DE1643039C3 - Bromoacetylureas, processes for their preparation and biocidal agents containing them - Google Patents

Description

in which R has the meaning given, with compounds of the general formula

BrCH, - CO - R ¹

b) compounds of the general formula
O = C = NR

with bromoacetamide of the formula

BrCH ^ - CO - NH ₂

converts, where R ^{1 is} halogen or the group BrCH ₂ CO-. The reactions are preferably up to e, twa conducted in the presence of inert organic solvents and if appropriate with addition of acid-binding agents at temperatures in the range of about 15 150 ⁰ C.

The reactants are used in approximately equimolecular amounts. As an inert, organic solution Chlorinated organic hydrocarbons, ethers, nitriles and amides have proven suitable solvents, such as z. B. chlorobenzene, dioxane, acetonitrile, ethyl acetate and dimethylformamide.

The reaction proceeds at temperatures ranging from about 15 up to about 150 ⁰ C. ZurReaktionsbeschieunigung, and around which, in use before. To bind Bromace'ylhalogeniden resulting hydrogen halide, z. B. tertiary amines such as triethylamine or pyridine are added. The reaction mixture can be worked up by distilling off the solvent and recrystallizing the residue in a solvent. It is also possible to precipitate the reaction product with water and recrystallize it by filtration after isolation.

The resulting bromaceiylureas are free from by-products. The yields are good. -

The following examples illustrate the manufacturing processes.

Name of the connection

Physical
constant

N-bromoacetyl-N'-methyl-189

urea (under

Decomp.)

N-bromoacetyl-N'-ethyl-144

urea

N-bromoacetyl-N'-propyl-134

urea

N-bromoacetyl-N'-isopropyl-84

urea

N-bromoacetyl-N'-cyclopropyl-126
urea

N-bromoacetyl-N'-allyl- 139

urea

N-bromoacetyl-N'-isobutyl-140

urea

8th
9
10
H
12th
13th
14th
15th

Name of the connection

example
Nn-butyl-N'-bromacelylurea

58 g of n-butylurea are dissolved in 200 ml of dimethylformamide and 40 ml of pyridine dissolved. Then 1 g of bromoacetyl bromide is left with water cooling add dropwise, stir for 30 minutes and precipitate with ice water. The suctioned off reaction product is recrystallized from 300 ml of acetonitrile.

Yield: 57 g = 48% of theory.

In the following table there are others in accordance with the invention active ingredients to be used listed.

JS Physical constant

CC)

N-bromoacetyl-N '
urea

N-bromoacetyl-N '
urea
N-bromoacetyl-N '
urea

N-bromoacetyl-N '

urea

N-bromoacetyl-N '

urea

N-bromoacetyi-N '

urea

N-bromoacetyl-N '

urea

N-bromoacetyl-N

ethyl urea

-tertiary butyl- - n-amyl- -n-hexyl- -benzyl- -furfurylrf-chloroethyl- -zi-bromoethyl-V-methoxy-

110 128 123 172 168 141 136 136

The specified melting points are not corrected.

The compounds are crystalline substances with a characteristic melting point. They are soluble in chlorinated organic hydrocarbons, ethers, nitriles and amides, such as. B. chlorobenzene, dioxane, Acetonitrile, ethyl acetate and dimethylformamide. ·

The following examples explain the biocidal effect of connections.

Application example 1

Steamed compost soil was inoculated with mycelium from Pythium ultimum. After evenly mixing of the preparations with the contaminated soil, the preparations were in the form of 20% powder preparations before, the sowing of 25 corn peas of the variety followed without a waiting period per concentration "Miracle of Kelvedon" in I 1 earth-holding clay bowls. The table shows the number of accrued healthy peas and the root rating (1-4) after a cultivation period of 26 days at 22 to 25 C. MANEB (Manganese (II) - [N, N'-ät: iyIen-bis (dithiocarbamate)]) and CAPTAN '(N- (Trich! ormcthyllhio) -cyclohex-4-en-l; 2-dicarboximid) used.

preparation

55 N-bromoacetyl-N'-ethyl-

urea

N-bromoacetyl urea

N-bromoacetyl-N'-allylurea

Root rating:

4 - white roots without fungal necrosis.

1 = white roots, slight fungal necrosis.

2 = brown roots, already stronger fungal necrosis. I - severe fungal necrosis. Rotten roots.

Concentration mg active substance / liter earth

50
100

50
100

50
100

Number of healthy peas after 26 days

22 21 20 20 20 23

Root rating (I to 4)

4 4 4 4 4 4

continuation

Prepi'al

preparation

Concentration mg active ingredient / liter of soil

Number of healthy peas after 26 questions

Wurzelbonil ür Il to 4 |

N-bromoacetyl-N, N'-ethylene urea
N-bromoacetyl-N'-n-propyl-harastofF

N-bromoacetyl-N'-zi-methoxyethyl urine

N-bromoacetyl-N '- ^ - chloroethyl urea

N, N'-bis-bromoacetylethylene-urea

N-bromoacetyl-N'-cyclopropyl-urea

N-bromoacetyl-N -isobutylurea

MANEB

CAPTAN

Subdued floor
(3 control attempts)

Untreated soil (3 control attempts)

50 100

50 1st floor

50 100

50 100

50 100

50 100

50 100

50 100

50 100

A B C A B C

18th

24

18th

22nd

23 22 21 22 21 20 19 20

21

7 2

21

18th

21

4 4 4 4 4 4 4 4 4 4 4 4

4 4 4

Root bonilur:

4 = white roots without fungal necrosis.

3 = white roots, slight fungal necrosis.

2 = brown roots, already stronger fungal necrosis.

I - severe fungal necrosis, rotten roots .

Application example 2

35

40

Steamed compost soil was suspended in spores from Fusarium oxysporum f. Callistephi inoculates. After the preparations have been evenly mixed with the contaminated soil, the preparations were available as 20% powder formulations, followed after a waiting period of 5 days the planting of three young plants of the host plant Callistephus chinensis, master aster "sun ray", depending on the concentration. The table shows the number of infected plants after a cultivation period indicated by 3 weeks. CAPTAN (N- (trichloromethylthio) -cyclohex-4-ene-1,2-di-carboximide) was used as a known comparative agent.

55

preparation

N-bromoacetyl-N'-ethylurea

N-bromoacetyl urea

Conc Infestation tration after mg effective 3 weeks substance liter Earth 200 0 .1 (X) 0 400 0 2 (K) 0 300 0 4 (X) 0

Concentration infestation (ration according to mg active substance 3 weeks / liter Earth

N-bromoacetyl-N'-ailyiurea

N-bromoacetyl-RN'-ethylene urea

N-bromoacetyl-N'-benzylurea

N-bromoacetyl-N'-hexylurea

N-bromoacetyl-N'-isopropylurea

N-bromoacetyl-N'-n-propylurea

N-bromoacetyl-N '- / i-methoxyethyl urea

N-bromoacetyl-N'-p'-chloroethyl urea

Ν, Ν'-bisbromoacetyl-ethylene urea

N-bromoacetyl-N'-cyclopropylurea

N-bromoacetyl-N'-furfurylurea

CAPTAN

Subdued floor
(3 control attempts)

Untreated soil
(3 control attempts)

200

300

400

20Ö

300

400

200

300

400

200

300

400,

200 '

300

400

200

300

400

200
300
400
200
300
400
200
300
400
200
300
400
200
300
400
200
300
400

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

0 0 0

3 0 0 3 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0 0 0 3 3 3 0 0 0

3 3

Application example 3

Limit concentrations of fungicidal effectiveness when the preparations are mixed evenly the contaminated soil. The prerequisites for the assessment are healthy root formation and splitting the seeds run by at least 90% compared to the achieved results in the steamed soil. Depending on the concentration ti.ilion was the sowing of 25 grain peas of the variety "Wunder von Kelvedon" (pea peas) without> Karen /./. C'.t. The duration of the experiments! was 21 to 26 days at a temperature of 22 bi C. As a means of verification, (Man

güH (II) -1 N, N '- iithylen - bis - ulithiocarb; imul) l) uiul CAPTAN (N - (Trichlor - methyl - Ihio) - cyclohex-4-en-1.2-diearboximide) used.

a) Pythium ultimum:

Steamed compost soil was inoculated with mycelium from Pythium ultimum.

b) So-called damping-off fungi:

Normal compost was used for this experiment.

c) Rhizoctonia solani:

Steamed compost soil was inoculated with mycelium from Rhizoctonia solani.

Limit concentrations of fungicides !! Efficacy (mg active substance per liter of soil)

preparation Pythium ultimum Ι) ίΐηιρίημ-οΓΓ-Ι · Ίιιιμ! Khi / octnnia solani (mg) (mg) (me) N-bromoacetyl hamstoiT 25 50 50 100-200 N-bromoacetyl-N'-methyl-urinary acid 50 50 100 200-300 N-bromoacctyl-N'-ethyl urea 25th 50 100 200 N-bromoacetyl-N'-n-propyl urea 25th 50 100-200 N-bromoacetyl-N'-isopropyl urea 50 KX) 100 N-bromoacetyl-N'-cyclopropyl- 25th 25 50 200-3 (X) urea N-bromoacetyl-N'-allyl urea 50 50 KX) 200-300 N-bromoacetyl-N'-n-bulyl urea - KX) - N-bromoacetyl-N'-isobutyl urea 100 100-2 (X) 200-300 N-bromoacetyl-N'-lert.-butyl-urethane 100 100 300 N-bromoacetyl-N'-hexyl urea 300 300 N-bromoacetyl-N'-n-amyl urea - 200-300 300 N-bromoacetyl-N-benzyl urea 200 - N-bromoacetyl-N'-rurfuryl urea 50 ICK) 100 200 N-bromoacetyl-KN'-ethylene urea 50 50 KX) --- N.N'-bisbromoacetyl-ethylene-urea 50 50-100 300 N-bromoacetyl-N'-fi-chloroethyl 50 50 200-300 urea N-bromoacetyl-N '- ^ - methoxyethyl- 50 50 200-300 urea N-bromoacetyl-N'-i -'- bromoethyl- 100 200 300 urea MANEB 200-300 200-300 over 400 CAPTAN 300-400 300-400 over 400

Application example 4

Of the preparations listed, the one shown is N-bromoacetyl-N'-furfurylurea very high plant tolerance. With a concentration of 0.5% Active substance, for example, tomatoes sprayed to runoff showed no damage to plants.

As a dressing, about 1 g of active ingredient / kg of peas is sufficient for good success, as the following experiment shows.

Peas pickled with a 50% formulation were sown in normal compost, 25 seeds Peas of the “Wunder von Kelvedon” variety (marker pea) per concentration. After a cultivation period of The number of healthy peas that had emerged was recorded for 14 days at 22 to 25 ° C. CAPTAN (N- (trichloro-methyl-thio) -cyclohex-4-en-l, 2-dicarboxinide), MANEB (Manganese (ll) - [N.N '- ethylene - bis (dithiocarbamate)]) and TMTD (tetramethyl thiuram disulfide) is used.

Number of healthy peas

preparation 0.5 g A. 1.0 g 23 2.0 g B. Really 24 Really Really fabric / kg fabric / kg N-bramaeetyl- fabric / kg 20th 23 N'-furfuryl urea 20th A. 1 CAPTAN B. 12th 0 23 MANEB 8th 4th 12th TMTD 0 3 17th Dampened floor, 0 Seeds without Pickling (2 control tries) Untreater Soil, seeds without pickling (2 control attempts)

-509 6

id

Application example 5

Are the preparations listed below in a Application rate of 200 to 300 mg active ingredient / liter of soil due to root knot nematodes (Mcloidogyne) Adding heavily contaminated soil and sowing cucumbers after a waiting period of 8 days, so the young cucumber plants remain invisible after a cultivation period of 4 weeks at 22 to 25 ° C Root knot infestation.

N-bromoacetyl urea,

N-bromoacetyl-N ' _: methy! -Urea,

N-bromoacetyl-N'-ethyl-urine,

N-bromoacetyl-N'-cytlopropyl urea,

N-bromoacetyl-N'-n-amylurea,

RN'-bisbromoacetyl-ethylene-urea,

N-bromoacetyl-N '- / f-chloroethy] urea.

υ ου

Application example 6 ^M

Field experiment

A duich Fusarium oxysporum f. Callistephi highly contaminated e ^r de were added to the preparations in the • ngegebenen rates of 10 to 15 cm deep hooking up. After a waiting period of 14 days, 20 young aster plants of the susceptible master aster "sunbeam" were planted per concentralization. The table shows the percentage of plant loss after a culture period of 5 weeks. At the same time, the herbicidal effect was determined by counting the weeds that had emerged.

preparations

Concentrated plant herbicides

iratioii failure effect

g effective after

fabric / m ² 5 weeks

N-bromoacetyl-N'-ethereal urea

N-bromoacetyl

N'-n-propyl-

urea

Untreated

20th
40
60
80
20th
40
60
80

75

55

20th

100

70
82
86
92
77
84
94
98
0 assessment:

--- white roots without pil / nck roses.

- ■ - white roots, slight mushrooms.

= brown roots, already stronger pin cone.
= strong pil / necrosis. Rotten roots.

Pylhiuin ultimum

Pr.ipaial

N-methyl

N'-broniacclyl-

hanistoff

N-Äihyl-

N'-bromoacetyl-

urea

Fhioracetylurea

N-fluoroacetyl

N'-methyi-

urea

Comparative experiment
1. Soil fungicidal effectiveness

N-Fluoraeetyl-

N'-phenyl-

urloff

N-Fluorac?: Yl-N'-amy! -Urea

Steamed compost soil was inoculated with Mycei from Pythium ultimum. After evenly mixing of the preparations with the contaminated soil, the preparations were 20% powdery preparations before, 25 corn peas of the variety were sown without a waiting period per concentration "Miracle of Kelvedon" in 1 1 clay bowls. The table shows the number of running healthy peas, the fresh plant weight and a root rating (1 to 4) after a cultivation period indicated for 22 days at 22 to 25 ° C.

Chloroacetylurea

mg active Λη / ahl sloiT I.iler μο-Hrdc sunder

Krbscn after 22 do.

100

150

200

25th

50

75

100

150

200

50

75

! 00

150

200

50

75

100

150

2 (X)

25 50 75

100

150

200

25th

50

75

100

150

200

25th

50

75

100

150

200

24 2 ")

24 23 24 23 7

24 ·

24

23

24

23

13th

14th

12 8 3 3 8 p

15th

0 3

20 22 15

Plant root Irish rating ücwichl (I to 4)

20th

2!

"IT

19 19 17 4 23 24 20 17 20

1 1

4 6

3 2

2 2 5 3 1

12th

19th

4 4 4 4 4 4 1

4 4 4 4 4

4 4 3

1 b 43

continuation mp effective Quantity Plant- Wur / cl- before, followed without 20% a week at 17 to mg active
itnfT'I itf> r Freshly weighed plants % to the % to the IO Pia ready mg active Vegetable fish weighed % to the % to the stolT / l.iler ge fresh- rating time per concentration the sowing of Parental leave The fresh weight of the plants was determined at 20 ° C. Mim / i ^ ncr
Earth (G) unconcerned
hanr! elten
Com ge
damp
th stolT'liter uncomfortable: - ge preparation Earth sinner geuidii (I his 4) (Lepidium sativum) 1 g of cress seeds posterde Com
post Brde te) handdten dämpl lirbsen clay bowls holding earth in I 1. Earth I ς Com th after After a cultivation period of ¹ J posterde Com HTg. <e> 246 114 post Plant compatibility (Lepidium sativum) 25th 16.2 233
175 108
81 Earth Fresh plant weights 50
75 ! 5.3
11.5 149 69 25th 0 0 100 9.8 95 44 20th 159 74 50 3 1 1 preparation 150 6.3 49 23 102 4S N-chloroacctyl- 75 10 1 200 3.2 227 105 N-Äihyl- 100 10.5 67 31 N-methyl-
IvI γικΙ ill Γ KH) 15th 6th I. 25th 14.9 255 118 N'-bromoacetyl- 150 6.7 70 32 1 Iill I ΙΛΙΑΜ I 150 17th 10 I. 50 16.8 214 100 25th urea 200 4.4 52 24 200 15th 10 4th 75 14.1 Fluonicetyl 25th 4.6 23 11th 25th 0 0 urea 50 3.4 37 17th 50 0 0 N-methyl 75 1.5 62 29 N-phenyl- 75 0 \) N'-bromoacetyl-
urea 30th 100 2.4 10 5 N'-chloroacetyl- 100 0 0 150 4.0 61 28 har nsi off 150 0 0 200 0.7 39 18th 200 0 0 N-fluoroacetyl 25th 4.0 25th 11th 24 23 4th N-ethyl 35 N'-methyl- 50 2.5 26th 12th 25th 22nd 4th N'-bromoacetyl-
L _rt *** »- * _Λ CC urstoff 75 1.6 13th 6th Subdued floor 22nd 4th urea 100 1.7 3 1 Subdued floor 0 0 150 0.8 67 31 Subdued floor 40 200 0.2 44 20th Untreated 0 0 ■ - N-fluoroacetyl 25th 4.4 44 20th floor N'-phenyl- 50 2.9 38 17th Untreated 2 1 I. urloff 75 2.9 24 11th floor 100 2.5 14th 6th Untreated 2. Plant compatibility 45 150 1.6 46 21 Clearing After even incorporation of the preparations in 200 0.9 38 17th normal compost soil, the preparations lay as N-fluoroacetyl 25th 3.0 24 11th powdered preparations 50 N'-amyl-urea 50 2.5 20th 9 75 1.6 0 O 100 1.3 \ J
f \ 55 1 ^ O 0.0 0 U IJU 0.0 108 50 200 7.1 114 53 Chloroacetyl 25th 7.5
O ι 123
105 57
49 6o urea 50 8.1
6.9 Π7 54 75
100 7.7 71 33 150 4.7 140 65 200 9.2 107
140 49
65 65 N-chloroacetyl 25th 7.0
9.2 114 53 N'-methyl-
urea 50
75 7.5 114 5? 100 7.5 Qf 150 79 90 4: 700 * »"
5.9 112
87 s:
4Γ N-phenyl- 25th 7.4
5.7 68 3: N'-chloroacetyl-
urea 50
75 4.5 67 31 100 4.4 58 2 ' 150 3, p 2! 5 IOC 200 14.17 100 4f Subdued floor 6.59 Untreated floor

The l ^; luoiaceiylharnstoi! e / own insufficient effectiveness in the control of Pythium. In addition there is a high Phvtotoxizilül with the application of these connections over the soil.

While with the checked ChioraceiNlluirnsioffen

ice cream! ah HH) mg AS I Line a fungicidal effect becomes visible. /. B. chloroacetylurea, bring the N-Metlnl- and N-Ethyl-N'-hroniaeelyl-urea already: viii 25 to 50 mg ^/ \ S / I have an excellent bactericidal effect.

Claims (3)

Patent claims: j. Bromoacetylurea of the general formula 5 BrCH ₂ -CO-NH-CO-NH-R in dsr R is a C ₁ -C ₆ alkyl radical with a straight or branched chain, a 0-chlorine or a f-bromethyl radical, a methoxyethyl radical, a benzyl radical, a furfuryl radical, a cyclopropyl radical or an allyl radical 2. Process for the preparation of bromoacetylureas according to claim 1, characterized in that in a known manner a) Compounds of the general formula H ₂ N-CO-NH-R with compounds of the general formula BrCH ₂ -CO-R ' or b) compounds of the general formula O = C = N-R with bromoacetamide of the formula BrCH ₂ - CO - NH ₂ reacted, where R has the abovementioned meaning and R ^{1 is} halogen or the group BrCH, - COO- 35 represents. 3. Bioeide means containing as active ingredient one or more bromoacetylureas according to claim 1. 45 The invention relates to bromoacetylureas with a biocidal effect, soft in particular for soil and seed treatment can be used. Urea derivatives have so far only become known predominantly with herbicidal effects. A broad one In contrast, biocidal effects have not yet been observed. It has now been found that compounds of the general formula can therefore be used, inter alia, in the Agriculture or horticulture, especially for general soil treatment. In addition to the Fight against soil-borne fungi are also plant-parasitic nernatodes and seed weeds, z. B. Senecio vulgaris, Chenopodium album, Stellaria media, with recorded. The connections are more suitable or less also as a dressing for seed treatment to combat parasitic fungi on the seed. With regard to their fungicidal and fungistatic effectiveness, the active ingredients are surprising even superior to the most well-known compounds with the same direction of action, such as those listed below Show comparative tests. The active ingredients can be used alone or as mixtures of several active ingredients. If so desired can use other fungicides, nematicides, herbicides, seed dressings or other pesticides - depending on the desired purpose - can be added. If a herbicidal use is intended, in the mixtures z. B. also find fertilizers use. Become useful the active ingredients in the form of preparations, such as. B. powders, grit, granules, solutions, emulsions or suspensions, with the addition of liquid and / or solid carriers or diluents and optionally used by wetting agents, adhesives, emulsifying agents and / or dispersing agents. Suitable liquid carriers are water, mineral oils or other organic solvents, e.g. B. Xylene, chlorobenzene, cyclohexanol, cyclohexanone, dioxane, acetonitrile, ethyl acetate, dimethylformamide or Dimethyl sulfoxide. Lime, kaolin, chalk, talc, attaclay and other clays are suitable as solid carriers natural or synthetic silica. The following surface-active substances should be mentioned: z. B. salts of lignin sulfonic acids, salts of alkylated Benzenesulphonic acids, sulphonated acid amides and their salts, poiyäthoxyüerte amines and alcohols. If the active ingredients are to be used for seed dressing, dyes, such as. B. Neufuchsin et al., Can be added to give the dressed seeds a clearly visible color. The preparation of the various forms of preparation is carried out in a manner known per se, for. B. by milling or mixing processes. The active ingredients are - with one exception - the bromoacetylurea in the literature has not yet been described. They are produced by methods known per se by e.g. a) Compounds of the general formula BrCH ₂ - CO - NH CO - NH - R in which R is a C, -C ₆ -alkyl radical with a straight or branched chain, a / Ϊ-chlorine or a / ΐ-bromo-lithium radical, a methoxyethyl radical, a benzyl radical, a furfuryl radical, a cyclopropyl radical or an allyl radical, in particular a fungicidal, have fungiitic, nematicidal and herbicidal action and are therefore mainly suitable as soil and seed treatment or treatment agents. In particular, these compounds develop an excellent fungicidal and fungistatic effect. H ₂ N-CO-NHR