide, 2,3-dihydro-5-carboxanimide, 6-methyl-1,4-oxazine,

! - (N-ButylcarbamoylK ^ -methoxycarbonylaminobenzimidazole,

2- (4'-ThiazolyI) -benzimidazole, 1,2-bis- (3-ethoxycarbonyl-2-thioureido) -benzene, l, 2-bis (3-methoxycarbonyl-2-thioureido) -benzene, 2-amino-5-mercaptothiadiazole, 2-aminolhiadiazole,

O-butyl-S-benzyl-S-ethyldithiophosphate, O-ethyl-S ^ -diphenyldithiophosphate, Ο, Ο-DiisopropyI-S-benzyldithiophosphate, O, O-dimethyl-O- (3-methyl-4-nitrophenyl) -dithiophosphate,

S-Cl ^ -Bis-iäthoxycarbonyO-äthyH-CO-dimethyldithiophosphate,

O, O-dimethyl-S- (N-methylcarbamoylmethyl) -dithiophosphate,

O, O-diethyl-O- (2-isopropyl-6-methyl-4-pyrimidyl) thiophosphate,

1,3-bis (carbamoylthio) -2- (N, N-dimethylamino) propane hydrochloride, 3,4-dimethylphenyl-N-methylcarbamate, I-naphthyl-N-methylcarbamate, 2-chloro-4,6-bis (äthyIamino) -S-triazine, 2,4-dichlorophenoxyacetic acid and its salts and Ester,

2-methyl-4-chlorophenoxyacetic acid and its Salts and esters,

2,4-dichlorophenyl-4-nitrophenyl ether, N- (3,4-dichlorophenyl) propionamide, 3- (3 ', 4'-dichlorophenyl) -1,1 -dimethy! Urea, 4-chlorobenzyl-N, N-dimethyl thiol carbamate, l, i '' - Dimethyi-4,4 '' - bipyridiumdichiorid,

lAo-trichlorophenyW-nitrophenyl ether,

N '- (2-methyl-4-chlorophenyl) -N, N-dimethvl-

formamidine,

N, N-diallyl-2-chloroacetamide,

Ethyl (or cyclohexyl) - / f - (. 2,4-dichlorophenoxy) acrylate,

S-n-heptyl-S '- (p-tert-butylbenzyl) -N- (3'-pyri-

dylj-imidodithiocarbonate or S-n-butyl-

S '- (p-tert-butylbenzyl) -N- (3-pyridyl) -imido-

dithiocarbonate.

The fungicidal agents of the invention can also contain one or more substances with bactericidal, insecticidal, nematocidal, acaricidal or herbicidal activity, fertilizers, soil conditioners or plant growth substances contain.

Typical examples of the fungicidal agents according to the invention are:

a) Dusts obtained by dispersing at least one compound of the general formula I in a concentration of 0.1 to 30 percent by weight in an inert carrier, for example talc, Diatomaceous earth, wood flour or clay,

b) wettable powder obtained by dispersing at least one compound of the general formula I in a concentration of 0.2 to 80 percent by weight in an inert, adsorbent

jo carriers, for example diatomaceous earth, together

with a wetting and / or dispersing agent such as an alkali metal salt of a long chain aliphatic Sulphate, a partially neutralized sulfuric acid derivative of either a petroleum component or a naturally occurring glyceride, or a condensation product of an alkylene oxide with an organic acid be obtained

c) emulsifiable concentrates, which by dispersing at least one compound of the general Formula I in a concentration of I to 50 percent by weight in an organic Solvent, such as dimethyl sulfoxide, together with a wetting and / or dispersing agent, such as an alkali metal salt of a long chain aliphatic sulfate, a partially neutralized one Sulfuric acid derivative of either a petroleum component or a naturally occurring one Glyceride, or a condensation product

so obtained an alkylene oxide with an organic acid and

d) fungicidal agents that formulate a compound of general formula I in a manner included, as is common with fungicidal incense.

The comparative tests show the superiority of the fungicidal agents according to the invention. In the following experiments, comparative

bo is used for the purposes of the compounds listed in the table below, the compounds no.! to 7 in US-PS 32 15 597, and compounds No. 8 to 10 in FR-PS 20 35 073 are described. Compound no. I 1 is a known, highly effective fungicide which is described in NL-OS 67 06 331. Compound 12 is the fungicide known under the name thiophanato-methyl. Compound no. \ 3 is known from US Pat. No. 3,261,845.

Connection structure application no.

COOH

Cl

CONH

COOH

CH ₂

CONH

COOH

Cl

CONH

COONa

s v

CONH

COOH

S \

CO

CH ₂

CO

COOH

CH ₂

Connection structure application no.

10

Il

12th

13th

CO

8 I H I N

CO

CO

co co

CO

V V

CI

CI

Cl

Cl

Cl

Cl

NHCOOCH ₃

/
N
i
CONHC ₄ H ₉

NH-CS-NH-COOCH ₃ NH-CS-Nh-COOCH ₃

CO

CO

Cl

Cl

CONH

Attempt a

A dust containing 3 percent by weight of the test compound is used in an amount of 3 kg of the Dust per 10 Araufin pots of 9 cm diameter used planted rice plants that have been grown to a height of about 60 cm. After 1 day, the Blattschcidc with a mycelium disc of Pellictilaria sasakii (diameter 5 mm) infected as a vaccine preparation. After 5 days, the condition of the blaltschekle is observed, and

7 8

(The extent of the infestation is calculated using the following equation:

^ _r ,, infestation index χ number of stems,

Bcfa sgrad = = , τ-. - ~: = 100

^& Total number of stems χ 3

where the Bcfallsindcx is determined according to the following features ^, ..: ^Table '

Infested state of infestation

No infestation points on the BlaUscheidc
Afflicted. spotted spots
Spills less than 3 cm in size
Infestation spots of at least 3 cm in size

St.

Test connection

15th Amount of infestation (as 3% dust

The results are shown in Table I. From Table I it can be seen that the compound of Formula I-b (R = H) a considerably larger fimsiizide Activity than the analogous compounds, ziin ^ example the corresponding monochlorinated compounds, owns.

connection connection I-b (R = H)

comparison
Connection no 3
Connection No. 4
Compound No. 5
untreated

0.0

3 100.0 3 KKlO 3 77.8 100.0

Attempt B

A test compound in the form of a wettable powder is after dilution with water in an amount of 10 ml of the dilution per pot is applied to bean seedlings which are grown in pots of g p

9 cm in diameter and planted up to two leaves is determined using the following equation: stage have been drawn. After 4 hours will be

the leaves with a mycelial disc of Sclerotinia sclerotiorum (diameter 5 mm) infected as an inoculation preparation. The infected leaf areas are Observed 4 days later. The extent of the damage

lh

Degree of damage = 2 (infestation index χ number of leaves)

Total number of sheets

the infestation index being determined according to the following features : labeile Il

Infested-Infested areas index

No

Only around the vaccinated areas

Up to 1/5 of the total area of the inoculated leaf

^Over] / s and up to _^2/5 of the total area of the inoculated blade

More than _^2/5 and up to _^3/5 of the total area of the inoculated blade

More than ² I _{5 of} the total area of the inoculated leaf

The results are summarized in Table II. From Table II it can be seen that the compounds of Formula I-a (R = H), I-b (R = H), I-b (R = Na) and I-c a considerably greater fungicidal activity than the analogous compounds, for example the corresponding ones monochlorinated compounds.

60

65

Test connection Conc Damaging tration efficiency (ppm) invention Connection I-a (R = H) 100 0.2 Connection I-b (R = H) 100 0.0 Compound I-b (R = Na) 100 0.0 Connection I-c 100 0.0 comparison Connection No. 1 100 5.0 Connection No. 2 100. 5.0 Connection No. 3 100 5.0 Connection No. 4 100 5.0 Compound No. 5 100 3.0 Compound No. 6 100 3.8 Compound No. 7 100 5.0 Commercially available fungicide 2,6-dichloro-4-nitroaniline 100 2.4 Untreated 5.0

Book C

Hot bean seedlings placed in pots of 9 cm Diameter and have been planted up to / around the first leaf stage in the gc / ogcn (5 pots per plot), are exposed to the smoke or vapor of the test compound, the smoke or vapors by means of a heatable ™ smoking device. Touching takes place for 15 hours in a space that is closed off by plastic sheeting is; then the foils are removed.

10

In addition, as described above, the plants will undergo foliar treatment with an IO (X) Dilute a 3% wettable powder of the test compound in an amount of 100 liters of the dilution per K) Ar subject. Seventeen hours after both treatments are the top and the underside of the leaves with a mycelium disc infected by Sclerotinia sclcrotiorum as a vaccine. The infested area of the leaves is Observed 4 days later. The extent of the damage is determined using the following equation:

Degree of damage =

X (infestation index χ number of leaves)
Total number of sheets

whereby the Befaiisindex is determined according to the following characteristics:

Case

Infested area

Infestation index

0 None

1 Only around the vaccinated sites

2 Up to _{1/5 of} the total area of the inoculated leaf

^{More than 1} / s and up to 2 / _{s of} the total area of the inoculated leaf

Infested area

More than _^2/5 and up to ^J / ₅ of the total area of the sheet vaccinated

5 More than _^3/5 of the total area of the vaccinated

Sheet

The results are shown in Table III. It can be seen from Table III that Compounds 1-b (R = H) and I-c are excellent fungicidal Have activity, and not only when applied in the form of a wettable powder, but also when it is used as a smoking agent.

Table III Test connection lot Degree of damage vaccinated on the vaccinated on the bottom Top 0.0 link 500 mg / m ³ 0.0 0.3 Incense I-b (R = H) 100 mg / m ³ 0.0 0.8 25 mg / m ³ 0.0 0.0 link lOOL / lOa *) 0.0 leaves I-b (R = H) 0.0 link 500 mg / m ³ 0.0 0.0 Incense I-c 100 mg / m ³ 0.0 0.5 25 mg / m ³ 0.0 0.0 Connection I-c lOOL / lOa *) 0.0 leaves 1.0 comparison (Smoking) 25 mg / m ³ 0.0 5.0 Compound No. 13 - 5.0 Untreated

*) As a 100-fold dilution of the 30 percent wettable powder.

It turns out that the agents according to the invention are even superior to active ingredient No. 13.

Attempt D

Cucumber seedlings are placed in pots with a diameter of 9 cm pulled, and when the mono-leaf stage is reached, the leaf is trimmed. A test connection in After dilution with water, the form of a wettable powder is applied to the seed leaf of the plants applied in an amount of 10 ml of the dilution per pot. After 4 hours the leaves will be with a mycelial disc of Botrytis cinerea (5 mm diameter) infected as an inoculation preparation. The afflicted Areas of the leaves are observed five days later. The degree of damage is as in experiment C calculated.

The results are shown in Table IV. Table IV shows that the compounds of Formula I-a (R = H), I-b (R = H), I-b (R = Na) and I-c have a significantly greater fungicidal activity than the ana-

lied compounds, such as the corresponding monochlorinated compounds Connections.

Table IV Test connection

Concentration (ppm)

Degree of damage

invention

Compound I-a (R = H) 200 0.1

Compound I-b (R = H) 2 (X) 0.0

Compound I-b (R = Na) 2 (K) 0.0

Compound 1-c 200 0.0 comparison

Compound No. I 2 (X) 4.5

Compound No. 2 200 5.0

Compound No. 3 2 (X) 5.0

Compound No. 4 200 5.0

Compound No. 5,200 3.1

Compound No. 6,200 3.7

Compound No. 7 2 (X) 5.0

Test connection Try Conc Damaging tration efficiency (ppm) Commercially available fungicide 2.4-dichloro-6- (2-chloroaniline) - 200 1.4 s-triazine Uiibchandeh 5.0

In pots with a diameter of 9 cm, arable soil is first placed, then 10 ml of soil are added inoculated with Pellicularia filamentosa, spread over the surface. After fine "leased line in In the form of an emulsifiable concentrate, it has been diluted with water to a concentration of 500 ppm the dilution is poured into the pots in an amount of 15 ml per pot. After four hours 10 cucumber seeds are sown. Infestation of the growing seedlings is observed five days later.

The percentage status is calculated using the following equation:

Percentage =

Number of healthy seedlings in the treated plot Number of germinated plants in the untreated plot

100

The results are shown in Table V. Table V shows that the compounds of formula I-b (R = H) and I-b (R = Na) have a significantly greater fungicidal activity than the analogous compounds, like the corresponding monochlorinated compounds.

Table V Test connection

Concentration Percentage tual level (ppm) (%) Pot poured into the pot. After four hours, 20 radish seeds are sown. The infestation status of the grown seedlings is observed three weeks later. The percentage level is calculated as in Experiment G.

The results are shown in Table VI. Table VI shows that the compounds of formula I-b (R = H) and I-b (R = Na) have a significantly greater fungicidal activity than the analogous compounds, like the corresponding monochlorinated compounds.

invention

Connection I-b (R = H)

Compound 1-b (R = Na)

comparison

Connection No. 3

Connection No. 4

Compound No. 5

Untreated

Vaccinated

Not vaccinated

500 500

500 500 500

100 100

0 0 0

0 100

Attempt F

In pots with a diameter of 9 cm, arable soil is first put, then 10 ml of soil are added inoculated with Fusarium oxysporam F. raphani, spread over the surface a test compound in the form an emulsifiable concentrate is diluted with water to a concentration of 500 ppm, and the dilution is in an amount of 15 ml per

Table VI Test connection

invention

Compound Ib (R = H)
Compound Ib (R = Na)
comparison
Connection No. 3
Connection No. 4
Compound No. 5
Commercially available fungicide
3-hydroxy-5-methyl-isoxazole
Untreated
Vaccinated
Not vaccinated

Concentration more tual was standing (ppm)

500
500

500
500
500

500

100
100

35

45

0
100

Attempt G

Strawberry plants are made with an aqueous compound of a wettable powder containing the compound of interest three times at a distance sprayed from 7 days after flowering in an amount of 100 l / 10 ares. Sobaid the fruit are ripe, the number of fruits infected with Botrytis cinerea is determined. The level of instruction in each treated test area is calculated. On May 7th, May 14th and May 21st there will be a watery Dilution of a wettable powder containing the 7.11 test compound on the plants applied in an amount of 500 liters / 10 ares. The appearance of Sclerotinia is observed around May 10. The number of infected plants is determined on May 30th and the degree of infection is calculated (Average of 90 plants). The results are summarized in Table VIII.

where the degree of infection of the untreated area 15th Infectious Table VIII 8th Conc Infectious Phyto is assumed to be 100. Find in Degree 9 tration
(ppm) degree of toxicity
(%) Table VII summarized ^(%) 20 10 500 1.1 - Test connection 12th TaOeIIe VII 0.9 500 3.3 ■ - Test connection Conc 0.8 Connection I-a tration 1.0 ₂₅ (R = H) 500 3.3 (ppm) 0.4 Connection I-b 8.5 (R = Na) 500 0.0 Connection I-a (R = H) 200 9.2 Connection I-b 500 24.4 - Compound I-b (R = Na) 200 8.6 (R = H) 500 27.7 Connection I-b (R = H) 200 30th
8.6 Connection I-c 500 25.6 - Connection I-c 200 100.0 Connection no. 500 25.6 - Compound No. 8 200 Connection no. - 97.7 - Compound No. 9 200 Connection no. Compound No. 10 200 Connection no. Compound No. 11 200 Untreated Untreated

Attempt H

A field trial is carried out as follows: cucumber seedlings are transplanted into a greenhouse on March 20. 15 m ² are used per test area. The experiments are carried out in triplicate.

From the results of the above experiments, it can be seen that the fungicidal agents of the invention very good for combating plant diseases such as Sclerotinia red, Rhizoctonia red, and Botrytis Vegetables and field plants, rice blight, brown leaf spots or leaf heather powdery mildew on rice plants, are suitable. The concentration of the compounds of general formula I in the fungicidal agents can be about 0.1 to 90 percent by weight.

Claims (1)

Patent claims: 1. Fungicidal agents, labeled by a content of at least one 3,5-dichlorophenyl compound the general formula COOR (1-a)