DE2219174A1 - FUNGICIDALS - Google Patents

Description

From DOS 1 792 688 are salts of alkoxycarbonylaminobenzimidazoles known as fungicides. It's about Compounds of the general formula

jÜ? -NH-COOR A, H

wherein R is a C ₁ - C. alkyl radical and A is an acid with a

- 5th

.Ionization constants of over 1 χ 10 means.

As can also be seen from DOS 1 792 688, the preparation takes place of the ready-to-use fungicides in such a way that the carbalkoxycarbonylamiiiobenzimidazole salt is in a large excess dissolved in aqueous mineral acids or organic acids ο The excess acid is necessary to prevent hydrolysis To suppress salts and thus the precipitation of the benzimidazoles.

The free alkoxycarbonylaminobenzimidazoles also have a fungicidal effect, but because of their poor solubility in aqueous and lipophilic systems they have only limited systemic activity. This disadvantage is to be eliminated by the transfer to the salt fort, although a number of other disadvantages must be accepted. These consist, among other things, in the fact that the free Alkoxycarboiiylamdno-benzimidazoles in an excess of aqueous mineral acid]! must be dissolved so that the hydrolysis dor salts υηύ so that the precipitation of the benzimidazoles is suppressed. However, due to the necessary excess of free acid

3098U / 1 103

BATH ORIGINAL

a number of sensitive plants, especially in the root area, damaged.

It has been found that these disadvantages can be avoided if, instead of the free acids, certain salts of these acids are reacted with alkoxycarbonylciminobenzimidazoles.

The invention therefore relates to water-soluble, plant-compatible Compounds of the general formula 1

NH-COOR * / ~ AB_7 _n (i)

where R is alkyl, with 1- ^ t carbon atoms, preferably CI-I "

A is a urea of the formula R "NHCONHR", R ¹ and R "are alkyl with 1-4 carbon atoms or hydrogen, also guanidine or hydrazine,

B a mineral acid with a dissociation constant Iv

-7 -3 ^C

'-> 10, preferably> 10

and η is an integer from 1 to 3.

Compounds of the invention are also mixtures of the compounds of Formula I with one another or with an excess of component A,

Preferred as mineral acid "B" are HCl, HNO ", HpSOr, H-POj,, HJ, HBr et al., As "A", the unsubstituted urea is preferably used used.

The compounds of formula I are prepared so that one the corresponding compound of formula II

(Il)

and η-molar amounts of the compound A and the acid Π in water or low molecular weight alcohols such as methanol, Aethanoi, P.ro ~ panol, isopropanol etc. or mixtures thereof together :! bl ·, at temperatures from 0 to 100 C, preferably at room temperature, stirs until the complete solution or set-up and the?

309844/1103

BATH ORIGINAL

22 1917 A

Solution then evaporated to dryness.

The removal of the solvent can be done according to the in usual methods, e.g. B. distillation from boiler systems, via thin-film evaporator, in the spray tower process, etc., take place.

For use as fungicides, the products of the process are described in Dissolved in water and are immediately ready for use in this form. In contrast to the compounds of DOS 1 792 688, they are in aqueous solution can be kept indefinitely and therefore do not require any further stabilization. The application concentrates lie here depending on requirements at 0.005 to 0.5 ^.

In particular, the products of the process can be used in these concentrations in urea solutions, as they are usually used for fertilization via the green leaf. The urea concentration of the solution is up to 20 f _o .

Instead of being in an aqueous solution, the new products can also be used in other conventional solid or liquid preparation forms, e.g. B. as wettable powder or dust in combination with commonly used formulation auxiliaries such as adhesives, wetting agents and emulsifiers. Such preparations are particularly advantageous when the products with other - water-insoluble -. Fungicides, insecticides, acaricides and / or herbicides are combined. The Yirkstoffkonzentratio3ien in such formulations is preferably 5-90 ° i -

The compounds according to the invention act against phytopathogenic fungi such as trichophytes, microsporums, epidermophytes and others. Due to their good solubility, they are produced by plants through leaves and liurzeln well received and are üb insert as systemic Pf3anzenschutzmittel both relevant commercial products as well known from the DOS 1 79 ² 688 salts. They are more tolerant to plants than the latter and are safer to handle. They can be used prophylactically and curatively to combat fungal diseases. Another-

309844/1103

BAD ORJGfNAL

On the other hand, the inventive connections also work well dead organic material and therefore protect substances vie Paints, oils, wood, leather, egg white, paper and textiles Fungal attack.

BATH ORIGINAL

3098U / 11Q3

MANUFACTURING SBEJS FIELE

General manufacturing process

To 200-1000 ml of an aqueous, alcoholic or aqueous alcoholic solution of 1 to 3 mol of the acid B is the the same molar amount of component A is given. 1 mol of methoxycarbonylaminobenzimidazole is then added to the clear solution and then stir for about 20 minutes to 2 hours at room temperature (about 20 ° C.) or at an elevated temperature until implementation is complete. The solution is then concentrated to dryness at normal pressure or in vacuo.

The order of addition of the reactants is not critical, it can be arbitrary »also two or all can Reaction components together, all at once or in portions, are added to the solvent.

The table below gives an overview of the above Process made connections.

309844/1103

O CD OO

Tabel

Z =

-NH-COOCHi

example Link .. , ff ⁵ ) solvent yield 1 Z · (CH ₈ NH-CONHCHj'HCDi ', 5 124-126 water quantitatively 2 Z • (CH ₃ NH-CONHCH ₅ -HCl) ₂ 128-130 water quantitatively • 3 Z ' (CH ₃ Nh-CONHCH ₃ -HCI) ₃ 125-130 water quantitatively 4th Z. (CH ₃ NH-CONHCH ₃ * H ₃ PO ₄ ) _a 175 (decomp.) Methanol quantitatively 5 Z. (C ₄ H ₉ NH-CONH-C ₄ H ₉ ^ HCl) ₂ 160-165 V / ater quantitatively β Z · (C ₄ H ₉ NH-CONH-C ₄ H ₉ * H ₃ PO _{4) a} 180 (decomp.) Methanol /
water
80:20 quantitatively 7th Z is - (C ₄ H ₉ NH-CONH-C ₄ H ₉ H ₂ SO _{4) 2} 178-180 water quantitatively

example link Fp.
·· ( ⁰ C) solvent Yield - 8th Z • (C ₄ H ₉ NH-CONHC ₄ H ₉ • HNO ₃ ) ₈ 192-195 water quantitatively 9
r Z · ■ (NHgNH ₂ · 2 HCl) · 140-142 Ae tha.no 1 /
water
30:70 quantitatively 10 Z · (NH ₂ NH ₂ 'HCl) ₃ 142-145 water quantitatively 11 Z- (NHgNHg-H ₂ SO ₄ ) 190 water quantitatively 12th Z '(NH ₂ NH ₂ -H ₂ SO ₄ ) ₂ ■ 192-195 water quantitatively ■ 13 Z (HgN-C-NH ₂ 'HCl)
IT
NH 260 (decomp.) water quantitatively 14th Z • (H ₂ NC-NH ₂ -HCl) ₂
NH 265 water quantitatively 15th Z (H ₂ NC-NH ₂ -HNO ₃ )
ti
NH 255 water quantitatively

O CD OO

Example' . . Connection "·> ' Fp.
(° c) solvent yield 16 Z - (H ₂ NC-NH ₂ -HNOs) ₂
!!
NH 270-275 water quantitatively 17th Z - (H ₂ NC-NH ₂ -H ₂ COs) ₂
ti
NH 258-260 water quantitatively is: ¹ Z - (H ₃ NC-NH ₂ -HSCN) ₂
I!
NH 270 water quantitatively

Tabel "

Example 1 ■ link Fp.
( ⁰ C) Solvent 1 Mol-Gewient 19th ζ · - /, NH ₂ -CO-NH ₂ · HCl7 ₂ 150-153 water 384 20th ζ · / NH ₂ -CO-NH ₂ · HNO ₃ J ^ 260 Water/
Methanol
80:20 437 21 ζ · / NH ₂ -CO-NH ₂ · HNO ₃ J 137-140 water 560 22nd Z / NH ₂ -CO-NH ₂ 1/2 H ₂ SO ₄ JJ ' 198-202 Water/
Ethanol
50:50 409 23 Z / NH ₂ -CO-NH ₂ . H ₂ SO ₄ YY 220-225 water 507 2k ζ · / NH ₂ -CO-NH ₂ · H ₅ PO ₄ JJ $ 240-24 water : 5O7 25th Z / NH ₂ -CO-NH ₂ . H ₃ PO ₄ J ^ 262 Water/
Isopropanol
. 90.? 10 665- 26th Z / NH ₂ -CO-NH ₂ · ΗΒΓξ 240-242 Methanol
or
water 473

U) O CO CO

example Z * Tabel
link • HBr7, ·
3 . (I. S) solvent Mole weight 27 ζ · / NH ₂ -CO-NH ₂ Methanol /
water
20:80 614 28 ζ · / NH ₂ -CO-NH ₂ • HF ^ water 567 29 ζ · / NH ₂ -CO-NH ₂ • mj ₂ water 271 30th ζ · / NH ₂ -CO-NHg ' HClO ₄ J ^ water 351 31 Z * / NH ₂ -CO-NH ₂ ' HClO ₄ Jg Ethanol
or
Via ss he 353 _; 5 32 Z / NH ₂ -CO-NH ₂ • NH ₂ SO ₃ H ^ Ethanol
or
water 512 33 ζ · / NH ₂ -CO-NH ₂ . (C ₂ H ₅ O) ₂ PSBH ^ Water/
Methanol
80:20 662 / NH ₂ -CO-NH ₂ water
or
Isopropanol 932 continuation
Fp.
( ⁰ C) 148-150 113-115 228-230 250 260 265 210-215 185-190

The test results listed below explain the biological effect.

The salts of 2-methoxycarbonylaraino'benziiiiidazol with HCl, HNO ₃ , H ₂ SO ₄ and H ₅ PO ₄ in the preparations according to Examples 4, 5, 6, 7 of the dos 1,792,688 were used as comparison agents.

It means accordingly

VM I (comparison means)
(Example 4)

VM-II (comparison means)
(Example 6)

VM III (comparison means)
(Example 5)

VM IV (comparison means)
(analogous to example 7)

N ₅

n /

"■ -NH-COQCH :, · HCl

32.5 io tartaric acid 2.5 5 ^ polyglycol 300 / P 857

35.8

'Nv ^ -NH-COOCH ₃

.N- / H

64.2 io maleic acid

90

-NH-COOCH ₃ · H ₂ SO ₄

10 · io sodium bisulfate Monhydrat

25th

25 50

n /

p-Toluenesulfonic acid silica

-NH-COOCH ₃ · H ₃ PO ₄

309844/1103

ϊ 2 21 ^{91 7 / +}

APPLICATION EXAMPLES Example I

Sugar beet plants were grown in pots and were heavily infected in the 6-leaf stage with conidia of the pathogen of the leaf-spotted witch (Cercospora beticola) and incubated at a temperature of 25 ° C. and a relative humidity of 100 $ in a humidity chamber for hours. The infected plants were then placed in a greenhouse with a relative humidity of 85-90 % and a temperature of 23-25 ° C.

After an infection time of 7 days, the plants were treated with the claimed compounds in the application rates of 120, 60, 30 and 15 ppm treated to runoff.

The compounds mentioned above were used as comparison agents according to DOS 1 792 668 in the same use concentrations.

After the active ingredient coating had dried on, the plants were returned to the greenhouse and, after the onset of the disease, 3 weeks after infection, examined for infestation with Cercospora. The infestation was expressed in $ infected leaf area, based on the untreated, infected control.

The result of this experiment can be seen in Table I.

309844/1103

Example II

Rice plants were grown in the 4-leaf stage with conidia of Piricularia oryzae heavily infected and one day in a humidity chamber with a relative humidity of $ 100 and one Temperature of 23 ° C. Then they came in a Greenhouse with a relative humidity of 85 - 99 as well as a temperature of 23 ° - 25 ° C. They stayed there for 5 days and were then used with the claimed compounds 1 to 18 treated in application concentrations of 250, 120, 60, and 30 ppm.

The compounds mentioned above were used as comparison agents according to DBP 1 792688 in the same application concentrations. - .....

After the spray coating had dried on, the plants were in brought the greenhouse back and remained there until the onset of the known symptoms of the disease.

The disease infestation was assessed visually and expressed in tfo infected leaf area based on untreated, infected control plants.

The result is shown in Table II.

Example III .

4-leaf stage wheat plants were heavily infested with conidia of powdery mildew of wheat (Erysiphe grarainis) and then made 24 hours in a humidity chamber with a relative humidity of 100 <fo and a temperature of 22 ⁰ C. They were then placed in a greenhouse with optimal infection conditions (relative humidity 85-90, temperature 22 ° 23 ° C.). After an infection period of 5 days were

309844 / 1.103 '

them with the claimed compounds 9 to 18 in the • concentrations of 120, 60, 30 and 15 ppm.

The comparison means were those already in Tables I and II mentioned compounds DOS 1 792 688 in the same concentrations.

After the spray coating had dried on, the plants were returned to the greenhouse, where they remained until the disease broke out remain.

The degree of infestation was assessed visually and in $ infected leaf area compared to untreated, infected Expressed control.

The result is shown in Table III.

Example IV

Wheat plants were given the compounds at the 2-leaf stage 1 to 32 in the application rates of 2000, 1000, 500 and 25Ο ppm Treated active ingredient.

Those already mentioned above were used as grafting agents Links.

After the spray coating had dried on, the plants were brought into the greenhouse, where they remained up to the ^ -leaf stage. At this stage of development they were heavily infected with conidia of wheat powdery mildew (Erysiphe graminis) and placed in a humidity chamber with 100 ¹ Jo relative humidity and a temperature of 22 ° C. for 1 day. They were then placed in a greenhouse with high humidity and a temperature of 22-23 ° C.

After an incubation period of 1 ^ 1 days, the plants vurden Powdery mildew infestation investigated. The degree of infestation was determined after

3 0 9 8.4 4/1 1 0 3

22Ϊ9174

scliein assessed in comparison to untreated, infected Control plants and. is shown in Table IV.

309844/1103

Example V

Tomato plants were grown with in the fully grown 3-leaf stage Conidia of the pathogen causing brown spot disease (Cladosporium fulvum) are heavily infected and in a humid kettle for 1 day a relative humidity of $ 100 and a temperature incubated at 25 C. Then the plants came in Greenhouse with a relative humidity of 95 - 90 ^ and an optimal temperature of 23 - 25 C.

After an infection time of 7 days, the plants were treated with aqueous solutions of the compounds mentioned in Example 19-32 and the comparison agent in the application concentrations of 120, 60, 30 and 15 ppm treated to runoff.

After the Virkstoffbelags had dried on, the plants were brought back to the greenhouse with optimal infection conditions and remain there until the outbreak of the disease.

.Die'Beurteilung of infestation was made after the inspection and was expressed in * fo infected leaf area, relative to the untreated, infected control plants.

The result can be seen from Table V.

Example VJ

Apple seedlings were heavily infected in the 5-leaf stage with conidia of the apple powdery mildew (Podospliera leucotricha) and placed o 1 day in a humidity chamber at a 'temperature of 22 C and a relative humidity of 100 <?. They were then placed in a greenhouse with a relative humidity of 85-95 ° C. and a temperature of 22-23 C. After 5 days, the plants were treated with aqueous solutions of the compounds mentioned in Example 19-32 in concentrations of 100, 50, 2 ^ and 12.5 ppm treated dripping wet.

The comparison agents used were those already mentioned, as well as the benzimidazole-calcium-methyl-methyl ester (v? I V).

309844/1103

After the spray coating had dried on, the plants were in brought back the greenhouse and examined after an incubation period of 14 days for infestation with apple powdery mildew.

The infestation was assessed visually . The degree of infestation was expressed in tfo infected leaf area.

The result is shown in Table VI.

3098U71103

Table I.

Infection of sugar beet with "Cercospora in infestation of sugar beet with

example Treatment 7 Days after 1 60 30th : nfel ppm active ingredient 0 8th 120 0 3 15th 1 0 0 5 15th 2 0 0 10 10 3 0 0 8th 12th to 4th 0 0 8th 18th O
(O 5 0 0 5 14th co 6th 0 0 8th 15th 7th 0 0 ■ 3 12th 8th 0 0 3 14th O 19th 0 0 8th 8th 20th 0 0 5 10 . 21 0 0 8th 15th 22nd 0 0 5 12th 23 0 0 8th 15th '24 0 0 5 14th 25th 0 0 8th 16 26th 0 0 5 10 27 0 0 6th 12th 28 0 0 8th 10 29 0 0 8th 12th 30th 0 0 6th 14th 31 0 15th 32 0 14th

example Cercospora
Days after
Active ingredient
120 60 10 at treatment 7
Infection with ppm
3.0 15th 24 VM I 0 14th 14th 26th VM II 0 12th 18th 22nd VM III 0 100 16 00 unconcerned
acts 100 100 1

to

-ρ • rf

(Q • rf ο PS

ti

es • rf

to '

H pi H O • rf

(D U H -rf H ft Φ
fit -P ßj -rf E- "B

HH «J <H Φ FQ

ο • rf • p M

a

VO

• d

Gi Cf

(tf

<H T-tH O -P fi M

H U Xi -rf Cf Ϊ2 Ctf

<D ft ir> PiW

• rf

m • rf φ FP

> Λ N »Π 00» ΠνΟΟΟΟΟΟΟΟΟ O OvJO W ΙΓ \

co οο νο co η in η οο ιη ία νο οο

OOOOOOOOOÖOOOOOOOO

οοοοοοοοοοοοοοοοοο

ΙΛ (O VO

in

OO VO CO VO

ο ο ο ο ο

• Ρ HO)

H H t> H H H H

3 O 9 8 4 A / 1 1 O

Table III example

10 11 12

13 '14

15 16

17 18

VM I VM II VM III VM IV

untreated

infestation

4, ¥ eizenmenlta ^ when treated 5 days after infection with ppm active ingredient

10

120_ 0 0 0 0 0 0 0 0 0 0

60. 0 0 0 0 0 2 0 0 0 0

3 5 8

100

■

12th

14th

15 18

100

12 12 10 10

15 15

10 16

15th

20 26 28 28

100

Table IV 0 5 12th example 0 3 10 1 0 5 ' 15th 2 io wheat flour baptism case when treated with
ppm active ingredient in the 2-leaf stage - infect
tion in the 4-leaf stage
2000 1000 500 2 50 0. 8th 15th 3 0 • 0 8th 15th ■ ■ 4 0 0 5 12th 5 0 0 3 10 6th 0 0 8th 15. ■ 7th 0 0 8th 15th 8th 0 0 ». 10 12th 9 0 . ο 8th 12th 10 0 0 ■ . 12th 18th 11 0 0 10 20th 12th 0 0 8th 15th . 13th 0 Q 12th . 22nd 14th 0 0 12th 20th 15th 0 • 0. ■ 18 25th 16 0 0 12th 20th 17th 0 18th 0 0 0

Table IV continued

CD CO CO

$> Wheat powdery mildew infestation when treated with example ppm active ingredient in the 2-leaf stage - infection in the 4-leaf stage 2000 1000 500

19th O O O 3 20th 0. ■ O O O 21 O O O 8th 22nd O O O 5 23 O O O 8th 2k O O O 5 25th O O O 8th 26th O O 3 12th 27 O O 5 15th 28 O O 8th 16 29 O O 5 12th 30th O O 3 12th 31 O O 3 10 32 O O 5 12th

VM I O

VM II O

VM III O

VM IV O

untreated 100

15 18 20

25 100

25 30 28 32 100

Table V

$ Attack by · ^; Tomatoes with Cladosporium example fulvum when treated 7 days after infection with ppm active ingredient120 60 3 (5th

19th 0 . 0 5 8th 20 ' 0 0 8th 12th 21 0 0 8th 14th 22nd 0 0 10 * 15th 23 0 0 8th 14th Zk 0 0 12th 18th 25th 0 0. 10 16 26th 0 0 8th 16 27 0 0 10 14th '. 28 0 0 6th 15th 29 0 0 -8th 16 30th 0 ο. 12th 18th 31 0 ο ' 8th 14th 32 0 0 10 15th VM I 0 6th 14th • 26 WM II 0 10 18th 31 VM III 0 8th 16 28 VM IV 0 12th 20th 30th "untreated 100 100 100 100

Table VI

$ Apple powder rot infestation during treatment
Example 5 days after infection with ppm active ingredient

100 50 25 12.5

O CD OO

to

19th 0 0 0 5 20th 0 0 0 3 21 0 0 3 8th 22nd 0 0 5 8th 23 0 0 2 8th 2k 0 0 0 5 25th 0 0 5 8th 26th 0 0 0 5. 27 0 0 0 2 28 0 0 0 2 " 29 0 0 2 5 30 - 0 0 0 5 31 0 0 2 8th ' 32 0 0 5 10

VM I 0 8 15 20

VM II 0 5 10 18

VM III 0 3 12 22 jsj

VM IV 0 5 10 20 ' ¹ ^

VM V 0 10 18 x 25 HD

untreated 100 100 100 100 ^

Claims (6)

Claims 1) Compounds of the general formula J ^ -NH-COOR - / AB_ / _n I where R is alkyl with 1-4 carbon atoms, "voi-preferably CH", A is a urea of the formula R'NIICONHRJ ¹ , R ¹ and R "denote alkyl with 1-4 carbon atoms or hydrogen, furthermore guanidine or hydrazine, B a mineral acid with a dissociation constant K -7 -3 ° > 10, preferably> 10 and η is an integer from 1 to 3. 2) Process for the preparation of compounds ^ according to claim 1, characterized in that a benzimidazole of the general formula • -MI-COOR II with 1, 2 or 3 molar amounts of component A and acid B in water, low molecular weight alcohols or mixtures of these solvents and the solvent is distilled off. 3) Fungicidal agents, characterized by a content of one A compound according to claim 1 as an active ingredient. h) Fungicidal agents in the form of aqueous solutions, characterized by a content of 0.005-0.5 tfo, preferably 0.05-0 »2 °, of a compound according to claim 1. 5) Fungicidal agents in the form of aqueous solutions according to claim h, characterized in that they additionally contain up to 20 <fo urea. BAD ORIGINAL 3098A4 / 1103 ■; -, fb 6) Use of compounds according to Claim 1 for combating of fungal attack on living plants and dead organic substrates. BATH 309844/1103