DE2217169A1 - SUBSTITUTED BENZIMIDAZOLES - Google Patents

Description

FARBWERKE HOECHST AG, formerly Master Lucius & Brüning

f -.

2417169

File number: HOE 72 / F 113

Date: April 7, 1972 Dr. Tg / br

Substituted benzimidazoles

The invention relates to benzimidazoles of the formula I

--NH-COOCH ₃ (l)

W R

O = C-NH- (J-CH-COOR ^

RiR ₃
where R _{1 is} hydrogen, alkyl with "\ -h carbon atoms, vinyl or

Phenyl, which is optionally substituted by chlorine and / or nitro,
Rp hydrogen, -CH ,. or -CHpCl, R hydrogen or -CH ₃ ,

R and R "together a trimethylene, tetramethylene or ' ^H ₂ - group,

and Rr is alkyl with 1-4 carbon atoms.

The invention also relates to a method for production of compounds of formula I, which is characterized is that one

a) 2-methoxycarbonylamino-benzimidazole of the formula II

NH-COOCH ₃ (ll)

309842/1160

with isocyanates of the formula III-

O = C = N-C- CH- COOR., (III)

it ^H

or with carbaniic acid halides of the formula IV

Cl (Br) R ₂

O = C-NH-C-CH-COOR. (IV)

ι ι ^

R,

or

b) 1-chloro (or bromine) carbonyl-2-methoxycarbonylamino benzimidazole of formula V

^L NH-COOCH _g (V)

O = C -Cl (Br) with amines of the formula VI

H ₂ N - C - CH - COOR ^ (Vl)

R ₁ R ₃

implements.

The process according to (a) is advantageously carried out in an inert organic solvent such as dimethylformamide, methyl ethyl ketone, Methylene chloride, chloroform, chlorobenzene, tetrahydrofuran or acetonitrile in the temperature range from about 0 to 80 C. It is advantageous to use a small excess of isocyanate.

309842/1160

The benzimidazole derivative is generally used to carry out the reaction " (II) suspended in an inert solvent with stirring and the isocyanate (III) added, the reaction starts with heating. The reaction time is between 2 and 20 hours; T. catalytically by addition acting substances such as tertiary amines are reduced.

The 2-carbomethoxyamino-benziraid azole used as starting material can be obtained from isothiourea dicarbonate and o-phenylenediamine (j. Am. Chem. Soc. J ^ o ₅ 1 kk (193 ^))

The isocyanates are phosgenated by ß-amino acid esters accessible (see Annalen 575, p. 217 (1952). "

A carbamic acid halide is used instead of an xocyanate of formula IV, the preferred procedure is as follows:

First, the carbamic acid dichloride is prepared by adding an area of the formula VI at 0 to 25 ° C. to a solution of phosgene in an inert organic solvent such as benzene or tetrahydrofuran, filtering off the hydrochloride of the amine and distilling off excess phosgene in vacuo. Then 2-methoxycarbonylaminobenzimidazole of the formula II is added in an approximately stoichiometric amount and then an acid peak septor, Z ₀ B a tertiary amine or potassium carbonate, is added. The temperature

ο in this reaction step is generally between 0 and 35 C. It is then processed in the usual way «

According to method (b), for example, in the first "Stnte" ^ 2-methoxycarbonylaminobenzimidazole with a solution of phosgene in Qinem

ο ο indifferent organic solvent at approx. -20 C "to -! - 2G G, then an equivalent amount of a tertiary amine, such as dimethylaniline, triethylamine or pyridine, added and the hydrochloride separated off. After the excess phosgene has been distilled off, the product becomes reacted with twice the stoichiometric amount of an amine of the formula VI in the temperature range from about 0 to kO C and added in the usual way

^works · 309842/1160

The benzimidazoles according to the invention are distinguished by a very good fungicidal action. They are through leaves and Roots taken up and are superior to relevant commercial products in their systemic effect.

Examples of harmful fungi against which the compounds can be successfully applied are the following:

Powdery mildew mushrooms (Erysiphaceans), Rhizoctonia spp., Sclerotinia spp., Botrytis spp., rust fungi, Fusarium spp., Cercospora spp., Septoria spp., Microsphaerella spp., Fusicladium spp., Venturici spp., Cladosporium spp., Colletotrichum spp., Verticillium spp.

Their applicability for combating fungal diseases on plants, which is both prophylactic and curative, is supported by certain acaricidal and ovicidal properties against plant pests added.

The invention therefore also relates to agents for combating fungal diseases and animal pests, in particular helminths, containing from 5 to 90 ° of benzimidazoles of the formula (i) as active ingredients in the customary mixtures with solid or liquid formulation additives such as inert carriers, adhesive -, wetting, dispersing and grinding aids. They can be used as wettable powders, emulsions, suspensions, dusts or granulates. They can also be mixed with other fungicides with which they form compatible mixtures.

Mineral substances such as aluminum silicates, clays, kaolin, chalks, siliceous chalks can be used as carrier substances, Talc, kieselguhr or hydrated silica, or preparations of these mineral substances with special additives, e.g. Chalk greased with sodium stearate. All common and suitable solvents, for example toluene, xylene, diacetone alcohol, cyclohexanone, isophorone, benzime, paraffin oils, dioxane, dimethylformamide, Dimethyl sulfoxide, ethyl acetate, tetrahydrofuran, chlorobenzene and others are used. _ _

309842/1150

Glue-like cellulose products or polyvinyl alcohols can be used as hard materials be used.

All suitable emulsifiers such as oxyethylated can be used as wetting agents Alkylphenols, salts of aryl or alkylarylsulfonic acids, Salts of oleylmethyltaurine, salts of oxethylated phenylsulfonren or soaps can be used.

Cell pitch (salts of lignosulfonic acid), Salts of naphthalenesulfonic acid or salts of oleylmethyltaurine be used.

Suitable inorganic or organic salts such as sodium sulfate, ammonium sulfate, sodium carbonate, sodium bicaribonate, sodium thiosulfate, sodium stearate can be used as grinding aids. or
Sodium acetate can be used.

309842/1 1 50

MANUFACTURING EXAMPLES

Example 1;

l - (l ^! -Methyl-2'-methoxy carbonyl) -äthylcarbamoyl- 2-methoxy carbonylaminoben zi mid azpl

19.1 g (0.1 hol) 2-carbomethoxyaminobenzimidazole and 14.3 g (0.1 mol) of 1-methyl-2-methoxycarbonyl-ethyl isocyanate are stirred in 200 ml of chloroform at 30 ° C. for 15 hours. After filtration the solvent is largely distilled off. The reaction product crystallizes out from the residue.

Yield; 25 g m.p .: 290 ° -295 ° C (dec.)

-NH-COOCHg C ₁₅ H ₁₈ N ₄ O ₅ MW 334

O = C-NH-Ch-CH ₂ -COOCH ₃ calc .: N 16.75 %

CH _{3 found} : N 16.85 #

Example 2:

[L- (I ', 1'-Dimethyl -2'-methoxycarbonyl) -ethylcarbamoyl-2-methoxycarbonylaminobenzimidazole

19.1 g (0.1 mol) of 2-carbomethoxyaminobenzimidazole and 15.7 g (0.1 mol) of l, l-dimethyl-2-methoxycarbonyl-ethyl isocyanate are mixed in 300 ml of methylene chloride with 0.1 ml of triethylamine and 12 hours stirred at 20 ^{° C.} The work-up is carried out as under (l).

Yield: 27 g. Mp .: 288-290 ° C

'Nx
^ -HN-COOCH ₃ C ₁₆ H ₂₀ N ₄ O ₆ MW 348

W CH ₃

O = C-NH-C-CH _{8 -COOCH 3} calc .: N 16.1

Found: N 15.8

3 0 9 8 4 2/1 150

Example 5:

1- (1'-methyl-2'-isopropoxycarbonyl) -ethylcarbamoyl-2-methoxycarbonylamino-benzimidazole

Per 0.1 mol carbomethoxyamino and l-methyl-2-isopropoxycarbonyl-ethyl isocyanate are stirred for 10 hours at 25 ⁰ C in tetrahydrofuran. After adding twice the volume of petroleum ether, colorless crystals are obtained from the concentrated filtrate.

Expansion: 24 g melting point: 275 ° -278 < Example 4: 'C ^ i 7H ₂ g 1 tf ₄ o 6th 15, MG 362 \ j J-NH-COOCH ₃ ber .: N 15, VJl O = C-NH-CH-CHg-COOCH (CH ₃ ) _a found: N VJl CH ₃ 1- (1'-Butyl-2'-methoxycarbonyl) -äthylcarbamoyl-2 ~ methoxy- carbonylamino-benzimidazole

0.1 mol carbomethoxyamino and 0.1 mol l-butyl-2-carbomethoxy-ethyl isocyanate are stirred in 200 ml of methyl ethyl ketone ifil the addition of 0.1 'of triethylamine for 6 hours at 20 ⁰ C. A colorless powder is obtained from the filtrate after the solvent has been distilled off.

Yield: 28 g. Mp .: 295-299 ° C (dec.)

• Nx
^ -IiH-COOCH ₈ 'C ₁₈ H ₂₄ N ₄ O ₅ MG 376

O = C-NH-Ch-CH ₂ -COOCH ₃ calc .: "N 14.9 ^

C ₄ H ₉ ■ found: N 14.7 %

309842/1 150

Example 5:

1- (1'-vinyl-2'-methoxycarbonyl) -ethylcarbamoyl-2-methoxycarbonylamino-benzimidazole

The mixture of 0.1 mol carbomethoxyamino, 0.1 mol l-vinyl-2-methoxycarbonyl-ethyl isocyanate and 200 ml of chloroform is stirred for 18 hours at 30 ⁰ C. The solution is filtered and the solvent is distilled off.

Yield: 30 g. Mp .: 258-260 ° C

■ Nx
^ -NH-COOCH ₃ C ₁₆ H ₁₈ N ₄ O ₆ MW 346

O = C-NH-CH-Ch ₂ -COOCH ₃ calc .: N 16.2 $ CH = CH _{2 found} . : N 16.2 fo

Example 6;

1- C ₁ I'-methyl-2'-butoxycarbonyl) ethylcarbamoyl-2-methoxycarbonylamino-benzimidazole

The mixture of 0.1 mol carbomethoxyamino and 0.1 mol l-methyl-2-butoxycarbonyl-ethyl isocyanate in 300 ml of benzene for 10 hours at 4O ⁰ C stirred.

Yield? 25 g m.p .: 287-290 ° C

; -NH-COOCH ₃ C ₁₈ H ₂₄ N ₄ O ₆ MW 376

O = C-NH-CH-CH ₂ -COOC ₄ H ₉ calc .: N 14.9

CH ₃ • found: N 15.1

309842/1150

Example 7:

1- (1'-Phenyl-2'-methoxycarbonyl) -ethylcarbamoyl-2-methoxycarbonylamino-benzimidazole

A 0.1 mol approach carried out analogously to Example (1) Carbomethoxyaminobenziraidazole and phenyl-2-methoxycarbonylethyl isocyanate revealed

Yield: 32 g m.p .: 255 ° ~ 260 ° C

^ -NH-COOCH ₅ C ₂₀ H ₂₀ N ₄ O ₅ MW 396

O = C-NH-CH-Ch ₂ -COOCH ₃ calc .: N $

found : N 14.2 <? O

Example 8 :

l- / T '- (3-nitro-4-chlorophenyl) -2'-methoxycarbonyl7-ethylcarbamoyl-2-methoxycarbonylamino-benzimidazole

In 200 ml of toluene, 0.1 mol and 0.1 mol were carbomethoxyamino (5-nitro-4-chloro-phenyl) -2-methoxycarbonyl »ethyl isocyanate stirred under addition of 0.1 ml of triethylamine for 1 hour at 4O ⁰ C l. The reaction product, which was sparingly soluble in toluene, was filtered off with suction,

Yield: 37 g m.p .: 253 ° ~ 255 ° C

-NH-COOCH ₃ C ₂₀ H ₁₈ ClN ₅ O ₇ MW 475.5

O = C-NH-CH-Ch ₂ -COOCH ₃ calc .: N 14.7 Ji

found: N $ 14.7

^s N0 ₂ Cl

309842/1150

Example 8 a;

1- (2'-methoxycarbonyl) -ethylcarbamoyl-2-methoxycart) onylaininobenzimidazole

28.6 g (0.15 mol) of 2-carbomethoxyaminobenzimidazole are suspended in 300 ml of chloroform and a solution of 19.5 g (0.15 mol) of 2-methoxycarbonylethyl isocyanate in 20 ml of chloroform is added. After stirring for 8 hours at 25 ^° C., 44 g of reaction product are isolated from the chloroform-containing filtrate.

M.p .: 250 ° - 252 ° C (dec.) Nx

^ -NH-COOCH ₃ C ₁₄ H ₁₆ N ₄ O ₅ MW 320

O = C-NH-CH ₂ -CH ₂ -COOCh ₃ calcd .: N 17.5 $

found i N 17.6 %

Example 8 b:

1- ^ 2'-butoxycarbonyl) ethylcarbamoyl-2-methoxycarbonylaminobenzimidazole

28.6 g (0.15 mol) of 2-carbomethoxyamino and 25.6 g (0.15 mol) of 2-butoxycarbonyl-ethyl isocyanate are stirred for 10 hours at 25 ⁰ C in 300 ml of chloroform. After filtration, the chlorine is distilled off.

The residue left behind is 50 g of a colorless powder with the following structure:

Mp 55-57 ° C

Nx ^ -NH-

NH-COOCH ₃ C ₁₇ H ₂₂ N ₄ O ₆ MW 362

O = C-NH-CH ₈ -CHg -COOC ₄ H ₉ calcd .: N 15.5

Found: N 15.7

309842/1 150

Example 9:

1- (1 ', 2'-Dimethyl-2' - methoxycar b'onyl) ~ ethylcar bamo yl-2 - methoxycarbonylamino-benzimidazole

To the suspension of 0.1 mol carbomethoxyamino in 150 ml of chloroform is added dropwise at 20 ⁰ C 0.1 mole of 1,2-dimethyl-2-methoxycarbonyl-ethyl isocyanate and stirred for 20 hours. The reaction product is obtained as a colorless powder by concentrating the filtrate.

Yield: 21 g. Mp .: 268-270 ° C

-NH-COOCH ₃ C ₁₆ H ₂₀ N ₄ O ₅ MW 348

O = C-NH-CH-CH-COOCh ₃ calcd.: N 16.1

CH ₅ CH _{3 found} : N 15.9

Example 10:

a) 1- (1 '-Methyl-1' r -chlorinethyl-2 '-methoxy carbonyl) -äthylcarbamoyl- 2-methoxy-carbonylamino-benzimidazole

0.1 mol and 0.1 mol carbomethoxyamino manner analogous to Example (9) l-Methyl-l ~ chloromethyl-2 ~ 27 hours methoxycar'bonyläthylisocyanat stirred at 2O ⁰ C.

Yield: 12 g of colorless powder, mp. % 175-178 ° C

J-NH-COOCH ₅ C ₁₆ H ₁₉ ClN ₄ O ₅ MW 582.5 W CH ₃

O = C-NH-C-CH ₂ -COOCH ₃ calc. % N 14.6 #

CH ₂ Cl found: N 15.0 ? O

309842 / 11S0

In an analogous way one obtains:

b) 1 - / "(1-methyl-1-propyl-2-methoxycarbonyl-ethyl) -aminocarbonyl / -2 -ine thoxy carbonyl amino benzimidazole

c) 1 - / (1-methyl-1-vinyl-2-methoxycarbonyl-ethyl) -arainocaibonylj-2-methoxycarbonyl-aminobenzimidazole

^) 1 ~ / 0-methyl-1-phenyl-2-ethoxycarbonyl-ethyl) -amino-

carbonyl / -2-methoxycarbonyl-aminobenzimidazole e) 1 - / <1 ~ (3-Nitrcphenyl) -2-methoxycarbonyl-ethyi> -amino-

earbonyl7-2-methoxycarbonyl-aminobenzimidazole f) 1 - / <Cl - (4-Chlorph.enyl) -2-methoxycarbonyl-ethy ^> - amino-

carboiiyl / -2-methoxycarbonyl -amino-benzimidazole g) 1 - / <4 - (2, 4 ~ Di chi or phenyl) -2-methoxycarbonyl-ethy ^ ^> '-amino-

carb ony 1,7-2-η; ethoxy carbonyl-amino-benzimidazole

C ^ C-NH-QH-CH-COOCH

Γ ^ NHCOOCH ₀

O = C-NK-;

k) f I

O-C-NH-7 c-COOCH.,

309842/1

APPLICATION EXAMPLES

Example 11:

Rice plants were heavily infected in the 4-leaf stage with a conidia suspension of Piricularia oryzae and incubated in a humidity chamber at 100 $ humidity and 25 ° C for a period of 24 hours and then placed in a greenhouse with optimal infection conditions (relative humidity 80-90 $>, Temperature 22 ° - 23 ° C). After an infection time of 5 days, the plants with the claimed compounds according to Example 1, 2, 3, 4, 5 »6, 9 and 10 in the concentration of 60, 30, 15, 7.5 and 3.75 mg of active ingredient each Liters of spray liquid treated dripping wet. A commercial preparation based on benomyl (l-carbamoylbutyl-benzimidazole-2-carbamic acid methyl ester, cf. agent I) and a compound disclosed according to DOS 1.956.157 (l-carbamoyl-methyl-benzimidazole-2-carbamic acid methyl ester, cf. Medium II) in the same jföawßH-dung concentrations. In addition, a commercial preparation based on fentin acetate (cf. agent III) was also tested in the same concentrations as a comparison agent.

After the spray coating had dried on, the plants were returned to the greenhouse and remained here until Disease outbreak.

The disease infestation was assessed visually and expressed in $ infected leaf area in relation to untreated, infected control.

As can be seen from the comparison result in Table I, the compounds claimed have a significantly better one Effect than the comparison means.

309842/1150

Example 12;

Were 'practicing planting sugar. "" Betioolc with a conidial suspension of Cercospora, ö.e> L Srreger the ßlattfleckenkrankheit heavily infected and incubated for 24 hours in a Feufchtekammer at a temperature of 25 ⁰ C and relative humidity of 100 i ". The plants were then placed in a greenhouse with optimal conditions for the pathogen at a temperature of 25 ^° C. and a relative humidity of 80-90 °. 10 days after the infection the plants with the compounds mentioned in cakewalk stressed ;, Ii in the active compound Konzentrationer were: on 120, 60, 30 _f 15, 7.5 and 3.75 mg per liter Sprxtzfcrahe treated to runoff.

A commercial preparation based on Benomyl (cf. agent i), another analogous preparation according to, served as the comparison agent DOS 1.956.157 (cf. means II) and Maneb = Manganäthylenbisdithiocarbamat (See means III), in the same active ingredient concentrations.

After the spray coating had dried on, the plants were returned to the greenhouse where, after the outbreak of the Disease, 3 weeks after treatment, for severity of infestation.

As is generally the case, the infestation evaluation was carried out on the basis of visual inspection. The infestation of the disease was expressed in fo infected leaf area compared to the untreated control (= 100). As can be seen from the test result in Table II, the claimed compounds have a better activity than the comparison agents.

Example 13;

Tomato plants were heavily infected in the fully grown 3-leaf stage with conidia of the pathogen causing brown spot disease in tomatoes (Cladosporium fulvum) and for a period of time

309842/1150

of 24 hours in a humidity chamber at a temperature of 25 ⁰ C and a relative humidity of 100 % . The plants were transferred to a greenhouse having a temperature of 23 ° - 90 had fo - 25 ⁰ C and a relative humidity of 80 s. 10 days after infection, the plants were treated with the compounds mentioned in Example 11 until they were dripping wet. The concentrations used were 120, 60, 30, 15, 7.5 and 3.75 mg of active ingredient per liter of spray liquor. As a ver. A preparation based on benomyl (cf. agent I) and a preparation according to DOS 1.956.157 (cf. agent II) in the same application rates served as the same agent. After the spray coating had dried on, the plants were returned to the greenhouse with optimal growth conditions for the pathogen, where they remained until the symptoms of the disease broke out.

The disease infestation was assessed visually and was expressed in fo infected leaf area, based on the untreated control (= 100).

As can be seen from the result in Table III, the Compounds claimed a very good curative activity, which is better than that of the comparison agents used.

Example 14:

2-leaf stage cucumber plants were heavily infested with conidia of the cucumber powdery mildew (Erysiphe cichoracearum) and fo incubated in a moisture chamber for one day at a temperature of 20 ⁰ C and a relative humidity of 100 in. The plants were transferred to a greenhouse having a relative humidity of 80 - had 22 ° C - 90 f> and a temperature of 20 °. After a period of 5 days, the plants were treated with the compounds mentioned in Example 11 until they were dripping wet. The use concentrations were 60, 30, 15, 7.5 and 3.75 mg of active ingredient per liter of spray liquor.

309842/1150

A commercial preparation based on benomyl (cf. agent i), a preparation according to DOS 1.956.157, was used as a comparison agent (See means II) and a preparation based on Dinocap (see means III) in the same concentrations.

After the active ingredient coating had dried on, the plants were placed in brought back the greenhouse and examined after an incubation period of 14 days for infestation with cucumber powdery mildew. Of the Powdery mildew infestation was assessed visually and in $ infected leaf area compared to infected, however untreated control (= 100) expressed.

As can be seen from the result in Table IV, the Compounds claimed a significantly better curative effect than the comparative funds.

309842/1150

Table I.

preparation
according to
example (I] ^ -NH-COOCH ₃
R. io infestation
at mg
wages
60 with Pia
Act
η on ui
30th "iculari
3ff each I.
ibehande a oryza
, iter Sp
Ite Kon
7.5 e of rice,
cracked broth,
trolls = 100
3.75 2 CH ₃
R = CNC-CH ₂ -C-OCH ₃
1 »TJ t It
0 ⁿ CH ₃ 0 0 0 3.0 8.0 12.0 1 CH ₃
R s CNC-CHg-C-OCH ₃
ti TJ TJ H
o * "■ o 0 0 2.0 5.0 10.0, 3 CH ₃
R - CN-CH-CH ₂ -C-OCH
Il UI Ht
0 ⁿ CH ₃ 0 CH ₃ 0 0 2.0 8.0 I.
10.0 6th R - CN-CH-CH ₂ -C -OC ₄ H ₉
ti xj ι ti
0 ⁿ CH ₃ 0 0 0 0 4.0 8.0 4th 0
R * CN-CH-CHg-C-OCH ₃
0 ^H (CH ₂ ) _S -CH ₃ 0 0 2.0 8.0 10.0 ro
_A 9 R = CN-CH-CH-C-OCH ₃
Il UI t It
0 ^Ά CH ₃ CH ₃ O 0 0 0 3.0 _A
8.0 &>
⁷ CO

Preparation according to

example

r-NH-

Table I (continued)

Infestation with Piricularia oryzae on rice

NH-COOCH _S.

R = CN-CK-CH ₂ -Ct-DCH ₃ 0 ⁿ CH = CH ₂ with mg of active ingredient per liter of spray liquor, based on untreated control =

30th

7.5

3.0

5.0

C *> O CO

10

CH ₃

R = CNC-CH ₂ -C-OCH ₃ 0 ⁿ CHoCl

10.0

15.0

See means I.

-NH-COOCH ₃

■ N '

O = C-NH-C ₄ H ₉

5.0

12.0

20.0

See means II

See means III

-NH-COOCH ₃

O = C-NH-CH.

Sn-OCOCK,

15th

15.0

25.0

25.0

65.0

55.0

80.0

control

\ -r

infected - untreated

100

100

100

100

( Table II io with Cei
area
related
120 "cospora
at mg \
ι to unk
60 betico
firksto
> ehande
30th la befs
ff / ltr.
lte Cor
15th illene
Fuel
itroll
7.5 Sheet-
broth,
= 100
3.75 preparation
according to
example i | ^ -NH-COOCHg
f
R. O O O 5.0 12.0 21.0 .2 CH ₃
. R = CNC-CH ₂ -C-OCH ₃
Ii υ ι: t
0 ⁿ CH ₃ 0 O O O 2.0 8.0 15.0 1 CH ₃
R = CNC-CHp-C-OCH ₃
dd TJ TJ dd
0 ^{Ά h} 0 O O O 3.0 8.0 17.0 3 CH ₃
R = CN-CH-CHg-C-OCH
tt TJ t tt t
O ⁿ CH ₃ O CH ₃ O O O 2.0 5.0 10.0 6th R = CN-CH-CH ₂ -C-OC ₄ H ₉
ti π ι. dd
O ^Ά CH ₃ O O O O 5.0 15.0 20.0 4th O
R = CN-CH-CH ₂ -C-OCH ₃
8 ^H (CHg) _s -CHg O O O 2.0 5.0 15.0 9 R = CN-CH-CH-C-OCHg
it tr ι t tt
0 "CHgCHgO

preparation

according to the example

Table II (continued)

^l ^ -NH-

NH-COOCH

leaf infested with Cercospora beticola

area at-mg ¥ active substance / ltr. Spray mixture, based on untreated control = 100

60

30th

15th

7.5

3.75

R = CN-CH-CH ₈ -C-OCK ₃ 0 ⁿ CH = CH ₂

3.0

8.0

12.0 '

CD CO ■!> ■ NO

10

CH ₃ R - CNC-CH ₃ -C-OCH ₃

It XJ t ti

0 ⁿ CH ₂ Cl 0

8.0

15.0

25.0

See means I.

Nx

NH-COOCH,

O = C-NH-C ₄ H ₃

10.0

20.0

35.0

See means II

-NH-CDOCH ₃

O = C-NH-CH ₃

2.0

15.0

30.0

45.0

See.

Means III Maneb

H £ CH ₂ -N-CS-

CH ₂ -N-CS- ^M S

Mn

100

100

100

100

100

control

infected - untreated

100

100

100

100

100

Table III

preparation
according to
example HT ^ -NH-COOCH ₃
1
R. fo with CU
area
wages
120 .adosporii
ϊ at mg If
) Ώ on low
60 im f ulvuir
/ irkstofi
) e trades
20th ι befal.
VLtr.
, e cont.
15th lene Βίε
Injection
role =
7.5 ltt-
'• ow,
100
3.75 2 CH ₃
R = CNC-CH ₂ -C-OCH ₃
ti U t It
0 ⁿ CH ₃ 0 0 0 0 5.0 10.0 20.0 1 CH ₃
R =. CNC-CHg-C-OCH ₃
ti υ H »
0 0 0 0 0 3.0 8.0 15.0 3 CH ₅
R = CN-CH-CH ₂ -C-OCH
nut it t
0 ⁿ CHg 0 CHg 0 0 0 5.0 12.0 ι
18.0 *
ι 'β R = CN-CH-CH ₂ -C-OC ₄ H ₉
ti η '"
0 ^w CH ₃ 0 0 0 0 3.0 -8.0 12.0 A. 0
R = CN-CH-CH ₂ -C-OCH ₃
0 ¹ MCHg) ₃ -CH ₃ 0 0 0 8.0 12.0 25, O ₁ ^
ho 9 R = CN-CH-CH-C-OCHg
it υ »t π
0 ⁿ CH ₃ CH ₃ O 0 0 0 3.0 6.0 12.0 σ)
CD

preparation

according to the example

10

See.

Means I Benomyl

Table e III (continued)

-NH-COOCH.

Leaf surface infested with Cladosporium fulvum at mg active ingredient / ltr. Spray liquor, based on untreated control =

R = CN-CH-CH ₂ -C-OCH ₅

t! ff! ti

0 ^W CH = CH ₉ 120

60

30th

CH ₃ R for CNC-CH ₂ -C-OCH ₃

!! Ui Γ!

0 CH ₂ Cl 0

O = C-NH-C ₄ K ₉

8.0

15th

5.0

8.0

15.0

7.5

8.0

15.0

25.0

3.75

15.0

28.0

38.0

See means II

control

-NH-COOCH ₃

O = C-NH-CH,

infected - untreated

12.0

25.0

38.0

100

100

100

100

100

53.0

100 K)

Table IV

preparation
according to
example R = Il l "^ ^ -NH-COOCH ₃
t
R. fo with Gu3
jfig we]
on unl
60 rkenmehlts
cstoff ever
Dealt
30th IU befa
liter
3 contr
15th llene Bl
Spray br
olle = 1
7.5 att area at
Uhe, related
OO
3.75 2 R = CH ₃
CNC-CH ₂ -C-OCH ₃
Ö ^H CH ₃ 8 0 0 O 8.0 15.0 1 R _ CH ₃
, CNC-CH ₂ -C-OCH ₃
tt w Ή tt
0 ^{n rt} 0 0 0 O 3.0 10.0 3 R = CH ₃
CN-CH-CH ₂ -C-OCH
π υ ι it t
0 ^Ά CH ₃ 0 CH ₃ 0 0 O 5.0 15.0. j β R = CN-CH-CH ₂ -C-OC ₄ H ₉
dd ff! -It
0 ⁿ CH ₃ 0 0 0 O 3.0 10.0 4th R = 0
CN-CH-CH ₂ -C-OCH ₃
δ ^H (CH ₃ ) ₂ -CH ₃ 0 0 O 8.0 15.0 9 CN-CH-CH-C-OCH ₃
Il ti tt tt
0 ⁿ CH ₃ CH ₃ O 0 0 O 3.0 8.0

preparation
according to

example

-NH-COOCH

Table IV (continued)

leaf area infested with cucumber powdery mildew with mg active ingredient per liter spray mixture, based on untreated control =

15th

7.5

3.75

R = CN-CH-CH ₂ -C-OCH ₃

Il Vt »t!

0 ⁿ CH = CH ₂ 0

2.0

10.0

10 '

CH ₃ R = CNC-CH ₂ -C-OCH ₃

• ti R I t!

0 ^π CH ₂ Cl 0

5.0

15.0

See.

Means I.
Benonyl

Vnh-

NH-COOCH ₃

O = B-NH-C ₄ H ₀ 3.0

10.0

25.0

See.
Means II

-NH-COOCH ₃

O = C-NH-CH,

8.0

15.0

36.0

See.

Means III
Dinocap

. 0

O-C-CH = CH-CH ₃

CH,

NO ₅

45.0

85.0

100

control

infected - untreated

100

100

100

100

Claims (3)

Patent claims 1 ¥ compounds of the formula (ι) ? 2 0 = C -NH-C-CH-COOR ,, dd Mr. ₁₃ where R is hydrogen, alkyl with 1-4 carbon atoms, vinyl or phenyl, which is optionally substituted by chlorine and / or nitro, R _{2 is} hydrogen, -CH "or R" is hydrogen or -CH, and R_ together is a trimethylene, tetramethylene or and R. denote alkyl with Λ-h carbon atoms. 2) Process for the preparation of compounds of the formula I, characterized in that in a known manner a) 2-methoxycarbonylamino-benzimidazole of the formula II (H) H with isocyanates of the formula III O = C = N-C-CH-COOR. (Hl) ι f ^ R ₁ R ₃ or with carbamic acid halides of the formula IV Cl (Br) R ₂ O = C-NH-C-CH-COOR. (iv) ι ι ^ R ₁ R ₃ 309842/1150 b) 1-Chloro- (or Broni) -carbonyl-2-methoxycarbonylatninobenzxmidazole of Formula V -NH-COOCH (V) with Amxnen of Formula VI HN -C-CH- COOR. (Vl) t ι ^
R ₁ R ₃ implements. 3) Fungicides »characterized by a content of 5 - 90 to Veroiiia Ji; geii of the formula I as Yirkstoff. 309842/1150