DE2426971C2 - Phenylenediamine derivatives, process for their preparation and their use as pesticides - Google Patents

Description

The invention relates to the subject matter characterized in the claims.

The term "lower" means radicals with a maximum of 8, preferably a maximum of 5 and in particular a maximum of 3 carbon atoms. All hydrocarbon radicals, such as the alkyl, alkenyl or alkynyl radicals, can be lower (Ci-Cs) or higher (Cg-C ₃ O) radicals, unless they are expressly referred to as lower hydrocarbon radicals. The halogen atoms are fluorine, chlorine, bromine or iodine atoms. Examples of substituents that can be on the benzene ring are lower alkyl, lower alkoxy, lower

Table I.

Alkyl mercapto, nitro or cyano groups, halogen atoms and lower alkylenedioxy groups. Lower alkyl and lower alkyl mercapto radicals are particularly preferred, Nitro and cyano groups and halogen atoms for the substituents on the benzene ring, which is represented by the radical Rt is shown, and lower alkyl and lower alkoxy radicals, nitro groups, halogen atoms and lower Alkylenedioxy groups for the substituents on the benzene ring in the phenylalkyl group A.

Specific examples of compounds of general formula I are given in Table I below:

Connection no.

Structural formula

Melting point, ⁰ C

153-153.5

124-125

115-116

121-122

142.5

continuation Connection no. Structural formula Melting point, ⁰ C

S O

H Il

NHCNHCOC ₂ H ₅

OCH ₃ NHP

Il \

O SC ₃ H ₇ (Ii) SO

Il Il

NHCNHCOC ₂ H ₃

OCH ₃ NHP

O SCH ₂ CsCH

S O

Il Il

NHCNHCOCHj

OC ₂ H ₅ NHP

H\

O SC ₂ H ₅ SO

Il Il

NHCNHCOC _{2 HY}

OC ₂ H ₅ NHP

H\

O SC ₂ H ₅ S

ti Il

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

ll \

O SC ₃ H ₇ Oi) S.

U U

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP O

152 ^ -153 135-135.5 160-161

162

162-162.5 158-158.5

continuation Connection no. Structural formula Melting point, ⁰ C

S O

Il H

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

Il \

0 SC ₄ H ^ n) S

Il Il

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

Il \

0 SC ₅ H ₁₁ Xn) SO

Il Il

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

O SC ₄ H, <sec)

S O

Il Il

NHCNHCOC _{2 HY}

OC ₂ H ₅ NHP

l \

0 SCH ₂ CHe = CH ₂

S 0

Il Il

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

Il \

O SCH ₂ C = CH SO

H Il

NHCNHCOC ₂ H ₅

OC ₂ HjCH ₃ NHP

ir

152.5-153.5 151-152 151-151.5 143-145 149-1494

230 245/178

continuation Connection no.

Structural formula

10

Melting point, ⁰ C

S O

Il Il

NHCNHCOC ₂ Hj OC ₂ H ₅

NHP

O SCH ₂ SO

Il Il

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

ll \ s _v

0 SCH ₂ - <> - Cl S 0

Il Il

NHCNHCOC ₂ H ₅ OC ₂ H ₅

NHP

Il \

O SCH ₂

S 0

Il Il

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

l \

0 SCH ₂ CH ₂ -SO

Il Il

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

Il \

O SCH ₂ COOC ₂ Hj S 0

Il Il

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

0 SCH ₂ CH ₁ SCH,

C ₄ H, (tert)

-161.5

181-182 140-142 134-134.5 115-116

168

continuation

11th

12th

Connection no. Structural formula Melting point, ° C

S O

ld

NHCNHCOC ₂ H ₅

/ II OC ₂ H ₅

NHP

O SCH ₂ CH ₂ OC ₂ H ₅

S 0

U Il

NHCNHCOC ₂ H ₅

S O

Il Il

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

ll \

O SCH ₂

S 0

Il Il

NHCNHCOC ₂ H ₅ OC ₂ H ₅

NHP

Il \

O SCH ₂

Cl

Cl

155.5-156

163-163.5

157.5-158

161-162

173.5-174

continuation

13th

Connection no. Structural formula Melting point, ⁰ C

S O

H Il

NHCNHCOC ₂ H ₅

NHP

OC ₂ H ₅

160.5-161

CH ₃

161-161.5

S 0

Il Il

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

Il \

O SCH ₂ SCHj 144.5-145

S O

Il Il

NHCNHCOC ₂ H ₅

CjH ₇ (ISO)

161.5-162

S 0

Il U

NHCNHCOCh ₃ OCH ₃

NHP

O SCH ₂

161.5-162

continuation

15th

Connection no. Structural formula Melting point, ° C

S O

Il Il

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

Il \

O SCH ₂ C OOC, H ₇ (iso) SO

Il Il

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

Il \

O SC ₅ H ₁₁ (ISG) SO

Il Il

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

Il \

O SCH ₁₃ (Ii)

SO NHCNHCOC ₂ Hj

OC ₂ H ₅ NHP

Il \

O SC ₇ H ₁₅ (Ii) SO

Il Il

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

Il \

O SC ₁ H ₁₇ Gi) SO

Il H

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

Il \

O SC, H _M (n) 78-79

161-161.5 127-127.5 120-121

114-114.5 108-1084

230245/178

continuation

17th

Conclusion no. Structural formula Melting point, ⁰ C

S O

Il Il

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

ll \

O SCH ₂

S O

Il Il

NHCNHCOC ₂ H ₅ OC ₂ H ₅

NHP

ll \

O SCH ₂

S O

Il Il

NHCNHCOC ₂ H ₅

CH ₃

OC ₂ H ₅

NHP

ll

S O

Il Il

NHCNHCOC ₂ Hj Il OC ₂ H ₅

VA /

NHP

OCH ₃

155-155.5 161-161.5 133-134 165.5-166.5

184-185

continuation

19th

20th

Connection no. Structural formula Melting point, ° C

S O

U Il

NHCNHCOC ₂ H ₅

OC ₂ HY

NHP

ο SCH ₂ - fy — c \

Cl S O

Il Il

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

Il \

O SC ₁₀ H ₂₁ (Ii) S 0

Il Il

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

Il \

0 SC ₁₁ H ₂ ^ n) 160-161.5

101-101.5

94.5-95.5

S 0

Il Il

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

Il \

92-92.5

S 0

Il Il

NHCNHCOC _{2 HY}

OC ₂ H ₅ NHP

Il \

O SCH ₂

141-142

continuation

21

22nd

Connection no. Structural formula Melting point, "C

S O

H Il

NHCNHCOC ₂ H ₅ OC ₂ H ₅

NHP

Il \

O SCH ₂

158-160

S O

Il Il

NHCNHCOC ₂ H ₅

C ₂ H ₅

139-140

S O

Il Il

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

ll \

0 SCH ₂ SO

H Il

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

Il \

O SCH ₂

180.5-181

153-154

S O

Il Il

NHCNHCOC ₂ H ₅ II OC ₂ H ₅

Λ /

NHP 0

93.5-94.5

continuation

23

24

Connection no. Structural formula Melting point, ⁹ C

S O

H H

NHCNHCOC ₂ H ₅

NHP

OC ₂ H ₅

O SCH ₂ COOC ₄ HjOsO) SO

Il Il

NHCNHCOC ₂ H ₅

OCH ₃ NHP

Il \

O SC ₄ H, (n) SO

Il Il

NHCNHCOC ₂ Hj OCH ₃

NHP

ll \

O SC ₄ H ₁₁ (M) SO

Il Il

NHCNHCOC ₂ H ₅

OCH ₃ NHP

S 0

Il Il

NhCNHCOCH ₃

OCH ₃ NHP

O SC ₄ H, (n)

S O

U Il

NHCNHCOC ₂ H ₅

OC ₂ H ₅ NHP

Il \

0 SC ₁₄ H »(n)

OCH ₃

98-984

136-136.5

152.5-1534

133-135

160-160.5

92.5-93.5

230246/178

continuation Connection no.

Structural formula Melting point, ⁰ C

40-43

NHCNHCOC ₂ Hs OCH ₃

138-140

The amidophosphoric acid esters of the general formula Π used according to the process can, for example be prepared according to the following reaction schemes:

NH ₂ R ₁ O

NH ₂

NH ₂

(B) fY OR ₁ + MSH

NHP

IN

S OR ₃

NH ₂

OR ₁

/ \ Solvent V / N /

AS Cl NHP

MN

X SA

NH ₂

OR ₁

NHP

«Ν

O SM

AZ

solvent

NH

In the general formulas, R3 means one lower alkyl radical, M an alkali metal atom, Z a halogen atom and Ri, A and X have the above given meaning.

Specific examples of amidophosphoric acid esters of the general formula II used according to the process are:

CS-dimethylphosphoryl-o-phenylenediamine, CS-diethylphosphoryl-o-phenylenediamine,

O-methyl-S-ethylphosphoryl-o-phenylenediamine, O-ethyl-S-methylphosphoryl-o-phenylenediamine, O-methyl-S-n-propylphosphoryl-o-phenylenediamine, O-methyl-S-n-butylphosphoryl-o-phenylenediamine, O-ethyl-S-n-propylphosphoryl-o-phenylenediamine, O-ethyl-S-isopropylphosphoryl-o-phenylenediamine, O-ethyl-S-n-butylphosphoryl-o-phenylenediamine, O-ethyl-S-sec.-butylphosphoryl-0-phenylenediamine, O-ethyl-S-n-amylphosphoryl-o-phenylenediamine, O-ethyl-S-benzylphosphoryl-o-phenylenediamine, O-ethyl-S-p-chlorobenzylphosphoryl-o-phenylene-

diamine, O-ethyl-S-p-tert-butylbenzylphosphoryl-

o-phenylenediamine, O-ethyl-S-p-bromobenzylphosphoryl-o-phenylene-

diamine, O-ethyl-S-p-nitrobenzylphosphoryl-o-phenylene diamine,

O-methyl-S-benzylphosphoryl-o-phenylenediamine, O-methyl-S-2-phenethylphosphoryl-o-phenylene diamine,

O-ethyl-S-2-phenäthylphosphoryl-o-phenylenediamine, O-ethyl-S-3-phenylpropylphosphoryl-o-phenylene-

diamine, O-ethyl-S-2-methylmercaptoäthylphosphoryl-

o-phenylenediamine, O-ethyl-S-2-chloroethylphosphoryl-o-phenylene diamine,

O-ethyl-S-cyanomethylphosphoryl-o-phenylenediamine, O-ethyl-S-2-ethoxyethylphosphoryl-o-phenylene-

diamine, O-ethyl-S-ethoxycarbonylmethylphosphoryl-

o-phenylenediamine, O-ethyl-S-methoxycarbonylmethylphosphoryl o-phenylenediamine,

O-ethyl-S-allylphosphoryl-o-phenylenediamine, O-methyl-S-allylphosphoryl-o-phenylenediamine, O-ethyl-S-2-bromopropenylphosphoryl-o-phenylenediamine ,

O-ethyl-S-methallylphosphoryl-o-phenylenediamine, O-ethyl-S-propargylphosphoryl-o-phenylenediatnine, O-methyl-S-propargylphosphoryl-o-phenylenediamine, O-ethyl-S-phenylphosphoryl-o-phenylenediamine, O-methyl-S-p-tolylphosphoryl-o-phenylenediamine, O-methyl-S ^ AS-trichlorophenylphosphoryl

o-phenylenediamine, O-ethyl-S-p-chlorophenylphosphoryl-o-phenylene-

diamine, O-ethyl-S-p-nitrophenylphosphoryl-o-phenylene diamine,

O-phenyl-S-methylphosphoryl-o-phenylenediamine, O-p-Tolyl-S-methylphosphoryl-o-phenylenediamine, O-p-chlorophenyl-S-ethylphosphoryl-o-phenylene-

diamine, O-p-nitrophenyl-S-methylphosphoryl-o-phenylene-

diamine, O-p-methylmercaptophenyl-S-ethylphosphoryl-

o-phenylenediamine, O-p-Cyanophenyl-S-ethylphosphoryl-o-phenylene diamine,

O-phenyl-S-phenylphosphoryl-o-phenylenediamine, O.S-Dimethylthiophosphoryl-o phenylenediamine, O.S-diethylthiophosphoryl-o-phenylenediamine, O-methyl-S-ethylthiophosphoryl-o-phenylenediamine, O-ethyl-S-methylthiophosphoryl-o-phenylenediamine, O-methyl-S-n-propylthiophosphoryl-o-phenylene-

diamine, O-methyl-S-n-butylthiophosphoryi-o-phenylene-

diamine, O-ethyl-S-n-propylthiophosphoryl-o-phenylene-

diamine, O-ethyl-S-isopropylthiophosphoryl-o-phenylene diamine,

O-ethyl-S-n-butylthiophosphoryl-o-phenylenediamine, O-ethyl-S-sec-butylthiophosphoryl-0-phenylene diamine,

O-ethyl-S-n-amylthiophosphoryl-o-phenylenediamine, O-ethyl-S-benzylthiophosphoryl-o-phenylenediamine,

O-ethyl-S-p-chlorobenzylthiophosphoryl-o-phe-

nylenediamine, O-ethyl-S-p-tert-butylbenzylthiophosphoryl-

o-phenylenediamine, 5 O-ethyl-S-p-bromobenzylthiophosphoryl-o-phenylene-

diamine, O-ethyl-S-p-nitrobenzylthiophosphoryl-o-phenylene diamine,

O-methyl-S-benzylthiophosphoryl-o-phenylenediamine,

O-methyl-S-2-phenäthylphosphoryl-o-phenylene-

diamine, O-ethyl-S-2-phenethylphosphoryl-o-phenylene diamine, O-ethyl-S-3-phenylpropylthiophosphoryl-

o-phenylenediamine, O-ethyl-S-2-methylthioethylphosphoryl-o-phe nylenediamine,

O-ethyl-S ^ -chloroethylthiophosphoryl-o-phenylenediamine,

Oethyl-S-cyanomethylthiophosphoryl-o-phenylene-

diamine, O-ethyl-S-2-ethoxyethylthiophosphoryl-o-phe nylenediamine, O-ethyl-S-ethoxycarbonylmethylthiophosphoryl-

o-phenylenediamine, O-ethyl-S-methoxycarbonylmethylthiophosphoryl o-phenylenediamine,

O-ethyl-S-allylthiophosphoryl-o-phenylenediamine, μ O-methyl-S-allylthiophosphoryl-o-phenylenediamine, O-ethyl-S-2-bromopropenyhhiophosphoryl-

o-phenylenediamine, O-ethyl-S-methallylthiophosphoryl-o-phenylene diamine, O-ethyl-S-propargylthiophosphoryl-o-phenylene-

diamine, O-methyl-S-propargylthiophosphoryl-o-phenylene diamine,

O-ethyl-S-phenylthiophosphoryl-o-phenylenediamine, O-methyl-S-p-tolylthiophosphoryl-o-phenylene-

diamine, O-methyl-S ^ AS-trichlorophenylthiophosphoryl o-phenylenediamine,

O-ethyl-S-p-chlorophenylthiophosphoryl-o-phenylenediamine,

O-ethyl-S-p-nitrophenylthiophosphoryl-o-phe-

nylenediamine, O-phenyl-S-methylthiophosphoryl-o-phenylene diamine, O-p-Tolyl-S-methylthiophosphoryl-o-phenylene-

diamine, O-p-Chlorophenyl-S-ethylthiophosphoryl-o-phe nylenediamine,

O-p-nitrophenyl-S-methylthiophosphoryl-o-phenylenediamine,

O-p-methylthiophenyl-S-ethylthiophosphoryl-

o-phenylenediamine, O-p-Cyanophenyl-S-ethylthiophosphoryl-o-phenylene diamine and O-phenyl-S-phenylthiophosphoryl-OTphe nylenediamine.

Specific examples of those used in accordance with the procedure Alkoxycarbonyl isothiocyanates of the general formula Hl are methoxycarbonyl isothiocyanate and ethoxycarbonyl isothiocyanate.

The implementation of the amidophosphoric acid ester general formula II with the alkoxycarbonylisothio-

cyanates of the general formula III is preferably in a non-polar solvent such as benzene or Toluene, at room temperature or with heating, preferably to temperatures of about 10 to 100 ° C and preferably carried out with stirring. The compounds of general formula 1 are in obtained excellent yields.

The compounds of general formula I are valuable pesticides that are used against the most diverse Microorganisms, in particular phytopathogenic bacteria and fungi, such as Piricularia oryzae, Cochliobolus miyabeanus, Pellicularia sasakii, Sphaerotheca fulginea, Botrytis cinerea, Alternaria kikuchiana, Alternaria mali, Glomerella cingulata, Pythium aphanidermatum, Pellicularia filamentosa, Corticium rolfsii, Selerotinia selerotiorium, Aspergillus niger, Xanthomonas oryzae, Diaporthe citri, Colletotrichum lagenarium and Fusarium oxysproum f. lycopersici, can be used. The connections are extremely low Warm-blooded toxicity and very low phytotoxicity. Due to their broad spectrum of action, you can they are used for the simultaneous prevention and control of several plant diseases.

The examples illustrate the invention.

example 1

0.1 mol of O, O-dimethylthiophosphoryl chloride is added dropwise to a suspension of 0.1 mol of o-phenylenediamine in 20 percent sodium hydroxide solution at room temperature and while stirring. After the reaction has ended, the reaction mixture is acidified and extracted with benzene. The benzene extract is washed with water, dried and evaporated under reduced pressure. The Ο, Ο-dimethylthiophosphorylo-phenylenediamine is obtained in 85 percent yield. F. 71 to 72 ⁰ C.

Example 2

0.1 mol of OO-diethylthiophosphoryl-o-phenylenediamine prepared according to Example 1 is added dropwise to a solution of 0.1 mol of sodium hydrosulfide in methyl cellosolve. The resulting mixture is ^{heated to 105 to HO 0} C for 5 hours, then the methyl cellosolve is distilled off. Benzene and water are added to the residue, and the aqueous solution is separated off, washed with benzene and evaporated. The sodium salt obtained is dissolved in ethanol, treated with an equimolar amount of ethyl iodide and heated for 1 hour at 80 ⁰ C. After the ethanol has been distilled off, the residue is extracted with benzene, and the benzene extract is washed with water, dried and evaporated. The OS-diethylphosphoryl-o-phenylenediamine is obtained in 81 percent yield. F. 60 to 62 ° C. The product is dissolved in benzene and an equimolar amount of ethoxycarbonyl isothiocyanate is added. The crystalline precipitate formed is filtered off and dried. There is obtained the NO, S-Diäthylphosphoryl-N'-äthoxycarbonylthioureido-o-phenylenediamine, melting at 162 ⁰ C in 95prozentiger yield.

Example 3

A solution of 0.1 mol of o-phenylenediamine in diethyl ether is mixed with 0.1 mol of O-ethyl-Sn-propylphosphoryl chloride. Then 0.1 mol of triethylamine is added dropwise at a temperature below 10 ^{0 C.} The mixture is stirred for 3 hours at room temperature, then washed with water and the ether is distilled off. The brown oily residue is dissolved in benzene, an equimolar amount of ethoxycarbonyl isothiocyanate is added and the mixture is left to stand for 15 to 18 hours. The crystalline precipitate formed is filtered off and recrystallized from a mixture of benzene and η-hexane. The NO-ethyl-Sn-propylphospho-

ryl-N'-o-phenylenediamine to äthoxycarbonylthioureido-162,5 ⁰ C obtained from F. 162 in 85prozentiger yield.

Example 4

0.1 mol of O-ethyl-S-ethoxycarbonylmethylphosphoryl-o-phenylenediamine prepared according to Example 2 are dissolved in a little benzene and treated with an equimolar amount of ethoxycarbonyl isothiocyanate. To The crystalline precipitate formed is filtered off for a few minutes. It is the N-O-Ethyl-S-ethoxycarbonyl-

methylphosphoryl-N'-ethoxycarbonylthioureido-ophenylenediamine from 115 to 116 ° C in 93 percent Yield obtained.

In the same way as described above, the compounds listed in Table 1 are the general formula I produced.

The compounds of general formula I can be used as pesticides alone or in admixture with customary Carriers and / or diluents and / or auxiliaries, such as emulsifiers, in the form of granules, Dusts, wettable powders or emulsifiable concentrates are used. Examples of fixed Carriers or diluents are talc, bentonite, clay, kaolin, diatomaceous earth, vermiculite and Calcium carbonate. Examples of liquid carriers or diluents are benzene, alcohols, acetone, xylene, dioxane, methylnaphthalene and cyclohexane. as Emulsifiers can be alkyl sulfates, alkyl sulfonates, aryl sulfonates, polyethylene glycol ethers and polyvalent esters Alcohols are used. If necessary, the pesticidal agents can also contain other active ingredients, such as fungicides, insecticides, lanatocides, herbicides or fertilizers.

The following experiments show the excellent pesticidal action of the compounds of general formula I and their superiority over commercial pesticides.

Attempt 1

Growth-inhibiting effect opposite
Microorganisms

The growth-inhibiting effect of the compounds of general formula I compared to five phytopathogenic microorganisms are determined by the agar dilution method. The evaluation takes place as follows:

A: Complete inhibition at a concentration of 50 ppm.

B: Inhibition to less than 5 percent at a concentration of 50 ppm compared to a untreated control sample.

C: Inhibition to less than 10 percent at a concentration of 50 ppm compared to that Control sample.

D: Inhibition to less than 20 percent at a concentration of 50 ppm compared to Control sample.

E: Inhibition to less than 50 percent at a concentration of 50 ppm compared to Control sample.

Q: No inhibition at a concentration of 50 ppm.

The results are summarized in Table II. The abbreviations have the following meanings:

Cm: Cochliobolus miyabeanus Cc: Glomerella cingulata Ss: Sclerotinia sclerotiorum Cl: Colletotrichum lagenarium Bc: Botrytis cinerea. Table II link

Cm

Gc

A. B. B. A. C. B. B. B. C. B. B. A. B. B. B. B. A. B. B. A. B. B. C. B.

Table III

A. A. A. A. A. A. B. A. A. A. A. A. A. A. A. A. A. B. A. A. A. A. A. A.

Ss

B A A A A A A A A B B B B A B A A A A B B B B B

Cl

A A A A A A A A A A A A A A A A A A A A A A A

A B A A A B A A A A A B B B B B B A B A A A B A

Connect ims

No.

(ic

Ss

Cl

Bc

B. A. A. A. B. B. A. A. A. B. B. A. A. A. B. B. A. A. A. B. B. A. A. A. A. B. A. A. A. A. B. A. A. A. A. B. A. A. A. B. Attempt 2

Growth-inhibiting effect against microorganisms

The growth-inhibiting effect of the compounds of general formula I against new various phytopathogenic microorganisms is determined by the agar dilution method. The evaluation was carried out as follows:

A: Complete inhibition at one concentration

of 25 ppm. B: Inhibition to less than 10 percent in one

Concentration of 25 ppm. C: Inhibition to less than 20 percent in one

Concentration of 25 ppm.

The results are summarized in Table IH. The abbreviations have the following meanings:

Dc: Diaporthe citri Ps: Pellucularia sadakii Po: Piricularia oryzae Xo: Xanthomonas oryzae FoI: Fusarium oxysporum f. Lycopersici ₍ Gc, Ss, Bc, and Cl have the meaning given in Experiment 1.

link No.

Gc

Ss

Dc

Cl

Bc

Po

Xo

FoI

1 A. A. A. A. A. A. A. B. A. 230245/178 2 A. A. A. B. A. A. A. A. B. 3 A. A. A. A. A. A. A. C. B. 4th A. A. A. A. A. A. A. A. A. 5 A. A. A. B. A. A. A. B. A. 6th A. A. A. B. A. A. A. C. B. 7th A. A. A. A. B. A. A. C. A. 8th A. A. A. A. A. A. A. A. A. 9 A. A. A. A. A. A. A. C. A. 11th A. A. A. B. A. A. A. C. A. 16 A. A. A. B. B. A. A. B. B. 31 A. A. A. A. A. B. A. C. A. 32 A. A. A. B. A. A. B. C. A. 33 A. A. A. A. A. A. A. B. B. 34 A. A. A. A. A. A. A. B. B. 35 A. A. A. A. B. A. B. A. A. 41 A. A. A. A. A. A. B. B. A. 47 A. A. A. A. B. A. B. A. B. 51 A. A. A. B. A. A. A. C. A. 56 A. A. A. A. A. B. B. C. A. 62 A. A. A. A. A. A. A. B. B.

Experiment 3 Control of Piricularia oryzae

The compound to be investigated is applied to rice plants in the form of an emulsifiable concentrate, which are grown in flower pots with a diameter of 9 cm to the 5-leaf stage. the The amount is 10 ml of the preparation per flower pot. The preparation is sprayed with a spray gun.

After 24 hours, the plants are inoculated with a spore suspension of Piricularia oryzae which were grown on an oatmeal medium. The plants are at 26 ° C in high humidity 5 left. 3 days later, the damage is based on the percentage of infected areas the degree of damage and the disease-suppressing effect calculated according to the following equations:

Degree of damage =

_ Σ (infection index X number of leaves)

Total number of sheets x 5

x 100.

The infection index is determined as follows:

Infection index Infection status

0
1

3
4th
5

no infected areas
infected areas only around the vaccination site
infected sites at about Vs the infected leaves

infected sites at about _^2/5 of the infected leaves

infected sites at about _^3/5 of the infected leaves

infected areas at about * / ₅ or more
of infected leaves.

(Number of infected sites

" ...,. . . ..,. "", In untreated plants) Disease-suppressive effect =

(Number of infected sites on treated plants)

Number of infected sites in the untreated plants

x 100

The results are. summarized in Table IV | and with O.O-Diisopropyl-S-benzylthiophosphate, a commercially available fungicide.

Table IV Concentration, Degree of damage, 0 disease under Phytotoxicity link ppm % 1.0 oppressive effect No. 500 0 100 no 1 500 2.0 99 no 3 500 3.5 100 no 4th 500 4.0 98 no 6th 500 3.5 % no 12th 500 0 96 no 13th 500 0 96 no 15th 500 1.0 100 no 20th 500 1.0 100 no 21 500 1.0 99 no 22nd 500 2.0 99 no 26th 500 3.0 99 no 34 500 3.0 98 no 37 500 0 97 no 41 500 4.0 97 no 46 500 2.0 100 no 48 500 3.5 96 no 51 500 1.0 98 no 55 500 96 no 58 500 5.5 99 no 59 100.0 0,0-diisopropyl-S- 200 94 no benzyl thiophosphate - - no untreated

The disease-suppressing effect was also demonstrated on retplants with compounds no. 4 and 9 and the in the DE-OS 22 63 599 described, the compounds according to the invention closest, in carried out a further comparison test. The results are summarized in Table IVa below.

Table IVa link

Disease suppressive effect SOO ppm 100 ppm

SO ppm

S OC ₂ H ₅

II /

NHP Γ JT OC ₂ H ₅

NHCNHCOC ₂ H ₅

Il Il s ο

DE-OS 22 36 599

O SC ₂ H ₅

II /

NHP OC ₂ H ₅ NHCNHCOC ₂ H ₅

70

100

100

80

No. 9

No. 4

NHCNHCOC ₂ H ₅

100

100

100

Attempt 4 Control of Piricularia oryzae (field trial)

Rice plants are grown in a field. The test fields are each 1 m ^{2 in} size. The plants are infected in the 3 to 4 leaf stage with Piricularia oryzae between the stems. As soon as initial sites of infection can be identified, the compound to be tested is applied in the form of a dust to the rice plants in an amount of

Table V

4 kg / 10 ar sprayed. After 7 days, the dust is applied again in the same amount Rice plants applied. 10 days after the second treatment, 25 rice plants are examined for the first time in each test field. The second and third Examination takes place every 10 days. The results are summarized in Table V. as Comparative fungicides were 4,5,6,7-tetrachlorophthalide (Compound A) and O.O-Diisopropyl-S-benzylthiophosphate (Compound B).

link concentration Extent of infected areas,% phytotoxicity

1st observation 2nd observation 3rd observation

4th 3% (dust) 9.69 20.95 30.85 no A. 3% (dust) 12.91 13.40 20.97 no B. 48% (emulsion) ·) 15.81 29.89 70.95 no untreated - 32.35 63.35 92.22 no

·) Application quantity 150 liters / 10 Ar.

Attempt 5 Combating rice leaf rot

The compound under investigation is in the form of a wettable powder with the help of a spray gun in an amount of 10 ml preparation on rice plants applied, which are drawn in flower pots with a diameter of 9 cm to a height of 60 cm will. After 24 hours, the leaf sheaths become with

a mycelial disc inoculum (5 mm diameter) of Pellicularia sasakii, which was grown on a PS-synthetic medium. The plants are incubated ^{at 28 ° C.} 4 days later, the infection status of the leaf sheaths is observed and the size of the diseased areas is measured. The degree of damage and the extent of the disease-suppressing effect of the compound under investigation is calculated according to the following equations.

Degree of damage

Σ (Infection index x number of strains) Total number of strains x 3

X 100.

The infection index is determined as follows: Infection index Infection status

0 no infected areas on the leaf sheaths

1 infected, patch-like parts

2 infected spots less than 3 cm in size

3 infected spots with a size of at least 3 cm.

Extent of disease suppressive effect

_ (Degree of damage in the untreated plants) - (Degree of damage in the treated plants)

Degree of damage in the untreated plants

The results are summarized in Table VI. A 3.0 percent solution was used as a comparison compound used by Polyoxin PS as a commercial fungicide

Table VI

link Concentration, Degree of damage, 0 disease sub- Phytotoxicity No. ppm % 0 oppressive effect 1 500 0 100 no 2 500 0 100 no 3 500 0 100 no 4th 500 0 100 no 5 500 0 100 no 6th 500 0 100 no 9 500 0 100 no 15th 500 0 100 no 20th 500 0 100 no 21 500 0 100 no 22nd 500 1.8 100 no 24 500 1.8 100 no 30th 500 0 98 no 31 500 0 98 no 32 500 0 100 no 34 500 0 100 no 35 500 0 100 no 36 500 0 100 no 37 500 0 100 no 38 500 0 100 no 39 500 3.6 100 no 40 500 0 100 no 42 500 0 94 no 46 500 0 100 no 47 500 1.8 100 no 48 500 0 100 no 49 500 0 98 no 56 500 4.8 100 no 59 500 100.0 100 no Polyoxine PS 1000 *) 95 no untreated _ ■ "- no

·) 100-fold dilution

attempt

Control of Xanthomonas oryzae in rice plants

Two platinum loops of a spore suspension of Xanthomonas oryzae are placed on the second leaf of Rice plants applied, which are grown in pots 9 cm in diameter to the leafy stage will. After 24 and 48 hours, the compound under investigation becomes in the form of a wettable Powder applied to the plants. 7 days after the

Table VII

10 Infection, the plants are examined, and the The degree of damage is calculated according to test 5. The results are summarized in Table VII Comparative compound was a 10 percent wettable powder of phenazine 5-oxide (compound C) as commercial fungicide used.

link

No.

Concentration, ppm

Number of leaves Degree of damage, phytotoxicity

7th 1000 30th 10.0 no 12th 1000 30th 10.0 no 18th 1000 30th 16.7 no 50 1000 30th 13.3 no 51 1000 30th 9.6 no 58 1000 30th 16.7 no C. 1000 *) 30th 26.7 no untreated - 40 97.5 no ·) 100 times dilution Trial 7 Control of powdery mildew

The compound under investigation is in the form of an emulsifiable concentrate on the seed leaves of Cucumber plants with the help of a spray gun in an amount of 7 ml / flower pot on cucumber plants applied, which are grown in flower pots with a diameter of 9 cm. The first developed The sheet is cut off. After 24 hours the Plants with a Sphaerotheca spore suspension fuliginea and incubated for 14 days at 28 ° C and 60 to 80 percent relative humidity the state of infection of the seed leaves is observed and the degree and extent of damage disease suppressive effect according to the following Calculated equations:

Degree of damage

Σ (infection index x number of seed leaves) x 100.

Total number of seed leaves x The infection index is determined as follows:

Infection index State of infection 0 no infection sites 1 Infection sites only around the vaccination site 2 Infection sites at about '/ s des inoculated leaf 3 Infection sites at about _^2/5 of the inoculated leaf 4th Infection sites at about _^3/5 of the inoculated leaf 5 Infection cells at about ⁴ / s or more of the inoculated leaf.

Extent of disease suppressive effect

(Number of infection sites _ (number of infection sites in the untreated plants) in the treated plants) Number of infection sites in the untreated plants

x 100.

The results are summarized in Table VIII. The comparison compound used is 6-methyl-2-oxo-1,3-dithio (4,5-b) quinoxaline (compound D) in the form of a 25 percent wettable powder.

23O24S / 178

Table VIII link

No.

Concentration, ppm

Degree of damage,

kraakhctts-suppressive effect

Phytotoxicity

1 500 0 i 100 no 2 500 0 i 100 no 3 500 ο ·; 100 no 4th 500 0 100 teine 5 5Φ0 0 100 no 6th 500 0 100 no 7th 500 0 100 no 8th 500 0 100 no 9 500 0 100 no 11th 500 0 100 no 12th 500 0 100 no 13th 500 0 100 no 14th 500 0 100 no 15th 500 0 100 no 16 500 0 100 no 17th 500 0 100 no 18th 500 0 100 no 20th 500 0 100 no 21 500 0 100 no 22nd 500 0 100 no 23 500 0 100 no 24 500 0 100 no 25th 500 0 100 no 26th 500 0 100 no 29 500 0 100 no 30th 500 0 100 no 32 500 7.6 92 no 35 500 7.0 93 no 36 500 4.8 95 no 37 500 6.6 93 no 38 500 7.6 92 no 39 500 0 100 no 41 500 7.6 92 no 42 500 4.0 96 no 44 500 7.6 92 no 46 500 4.8 95 no 47 500 1.7 98 no 48 500 2.6 97 no 49 500 0 100 no 50 500 9.2 91 no 51 500 4.8 95 no 53 500 6.6 93 no 54 500 1.7 ; 98 no 55 500 6.6: 93 no 56 500 7.6 92 no 57 500 0 100 no 58 500 4.8 ι 95 no 59 500 6.6 93 no 60 500 0, 100 no D. 200 10.8 Y 87 no unbchandeh _ 100.0 ^{; i} - no

Trial 8 Combating anthracnose in cucumbers

The compound under investigation is in the form of an emulsifiable concentrate with a spray gun in in an amount of 7 ml per flower pot applied to the seed leaves of cucumbers grown in flower pots 9 cm in diameter. After 24 Hours the plants are infected with a spore suspension of Colletotrichum lagenarium, which on

Potato agar was grown. The plants will

relative at 2O ⁰ C and 95 percent humidity incubated. 5 days later, the state of infection becomes the

Seed leaves observed and the degree of damage and

the extent of the disease suppressive effect calculated according to experiment 7. The results are in

«5 Table IX summarized. As a comparison compound 'becomes N-trichloromethylthio-i-cyclohexene-l ^ -dicarboxi mid (compound E) as 80 percent wettable

Powder used.

43 Concentration, 24 26 971 44 disease sub- Phytotoxicity ppm oppressive effect Table IX 200 100 no link 200 Bulk ratio, 100 no No. 200 % 100 no 1 200 0 9β no 3 200 0 100 no 5 200 0 100 no 7th 200 1.9 100 no 9 200 0 100 no 10 200 0 100 no 12th 200 0 100 no 13th 200 0 100 no 14th 200 0 100 no 15th 200 0 100 no 17th 200 0 98 no 19th 200 0 100 no 21 200 0 96 no 23 200 1.9 100 no 24 200 0 92 no 25th 200 3.8 98 no 26th 200 0 94 no 27 200 7.6 100 no 28 200 1.9 100 no 29 200 5.7 96 no 30th 200 0 % no 31 200 0 98 no 33 200 3.8 100 no 35 200 3.8 100 no 36 200 1.9 98 no 40 200 0 100 no 41 200 0 100 no 43 200 1.9 100 no 44 200 0 100 no 45 200 0 96 no 48 200 0 100 no 49 200 0 98 no 50 200 3.8 98 no 51 200 0 100 no 52 200 1.9 96 no 53 200 1.9 73 no 57 - 0 _ no 60 3.8 E. 25.6 untreated 98.2

Experiment 9 Combating emergence sickness

Flower pots with a diameter of 9 cm are placed in the flower pots. After 4 hours will be are filled with soil. On this earth 55 cucumber seeds are sown in each flower pot. 5 days

a quantity of 10 ml of soil infected with Rhizoctonia solani. The one to be examined Compound is diluted with water as a wettable powder and in an amount of 9 ml per flower pot

later the state of infection is observed and the percentage of healthy seedlings after the following Calculated equation:

Percentage of healthy seedlings (* / »)

₌ Number of healthy seedlings on the treated plants

Number of healthy seedlings in the uninfected and untreated plants

X 100.

45

The results are summarized in Table X. The known fungicide was used as a comparative compound Pentachloronitrobenzene (compound F) was used.

Table X link

Concentration, ppm

Prowttutz act gamaden Säraknge,%

Phytotoxicity

none none none

no no no no no no no no no no no no no no no no no

Flower pots with a diameter of 9 cm are filled with soil. Then be on each Flower pot given 10 ml of soil infected with Fusarium oxysporum f. Raphani

1 500 100.0 Attempt 10 2 500 90.0 3 500 100.0 4th 500 100.0 5 500 86.7 7th 500 100.0 8th 500 90.0 16 500 93.4 20th 500 86.7 22nd 500 100.0 31 500 100.0 32 500 86.7 34 500 100.0 46 500 93.4 47 500 86.7 54 500 93.4 55 500 90.0 57 500 93.4 F. 500 76.7 untreated - 96.7

Compound is in the form of a wettable powder diluted with water and placed in flower pots in a A quantity of 18 ml / pot is given. Then 20 radish seeds are sown in each flower pot.

The state of infection is observed after 3 weeks

and the percentage of healthy seedlings according to

Run 9 calculated The results are in Table XI

is summarized as a comparison connection

N-trichloromethylthio ^ cyclohexene-1,2-dicarboximide

(Compound E) used in the form of an 80 percent wettable powder.

Table XI Connect and

No.

Concentrate ioe, ppm

percentage

Phytotoxicity

Seeds, %

26 1 500 100.0 no 3 500 88.7 no 4th 500 100.0 no 5 500 100.0 no 6th 500 94.4 no as 9 500 90.8 no 10 500 100.0 no 11th SOO 100.0 no 12th 500 94.4 no 18th 500 94.4 no »24 500 100.0 no 47 500 98.0 no 52 500 88.7 no 53 500 88.7 no 58 500 98.0 no 35 60 500 94.4 no E. 500 72.0 no untreated - 100.0 no

Claims (1)

Patent claims: 1. Phenylenediamine derivatives of the general formula I S O H fl NHCNHCOR ₂ (D 10 15th in which Ri is a lower alkyl radical or a phenyl group optionally substituted by 1 to 5 radicals, R2 is a lower alkyl radical, A is an alkyl, alkenyl, alkynyl, haloalkyl, phenyl, cyanoalkyl, lower alkylmercaptoalkyl, haloalkenyl, means lower alkoxyalkyl, lower alkoxycarbonylalkyl, lower alkylcarbamoylalkyl or phenylalkyl radical which is optionally substituted by 125 to 5 radicals on the benzene ring, and X represents an oxygen or sulfur atom. 2. Phenylenediamine derivatives of the general formula 30th S O NHCNHCO-lower alkyl O-lower alkyl 3. Phenylenediamine derivative of the formula S O It Il NHCNHCOCH3 4. Phenylenediamine derivative of the formula S O Il Il NHCNHCOC ₂ H ₅ OC ₂ H ₅ NHP O SCH ₃ 35 40 45 50 55 60 65 S. Phenylenediamine derivative of the formula S O Il Il NHCNHCOC ₂ H ₅ 6. Phenylenediamine derivative of the formula S O Il Il NHCNHCOCH3 OCH ₃ 7. Phenylenediamine derivative of the formula S O Ii n NHCNHCOC ₂ H ₅ OC ₂ H ₅ NHP l \ O SCH ₂ CH = CH ₂ 8. Process for the preparation of the compounds according to claim 1, characterized in that one in a manner known per se an amidophosphoric acid ester of the general formula Π NH (Π) in which R ₁ , A and X have the meaning given in claim 1, with an alkoxycarbonyl isothiocyanate of the general formula IH R ₂ OCNCS in which R _{2 has} the meaning given in claim 1, brings about implementation. 9. Use of the compounds according to Claims 1 to 7 as pesticides.