DE1930540A1 - Thioureidobenzenes and process for their preparation - Google Patents

Description

concerning:

"Thioureidobenzole un ^v d process for their preparation"

The invention relates to novel substituted thioureidobenzenes and a method for their production. The invention also relates to fungicides and acaricides with a content of one or more of the compounds according to the invention as active ingredients.

With the advances in agricultural chemistry in recent "years, more fungicides have been developed and as a result the number of diseases that were previously considered unaffected has gradually decreased. However some diseases remain due to the lack of suitable fungicides and cause year after year

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Year severe damage to plants, so that development of effective fungicides is still highly desirable is.

Besides, mites also 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 is the development of effective acaricides is particularly desirable.

Surprisingly, it was found that the use of the agents according to the invention on plants is complete Protection or at least a sharp reduction in damage caused by both fungi and mites guaranteed, the funds being used in small amounts.

The compounds of the invention can be presented are given by the following general formula:

S O

It Il

NH-C-NH-C-O-R.

wherein X is hydrogen, chlorine, a nitro or a

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- 3 represents a methyl group;

Z -N """-, ~ ^Ν Χ ^ · ^Α or -N = R. Means;" ^ R ₃ R ₃

R ^ is an alkyl of 1 to 4 carbon atoms;

the ·

R2 represents hydrogen or / or methyl group;

R ₃ for hydrogen, methyl, formyl, alkylcarbonyl with 2 or 3 carbon atoms, cyclopropyicarbonyl, benzoyl, alkyloxycarbonyl with 2 or 3 carbon atoms, alkylaminocarbonyl with 4 or 5 carbon atoms, thioformyl, aminothiocarbonyl, which optionally with an alkyl radical with 1 to 3 carbon atoms is substituted, 3,3-dimethylureidocarbonyl, or 3,3-dimethylthioureidocarbonyl;

R. denotes benzal, which can optionally be substituted by a chlorine atom, a nitro or a methoxy group; and

A is an inorganic or an organic acid.

The superior fungicidal and acaricidal effectiveness of the compounds according to the invention has an effect, for example against the following organisms, without being limited to: Botrytis cinerea, Cercospora beticola, Cladosporium fulvum, Colletotrichum lagenarium, Corynespora melongenae, Elsinoe fawcetti, Glomerella cingulata, Helminthosporium signoideum, Mycosphaerella pomi,

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Pellicularia sasaki, Penicillium spp., Phaeoisariopsis vitis, Piricularia oryzae, Podosphaera leucotricha, Pseudoperonospora humuli, Sclerotinia cinerea, Sderotinia sclerotiorium, Sphaerotheca fuliginea, Sphaerotheca humuli, Venturia inaequalis.

The compounds of the invention are also extreme effective against mites and their eggs, for example against Panonychus citri, Panonychus ulmi, Tetranychus desertorum, Tetranychus urticae.

It is of particular advantage that the compounds according to the invention have a very low toxicity towards mammals. For example, the acute oral toxicity (LD-50) values for mice of 2- (3-methoxycarbonyl-2-thioureido) aniline (compound 1), 2- (3-methoxycarbonyl-2-thioureido) aniline hydrochloride, 2 - (3-Methoxycarbonyl-2-thioureido) aniline oxalate (compound 8), 2- (3-ethoxycarbonyl-2-thioureido) aniline p ~ toluene sulfonic acid (compound 12), 1-acetamido-2 - (3-methoxycarbonyl-2-thioureido) -benzene (Compound 18) and W 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 or more than 500 mg / kg.

The compounds of the invention can be prepared using the following reactions, wherein X, Z, R _-1 , R ₂ , R ₃ , R ₄ and A have the same meaning as above?

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ι O

U = O

υ -

U)

cn

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The reactions (1) and (2) described above can be carried out in inert organic solvents such as acetone, ethyl acetate, methyl ethyl ketone, methanol, ethanol, dioxane, benzene or toluene at temperatures from -20 to +50 ⁰ C, preferably between -10 and +30 Cf the implementation time is usually 10 minutes to 1 hour, but occasionally several hours.

The reaction indicated by (3) above can be carried out in an inert organic solvent such as Acetone, dioxane, methanol or ethanol. The reaction temperature is generally not critical. Ambient temperature is preferred.

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Ci

I-S

OT =

οι

»Κ« ο

SM «H 49

O UU CK «ΙΌ ^,

r-i O

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The reaction (4) can be carried out by reduction of o-nitrothioureidobenzenes with iron and an aqueous one Acid in an inert solvent such as methanol.

The reaction indicated by (5) can be carried out by reacting 2- (S-alkoxycarbonyl-Z-thioureido) anilines with an acid, an acid chloride, an alkyl chloroformate, an alkyl isocyanate, a Alkyl isothiocyanate, a dimethylthiocarbamoyl isothiocyanate or an alkylthionoformate without a solvent or in an inert organic solvent such as Acetone, methyl ethyl ketone, methanol, ethanol, dioxane, benzene or toluene.

The examples serve "to explain the invention in more detail, without restricting them.

example 1 2- (3-methoxycarbonyl-2-thioureido) aniline or 1- (2-aminophenyl) -S-methoxycarbonyl ^ -thiourea (Connection 1)

47 g (0.5 mol) of methyl chloroformate slowly added 50 g CO (51 mol) potassium thiocyanate in 150 ml acetone Room temperature was added with stirring and the mixture was refluxed for 30 minutes. The mixture, which then contained methoxycarbonyl isothiocyanate was cooled and kept in a cold mixture at ~ 10 ° C. The mixture was then poured into a solution of 52 g (0.48 mol) of o-phenylenediamine in 1OO ml of acetone, which was kept at -10 ° in the cold mixture,

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added dropwise, a temperature of -5 C was not exceeded. The mixture was left at room temperature for 30 minutes stirred further. When about 1 liter of water was added to the mixture, pale yellow crystals separated off, which is filtered off and washed with water and dried became.

There were 43.5 g (0.19 mol) of crude crystals of 1- (2-aminophenyl) -S-methoxycarbonyl ^ -thiourea

obtained which had a decomposition point of 177 ° C.

The crude crystals were heated in 600 ml of 10% strength Dissolved hydrochloric acid and the solution filtered and cooled to room temperature. By neutralizing the solution with ammonia water, crystals were obtained with a decomposition point of 182 ° C., which was recrystallized from methanol or dioxane increased to 184-185 ° C.

Analysis: * "" 9 ^ 11 ^ 3 ^ 2 ^

calculated found

example

48 , 00 4th , 89 18th , 67 47 , 80 4th , 96 18th , 45

2- (S-methoxycarbonyl-1- thioureido) aniline or 1- (2-aminophenyl) -3-methoxycarbonyl-2-thiourea

(Connection 1)

255 g (1.0 mol) of 1- (2-nitrophenyl) -3-methoxycarbonyl-2-thiourea, 1.5 l of methanol, 300 ml of water and 40 g

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- 10 -

Crystallized ferrous chloride (0.32 moles) were mixed and heated to 70 ° C. Then the mixture was slowly added over 30 minutes at 70 ° C. with vigorous stirring 190 g (3.41 mol) of electrolytic iron with a grain size of about 0.06 mm and the mixture stirred under reflux for a further 30 minutes. Then the mixture was cooled to room temperature and suctioned off filtered; the filter cake was dark brown and contained the l- (2-amino-phenyl) -3-methoxycarbonyl-2-thiourea formed. The cake was extracted 3 times with 600 ml of 10% sodium hydroxide solution each time at -5 ° C. By neutralizing of the extract with hydrochloric acid, 187 g (0.83 mol) of colorless crystals with a decomposition point of 177 ° C. were obtained obtained which, after recrystallization from methanol or dioxane, had a decomposition point of 185 ° C. »The crystals and the substance from Example 1 with the decomposition point of 184 to 185 ° C were determined by the infrared absorption spectrum, the ultraviolet ray absorption spectrum and other tests identified "

The above-mentioned 1- (2-nitrophenyl) -3 ~ methoxycarbonyl-2-thiourea was made in the following way:

56.0 grams (0.64 moles) of ethyl acetate, 20.4 grams (0.21 moles) of potassium thiocyanate, and 18.9 grams (0.2 moles) of ethyl chloroformate were mixed and the mixture stirred under reflux for 1 hour, whereupon 12.8 g (0.1 mol) of o-nitroaniline added and stirred under reflux for a further hour. Then the mixture was brought to room temperature cooled and added about 200 ml of water, whereupon

"- 11 -

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- 11 -

Stirred for 5 minutes and the mixture was filtered off with suction. The yellow crystals obtained were washed with water and Washed methanol and dried.

28.6 g (0.11 mol) of crude crystals of 1- (2-nitrophenyl) -3-ynethoxycarbonyl-2-thiourea with a decomposition point of 180.5 to 181.5 ° C were made in this way obtain; after recrystallization from dioxane, the substance had a decomposition point of 183 to 183.5 ° C on.

Example 3_

l-Fartnan> ido-2- (3-nethoxycarbonyl-2-thioureido) benzene (Connection 16)

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

The decomposition point of the crystals could be raised to 185 ° C. by recrystallization from a mixture of acetone with dioxane.

- 12 -

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Analysis:

C ₁₀ H ₁₁ N ₃ O ₃ S CH N

calculated ⁴⁷ » ⁴³ 4.35 16.60 %

found . 47.40 , 4.53 16.60 %

Example 4

1-Acetamido-2- (3-methoxycar'bony 1-2-thiour eido) benzene (Connection 17) '

2.6 g (0.03 mol) of acetyl chloride were slowly added to a solution of 5.6 g (0.03 mol) of 1- (2-aminophenyT) -3-methoxycarbonyl-2-thiourea with stirring at room temperature added in 50 ml of toluene and the mixture kept under reflux for 1 1/2 hours, cooled to room temperature and sucked off. Colorless crystals were obtained with Methanol and then washed with water and dried, and then 6 g (0.02 mol) of crude crystals of l-Acetamido-2- (3-methoxycarbonyl-2-thioureido) benzene with represented a decomposition point of 191 ° '.

The decomposition point of the crystals was established by recrystallization from a mixture of acetone and methanol increase from 191 ° C to 192.5 to 193.5 ° C.

Analysis:

^C lih3 ^N 3 ° 3 ^SC . ^HN

calculated found

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49 , 44 4th , 87 15th , 73 49 , 38 4th , 97 15th , 70

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Example 5_

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

3.5 g (02 mol) of acetyl chloride were slowly stirred at room temperature to give 5.3 g (0.02 mol) of 1- (2-aminophenyl) -3-ethoxycarbony1-2-thiourea in 50 ml of toluene was added and the mixture was refluxed for 3 hours. Received when working up according to Example 4 6 g (0.02 MoD crude crystals of l-benzamido-2- (3-ethoxycarbonyl-2-thioureido) -benzene with a decomposition point of 190 C, which could be increased to 193 ° C by recrystallization from acetone and methanol. ·

Analysis:

C ₁₇ H ₁₇ N ₃ H ₃ SC HN

calculated _v

found

example

59 , 48 4, 96 12, 24 59 , 60 4, 92 12, 18th

l-ethoxycarbonamido-2- (3-methoxycarbonyl-2-i: hioureido) benzene (compound 22)

3.3 g (0.03 mol) of ethyl chloroformate were added at room temperature slowly with stirring to give 5.6 g (0.02 mol) of 1- (2-aminophenyl) -3-methoxycarbonyl-2-thiourea in 50 ml of toluene was added and the mixture was refluxed for one hour. 4 g (0.01 mol) of crude colorless material were obtained Crystals of l-ethoxycarbonamido-2- (3-methoxycarbonyl-2-thioureido) benzene with a decomposition point of 147 to 149 ° C.

Analysis:

^C 12 ^H 15 ^N 3 ° 4 ^S 'CHN

calculated - 48.48 ■ .5.04 14 _S 14 %

found 48.61 5 _S 12 14 _s 10 % - 14 -

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- 14 -

Example 7

1- (3-n-Butylureido) -2- (3-ethoxycarbonyl-2-thioureido) benzene (compound 23)

4.5 g (0 05 mol) of n-butyl isocyanate were at room temperature slowly with stirring to 7.2 g (0 03 mol) of 1- (2-aminophenYl) -3-ethoxycarbonyl-2-thiourea in 60 ml of dry benzene was added and the mixture was refluxed for 1 1/2 hours, cooled to room temperature and sucked off. 9 g of crude crystals of 1- (3-n-butylureido) -2- (3-ethoxycarbonyl-2-thioureido) benzene were obtained with a decomposition point of 182 C, which were washed with ethanol and dried. The decomposition point the crystals remained at 182 ° C. even after recrystallization from ethanol.

Analysis: _v

C ₁₅ H ₂₂ N ₄ O ₃ SCH NS

calculated found

Example, 8

l- (3-n-propyl-2-thioureido) -2- (3-ethoxycarbonyl-2- thioureido) benzene (compound 29)

2.4 g (O 02 mol) of n-propyl isothiocyanate were slowly added to 5.7 g (0.02 mol) at room temperature with stirring l- (2-aminophenyl) -3-ethoxycarbonyl-2-thiourea in 3O ml of acetone were added, the mixture was refluxed for 4 hours, cooled to room temperature and poured out in water. An oil was obtained from which

53 , 20 6th , 51 16 , 57 9 , 47 53 , 00 6th , 25 16 , 40 9 , 25

- 15 -

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When standing overnight, crystals separate out, which are washed with 10% hydrochloric acid, and then with water and were dried. After recrystallization from aqueous ethanol, the light yellow crystals had a decomposition point of 132.5 to 133.5 ° C.

Analysis:

^C 14 ^H 2 O ^N 4 ° 2 ^S 2 ^CHN

calculated found

Example 9

49 , 41 5 , 88 16 , 47 49 , 55 5 , 98 16 , 50

2- (3-Ethoxycarbonyl-2-thioureido) -N, N-dimethyl-aniline or 1- (N, N-dimethylamino) -2- (3-ethoxycarboriyl-2-thioureido) benzene (compound 14)

8.2 g (0.08 mol) of ethyl chloroformate were slowly added with stirring to 7.5 g (0.08 mol) of potassium thiocyanate in 35 g of ethyl acetate at room temperature and the mixture was refluxed for one hour. The mixture, which contained the ethoxycarbonyl isothiocyanate formed, was cooled to room temperature and 6.8 g (0.04 mol) of Ν, Ν-dimethyl-o-phenylenediamine were added and the mixture was cooled with stirring. The mixture was then stirred for a further 30 minutes at room temperature and poured into water, the whole was filtered and the crystals obtained were washed with water and dried. This gave 11.3 g (0 04 mole) of crude crystals of 1- (N, N-dimethylamino) -2- (3-ethoxycarbonyl-2-thioureido) benzene, which had a SchmelzDunkt of 110 ⁰ C.

- 16 -

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After recrystallization from aqueous methanol, the light yellow crystals melted at 111 to 113 ° C.

Analysis:

C ₁₂ H ₁₇ N ₃ O ₂ SCHN

calculated 53.93 6.37 15.73%

found 53.75 6.42 15.85 %

Example. 10

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

(Compound 9)

1 ml of concentrated hydrochloric acid was slowly dissolved in 2.4 g (0.01 mol) of 2- (3-ethoxycarbonyl) at room temperature with stirring. 2-thioureido) aniline in 25 ml of dioxane added dropwise and the The mixture was kept at room temperature for a further 30 minutes, after which it was concentrated under reduced pressure, to remove the dioxane present as solvent

After washing the residue with acetone, 2.5 g were obtained

Crystals are obtained which have a decomposition point of 188 ° C

had. C. * H N S. Analysis: 43.56 5.08 15.25 11.62 C ₁₀ H ₁₄ ClN ₃ O ₂ S 43.60 5.12 15.20 11.45 calculated found

Example 11

l-benzylideneamino-2- (3-methoxycarbonyl-2-thioureido) -

benzene (compound 32)

10.4 g (0.11 mol) of methyl chloroformate were at room temperature

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- 17 -

temperature slowly with stirring to 11 g (0.11 mol) of dry potassium thiocyanate in 30 ml of acetone and the The mixture was refluxed for 30 minutes. The mixture, which the resulting methoxycarbonyl isothiocyanate contained, was cooled to below -5 C in a cooling mixture. At this temperature the mixture dropwise with stirring 19.6 g (0.1 mol) of 2-benzylideneaminoaniline, dissolved in 30 ml of acetone, added dropwise, whereupon the mixture was stirred for a further 30 minutes was kept at room temperature. After the addition of about 200 ml of water, pale yellow crystals separated off, 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

up to 146 ° C. C. H 79 N 42 S. 22nd Analysis: 61.34 4, 75 13, 37 10, 25th ^C 16 ^H 15 ^N 3 ° 2 ^S. 61.37 4, 13, Ίο, calculated 12th found example

! ■ »(3-N, N-dimethylthiocarbamoyl-2-thioureido) -2- (3-methoxycarbonyl-2-thioureido) benzene (compound 3O)

20 ml 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 ml of acetone were added, the reaction mixture being kept below ⁰ ° C.

. ■ · - 18 -

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- 18 -

and was stirred; then the reaction mixture was still Maintained at room temperature for 1 hour with stirring. After stripping off the acetone under reduced pressure 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

obtain. C. H - N S. Analysis: 41.94 4.58 18.87 25.88 C ₁₃ H ₁₇ N ₅ O ₂ S ₃ 41.85 4.60 18.85 25.80 calculated found

Example 13 _v

l-thioformamido-2- {3-ethoxycarbonvl-2-thioureido) benzene (compound 26)

30 ml of an ethanol solution of 10.8 g (0.12 mol) of Ethylk thionoformat were slowly poured into a

kept below 0 ° C solution of 30.8 g (O ₁ Il mol) 2- (3-ethoxycarbonyl-2-thioureido) aniline in 100 ml of ethanol was added dropwise, whereupon the reaction mixture was brought to room temperature and kept stirring for one hour . Then the mixture was concentrated to 40 ml under reduced pressure to drive off the solvent, cooled and filtered.

Crystals with a decomposition point of 172 ° C. were obtained. -

• ■ · - 19 -

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Analysis: C. 64 4th H η 84 S. 61 ^C 11 ^H 13 ^N 2 ° 2 ^S 2 46, 65 4th , 59 14, 78 22 71 calculated 46, , 40 14, 22 found

In Table I are some typical compounds of the invention with their properties, without the list being exhaustive or restrictive Has.

TABEL

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TABEL

co ο co

link

No*

Structural formula description

Melting point

bsw. Decomposition point In ⁰ C

s φ

JiS ^ NH-C-NH-C-O-CH

!

NH-C-NH-COC ₂ H ₅

S.

CH ₃

s

NH-C-NH-CO-CH ₃ NH ₂

S Cl ^^ n ^ NH-C-NH-COC ₉ He

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

2- (3-X thoxycarbonyl-2-thioureido) aniline

2- (3-iso-propoxy-

car bony 1-2-thioureido) -

aniline

1- (2-Araino-4-methyl
phenyl) -3-raethoxy-

carbonvl-2-thio urea

l- (2-amino-5-chloro
phenyl) -3-methoxycarbonvl-2-thio-
harnet & ff

184 - 185 (Z)

162-162.5 (Z)

137-138

167.5-168.5 (Z)

182-182.5 {2)

—Ι

CD CO O

Continued to

TABEL

6th ¹ § 9 ■
NO _9. ^ V NH-C-NH-COC ₀ H ₁ -
I Il
k ^ NH ₂ l- (2-amino-5-nitro-
phenyl) -3-methoxy-
carbonv ¹ -2-thio -
harn & toff 202 - 203 (Z) 7th SO
^ yNH-C-NH-CO-CH ₃
W ^ NH ₂ - HNO ₃ 2- (3-methoxycarbonyl-
2-thioureido) -aniline-
Mitrat 153 ( Z) 8th SO
>f> y NH-C-NH-CO-CH ₃
U ₅ J ^ NH ₂ -OOOH
COOH 2- (3-methoxycaxbonyl-.
2-thioureido) -aniline-
oxalate 151.5-152 (2) t
9
r
t
I. SO
^ vNIl-C-NH-COC ₂ H ₅
W> NH _O · HCl 2- (3-ethoxycarbonyl-
2-thioureido) -aniline-
Hydrochloride 188 (Z) I.
10 SO
jijsv ^ NH- C-NH-OO-CaH ₅
W ^A NH ₂ - HNO ₃ "■ 2- (3-achoxycarbonyl-
2-thioureido) -aniline- ·
Nitrate 140.2-140.3 (Z)

CD CO CU cn

Continued to

TABEL

CQ O co CD OQ Ni

cn

11th SO
■ Ty NH-C-NH-COC _? H ₅
W ^ NH ₉ -COOH
COOH 2- (3-Ä 'hoxycarbonyl-
? -thi (>'ireido) -aniline-
Oxalai 140 (7) 12th S 0
^ v-NH-C-NH-COC ₂ H ₅ ,
W ^ NH ₂ ■ CH3— ^ ~ ^ —SO ₃ H 2- (3-W \ .hoxycarbonyl-
2-thi 'aure.ido) aniline
ρ —ToIu oil sulfonate 174U) 13th SO
f ^ y NII-C-NH-COC ₂ H ₅
W ^ NHCH ₃ 2- (3-Ä boxy ^ arbonyl- "
2-thi »iurv: idü) -N-methyl-
aniline 171 " 14th
I.
I. SO
^. "v. NH-C-NH-COC., Ης 2- (3-A '! ^V ioxycarbonyl «
2 ~ tli.ioureiijo) -N, N-
dimethylaniline 111-113
I. I.
15th ■ s ^v o
! «Rsy NH-C-NH-COC ₂ H ₅
^ ^{N <} CH ³ ' ^HC1 2- (3-Aiho; <carbonyl «-2-
thioureido) -N, N-Ui-
methylanilirs-
hydrochloride 167 - 168 (Z)

IS »

ST- * ·

CD CO O

4> O

Ports see below

TABLE LE

te

ω φ

β ©

-3

17th

18th

19th

20th

s 9

NH-C-NH-CO-CH ₃

NH-C-H

l-Formamido-2 «(3-methoxycArbonyl-2 thiouroido> bt »n? ti

i? 0 NH-C-NH-CO-CH ₃

ς- € Η, 0

1 -Acel to ido.-2- (3-mGthoxycarbonyl-2 thi only .2ido) -ben / c [

s ρ

NH-C-NH-COC ₂ H ₅

i-pr'opionanido-2- ( ethoxycarbonyl-2-

S.
NH-C-

O NH-CO-CH ₃

if!

l-Cycl.'ipr opancarbonamidu-2- ( 3-iT5ethoxycarbon vl-2-thioureido) -

'ben ;? ci

185 (L)

192 _β 5-193 _β 5

170 - 171.5

191-192 (7.)

NH

S 0

-C-NH - (^ - OC ₂ H ₅

l-Benznmido-2- (3-ir.et h oxycar bony I - 2-thioureiclo) -benzOl

192 -

CO CO CD

Ports, too

TABEL

CO O CO CO OO

ro

cn

> 1 . . . 1 σ ο ο ζ P.

21 SO
- ^ _n -NH-C-NH-COC ₀ H ₁ -
X \ "
KA NH-CO-CH ₃ l-mothoxyrarbonamido-2-
(3-fi '.. hoxycarbonyl-2-
thioureirio / ben: -1 168-170 (Z) 22nd SO
Ji ^ NH-C-NH-CO-CH ₃ ,
k, ^ NH-COC ₂ H ₅ 1-At hoxycarboneimido-2-
(3-methoxycarbonyl-2-
thioureidoj-benreu 147 ^ 149j % I. 23 SO
^ Y NH-C-NH-CO-CH ₃
W- ^ NH-g-NH-C ^ H ₇
ό l- (3-n-propylureido) -2-
(3-methoxycarbon ^ 'l -2-
th i.oui * eido) -bcn ^ ol 132.5-133.5 ' 24 ■ s ο
J ₄ ^ yNH-C-NH-CO-CH ₃
U ₁ ^ NH-C-NII-C ₄ H ₉
0 l- (3-n-3utylureido) -2-
(3-methoxycarbonyl-2-
thioureido) benzene 182-1Θ3 25th SO
^ S-NH-C-NH-CO-CaH ₅
U ₁ ^ NH-C-NH-C ₄ H ₉
Ö 1- (3-n-butylureido) -2-
. (3-i thoxycarbony1-2-
thioureido) ^ ben2ol I.
182
, - ..,. . I.

ro

σ »CD

O cn

Forts, too

TABEL

CO CO OO

26th SO
^ r ^ NH-C-NH-COC ₉ H ₁ -
¹ ^ i ₁ X-'NH-ς-H
S. 1-thioformamido-2- (3-
Öthoxycarbony1-2-
, thioureido) benzene 172 148-149 (Z) 27 SO
^ rs ^ NH-C-NH-COC ₂ H ₅
kj ^ NH-C-NH ₂
S. l- (2-thiocarbaTnoyl-
aminophenyl) - 3- ¹ SLt hoxy-
carbonyltliiohernstoff f 157 (2) 28 SO
sf ^ f NH-C-NH-CO-CpH ₁ =
Sx ^ NH-C-NH-CHo
^S. l- (3-ethoxycarbonyl-2-
thioureido) -2- {3 _r
inethyl-2-thioureido) -
benx oi. 160-161 29 SO
_r ^ Nj, NH-C-NH-C-0-C2H ₅
'^5; ^ NH-C-rN'H-.C ₃ H ₇
>> 1_ (3-n-propyl-2-thio-
ureido) -2- (3-aihoxycar-
bonyl-2-thioureido) -
ben ^ ox 132.5-133.5 (Z) 30th SO ^
_f ^ Y NH-C-NH-CO- C ₂ H ₅
^ ⁴ V / ¹ - NH- C-NH-CN <HJ ³
SS ^C 3 l- (3-N, N-methylcarbonyl ~ \
2-thioureido) -2- (3-athoxy
-car bony 1-2- thi our e id o) -
benz ol

CO OJ CD

Forts, too

TABEL

co ο co co

cn

Q ■ z

31 sq
, ^ "VNH-C-NH-CO-CHo
Γ J CU
^> NH-C »NH-CN < Z. 3 ·
SO ^CH 3 1 ~ (3-N, N-dimethylamino-
carbonyl-2-thiournido) -
2 - (- 3-methoxycarbonyl-2-
thioureido) -benz ol 159-160 (II 32 S 0
VV ^ NH-C * -NH-CO-CH ₃
V ^ N = CH- {3} 1-benzylideneamino-2-
(3-methoxycarbonyl-2-
thioureido) benz.cl 145-146 33 s 9
^ YNH-C-NH-CO-CH ₃
^ v ^ Ν «C! I- / ~ ^S >) - C 1 l- (4-chloro-benzylidene-
fimino) -2 ~ (3 «m (3thoxy-
carbonyl «" 2-thioufGido) -
ben ^ ol 183-183.5 (Zl 34 S 0
^ ₁ -NH- (J] -NH-OO-CH ₃
W * * N = aW ^r "V-ocn ₃ 1- (4-Methoxybenzylidene-
amino) -2- (3-racthoxy-
carbMnyl -2-thioureido) -
bens ol 159-159.5 (Z) 35 s 9
jT ^ r NH-C-NH-COC ^ H-
S ^ N-CH- (^
^ C NQ ₂ l- (3-nitrobenzylidene-
atnino-2- (3-ethoxy-
car bony 1-2-thiour eider) -
benisol 185 (2)

to he"

CO

ω ο cn

193-540

la-36 476

- 27 -

Compared with known compounds used for the same purpose, the compounds listed in Table I have a far superior fungicide and acaricide Effectiveness on.

When used for combating fungal and other plant diseases, mites and mite eggs, a relatively small amount of the compounds according to the invention, which is applied to the plant surface by spraying, brushing on or atomizing, is sufficient. The concentrations of the active ingredients in the fungicides or acaricides according to the invention vary depending on the batch in question; for wettable powders, for example, they are in the range from 5 to 80, preferably from 10 to 60% by weight; for emulsifiable concentrates at 5 to 70, preferably 10 to 50% by weight; for powder agents is in the range of 0.5 to 10, preferably from 1 to 5 wt .-% _o In the compositions of the invention may contain excipients, for example, inorganic powder ", such as clay, talc, or diatomaceous earth, dispersing agents such as casein and Katriumligninaulfonat or wetting agents, such Alkylarylsulfonate or polyoxyethylene alkylphenol can be used, depending on whether the agents are intended to control fungi, bacteria or mites. Of course, the agents can also be mixed with other fungicides, insecticides, acaricides, agents for influencing plant growth and fertilizers.

The following are examples of some regulations given for fungicides or acaricides according to the invention:

- 28. 909882/1754

la-36 476

- 28 Example 14

Wettable powder Parts by weight * 20th
5 Connection 1
Sodium alkyl sulfonate

Diatomaceous Earth '75

The components are mixed and comminuted to a particle size of 10 to 30 µ. When used in In practice, the comminuted mixture is diluted with water to a concentration of 0.01 to 0.05% active ingredient. The suspension is sprayed or brushed on.

Example 15

Emulsifiable concentrate Parts by weight 10 Connection 2 5 Alkylaryl polyoxyethylene 50 Dimethylformamide 35 Xylene

The ingredients are mixed and dissolved. When used in practice, the solution is diluted with water to a concentration of 0.1 to 0.05 % active ingredient and the suspension is sprayed or brushed on.

909882/1754

la-36 476

- 29 -

Example

16

Powdered agent

link

talc

Alkylaryl polyoxyethylene

The ingredients are mixed and pulverized very finely. The powder is usually sprayed in an amount of 3 to 5 kg / a.

Weight parts 5 94 ,1 O ,1

example

17th

Mixed wettable powder

Connection 4

Bis (4-chlorophenyl) methyl carbinol Sodium alkyl sulfonate Sodium alkyl naphthalene sulfonate Sodium Lignosulfonate Diatomaceous Earth

Parts by weight

15 15

1 63

The ingredients are mixed, crushed and used according to Example 14 «

Examples 14 to 17 are not restrictive with regard to the emulsifiers, wetting agents or agents listed Dispersants, carriers and solvents.

- 30 -

909882/1754

la-36 476

- 30 -

The following example describes 7 individual experiments the superior fungicide and acaricide effect of the invention Links.

Example 18

Experiment 1: Attempt to combat anthracnose in cucumbers

Cucumber plants in pots which had developed 3 leaves were sprayed with the water-diluted solution of the wettable powder, prepared according to Example 14, in an amount of 50 ml per 3 plants. The next day, the plants were inoculated with a spore suspension of the cucumber anthracnose fungus, Colletotrichum lagenarium, and kept for 20 hours under conditions that favored development (about 100 % relative humidity, 26 ° G). Then the plants were taken to 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 of damage in untreated plants. The results are shown in Table II.

- 31 -

909882/1754

la-36 476

TABLE II

Compound active ingredient avg. No. Concentra- number Scha ™ tion endings ever

'i> ^sheet

Phyto suppression toxicity in%

2 300
5OO O
O 100
100 no
no 4th 300 0 100 no 13th 3OO . 12.2 92 no 3O 3OO 10.1 93.4 no 31 3OO 13.3 90.8 no Comparison
attempt · 300 0 100 no Empty
search - 153 0 -

• For comparison, a fungicide containing 2,4-dichloro-6- (2-chloroanilino) -s-triazine was used used as an active ingredient.

Experiment 2: Attempt to control powdery mildew on cucumbers - - -

At the beginning of the experiment, seriously diseased plants became

908882/1754 - 32 -

19305AO

LA-36 476 - 32 -

(Cucumber plants, infected with powdery mildew, Spaerotheca fuliginea) around the test plants (cucumber plants in the 3-leaf stage) arranged to cause natural infection. If the plants with Powdery mildew were infected, they were prepared with the diluted with water solution of according to Example 14 wettable powder is sprayed in an amount of 50 ml per pot and then brought into the greenhouse. 7 days after the spraying, the average number of damages per leaf was counted and based on the Damage to the untreated plants, the percentage disease is calculated. The results are shown in Table III emerged.

TABLE III

Verbin- active ingredient- percentage phytodung concentration- disease toxicity No. tion

(^ / ml)

2 300 0 no 5 300 0 no 13th 300 0 no 30th 300 0 no 31 300 0 no Comparison
attempt 150 3.5 no Empty
search . . 100

• For the comparison experiment jvjarde .. a, Fung ic id used that

la-36 476

-33-

as active ingredient e-methyl - ^^ - quinoxalinedithiol, cyclic Carbonate.

Experiment 3: Attempt to control the sandhill crane

The experiment was carried out to determine the effectiveness of the compounds according to the invention for combating rice blight (Piricularia oryzae) in the open field

investigate. There were 4 test strips of 1,, I m evaluated. The diluted broth was in one at a time

Sprayed amount of 250 ml / 11 m. The first spraying was carried out the day after the beginning on the leaves Infection was detectable, the second spraying 4 days after the first Plants evaluated 3, 7 and 11 days after the first spray. The decisive factor for the severity of the disease Disease index was set on a scale from 0 to 5, where O means no infection of the plants and 5 means that most of the plants are infected had died.

The results are shown in Table IV.

- 34 -

9098 82/17

la-36 476

- 34 -

TABEL

IV

«Er active ingredient

am- concent-

dung tration

No. (// ml)

Disease index

3 days 7 days 11 days

Phyto-

toxic

ity)

16 500 0 , 5 1 , 0 2.0 no 17th 500 0 , 75 i , 0 1.5 no 18th 500 0 , 5 1 , 0 1.5 no 19th 500 0 , 5 1 , 0 2.0 no 20th 500 0 , 25 1 , 5 1, O no 21 500 0 , 25 1 , 5 2.0 no 22nd 500 O. 1 , 0 2.0 no 24 . 500 0 _; , 5 0 , 5 1.5 no 25th 500 Ο, , 0 0 , 5 no 27 500 O ₁ , 2 1 , 0 1.25 no 28 500 O, 0 0 , 5 1.75 no Comparison
attempt *
500 ο, 5 1. , 0 2.0 no Empty
search - 1, 0 2, ⁴ > ⁵ -

• A comparison substance was used to combat Rice brandy known fungicide with pentachlorobenzyl alcohol as the active ingredient. · · "*"

909882/1754

- 35 -

la-36 476

- 35 -

Experiment 4:

Attempt to combat rice blight

For the experiment, potted rice plants with 3 leaves were used which had been sprayed with a spore suspension of the rice fungus, Pericularia oryzae, and kept for 24 hours under conditions favorable for incubation (about 100 % relative humidity, 26 ° C.). The plants were then moved to the greenhouse. The next day, the compound to be tested was applied to the plants as a dilute aqueous solution of a wettable powder, prepared according to Example 14. 10 days after the incubation, the number of diseased areas per pot was determined and the degree of suppression was calculated in% against the untreated plants. The results are shown in Table V.

TABLE V

Connect
manure
No.

active ingredient concentration

average Number of damages per pot

oppression

in %

Phytotoxicity

7th 300 0 100 no 8th 300 4th 95 no 9 300 6th 93 no 10 300 2 98 no 11th 300 2 98 no

Continued Table V:

- 36 -

909882 / 175A

la-36 476

300

100

no

(2 % active) (comparison) 20

(Water)

94

no

Empty attempt -

84

• O

• The comparison substance is a known fungicide for combating rice blight with a content of Antibiotics. "Kasugamycin" is a protected trade description.

Experiment 5: Attempt to control the early bloom (vaginal bloom) in rice

Young rice plants were cut back to 5 to 7 cm and these parts of the rice plants became a few minutes immersed in a water-diluted solution of the wettable powder prepared according to the example. After this The plants were dried on the saplings with a Colony of fungus causing early flowering in rice immersed and in a humid chamber for 5 days held. 3 days and 5 days after the inoculation, the average length of the damaged parts on the Scroll determined and the severity of the disease using the following scale (disease index, mean value) evaluated: 0 = not infected; 1 = very easy infected; 2 = damaged areas shorter than 1 cm; 3 = damaged areas 1 to 2 cm long; 4 = damaged areas longer than 2 cm. '

The results are shown in Table VI.

909882/1754

- 37 -

la-36 476

TABLE VI

Compound active substance concentrate no. tration

Disease index

3 days

5 days

Phytotoxicity

7th 500 - 0 0 no 8th 500 0 0.2 no 9 500 0 0 no 10 500 0.5 1.0 no 11th 500 0 0.2 no 12th 5 00 0 0 no 24 500 0.2 0.5 no 25th 500 0 0 no 27 500 0 0 no 28 500 0 0.2. no 32 500 0.2 0.5 no 33 500 0 0 "no 34 500 0 0 no 35 500 0.5 1.0 no Ver *
equal
attempt 43.3 0.5 1.0 no Empty-
attempt 3.0 4.0 -

• The comparison substance is a fungicide with a content of ferric methyl arsonate as an active ingredient. - 38 -

. 90 9882 / T754

mSPEGTED

la-36 476

- 38 -

Experiment 6: Attempt to combat early bloom (vaginal bloom) in rice (2)

The compounds to be tested were prepared as a solution of a wettable powder diluted with water according to Example 14, applied. 30 cm high rice plants in pots were each pot with 25 ml of the above Solution sprayed. The treated rice plants were left 2 hours, 3 days, 5 days and 14 days after the spraying, respectively brought to a -F you t air tk ammer and with a colony of the early flowering fungus in rice inoculated on the shoots. The severity of the disease was determined 3 days and 4 days after the inoculation, respectively evaluated using the method used in experiment 5. The results are shown in Table VII.

TABLE VII:

- 39 -

909882/17

TABLE VII

co ο co CX) CX) K)

Link

No.

Active ingredient concentration

(ppm)

average infection

! .Day 3rd day 7th day 14th day

Phyto-

toxi-

ity

16 500 0.0 1.0 1.5 2.0 no 17th 500 0.0 0.5 , 1.0 1.5 no 18th 500 0.5 1.0 1.0 1.2 no 19th 500 1.0 1.0 1.5 2.0 · no 20th 500 0.5 0.5 1.0 .1,2 no '21 500 0.0 1.0 1.5 2.0 no .22 500 0.5 0.5 1.0 1.2 no 26th 500 0.0 0.5 1.0 1.2 no Polyoxime
(Comparative
attempt 1)
100 0.5 1.0 1.5 2.0 • no Comparison
attempt 2) **
25th 3.0 3.5 4.0 , 4.0 no

LU

to

cn

CD

CD CjO

la-36 476

- 40 -

• For comparative experiment 1, a fungicide against early flowering in rice with a content of antibiotics was used used.

·· In comparative experiment 2, a fungicide commonly used in agriculture was used with a content used on methylarsine sulfide as an active ingredient.

Experiment 7: Attempt to control Tetranvchus mites

About 30 adult female mites of the species Tetranychus desertorum were placed on the main leaves of bean plants in pots which 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 containing 0.05 % of the compound prepared according to Example 15. 3 days after the spraying, the adult mortality was counted, and then the surviving adult mites were removed. The viability of eggs laid during this period was assessed 14 days after spraying.

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

Viability in %: (ä-b) _x iqo

.a: Number of living mites on untreated plants

b: number of surviving mites on treated plants

909882/1754 ~ 4-

ORlGINAU

la-36 476

Ovxcid effect of the agent in%: Ca'-b ¹ ) _x

a

a ': number of laid eggs b ^f : number of hatched animals

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

Mortality or Ovicide Effect Rating

100 %

80-99 %

50-79%

0-49 %

The results are shown in Table VIII.

TABLE VIII

Connection no. Rating

mortality

Ovicidal action

909882/1754 - 42 -

Cont. 1930540
la-36 476 - 42 - • to TABLE VIII valuation Connect
manure Mortality Ovicidal Effect No. Z 11th • ₊ 12th 13th ₊ 14th + ■ + ■ + 15th + ■ 16 . - 17th 18th 19th 20th + ₊₊ 22nd '+' ₊₊₊ 23 24 ■ + +++ 25th 26th - +++ 27 '■ + ■ ₊₊₊ 28 + +++ 29 + ++ + 30th +. + + 31 -. ■ 32

9 0 9 8 8 2/1754

lA-36 - 43 - 1930540
476 • TABLE VIII Forts, too valuation Connect
manure
No. mortality 33 ₊ Ov ic id effect 34 ₊ · 35 + + +

2,4,5,4 · tetrachlorodiphenyl sulfone

(Comparative experiment ·) - +++

• Note: reference substance is one under the

protected trade name "Tetradifon" known mite repellant.

PATENT CLAIMS

9098 8 ° -Ί "5

Claims (7)

PATENT CLAIMS wherein X is a hydrogen or chlorine atom or a Is nitro or methyl group; Z for the groups R R -N ^ ² , -N <; 2. a or -N = R ₄ ; F. one Represents an alkyl group of 1 to 4 carbon atoms; R _{2 is} a hydrogen atom or a methyl group; R _{3 has the} following meanings: hydrogen; Methyl; Formyl; Alkylcarbonyl with 2 or 3 carbon atoms; Cyclopropylcarbonyl; Benzoyl; Alkyloxycarbonyl with 2 or 3 carbon atoms; Alkylaminocarbony1 with 4 or 5 carbon atoms; Thioformyl; Aminothiocarbonyl; Aminothiocartoonyl substituted with an alkyl group having 1 to 3 carbon atoms; 909882/1754 1930 ^ 40 la-36 476 3,3-dimethylureidocarbonyl; or 3,3-dimethylthioureidocarbonyl; R, the benzal group, optionally with Is chlorine substituted by nitro or methoxy group; and A for an inorganic or organic one Acid stands. · * 2) Process for the preparation of the Thxourexdobenzenes according to claim 1, characterized by * that you get a compound of the formula: or implements with SCN - C - O - ti 3) Process for the preparation of the Thxourexdobenzenes according to claim 1, characterized in that a compound of the formula: 909882/1754 lA-36 -V • I Il NH-C-NH-C-O-R, with an inorganic or organic acid. · 4) Process for the preparation of the thioureidobenzenes according to claim 1, characterized in that that a compound of the formula: S 0 Il Il NH-C-NH-C-O-R. reduced with iron powder and water. 5) Process for the preparation of the thioureidobenzenes according to claim 1, characterized that you have a compound of the formula: S 0 Il Il NH-C-NH-COR ₁ 909882/17 Sk la-36 476 with RqOH or R_C1. 6) Process for the preparation of the thioureidobenzenes according to claim 1, characterized in that a compound of the formula: NH-C-NH-COR ₁ with isocyanate or isothiocyanate. 7) Use of thioureidobenzenes according to claim 1 as active ingredients in fungicides and acaricides (agents for Control of fungal diseases and mites in plants). 9 0 9 8 8 ^{2/1 η} 5 L