DE1930540B2 - ALCOXYCARBONYLTHIOUREIDOBENZOLE AND ITS USE AS POULTRY INHIBITORS - Google Patents

Description

R ²

- N

HN

Furthermore, mites cause a lot of damage to plants, and some species of mites are against that Acaricid, which was continued to be used against them, became resistant. To combat these mites the development of effective acaricides is particularly desirable

Surprisingly, it has now been found that the application of the new compounds in plants provide complete protection or at least a sharp decline the damage that can be attributed to both fungi and mites is ensured, with the active ingredients are to be used in small amounts and are characterized by very low mammalian toxicity. Compared to known compounds used for the same purpose, they have a far superior one fungicide and acaricide effectiveness.

The new alkoxycarbonylthioureidobenzenes correspond to the general formula

NH-C-NH-C-O-R

" i!

S O

or - N =]

where R ^{2 is} a hydrogen atom or a methyl group, R ^{3 is} hydrogen, methyl, acyl having 1 to 3 carbon atoms; Cyclopropylcarbonyl; Benzoyl; Methoxycarbonyl or ethoxycarbonyl; n-propylaminocarbonyl or n-butylaminocarbonyl; Thioformyl, aminothiocarbonyl, methylaminothiocarbonyl or n-propylaminothiocarbonyl, 3,3-dimethylureidothiocarbonyl or 3,3-dimethylthioureidothiocarbonyl, R ^{4 is} the benzal group optionally substituted with a chlorine atom, a nitro or methoxy group and A 'for the anion of hydrochloric acid, nitric acid, Oxalic acid or p-toluenesulfonic acid.

2. Use of the alkoxycarbonylthioureidobenzenes according to claim 1 as fungicides and Acaricide.

in which R represents a C, -C ₃ -alkyl group. X denotes a chlorine atom or the methyl or nitro group and Z denotes the groups

- N

R ³

R ²

R ³

45

The invention relates to new alkoxycarbonylthioureidobenzenes which are used as fungicides and acaricides Find.

With the help of the numerous fungicides developed in recent years, the number of plant diseases, which were previously considered to be unaffected, gradually diminished. But there are still diseases which cause severe plant damage year after year due to the lack of suitable fungicides or which can only be effectively combated with agents that endanger humans and animals or other plants. So z. B. arsenic compounds or antibiotics are still used against rice diseases. It is well known that the highly toxic arsenic compounds can only be used with special protective measures be handled. In addition to phyto- and henna toxicity, antibiotics are generally used some species also oppose their instability as well as price and production difficulties. the Development of effective new fungicides therefore remains highly desirable.

A or -N = R ⁴

where R ^{2 is} a hydrogen atom or a methyl group, R ^{3 is} hydrogen, methyl, acyl having 1 to 3 carbon atoms; Cyclopropyl carbonyl; Benzoyl; Methoxycarbonyl or ethoxycarbonyl; n-propylaminocarbonyl or n-butylaminocarbonyl; Thioformyl, aminothiocarbonyl, methylaminothiocarbonyl or η-propylaminothiocarbonyl. 3,3 - Dimethylureidothiocarbonyl or 3.3 - Üimethylthiourcidothiocarbonyl, R ^{4 is} the benzal group optionally substituted with a chlorine atom, nitro or methoxy group and A stands for the anion of hydrochloric acid, nitric acid, oxalic acid or p-toluenesulfonic acid.

The superior fungicidal effectiveness of the new compounds counteracts, for example the following organisms: Botrytis cinerea, Cercospora beticola, Cladosprium fulvum, Colletotrichum lagenarium, Corynespora melongenae, Elsinoe fawcetti, Glomerella cingulata, Helminthosporium signoideum, Mycosphaerella pomi, Pellicularia sasaki, Penicillium spp., Phaeisariopsis vitis, Piricularia oryzae, Podosphaera leucotricha, Pseudoperonospora humuli, Sclerotinia cinerea, Sclerotinia sclerotiorium, Sphaerptheca fuliginea, Sphaerotheca humuli, Venturia inaequalis.

The new compounds are also extremely effective against mites and their eggs, for example against Panonychus citri, Panonychus ulmi, Tetranychus descrtorum, Tetranychus urticae.

The very low mammalian toxicity of the new compounds is of particular advantage. For example, the acute oral toxicity (LD _S0 ) values for mice of 2- (3-methoxycarbonyl-2-thioureido) aniline (compound 1), 2- (3-methoxyearbonyl - 2 - thioureido) - aniline - hydrochloride, 2 - (3 - methoxycarbonyl - 2 - thioureido) - aniline - oxalate (compound 8), 2- (3-ethoxycarbonyI-2-thioureido) -amlin -p-tolu oil sulfonic acid (compound 12), 1-acetamide - 2 - ( 3 - methoxycarbonyl - 2 - thioureido) benzene (compound 18) and 1 - ethoxycarbonamido-2 - (3 - methoxycarbonyl - 2 - thioureido) benzene (compound 22) more than 500 mg / kg, more than 500 mg / kg, 297 mg / kg, 500 mg / kg or more than 500 mg / kg and more than 500 mg / kg.

To combat fungal and other plant diseases, mites and mite eggs, the new active ingredients sprayed on the surface of the plant, brushed or atomized. The active ingredient concentration in the fungicides or acaricides is in the various application forms in the usual Ranges and is generally Rir net / bare powder 5 to 80, preferably 10 to 60 percent by weight, for emulsifiable concentrates 5 to 70, preferably 10 to 50 percent by weight, Rir dust 0.5 to 10, preferably 1 to 5 percent by weight. For assembly the pesticides can contain the usual auxiliaries. z. B. inorganic powders, like clay. Talc and diatomaceous earth, dispersant, such as sodium lignosulfonate or casein and wetting agents such as alkylarylsulfonate or polyoxyethylene alkylphenol. be used depending on whether the means of combating fungi. Bacteria or Mites are determined. Of course, the remedies are also used with other fungicides, insecticides, Acaricids. Means for influencing plant growth and fertilizers are mixed.

The preparation of the new compounds takes place either in a manner known per se, if appropriate appropriately substituted o-phenylenediamine reacted with an alkoxycarbonyl thiocyanate or an o-nitro-alkoxythioureidobenzene first reduced on the nitro group and then optionally with an acid, an alcohol, alkyl chloride. Isocyanate or isothiocyanate is implemented. Possibly the reaction product is still converted into its addition salt.

The first reaction takes place in inert organic solvents such as acetone, ethyl acetate, methyl ethyl ketone, Methanol, ethanol, dioxane, benzene or toluene at temperatures from -20 to + 50 "C, preferably - 10 and +30 C; the reaction time is usually 10 minutes to 1 hour, but occasionally also several hours.

The reduction of the o-nitrothioureidobenzenes is with iron and an aqueous acid in an inert solvent such as methanol, made and the Reaction of the 2- (3-alkoxycarbonyl-2-thioureido) anilines obtained with an acid, an acid chloride, Alkyl chloroformate, alkyl isocyanate, alkyl isothiocyanate, dimethylthiccarbamoyl isothiocyanate or alkylthioformate either without a solvent or in an inert organic solvent such as acetone, Methyl ethyl ketone, methanol, ethanol, dioxane, Benzene or toluene.

The conversion into the addition salt takes place in an inert organic solvent, e.g. B. in acetone. Dioxane. Methanol or ethanol. The reaction temperature is generally not critical, room temperature is preferred.

The following examples and books illustrate the preparation of some compounds according to the invention and the known active ingredients compared to the superior fungicidal and acaricidal effects of the new compounds described.

example 1

2- (3-methoxycarbonyl "2-thioureido) aniline or
l- (2Aminophenyl) -3-methoxycarbonyl-2-thiourea (compound 1)

1st way

47 g (0.5 mol) of methyl chloroformate were slowly added to 50 g (0.51 mol) of potassium thiocyanate in 150 cm ^{3 of} acetone at room temperature with stirring. The mixture was refluxed for 30 minutes, then contained methoxycarbonyl isothiocyanate.

was cooled and kept at -10 C in a cold mixture. It was then added dropwise to a solution of 52 g (0.48 mol) of o-phenylenediamine in 100 cm ^{3 of} acetone, kept at -10 ° C., while stirring, within 30 minutes, a temperature of -5 ° C. not being exceeded. The mixture was then stirred for a further 30 minutes at room temperature. When about 1 liter of water was added, pale yellow crystals separated out, which were filtered off, washed with water and dried.

43.5 g (0.19 Moll crude crystals of 1 - (2 - aminophenyl - 3 - methoxycarbonyl - 2 - thiourea, which had a decomposition point of 177) were obtained.
The crude crystals were dissolved in 600 cm ^{3 of} 10% strength hydrochloric acid while hot, and the solution was filtered and cooled to room temperature. By neutralizing the solution with ammonia mass. crystals obtained had a decomposition point of 182 ° C., which rose to 184 to 185 ° C. by recrystallization from methanol or dioxane.

Analysis: C ₉ H ₁₁ N ₃ O ₂ S.

Calculated ... C 48.00 H 4.89. N 18.67%;
found .... C 47.80. H 4.96, N 18.45%.

2nd way

255 g (1.0 mol) of 1- (2-nitrophenyl) -3-methoxycarbonyl-2-thiourea, 1.5 1 of methanol, 300 cm 'of water and 40 g (0.32 mol) of crystallized iron (II) chloride were mixed and dissolved 70 C heated. 190 g (3.41 mol) of electrolytic iron with a grain size of about 0.06 mm were then slowly introduced into the mixture over a period of 30 minutes at 70 ° C. with vigorous stirring and stirred under reflux for a further 30 minutes. It was then cooled to room temperature and filtered with suction; the filter cake was dark brown and contained 1- (2-aminophenyl) -3-methoxycarbonyl-2-thiourea. It was extracted 3 times with 600 cm ^{3 of} 10% sodium hydroxide solution each time at -5 ° C. By neutralizing the extract with hydrochloric acid were obtained colorless crystals having a decomposition point of 177 ° C 187 g (0.83 mol), which had a decomposition point of 185 ^C C after recrystallization from methanol or dioxane. The crystals and the substance obtained according to the 1st route with the decomposition point of 184 to 185 ^° C. were identified by IR and UV absorption spectra and other tests.

The starting material 1 - (2 - nitrophenyl) - 3 - methoxycarbonyl - 2 - thiourea was made hot in the following manner: 56.0 g (0.64 mol) of ethyl acetate, 20.4 g (0.21 mol) of potassium thiocyanate and 18 9 g (0.2 mol) of ethyl chloroformate were mixed and the mixture was stirred under reflux for 1 hour, whereupon 12.8 g (0.1 mol) of o-nitroaniline was added and the mixture was stirred at reflux for an additional hour, followed by cooling to room temperature , about 200 cm ^{3 of} water were added, the mixture was stirred for a further 5 minutes and the mixture was filtered off with suction. The yellow crystals obtained were washed with water and methanol and dried. Yield 28.6 g (0.11 mol) of crystals with a decomposition point of 180.5 to 181 , 5 ° C, which rose to 183 to 183.5 ° C after recrystallization from dioxane.

Example 2

l-Formamido-2- (3-methoxycarbonyl2-thioureido) -benzene (Compound 16)

A mixture of 9 g (0.04 mol) 1- (2-aminophenyl) -3-nr: thoxycarbonyl-2-tniourea and 9 g (0.19 mol) of 99% formic acid were stirred under reflux for 40 minutes. After cooling to room temperature the mixture was poured into water and the deposited crystals were filtered, washed with water and dried. 9 g (0.04 Mo!) Of crude crystals of 1 -formamido-2- (3-methoxycarbonyl-2-thioureido (-benzene with a decomposition point of 174 C.

The decomposition point of the Raise crystals to 85 C.

Analysis: C ₁₀ H ₁₁ N ₃ O ₃ S.

Calculated ... C 47.43, H 4.35, N 16.60%;
found .... C 47.40, H 4.53, N 16.60%.

35

Example 3

1-Acetamido-2- (3-methoxycarbony! -2-thioureido) benzene (Compound 17)

2.6 g (0.03 Mo '; acetyl chloride were slowly added at room temperature with stirring to a solution of 5.6 g (0.02 mol) 1- (2-aminophenyl) -3-thioxycarbonyl-2-thiourea in ^c > 0 _{cm 2 of} toluene were added and the mixture IV was refluxed for 2 hours, cooled to room temperature and filtered off with suction. Colorless crystals were obtained, which were washed with methanol and then with water and dried. Yield: 6 g (0.02 mol ) of crude 1-acetamido-2- (3-methoxycarbonyl-2-thioureido) benzene with a decomposition point of 191 ⁰ C. After recrystallization from a mixture of acetone and methanol, the decomposition point rose to 192.5 to 193.5 C.

Analysis: C ₁₁ H ₁₃ N ₃ O ₃ S.

Calculated ... C 49.44, H 4.8 "?, N 15.73%;
found .... C 49.38, H 4.97, N 15.70%.

60

Example 4

1-Benzamido-2- (3 -;! thoxycarbonyl-2-thioureido) benzene (Compound 20)

3.5 g (0.02 mol) of acetyl chloride were slowly added to 5.3 g (0.02 mol) of 1 - (2 - aminophenyl) - 3 - ethoxycarbonyl - 2 - thiourea in 50 cm ^{3 of} toluene with stirring at room temperature and the mixture was refluxed for 3 hours. When worked up according to Example 3 6 g (0.02 mol) yielded crude crystals of l-benzamido-2- (3-äthoxycarbonyI-2-thioureido) benzene with a decomposition point of 190 ⁰ C, which on recrystallization from acetone and methanol 193 "C could be increased.

Analysis: C ₁₇ H ₁₇ N ₃ H ₃ S.

Calculated ... C 59.48, Ii 4.96, N 12.24%;
found .... C 59.60, H 4.92, N 12.18%.

Example 5

l-ethoxycarbonamido-2- (3-methoxycarbonyl -. "" - thioureidoj-benzene (Compound 22)

3.3 g (0.03 mol) of ethyl chloroformate were slowly added to 5.6 g (0.02 mol) of 1 - {2 - aminophenyl) -3 - methoxycarbonyl-2-thiourea in 50 cm ^{3 of} toilet oil with stirring at room temperature given and the mixture held for 1 hour under Rückn-.ß. 4 g (0.01 mol) of crude colorless crystals of

1 - ethoxycarbonamido - 2 - (3 - methoxycarbonyl-

2 - thioureido) - benzene with a point of decomposition from: 47 to 149'C.

Analysis: C ₁₂ H ₁₅ N ₃ O ₄ S.

Calculated ... C 48.48, H 504, N 14.14%;
found .... C 48.61, H 5.12, N 14.10%.

Example 6

1- (3-n-Butylureido) -2- (3-ethoxycarbciiyl-2-thioureido) benzene (Compound 23)

4.5 g (0.05 mol) of n-butyl isocyanate were at room temperature slowly while stirring to 7.2 g (0.03 mol)

1 - (2 - aminophenyl) - 3 - ethoxycarbonyl - 2 - thiourea was added to 60 cm ^{3 of} dry benzene and the mixture IV _{was refluxed for 2} hours, cooled to room temperature and filtered off with suction. 9 g of crude crystals of 1 - (3 - η - butylureido) -

2 - (3 - äthoxycarbonyl - 2 - thioureido) - benzene, which were washed with ethanol and dried and one Decomposition point of 182 C a -ifwiesen, which remained unchanged after recrystallization from ethanol.

Analysis: C ₁₅ H ₂₂ N ₄ O ₃ S.

Calculated ... C 53.20, H 6.51. N 16.57, S 9.47%; found .... C 53.00, H 6.25, N 16.40. S 9.25%.

Example 7

1 - (3-n-Propyl-2-thioureido) -2- (3-ethoxycarbonyl-2-thioureido) benzene (Compound 29)

2.4 g (0.02 mol) of n-propyl isothiocyanate were slowly added to 5.7 g (0.02 mol) of i - (2 - aminophenyl) - 3 - ethoxycarbonyl-2 - thiourea in 30 cm ^{3 of} acetone at room temperature with stirring; the mixture was refluxed for 4 hours, cooled to room temperature and poured into water. An oil was obtained from which crystals separated out on standing overnight, which were washed with 10% strength hydrochloric acid and then with water and dried. After recrystallization from aqueous ethanol to pale yellow crystals, a decomposition point of 132.5 to 133.5 ⁰ C. had

Analysis: C ₁₄ H ₂₀ N ₄ O ₂ S ₂ .

Calculated ... C 49.41, H 5.88, N 16.47%;

found

C 49.55. H 5.98. N 16.50%.

Example 8

2- (3-Ethoxycarbonyl-2-thioureido) -N, N-dimethylaniline or 1- (N, N-dimethylamino) -2- (3-ethoxycarbonyl-2-thioureido) benzene (Compound 14)

8.2 g (0.08 mol) of ethyl chloroformate were slowly added to 7.5 g with stirring at room temperature (0.08 mol) of potassium thiocyanate in 35 g of ethyl acetate and the mixture under reflux for 1 hour held. The mixture, which contained the ethoxycarbonyl isothiocyanate formed, was au * " Cooled room temperature, with 6.8 g (0.04 mol) of N, N-dimethyl-o-phenylenediamine added, cooled with stirring, stirred for a further 30 minutes at room temperature and poured into water. The whole thing was nitrided and the obtained crystals washed with water and dried. 11.3 g (0.04 mol) of crude crystals were obtained of 1 - (N, N - dimethylamine) - 2 - (3 - ethoxycarbonyl - 2 - thioureido) - benzene with a melting point of 110 ° C. After recrystallization from aqueous methanol, the light yellow crystals melted 111 to 113 ° C.

Analysis: C ₁₂ H ₁₇ N ₃ O ₂ S.

Calculated ... C 53.93, H 6.37, N 15.73%; found .... C 53.75, H 6.42, N 15.85%.

45

Example 9

2- (3-ethoxycarbonyl-2-thioureido) aniline hydrochloride (compound 9)

1 cm ^{3 of} concentrated hydrochloric acid was slowly added dropwise at room temperature with stirring to a mixture of 2.4 g (0.01 mol) of 2- (3-ethoxycarbonyl-2-thioureido) aniline and 25 cm ^{3 of} dioxane, and the whole thing for a further 30 minutes kept at room temperature; then the solvent was distilled off under reduced pressure. After washing the residue with acetone, 2.5 g of crystals with a decomposition point of 188 ^° C. were obtained.

Analysis: C _1n H ₁₄ ClN ₃ O ₂ S.

Calculated:

C 43.56, H 5.08, N 15.25, S 11.62%;
found:

C 43.60, H 5.12, N 15.20, S 11.45%.

Example 10

l-Benzylideneamino-2- (3-methoxycarbonyl-2-thioureido) -benzene (Compound 32)

10.4 g (0.11 mol) of methyl chloroformate were slowly added with stirring to 11 g (0.11 mol) of dry potassium thiocyanate in 30 cm ^{3 of} acetone at room temperature and the mixture was refluxed for 30 minutes. The mixture, which contained the methoxycarbonyl isothiocyanate formed, was cooled to below -5 ° C. in a cooling mixture and 19.6 g (0.1 mol) of 2-benzylideneaminoaniline dissolved in 30 cm ^{3 of} acetone were added dropwise at this temperature with stirring The mixture was then stirred for a further 30 minutes at room temperature. After the addition of about 200 cm ^{3 of} water, pale yellow crystals separated out, which were filtered off with suction, washed with water and dried (25 g). After recrystallization from ethanol, the crystals had a decomposition point of 145 to 146 ° C.

Analysis: C ₁₆ H ₁₅ N ₃ O ₂ S.

Calculated:

C 61.34, H 4.79, N 13.42, S 10.22%;

found:
C 61.37, H 4.75, N 13.37, S 10.25%.

Example 11

l- (3-N, N-dimethylthiocarbamoyl-2-thioureido) -

2- (3-methoxycarbonyl-2-thioureido) benzene

(Compound 30)

20 cm ^{3 of} acetone solution containing 7.3 g (0.05 mol) of freshly prepared dimethylthiocarbamoyl isothiocyanate was added dropwise to a solution of 11.3 g (0.05 mol) of 2- (3-methoxycarbonyl-2-thioureido) aniline in 50% cm ^{3 of} acetone were added, the reaction mixture being kept and stirred below 0 ° C. and then stirred for a further 1 hour at room temperature. The acelon was stripped off under reduced pressure and the residue was washed with water.

After recrystallization from ethanol, 12 g of crystals with a decomposition point of 148 to 149 ^° C. were obtained.

Analysis: C ₁₃ H ₁₇ N ₅ O ₂ S ₃ .

Calculated:
C 41.94, H 4.58, N 18.87, S 25.88%;

found:
C 41.85, H 4.60, N 18.85, S 25.80%.

Example 12

l-thioformamido-2- (3-ethoxycarbonyl-2-thioureido) benzene (Compound 26)

30 cm ^{3 of} an ethanol solution of 10.8 g (0.12 mol) of ethyl thionoformate were slowly stirred into a solution of 30.8 g (0.11 mol) of 2 - (3 - ethoxycarbonyl - 2 - thioureido, kept below 0 ° C.) ) - aniline was added dropwise to 100 cm ^{3 of} ethanol, whereupon the reaction mixture was brought to room temperature and kept there with stirring for one hour. Then the mixture was ^{concentrated to 40 cm 3} under reduced pressure to drive off the solvent, cooled and filtered. Crystals with a decomposition point of 172 ° C. were obtained.

Analysis: C _n H ₁₃ N ₁ O ₂ S ₂ .

Calculated:

C 46.64, H 4.59, N 14.84, S 22.61%; found:

C 46.65, H 4.40, N 14.78, S 22.71%.

All of the new compounds prepared by the procedures described are listed in Table I below.

209585/582

Table I.

10

link

Structural formula

description

Melting point or Decomposition point

in ^C C

! I Il

NH-C-NH-CO-CH ₃

CH,

Cl

S O

Il Il

NH- C - NH- C- O-

Vh ₂

s ο

Il Il

nh-c-nh-c-o-ch

Vh ₂

s ο

Il Il

NH - C --NH-C - 0 -

Vh ₂

s ο

Il Il

NH - C - NH - C - O

Vh,

CH ₃ H ₃

NH-C - NH - C - 0 -

NH ₂

S O

Il Il

NH-C - NH - C - O - CH ₃

NH ₂ · HNO ₃

S O

Il I!

NH-C-NH-C-O-CH ₃

NH ₂ • COOH COOH

2- (3-methoxycarbonyl-2-thioureido) aniline

184-185 (Z.)

2- (3-ethoxycarbonyl-2-thioureido) aniline

162-162.5 (Z.)

2- (3-iso-propoxycarbonyl-2-thioureido) aniline

137-138

- (2-Amino-4-methylphenyl) -3-methoxycarbonyl-2-thiourea

- (2-Amino-5-chlorophenyl) -3-methoxycarbonyl-2-thiourea T.

- (2-Amino-5-nitrophenyl) -3-methoxycarbonyI-2-thiourea

2- (3-methoxycarbonyl-2-thioureido) ani] inn nitrate

167.5-168.5 (2nd

182-182.5 (Z.)

202-203 (Z.)

153 (Z.)

2- (3-methoxycarbonyl-2-thioureido) aniline oxalate

151.5-152 (Z.)

link

11th

Continued 12

Structural formula

S O

I Il

NH-C - NH - C - O - C ₂ H ₅ NH ₂ ■ HCl

It

NH-C - NH- C - O - C ₂ H ₅

NH ₂ · HNO ₃

S 0

Il I

NH-C - NH - C - 0 - C ₂ H ₅

NH ₂ ■ COOH
COOH

S 0

Il Il

NH-C - NH - C - 0 - C ₂ H ₅

NH ₂ -CH ₃ - ^ f V-SO ₃ H

S O

Il Il

NH-C - NH-C - Ο - C ₂ H ₅

NHCH ₃

S O

Il Il

NH-C-NH-COC ₂ H ₅

. / CH ₃
^X CH ₃

S O

Il Il

NH-C - NH - C - 0 - C ₂ H ₅

VA / CH ₃

N <· HCl

N: h ₃

description

2- (3-Ethoxycarbonyl-2-thioureido) aniline hydrochloride

2- (3-ethoxycarbonyl-2-thioureido) aniline nitrate

2- (3-ethoxycarbonyl-2-thioureido) aniline oxalate

Melting point or Decomposition point

in "C

188 (Z.)

140.2-140.3 (Z

140 (Z.)

2- (3-ethoxycarbonyl-2-thioureido) aniline p-toluenesulfonate

2- (3-ethoxycarbonyl-2-thioureido) -N-methylaniline

2- (3-Ethoxycarbonyl-2-thioureido) -N, N-dimethylaniline

2- (3-Ethoxycarbonyl-2-thioureido} -N, N-dimethylaniline hydrochloride

174 (Z.)

171

111-113

167-168 (Z.)

link

13th

Continued 14

Structural formula

S O

Il Il

NH-C-NH-C-O-CH ₃ NH-C-H

Il ο

s ο

Il Il

NH - C - NH - C - O - CH ₃

NH-C-CH ₃ O

S O

I Il

NH - c - NH - c - υ - (J ₂ H ₅

NH-CC ₂ H ₅ O

/ S /

NH-C —NH-C —O —CH,

NH-C - <H

Il

S O

Il Il

NH-C - NH - C - O - C ₂ H ₅

Il ο

s ο

Il Il

NH-C-NH-COC ₂ O ₅

NH-CO-CH ₃ O

description

-Formamido-2- (3-methoxycarbonyl-2-thioureido) -benzene

-Acetamido-2- (3-methoxycarbonyl-2-thioureido) -benzene

Propionamido-2- (3-ethoxycarbonyl-2-thioureido) benzene

1-Cyciopropane carbonamido-2- (3-methoxycarbonyl-2-thioureido) benzene

Melting point or Decomposition point

in "C

185 (Z.)

192.5-193.5

170-171.5

-Benzamido-2- (3-methoxycarbonyl-2-thioureido) -benzene

-Methoxycarbonamido-2- (3-ethoxycarbonyl-2-thioureido) benzene

191-192 (Z.)

192-193

168-170 (Z)

15th

continuation

16

Melting point or Decomposition point

in ⁰ C

link

Structural formula description

S O

Il Il

NH-C-NH-CO-CH ₃

NH-COC ₂ H ₅ O

S O

11 11

NH-C-NH-CO-CH ₃

"NH-C-NH-C ₃ H ₇ O

S O

Il Il

NH-C-NH-CO-CH ₃

NH-C-NH-C ₄ H ₉ O

S O

Il Il

NH-C - NH - C - O - C ₂ H ₅

NH-C-NH-C ₄ H ₉ O

S O

Il Il

NH - C - NH - C - O - C ₂ H ₅

NH-C-H
S.

S O

Il Il

NH-C-NH-C-O-C ₂ H ₅

NH-C-NH ₂

Il s

Ethoxycarbonamido-2- (3-methxycarbonyI-2-thioureido) benzene

i- (3-n-Propylureido) -2- <3-methoxycarbonyl-2-thioureido) benzene

1- (3-n-Butylureido) -2- (3-methoxycarbonyl-2-thioureido) benzene

1- (3-n-Butylureido) -2- (3-ethoxycarbonyl-2-thioureido) benzene

147-149 (Z.)

132.5-133.5

182-183

182

l-thioforraamido-2- (3-ethoxycarbonyl-2-thioureido) benzene

172

- (2-Thiocarbamoylaminophenyl) -3-ethoxycarbonylthiourea "

157

connection

17th

continuation

18th

Structural formula description Melting point or Decomposition point

in ° C

S O

Il Il

NH-C-NH-COC ₂ H ₅ NH-C-NH-CH ₃

s s

SA

NH-C —NH-C —Ο -

Vh-C-NH-C ₃ H ₇

S O

il Il

NH- C - NH- C— O -

NH-C-NH-C-N

S.
S.

S O

C ₂ H ₅

H ₃ H ₃

NH-C-NH-CO-CH ₃

NH-C-NH-C-N

S.
S.

O O

H ₃ H ₃

NH-C —NH-C —O —CH,

N = CH - <f ~ \

S O

Il II

NH-C-NH-C-O

Cl S O

Il Il

NH- C - NH- C -

CH ₃

CH ₃

N = CH

OCH ₃ - (3-Ethoxycarbony I-2-thioureido) -2- (3-methyl- 'oioureido) benzene

160-161

1- (3-n-Propyl-2-thioureido) -2- (3-ethoxycarbonyl-2-thioureido) benzene

132.5-133.5 (Z)

1- (3-N, N-methylcarbonyl-2-thioureido) -2- (3-ethoxycarbonyl-2-thioureido) benzene

148-149 (Z.)

- (3-N, N-Dimethy laminocarbonyl-2-thioureido) -2- (3-methoxycarbonyl-2-thioureido !-benzene

159-160 (Z.)

-Benzylideneamino-2- (3-methoxycarbonyl-2-thioureido) benzene

145-146

- (4-Chloro-benzylideneamino) -2- (3-methoxycarbonyl-2-thioureido) -benzene

- (4-Methoxybenzylideneamino) -2- (3-methoxycarbonyI-2-thioureido) benzene

183-183.5 (Z.)

159-159.5 (Z.)

continuation

link

Structural formula

S O

I I!

NH-C-NH-COC ₂ H ₅

NO ₂

(ι

description

1 - (3-Nitrcbenzylideneamino-2- (3-ethoxycarbonyl-2-thioureido) -benzene

Melting point or Decomposition point

in ° C

185 (Z.)

The active ingredients are used in the following experiments in the following forms:

a) Wettable powder

Active ingredient 2.i. Sodium alkyl sulfonate 5.

Diatomaceous earth 75 parts by weight

The components were mixed and comminuted to a particle size of 10 to 30 μm. In the In practice, the crushed mixture was mixed with water to a concentration of 0.01 Diluted up to 0.05% active ingredient and sprayed or brushed on the suspension.

b) Emulsifiable concentrate, active ingredient 10. Alkytoryl polyoxyethylene 5, dimethylformamide 5½, xylene 35 parts by weight

The ingredients were mixed and dissolved. When used in practice, the solution was found with Diluted water to a concentration of 0.01 to 0.05% active ingredient and sprayed the suspension on or painted on.

c) Dusting agent active ingredient 5, talc 94.1, alkylaryl polyoxyethylene

0.1 part by weight The ingredients were mixed and very finely

20 powdered and sprayed the powder in an amount of 3 to 5 kg / a.

d) Wettable powder mixture

Active ingredient 15, bis-14-chlorophenyl) -methylcarbinol 15.

Sodium alkyl sulfonate 4, sodium alkyl naphthalene

sulfonate 2, sodium lignin, sulfonate 1, diatomaceous earth

63 parts by weight

The ingredients were mixed, crushed and used as a).

Attempt 1

Combating ainhiacnose in cucumbers

Cucumber plants grown in pots with three developed leaves were sprayed with wettable powder a) in an amount of 50 cm ³ suspension per 3 plants, inoculated the next day with a spore suspension of the cucumber anthracnose fungus, Colletotrichum Iagenarium, for 20 hours at about 100% relative humidity and 26 ° C. and brought into the greenhouse. 7 days after the incubation, the average number of damage per leaf was counted and the percentage suppression of the disease was calculated on the basis of the percentage damage in untreated plants. The results are shown in Table II.

Table II

link

Active ingredient concentration (• / .cm-'l

300 500 300 300 300 300 300

4th
13th
30th
31

Comparative experiment
with 2,4-dichloro-6- (2-chloroanilino) -s-triazine

Blind test

Attempt 2
Combating powdery mildew on cucumbers

Cucumber plants in the 3-leaf stage naturally infected with Spaerotheca fuliginea were treated with the dilute solution of the prepared according to a)

Average number of damages per HIaIt

153

oppression
in %

KK)

100

100
92
93.4
90.8

100

Plntotoxicity

no
no
no
no
no
no
no

wettable powder sprayed in an amount of 50 cm ³ per pot and then brought into the greenhouse. 7 days after the spraying, the average number of damage per leaf was counted and, based on the damage to the untreated plants, the percentage disease was calculated. The results are shown in Table III.

1 950 540 Γ / 21 Table III Attempt 3

Verbi.young Effective loft
focus
(ration Percentage
illness Phyto-
loxicity (y / cm ³ ) (%) 2 300 0 no 5 300 0 no 13th 300 0 no 30th 300 0 no 31 300 0 no Comparative experiment
with 6-methyl-
2,3-quinoxaline
dithio !, cycli-
nice carronat 150 3.5 no Blind test 100

Fighting rice blight

On four test fields of 1.1 m ² each was the

Effectiveness of the compounds according to the invention

in the fight against rice blight (Piricularia

oryzae) in the open field. The diluted broth

was in each case in an amount of 250cm ³ / lim ²

sprayed on. The first spray was on the day

to after the incipient infection on the leaves

was noticeable, the second spraying 4 days after

the first carried out. The degree of the disease

was 3, 7 and 11 days after the first spray

The door determines the severity of the disease Disease index was according to a scale

set from 0 to 5, with 0 no infection of the

Plants means and 5 means most

Plants had died from the disease.

The results emerge from Ta ^v :! Le IV.

V Active ingredient concentration request 4 Tabel IV 11 days Phytoloxi / uät link (; ■ cm ^J ) I. 2.0 500 3 position 1.5 no 16 500 0.5 F.rkrankungsinde 1.5 no 17th 500 0.75 2.0 no 18th 500 0.5 1.0 no 19th 500 0.5 2.0 no 20th 500 0.25 2.0 no • Λ ί 500 0.25 1.5 no 22nd 500 0.5 1.5 no 24 500 0.5 1.25 no 25th 500 0.0 1.75 no z7 500 0.2 2.0 no 28 500 0.0 no Comparative experiment 0.5 with pentachlor 4.5 benzyl alcohol - - - - Blind test 1.0 ifende verbi 7 days , 0 , 0 , 0 , 0 , 5 , 5 , 0 g became the pn 0.5 0.5 1.0 0.5 1.0 2.5 The next day

Fighting rice blight

Rice plants grown in pots, growth sta- 5c dium 3 leaves were sprayed with a spore suspension of Reisbrandfuiigus, Piricularia oryzae, Maintained at about 100% relative humidity and 26 ° C for hours and then placed in the greenhouse. as a dilute aqueous solution of a wettable powder prepared according to a) applied to the plants. 10 days after the incubation, the number of diseased areas per pot was determined and the degree u er suppression in percent compared to the untreated Plants calculated. The results are shown in Table V.

Table V

link

10
11th
12th

Active ingredient concentration

(ί '/ cra ³ )

300 300 300 300 300 300

Average number of damages per pot

oppression Phytotoxicity 100 no 95 no 93 no 98 no 98 no 100 ] cpir \ p

continuation

link Active ingredient concentration
(r / cm ') Average number
the damage per pot oppression
(%) Phytoloxylate Kasugamycin *)
(2% active)
(Comparison)
Blino / request 20th
(Water) 5
84 94
0 no

*) A well-known fungicide for combating rice blight with a content of antibiotics.

Attempt 5

Control of leaf sheath rot in rice (1)

Young rice cut back to 5 to 7 cm - the average length of the damage sites on the plants - were determined for a few minutes in a water-filled solution and the wettable solution prepared according to a) was diluted to determine the severity of the disease
Dipped in powder, inoculated on the root saplings after drying with a colony of the fungus causing leaf sheath rot in rice and 25 than 1 cm; ? = Damaged areas 1 to 2 cm long; Maintained in a chamber with humid air for 5 days. 4 = damaged areas longer than 2 cm. The results 3 days and 5 days after the inoculation were the

using the following scale (e-disease index, Average value) evaluated: 0 = not infected; 1 = very slightly infected; 2 = damaged areas shorter

are shown in Table VI.

Table VI

link Active ingredient concentration Disease index 3 days 5 days Phytotoxicity (// cm ³ ) 0 0 7th 500 0 0.2 no 8th 500 0 0 no 9 500 0.5 1.0 no 10 500 0 0.2 no 11th 500 0 0 no 12th 500 0.2 0.5 no 24 500 0 0 no 25th 500 0 0 no 27 500 0 0.2 no 28 500 0.2 0.5 no 32 500 0 0 no 33 500 0 0 no 34 500 0.5 1.0 no 35 500 0.5 IJO no Comparative experiment 43.3 no with ferrimethyl arsonate 3.0 4.0 Blind test

Trial 6
Control of leaf sheath rot in rice (2)

30 cm high rice plants in ^{pots were sprayed per pot with 25 cm 3 of} the water-diluted solution of a wettable powder according to a) and 2 hours,

3 days, 5 days or 14 days after spraying in a humid air chamber and infected there 3 days and 4 days after the inoculation, the severity of the disease was determined using the methods used in experiment 5 used method evaluated The results are shown in Table VIi.

209585/582

2902

I 930

Table VII

'τ

link Active ingredient
concentration I. day Average infection 7th day , 5 14th day Phytotoxicity (ppm) 0.0 3rd day , 0 ?., 0 16 500 0.0 1.0 , 0 1.5 no 17th 500 0.5 0.5 , 5 1.2 no 18th 500 1.0 1.0 , 0 2.0 no Q. ig 500 0.5 1.0 , 5 1.2 no· 20th 500 0.0 0.5 .0 2.0 no 21 500 0.5 1.0 .0 1.2 no 22nd 500 0.0 0.5 1.5
*, 0 1.2 no 26th 500 0.5
3.0 0.5 i 2.0
4.0 no Polyoxime
Comparative experiment 1 *)
Comparative experiment 2 **) 100
25th 1.0
3.5 no
no

*) Antibiotics.

*) Methylarsine sulfide.

Experiment 7 ^2S

Control of Tetranychus mites

About 30 adult female mites of the species Tetranychus desertorum were found on the main leaves from bean plants in pots that had grown 7 to 10 days after emergence. The next day the injured animals were removed from the plants. The compound to be tested was sprayed onto the plants as an aqueous suspension of the agent according to b) with a content of 0.05% active ingredient. 3 days after the spraying, the mortality of the adult animals was counted, whereupon the surviving adult mites were removed. The viability of the during Eggs laid during this period were examined 14 days after spraying.

The adult mortality and egg viability were determined as follows Approach calculated:

Viability in%:

{away)

100

a: Number of living mites on untreated plants:

b: number of surviving mites on treated plants.

Ovicidal effect of the agent in%:

^^ • 100
a

α ': number of eggs laid.

b ': number of animals that have escaped.

The evaluation of the ovicide effect was carried out according to the following scheme:

60

Mortality or Ovicide Effect Table VIII valuation Ovicidal uni 100% 4- 4- + 4-4-4- 80 to 99% 4- 4- 4-4-4- 50 to 79% 4- 4- 4- + 0 to 49% 4- 4- VIII. 4-4- 4-4- valuation 4-4- mortality 4-4-4- 4- 4-4- 4- 4- + 4- 4- + 4- 4-4- + 4-4-4- The results are shown in the table 4- 4- 4- 4- + 4- link 4- 4-4- + 4- 4- 1 4- 4-4- 2 + 4-4-4- 3 4- 4- ^ 4- 7th 4- 4-4-4- 8th - + 4-4- 9 4- 4-4-4- 10 + 4-4-4- 11th 4- 4-4- + 12th + 13th 4- 14th _ 15th + 16 + 17th - 18th + 19th 20th 4- 22nd 23 24 25th 26th 27 28 29

2902

Continuation

link valuation Ovicidal action mortality + + + 30th + + + 31 + + + 32 + + + 33 + + + + 34 + + + + 35 _

28

link valuation Ovicidal action mortality With 2,4,5,4'-tetrachlor diphenyl sulfone Ver parallel attempt, a under the protected Trade name "Tetradifon" known tes mite eradication + + + middle

2902

Claims (1)

Patent claims: 1. Alkoxycarbonylthioureidobenzenes of the general formula NH-C-NH-C-O-R ok in which R is a Q-C-α-alkyl group, X is Chlorine atom or the methyl or nitro group and Z for the groups