DE2113033A1 - New herbicidal ureas, their production and use - Google Patents

Description

<§) Int. CL:

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

German Ki.

C 07 d, 91/60

A 01 n, 9/22

12th _P) 9

451.9 / 22

Qy

(2t)

Offenlegungsschrift 2113 033

File number: P 21 13 033.6 Filing date: March 18, 1971

Disclosure date: September 30, 1971

Exhibition priority:

Union priority Date: Country: Case number:

March 19, 1970

Switzerland

4159-70

Name: New herbicidal ureas, their production and use

Addition to: Removed from: Applicant: Agripat S. A., Basel (Switzerland)

Representative according to g 16 PatG: Zumstein sen., F., Dr .; Assmann, E., Dr .; Koenigsberger, R., Dr .; Holzbauer, R., Dipl.-Phys .; Zumstein jun., F., Dr .; Patent Attorneys, 8000 Munich

Named the inventor Moser. Hans. Dr .. Basel; Bird. Christian, Dr., Binningen (Switzerland)

Notification according to Art. 7, Paragraph 1, Paragraph 2, No. 1 d. Ges. V. 4.9. 1967 (Federal Law Gazette I p. 960): -

An application for examination in accordance with Section 28 b PatG has been submitted

© 9.71 109 840/1833

AG R I PAT SaAa CH-4000B «» l21 <8chweJz / SwlteerlerKJ)

Dr. P. Zumsteln Sr. - Dr. E. Assmann Dr.HKoenigsberger - Dipl.Phys. R. Holzhauer

Dr. F. Zumatein jun.

Patenton v / old

8 Mönchen 2, Bräuhausstraße 4 / III

5a-3278 *

New herbicidal ureas, their production and use

The present invention relates to new ureas, processes for their preparation, furthermore herbicidal compositions which act as active ingredients contain such ureas and methods for controlling grass-like and dicotyledonous weeds using the new active ingredients or the agents containing them.

The new ureas correspond to the formula I: R-,

In this formula:

R _{1 is} a lower a-halo-alkyl radical,

R ₂ and Ro independently of one another are each hydrogen or a lower alkyl radical,

R, one optionally represented by cyano or alkoxy

substituted lower alkyl radical, a cycloalkyl radical, an alkoxy radical, an alkenyl, haloalkenyl or alkynyl radical,

X oxygen or sulfur.

109840/1833

In the general formula I are lower alkyl radicals R, to R, straight-chain or branched radicals with 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, as well as the pentyl and hexyl radicals, to be understood.

The lower ot-haloalkyl radicals R. contain 1 to 3 Halogen atoms in the first carbon atom and include radicals such as chloromethyl, dichloromethyl, trichlorine thy 1, trifluoromethyl, fluorodichloromethyl, Bromomethyl, dibromomethyl, α-chloroethyl, a-dichloroethyl, a-chloro-n-propyl, 1, l-dichloro-3-methyl-butyl etc.

fe A cycloalkyl radical R has 3 to 10 carbon atoms, preferably 3 to 6 carbon atoms; The cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl radical comes into consideration. Such a Cyclocilkyl radical can be substituted one or more times by lower alkyl, preferably methyl and ethyl, be substituted. An alkoxy radical R is one with 1 to 4 carbon atoms, for example methoxy, ethoxy, n-propoxy, isopropoxy, or a butoxy radical. Such alkoxy radicals also represent the substituents of a lower alkyl radical R 1. Alkenyl and haloalkenyl radicals are used for R, in particular the allyl, methallyl or butenyl radical in question, which can be substituted one or more times by chlorine and / or bromine. The propynyl residue (propargyl residue) or

fc an alkylpropynyl radical are preferred alkynyl radicals to pull.

The new ureas of the formula I are according to the present Invention prepared by adding an amine of formula II:

either with a halocarbonic acid ester or with phosgene in the presence of an acid-binding agent into a carbamic acid derivative Transferred and this with an amine the

109840/1833

Formula III:

^ ^R 4

implements. Chlorocarbonic acid phenyl esters are preferred as halocarbonic acid esters and phenyl chlorothiocarbonate are used, for example the following in good yield Carbamic acid derivatives are obtained as intermediates:

N- (3-trifluoromethyl-1,2,4-oxadiazolyl (5)) carbamic acid phenyl ester,

N- {3-trifluoromethyl-1,2,4-thiadiazolyl (5)] - carbamic acid

phenyl ester,

N- {3-Trichloromethyl-1,2,4-oxadiazolyl (5)] -carbamic acid phenyl ester,

N- [3-trifluoromethyl-1,2,4-thiadiazolyl (5)} - carbamic acid

phenyl ester,

N- [3-dichloromethyl-1,2,4-thiadiazolyl (5)] -carbamic acid phenyl ester, and the corresponding N-ί3-Trihalogenraethy1-1,2,4-oxa and thia-diazoly1 (5)] carbamoylchloride

and N- [3-dihalomethyl-1,2,4-thiadiazolyl (5) -carbamoyl-

chloride.

Tertiary amines, such as trialkylamines, pyridine bases, etc. are also preferred as acid-binding agents inorganic bases such as hydroxides and carbamates of alkali and alkaline earth metals are used. The reaction temperatures are each between 0 and 150 °.

The implementation of the carbamic acid derivatives thus obtained with a primary or secondary amine of the formula III takes place at temperatures between -40 and 150 °, preferably between 0 and 100 °.

The new ureas of the formula I, in which R-, hydrogen means, can according to a variant of the invention Process can be made by adding an amine

1 0 P "Ί / Ί β 3 3

BAD ORfGINAL

of the formula II with an isocyanate of the formula R ^ NCO.

The methods described are in the presence of Lb'sungs- or inert to the reactants Diluents carried out. For example the following: aliphatic and aromatic hydrocarbons and halogenated hydrocarbons, in particular Benzene, toluene, xylene, chloroform, chlorobenzene, ethers and ethereal compounds, e.g. dioxane, tetrahydrofuran, N, N-dialkylamides, such as dimethylformamide, diethylformamide, Ketones such as acetone, methyl ethyl ketone, Cyclohexanone, nitriles, such as acetonitrile, etc ..

Furthermore, the new ureas of the formula I can be obtained by mixing an amine of the formula II with a carbamic acid halide of the formula Hai - C - Nc ^ _D 3,

Ä ⁴

in which R- denotes a lower alkyl radical and R, which has the meanings given under formula I, in the presence acid-binding agents.

Some of the amines of the formula II are known or can be prepared by known processes. the Amines of the formula II in which X is oxygen can be prepared by adding trichloroacetamidine or trifluoroacetamidine a) with cyanogen bromide or b) with trichloroacetic anhydride to give the corresponding S-trihalomethyl-S-trichloromethyll, 2,4-oxadia?: ol reacts and then the trichloromethyl group with an amine of the formula NII2R2 against the -NHR "group exchanges. Condensation agents are used for these reactions such as tertiary amines, Ν, Ν-dialkylformamide, inorganic Bases, etc. required. As a solvent odor diluent for these reactions in addition to Also listed above are alkanols, e.g. methanol, Aethanolj isopropanol, can be used.

1OS? / 1 8 3 3

The new ureas of the formula I have excellent properties herbicidal properties and are used to control grass-like and broad-leaved weeds in a wide variety Suitable for crops. These active ingredients also include those that are difficult to control and deep-rooted, and perennial weed species are damaged or destroyed as they grow. So the new ureas of the formula I in low concentrations for selective weed control, for example to control chamomile species (Matricaria spp.)> Galium aparine, parsnip (Pastinaca sativa), foxtail species, e.g. Amaranthus spp., Mustard species (Sinapis spp.), grasses such as Echinochloa spp., Lolium spp., millet species (Panicum spp.), in cereals, maize,

Soy, sorghum, cotton, root crops, forage crops can be used. The ureas of the formula I can both before emergence (preemergence) as well as after emergence (postemergence) of the plants. In high concentrations, i.e. from 5 kg of active ingredient per hectare onwards, the new active ingredients can completely kill and "prevent serve for unwanted plant growth.

108840/1833

The herbicidal effect of the active ingredients fiction geniäs sen was determined on the basis of the following experiments:

1. Herbicidal effect before the plants emerge

a) The active ingredients are mixed with seed bed soil in a concentration of 100 mg active ingredient per liter of soil mixed. The following test plants are sown in this soil (seed trays):

Oats (Avena sativa), Italian ryegrass (Lolium multiflorum), millet (Setaria italica), mustard (Sinapis alba), vetch (Vicia sativa), tomato (Solanum lycopersicum). -

The seed trays are then kept in the greenhouse at 22-25 ° and 50-70% humidity. The experiment is evaluated after 20 days. The rating is based on the 9 index:

1 = plants dead

2-4 = intermediate stages of damage (over 50%)

5 «50% damage

6-8 ■ intermediate stages of weak damage (less than 50%)

9 = plants undamaged - control.

109840/1833

Table to la

Active ingredient: oats Ryegrass millet mustard Vetch tomato 1 1 1 1 (Vi _ N- (3-Trifluonnethyl-1.2 Λ-thladlazolyl (5)] - N'-methyl-urea 1 1 1 1 2 1 N- [3-Trlfluoromethyl-1,2,4-thiadlazolyl (5) JN ¹ N ¹ -dimethyl urea 1 1 1 1 2 N- [3-trichloromethyl-1,2,1'-thiadiazolyl (5)] -N-methyl-N'-cyclo-
propyl urea 3 3 2 (VJ - 2 N- [3-Trichlon-methyl-1,2-thladiazolyl (5)] -N '-methyl-urea 2 3 1 1 2 1 N- [3-Trlchloromethyl-1,2, i * -thiadiazolyl (5)] - N'.N'-dimethylurea (Vl VJl 3 2 _- (Vl 09 » N-l3-Trichloromethyl-1,2,1f-thiadlazolyl {5)] - N-methyl-N'-ethyl-
urea 3 1 1 1 1 N- [3-trichloromethyl-1,2,4-thiadiazolyl (5) JN-methyl-N ¹ .N'-dimethyl-
urea (VJ 1 1 1 3 1 OO
Ca) N- [3-trifluoromethyl-1,2, M - thladiazolyl (5) 1-N-methyl-N'-cyclopropyl-
urstoff 1 1 1 1 (VJ 1 Ca) N- [3-trifluoromethyl-1.2, n, -thiadlazolyl (5)] - N-methyl-N'-ethyl-
urea 2 (Vl 1 1 (VJ 1 N- {3-Trfluonnethyl-1.2 Λ-thiadiazolyü5)] - N-methyl-N'-isopropyl-
urea 1 1 1 1 1 N-13-trifluoromethyl-1,2, i + -thiadiazolyl (5) 1-N ¹ -methyl-N ¹ - (l'methyl-
propln-3-yl) urea 3 3 2 1 3 1 N-p-Trichloromethyl-1.2.i * -oxadlazolyl (i,)) -N'-methyl-urea 3 3 CVl 1 2 (VJ N- [3-Trichlonethyl-1,2,4-oxadiazolyl (5) 1-N ¹ -methyl-N'-methoxy-
urine cff CVJ 6th CVI 4th CVJ 9 N- [3-trifluonethyl-1,2.4-oxadiazulyl (5) J-N-N'-dimethyl urea

CO O CO CO.

co 00

00 co

Active ingredient: oats Ryegrass millet mustard Vetch tomato 2
3
1
1
1
1
1
1
1
1
1
1
3 1
1
1
1
1
1
1
1
1
1
2
2
3 1
2
1
1
1
1
1
1
2
1
2
2
3 1
1
1
1
1
1
1
1
1
1
2
1
1 2
2
2
1
2
2
7th
1
3
2
3
3
3 (M (MH HHHHH ii ti (M (M CVI N- [3-Triohlere «thy1-1,2 Λ-oxadiasolyl (5) JNK ¹ -dimethylurea
. N- [3-Trifluoraethy 1-1,2Λ-οχΛ (ί1 »!, 3 ·, ο1 ^ 1 (5) J-N ', N'-dimethyl urea
N-f3-trifluoromethyl-1,2-thiadiszolf1 (5)} N, N'-dimethylurea
N- [3-trifluoromethyl-1,2 Λ-thiadiasolyl (5)] N "-methyl-N · methoxy-
urea
N- [3-TrIfluoromethyl-1.2Λ-thiadiazolyl (5)] - N-methy 1-N'-allyl-urine-
material
N-l3-Trifluoraethyl-1.2.f-thl * diaxolyl (5)] - N, N'.N'-trimethyl-
urstoff
N- (3-Triohlornwthyl-l, 2 Λ-thiadiazolyl (5) J-N-ltnyl-N '-methyl-
urine toff
N-13-trifluoroethyl-1,2 Λ-thiadlazolyl (5) 1-N-ethyl-N -methyl-
urstoff
N-13-Trifluoromethyl-1,2. »», - thiadiazolyl- (5) I-Nnnethyl-N ¹ -n-propyl-
urea
N- [3-dichloro'ethyl-1,2, U-thiadiazolyl- (5) JN.N ¹ -dlmethyl-uretoff
N-13-dichloromethyl-1.2. »F-thiadiazolyl (5) 1-N.N *, M'-trimethyl-
urea
N- [3-dichloro "ethyl-1,2," f-thiadiazolyl (5) lN-methyl-N ¹ -ithyl-
urstoff
N-t3-dichloromethyl-1,2,4-thiadiazolyl (5) JN-methyl-N ^{1 -18opropyl-}
urea

00

CO CD CO CO

Active ingredient: oats Ryegrass millet mustard Vetch tomato 3
1
1 3
1
2 2
1
1 1
1
1 3
2 2
2
1 N- [3-Dichlormethjrl-1,2. «T-thiadiazolyl (5 ) ] -N-methyl-N · - {l" -methyl-
propynyl) urea
N- [3-dichloro'ethyl- 1,2-thiadiazolyl (5) ] -N'-methyl urea
M-lJ-dichloroethyl-l ^ .U-thiadiazolyKSJJ-N'N'-dimethyl- urea

OO Ci)

co σ co co

b) Immediately after the test plants have been sown, are the active ingredients as a liquid suspension? obtained from a 25% wettable powder on the Evdoberiläeh®. The seed trays are then kept at 22-23 ° and 50 ° 70% relative humidity. The experiment is evaluated after 28 days. The following were used as test pods:

LoIium raultiflorum Setaria italica Echinochloa crus galli Sinapis alba ^ · Galium aparine

Pastinaca sativa Poa trivialis Alopecurus myosuroides Digitaria sanguinalis Ipomoea purpurea Vicia sativa

The respective application rates in this experiment can be found in the table below.

The rating is based on the 9 index:

1 - plants dead

"2-4 * intermediate stages of severe damage (over 50%)

5 - 50% damage

6-8 "intermediate levels of weak damage (less than 50%)

9 * plants undamaged ^ control.

Composition of the 25% wettable powder:

25 parts of active ingredient, 10 parts of sodium aluminum silicate, 0.6 part of sodium dibutylnaphthylsulphonate, 1.0 part of naphthalenesulphonic acids-phenylsulphonic acids-formaldehyde condensate 3: 2: 1, 63.4 parts of kaolin. These wettable powders are equivalent in a 1000 liters per hectare What amount of water suspended.

BATH ORIGINAL 109840/1833

The active ingredients used were:

1. N- [3-Trifluoromethyl-1,2,4-thiadiazolyl- (5) 1-N, N ¹ -dimethylurea

2. N- [3-trifluoromethyl-1,2,4-thiadiazolyl- (5) 1-N, ¹ N'-dimethylurea

3. N- [3-Trifluorraethyl-1,2,4-thiadiazolyl- (5)] - N * -methyl-N ¹ -methoxy urea

4. N- [3-Trifluoromethyl-1,2,4-thiadiazolyl- (5) 1-N-ethyl-N'-methylurea

5. N-13-Trifluoromethyl-1,2,4-oxadiazolyl- (5) 1-N ¹ , N ¹ -dimethylurea

6. N- [3-dichloroethyl-1,2,4-thiadiazolyl- (5) 1- N, N'-dimethylurea

7. N- [3-dichloromethyl-1,2,4-thiadiazolyl- (5)] - N'-methyl urea

8. N- [3-dichloromethyl-l, 2,4-thiadiazolyl (5) 1-N ^1, N * dimethylurea

9. N- [3-methyl-1,2,4- ^{thiadiazolyl- (5) 1-N 1 -methyl urea}

known from the Dutch publication no. 68.13438 (Bayer)

10. N- {3-methyl-1,2,4-thiadiazolyl- (5) 1-N ¹ N'-dimethyl urea known from the Dutch patent application no. 68.13437 (Bayer)

11. N- [5-methyl-1,3,4-thiadiazolyl- (2) 1-N'-methy! -Urea

known from the Dutch publication no. 68.13438 (Bayer)

12. N- [5-Isopropyl-1,3,4-thiadiazolyl- (2) 1 -N'-isopropylurea known from the Dutch publication no. 68.13438 (Bayer)

109840/1833

Wiric-
itoff
Mr. 7th AUfMKMl-
■ length in
ks / ha Lollua
multi «.. Sataria
ltalica Echinoch.
cms galll Slnapla
alba Oaliua
aparin · Paetlnac »
satlvm Po *
trivial!" Alopecur »Digitaria
lEjroB s & nguin, - Ipoaoe &
purpurea Vicia
sativa Wti-
aen tree
wool Ha
fer Stop 1 1 3 1 3 1 - 2 - - - - - 8th - - - 2 1 1 3 1 3 1 - - - - 8th - - - 4th 1 1 , 2 1 2 1 - - - - - 8th - - - 2 1 2 k 3 2 3 1 - - - - - 9 9 - - 2 1 2 2 1 3 1 - - - - - 9 9 - - * 1 1 1 1 1 1 - - 2 - - 9 9 - - 3 0.5 2 1 2 1 3 1 3 7th 2 1 1 9 - 9 9 O
co 1 2 1 2 1 1 1 2 3 2 1 1 7th - 8th 8th 00 2 1 1 1 1 2 1 1 2 3 1 1 6th - 7th 7th O 0.5 5 2 7th m 6th - 1 2 2
1 9 7th 9 - 9 8th 18 3: 1
2 3
3 2
1 3
2 3
1 3 _m 1
1 ro ro 9 8th
1 2
2 9
9 ; 9
9 VJl OV to 5 0.5 3 VJl 8th 1 2 9 8th 1 3 9 - 8th 9 1 3 5 ι » 1 1 7th 3 5 i 2 8th' • - 8th 8th 2 2 2 2 1 2 1 5 2 8th 1 1 8th - 6th 7th 6th 0.5 6th 9 3 2 6th 9 3 3 2 7th 9 8th '7 7th 9 1 3 2 2 1 5 8th 1 3 2 3 9 7th cm 6th 8th 2 2 2 2 · 1 2 3 1 2 5 1 9 3 2 ' 3 7th 0.5 6th » 3 3 8th 7th 2 3 2 4th 9 8th 9 8th 8th 1 1 2 2 1 5 U.N. 1 2 2 2 a 8th 8th 3 7th 2 1 1 2 1 3 2 1 2 1 6th 3 7th 2 6th

co 00

00 CaJ

iiric- Λ-Cwaad- Loliun Sttaria Echinoch. Sinapis Galira Pastinaca Poa Alopeeuris Dlgitaria sanguine. lpe == «» Vicia White 3aun- Ha Quays ttoff ■ ultifl. ttallea erus gain alba aparlr.e »Ativa trivialls ■ 70s 1 purpurea »Ativa th wool fer 8th 0.5 2 1 3 1 8th 7th 1 2 1 1 7th 8th 9 7th 8th 1 2 1 2 1 2 2 1 2 1 1 4th 7th 8th 6th 7th 2 2 1 1 1 2 2 1 1 9 1 3 4th 7th 2 4th 9 0.5 9 9 9 4th 8th 7th 4th 8th 3 6th 9 8th _ 7th 9 1 8th 3 7th 2 5 3 3 7th 2 3 4th - 5 8th 2 7th 2 7th 1 3 2 1 3 9 1 3 1 - 3 8th 10 0.5 9 9 8th 8th 9 5 3 8th 8th 9 9 9 - 9 9 1 8th 9 8th 4th 7th 4th 2 6th 6 ' 4th 8th 8th - 8th 8th 2 2 2 3 1 3 - 2 2 5 - 5 7th 11 0.5 9 9 - 9 - - - - - - - - - 2 9 9 - 9 - - - - - - - - - 5 9 9 - 9 - - - - - - - - - - - L2 0.5 9 9 - 9 - - - - - - - - - 2 9 9 - 9 - - - - - - • - '- - 5 9 9 • 9 - - - - - - - - -

Ca) O CO CO

2. Herbicidal effect in the post-emergence test with sown Weeds

Oats, wheat and oats are used as test plants in seed trays Corn (cultivated plants) as well as the weeds

LoIium multiflorum Alopecurus myosuroides Setaria italica Digitaria sanguinalis

P Ämarantus retroflexus

Papaver rhoeas Sinapis alba
Matricaria chamomilla Galium aparine Fastinaca sativa

sown. At the 4-leaf stage, the plants were sprayed with a 2% aqueous emulsion. The plants are then kept ^{under daylight at 25-28 °} C. and 40-50% relative humidity.

The evaluation of the test takes place after 15 days, the assessment according to the 9 index

= Plants undamaged, like control = plants dead 9-2 - Intermediate stages of damage

The 25% aqueous emulsion was made by diluting with water from a 25% emulsifiable concentrate of the following composition obtained: 25 parts of active ingredient, 32.5 parts of isophorone, 32.5 parts of methyl ethyl ketone, 10 parts of a combination emulsifier, existing from nonylphenol polyoxyethylene and dodecylbenzenesulfonic acid calcium. Salt.

109840/1833

As an active ingredient were used:

1. N- [3-Trifluoromethyl-1,2,4-thiadiazolyl- (5) 1-N, N ¹ -dimethylurea

2. N- [3-Trifluonaethyl-1,2,4-thiadiazoly1- (5)] - N ¹ N'-dimethylurea

3. N- [3-trifluoromethyl-1,2,4- ^{thiadiazolyl- (5)] - N 1 -methyl urea}

4. N- {3-Trifluoromethyl- ^{1,2,4-thiadiazolyl- (5)] - N 1} -methyl-N ¹ methoxy urea

5. N-13-Trifluoromethyl-1,2,4-thiadiazolyl- (5)] -N-ethyl-N ¹ -methylurea

6. N- {3-trifluoromethyl-l, 2,4-oxadiazolyl (5)] - N ^l N ^t -diinethyl-urea

7. N- [3-dichloroethyl-1,2,4-thiadiazolyl- (5)] - N ¹ , N ¹ -dimethylurea

10984Π / 1833

ti

Λ vi

fs co «

m «

si! η

HS

• η δ

O as

Sl 0 ι-Ι ■ Ρ M Φ 43 M -rl

•H

■ II I III I I I I ΙΙΙΙ

oot — t -. *

I I I I 11 (1st

κ \ · -ιη ·

OO OO OO CN CO CO t-

(Vi «Η r-l

r-l f-4

CVI tr \ ι- »

H H

t r-l

f-l 1-4 r-l

r-l ft> - < I.

COt- ΚΛ «III I

I I I I III

VOK \ CVICVI

I I t I

S Il f- Λ

en

SS

in η οι O

in »-ι cv IT «r-l CVl O

in

to

1 «M

At it 109840/1833

iirfc-
ltcff
ir. Aiifuand-
■ cs «· in LoIiUB
humiliation Alopccurus
■ jros. Setaria
italiea Digltarla
sanguln. Amarantus
retrof1. Fapaver
rhoeas Sinapis
alba Katrlearia
cha «. Qallum
aparine 3 Fastinaca
satlva oats Veizen Mala 0.5 VJl 3 (VJ k If 1 1 - if 3 8th S. 7th 7th 1 3 3 1 Z CVJ 1 1 - 3 j 2
1 7th 7th 6th 6th ITV 2 1 1 1 1 3 1 1 1 1 9 9 1 1 5 1 1 1 1 1 1 1 1 1 8th 9 1 1 * 0.5 - - - - - 3 1 1 8th 5 7th 9 8th 1 - - - - - (VJ 1 1 7th 7th 9 8th C.
CC
CX 6th 2 - - - 1
1 1
1 1
1 2
1 3
3 8th
7th 8th
8th 0.5 6th 7th 3 3 (VJ 9 1 1 C. 9 9 9 cc 1 6th 7th 2 2 1 3 1 1 1 8th 8th 8th Approx
C * 7th 2 3 3 1 1 1 1 1 1 1 7th 7th 7th If 2 2 1 1 1 1 1 1 1 P. 6th 3

The preceding experiments show the broad spectrum of herbicidal activity of the active ingredients according to the invention. In contrast show known thiadiazolyl ureas, for example the 5-alkyl-1,3,4-thiadiazolyl (2) ureas of the Dutch Auslegeschrift No. 68.13433 and the 1,2,4-thiadiazolyl (5) ureas the Dutch patent application no. 68.13437, even in application rates of 5 kg of active ingredient low herbicidal effect per hectare floss.

To prepare herbicidal agents, the active ingredients are mixed with suitable carriers and / or distributors medium mixed. To broaden the spectrum of activity you can add other herbicides to these agents, for example from the series of triazines, such as halo-diamino-s-triazines, Alkoxy- and alkylthio-diamino-s-triazines, Triazoles, diazines, such as uracils, aliphatic ^ carboxylic acids and halocarboxylic acids, halogenated benzoic acids and Phenylacetic acids, aryloxyalkanecarboxylic acids, hydrazides, Amides, nitriles, esters of such carboxylic acids, carbamic and thiocarbamic esters, ureas, etc.

The following examples illustrate the preparation of the new ureas. Further ureas of the formula I, ^ prepared according to the method described in the examples can be found in the following table. The temperatures are given in degrees Celsius.

109840/1833

example 1

20 g of N- (3-trifluoromethyl-1,2,4-thiadiazolyl (5)] -carbamic acid phenyl ester - and 1 ml of triethylamine are refluxed in 200 ml of benzene. 5.4 g of methylamine, dissolved in 50 ml, are added to the boiling solution Benzene, added dropwise. The reaction mixture is refluxed for one hour and then stirred for 12 hours at room temperature. The precipitate is filtered off, washed with benzene and then with petroleum ether. After drying and recrystallization from methanol / water, the N-13-trifluoromethyll, 2,4-thiadiazolyl (5) IN ^I -roethyl urea, mp: 217-219 ° C.

Example 2

To a boiling solution of 32 g of N- [3-trifluoromethyl-1,2,4-thiadiazolyl (5) l-carbatinic acid phenyl ester and 1.4 ml of triethylamine in 300 ml of benzene are added dropwise with stirring a solution of 14.9 g of cyclopropylamine in 20 ml of benzene. After 16 hours Heating at reflux, the solvent is evaporated in vacuo and the residue is recrystallized from methanol / water. The N- [3-Trichloromethyl-1,2,4-thiadiazolyl (5)] - N'-cyclopropylurea has the mp: 177-18O ° C.

Example 3

A solution of 27 g of S-trichloromethyl-S-methylamino-1,2,4-thiadiazole in 350 ml of acetone is mixed with 1.8 ml of triethylamine and 17.5 ml of methyl isocyanate and refluxed for 24 hours. The solvent is then distilled off in vacuo and the residue is recrystallized from alcohol / water. The N- (3-trichloromethyl-1,2,4-thiadiazolyl (5) JN, N ¹ -dimethylurea has the melting point: 146-150 ° C.

109840/1833

Example 4

In a boiling solution of 10 g of N- [3-trichloromethyl-1,2,4-thiadiazolyl- (S)) - N-methyl-carbamoyl chloride a solution of 3.2 g of alpha-amino-isobutyric acid nitrile and 4.75 ml is added dropwise to 100 ml of benzene Triethylamine in 150 ml of benzene. The reaction mixture is refluxed for 16 hours. Then the deposited precipitate becomes separated and washed several times with water. After recrystallization from dioxane, the N- [3-trichloromethyl-1,2,4-thiadiazolyl (5)] - N-methyl-N '- (1 "-methyl-1" -cyano-ethyl) -urea the m.p .: 255 ° C.E.

Example 5

16.9 g of 3-trifluoromethyl-5-amino-1,2,4-thiadiazole and 50 ml of dimethylcarbamoyl chloride are stirred together for 5 hours at a bath temperature of 160 °. After cooling, the reaction mixture is poured onto ice water and the pH is adjusted to 5-6 using sodium hydroxide solution. An oil separates out, which becomes crystalline after a short time. It is filtered off, the residue is washed with water and introduced into 100 ml of 2N ammonia with stirring. After filtering, the filtrate is weakly acidified and the precipitate formed is filtered off with suction. After drying and recrystallization from benzene, 8.5 g of N- [3-trifluoromethyll, 2,4-thiadiazolyl- (5)] - N ', N ^l -dimethylurea of melting point 124-126 ° C. are obtained.

Example 6

20.6 g of S-trichloromethyl-S-amino-l ^^ - thiadiazole, 10 ml of methyl isocyanate and 100 ml of pyridine are stirred for 2 days at 80 °. It is concentrated in vacuo and the dark-colored residue is boiled with diisopropyl ether. The ether solution is allowed to cool, filtered and the filtrate is evaporated in vacuo. The residue is recrystallized twice from methanol / water. 12 g of N- [3-trichloromethyl-1,2,4-thiadiazolyl- (5)] - N ¹ -methyl-

urea with a decomposition point of 195 ° C.

- ■ 109840/1 833;

Active ingredient:

Melting point:

N- [3-trifluoromethyl-1,2,4-thladiazolyl (5) j -N , N'-dimethyl urea

N- [3-Trichloromethyl-l, 2,4-thiadiazolyl (5)] Ν ', Ν' -dimethyl-urea f,

N- [3-trichloromethyl-1,2,4-thiadiazolyl (5)] - N-methyl-N'-ethyl-urea,

N- [3-Trichloromethyl-1,2,4-thiadiazolyl (5)] - N, N ', N'-trimethylurea,

N- [3-trifluoromethyl-1,2,4-thiadiazolyl (5)) - N-methyl-N'-cyclopropyl urea,

N- [3-trifluoromethyl-1,2,4-thiadiazolyl (5)] - N-methyl-N'-ethyl-urea,

N- [3-trifluoromethyl-1,2,4-thiadiazolyl (5)] - N-methyl-N'-isopropyl urea,

N- [3-trifluoromethyl-1,2,4-thiadiazolyl (5) J-N ' -methyl-N '- (l'-methyl-propyne-3'-y 1) -urea,

N- [3-trichloromethyl-1,2,4-oxadiazolyl (5)] - N'-methyl urea,

N- [3-Trichloromothyl-1,2,4-oxadiazolyl (5)] - N'-methoxy-N'-methyl-urea,

N- [3-trifluoromethyl-1,2,4-oxadiazolyl (5)] - N, N'-dimethyl urea,

N- [3-Trichloromethyl-1,2,4-thiad ^ azolyi (5) 1-N ' -ir, ethyl-N '- (l-methyl-propin-3-yl) -urea,

N-l3-Trichloromethyl-l, 2,4-thiadiazolyl (5) l-N-methyl-N'-propyl-urea,

N-13-trifluoromethyl -1,2,4-thiadiazolyl (5) J -

N'-methoxy-N'-methyl urea,

N- [3-trifluoromethyl-1,2,4-thiadiazolyl (5) J- N -methyl-N'-allyl urea ,

N- [3-trifluoromethyl-1,2,4-thiadiazolyl (5) 1-N ₁ N ¹ , N'-triroethyl urea,

N- [3-Trichlorraethyl-1,2,4-thiadia * olyl <5) IN-ethyl-N'-methyl-urea ,

148 - 152 ° 133 ° dec. 156 - 158 ° 154 - 156 ° 126 - 128 ° 116 - 118 ° 89 - 90 ° 91 - 93 ° 227 ° dec. 176-179 °

80 - 82 ° 156 - 159 ° 133 - 135 °

79 - 80 ° 109 - 110 ^c

117-120 " 164-166 *

IO984O / t833

Active ingredients Melting point N- [3-trifluoromethyl-1,2,4-thiadiazolyl (5)] -
N-ethyl-N ¹ -methyl urea 139-141 ° N- [3-trifluoromethyl-1,2,4-oxadiazolyl (5)] -
N ¹ , N'-dimethyl urea 102-104 ° N-13-Trichloromethyl-1,2,4-oxadiazolyl (5)] -
N.N'-dimethyl urea 72-74 ° N- [3-Trichbrmethyl-1,2,4-thiadiazolyl (5)] -
N-methyl-N'-O-methoxy-ethyl) urea 113-114 ° N- [3-trifluoromethyl-1,2,4-oxadiazolyl (5)] -
N ¹ -methyl urea 184-186 ° N- [3-Trichloromethyl-1,2,4-thiadiazolyl (5)] -
N-methyl-N'-allyl urea 111-114 ° N- [3-trifluoromethyl-1,2,4-thiadiazolyl (5)] -
N-methyl-N'-n-propyl urea 116-118 ° N- [3-triluomethyl-1,2,4-thiadiazolyl (5)] -
N '- (3 "-chlorobutene-2" -y1) -urea N- [3-dichloromethyl-1,2,4-thiadiazolyl (5)] -
N.N'-dimethyl urea 148-150 ° N- [3-dichloromethyl-1,2,4-thiadiazolyl (5)] -
N ', N'N'-trimethyl urea 106-108 ° N- [3-dichloromethyl-1,2,4-thiadiazolyl (5)] -
N-methyl-N ¹ -ethyl-urea 135-137 ° N- [3-dichloromethyl-1,2,4-thiadiazolyl (5)] -
N-methyl-N'-isopropyl urea 121-123 ° N- [3-dichloromethyl-1,2,4-thiadiazolyl (5)] -
N-methyl-N ^l - (l ^fl -methyl-propyne-3 ") - urea 83-85 ° N- [3-dichloromethyl-1,2,4-thiadiazolyl (5) J-
N'-methyl urea 222-224 ° N- [3-dichloromethyl-1,2,4-thiadiazolyl (5) 1-
N ', N'-dimethyl urea 90-92 ° N- [3- (l "l" -DichXor-3 ^{! I} -methyl-butyl-l, 2,4-
thiadiazolyl (5) JN ^f N ^f -dimethyl urea

109840/1833

The following are examples showing the manufacture of the starting materials of the formula II and the preparation of the carbamic acid derivatives are intended to illustrate. The table below shows some oxadiazoles not previously described and some phenyl carbamate.

Example A.

In a suspension of 17.7 g of 2,2,2-trichloroacetamidoxime lJ.Het.Chem. 3 ,, 214 (1966)] and 11.6 g of cyanogen bromide in 200 ml of benzene are left with stirring at 25-3O ° C Slowly add dropwise a solution of 15.4 ml of triethylamine in 25 ml of benzene. The reaction mixture is stirred for several hours at room temperature, then filtered off the resulting yellow precipitate and washed it thoroughly with water. To drying gives 15.3 g of S-trichloromethyl-S-amino-1,2,4-oxadiazole with the mp: 160-163 ° C. After recrystallizing once from methanol / water, the increases Mp at 165-168 °.

Example B.

302.5 g of 3-trifluoromethyl-5-amino-1,2,4-thiadiazole (melting point 188-190 °) are added together with 271 ml of phenyl chloroformate and 27.7 ml of dimethylformamide in 2 l of chlorobenzene were refluxed for 5 hours. Simultaneously to remove the HCl gas formed during the reaction, dry nitrogen is introduced. To After cooling, the precipitate is filtered off and washed him Γ ·! - · chlorobenzene and petroleum ether. 355 g are obtained N- [3-Trifluoromethyl-1,2,4-thiadiazolyl (5)] -carbamic acid phenyl ester, m.p .: 181-183 ° C.

1098 40/1833

Betspiel · C

To one. A solution of 58.4 g of 3-trifluoromethyl-5-methylamino-l, 2,4-thiadiazole (melting point: 124-125 °) and 49 ml of triethylamine in 600 ml of dioxane are stirred at 20-30 °, 44.2 ml of phenyl chloroformate added dropwise. After stirring for several hours at room temperature, the precipitated triethylamine hydrochloride is separated off and the filtrate is concentrated in vacuo. The residue crystallizes from isopropanol. The N- [3-trifluoro methyl-1,2,4-thiadiazolyl (5)] -N-methyl-carbamic acid phenyl ester has the melting point: 127-129 °.

Example D

178.3 g of S-trichloromethyl-S-methylamino-l ^^ - thiadiazole and 2 L Section. Benzene are heated to reflux. Be stirring 36 liters of phosgene were then introduced over a period of 7 hours. The mixture is stirred for 2 hours at reflux temperature and then for 16 hours at room temperature. The reaction mixture is then on Rotary damper evaporated. After recrystallization from cyclohexane, 191 g of N- [3-trichloromethyl-1,2,4-thiadiazolyl (5)] - N-methyl-carbamoyl chloride with a melting point of 93 ° -95 ° are obtained.

example E.

To 138 g of 3-trifluoromethyl-5-amino-l, 2,4-oxadiazole and 280 ml of triethylamine in 1.5 l abs. Dioxane are 253 ml with stirring Phenyl chloroformate was added dropwise. The temperature is rising during this up to 70 ° .. You can stir overnight at room temperature, the precipitated triethylamine hydrochloride is separated off, and the filtrate is concentrated in vacuo. The residue is crystallized from diisopropyl ether. The 3-trifluoromethyl-5- (dicarbophenoxy) -amino-1,2,4-oxadiazole melts at 120-122 ° and is in a yield of 265 g.

109840/1833

Example F

In 890 ml of trichloroacetic anhydride are stirred and good Cooling at temperatures below 40 ° 255 g of 2,2,2-trifluoroacetamide oxime registered. After the exothermic reaction has subsided, the mixture is heated to 100 ° for 1.5 hours. Pour after cooling the reaction mixture in ice water. The organic phase is separated off. The aqueous phase is extracted several times with ether; the ether extracts are combined with the organic phase and dried. After the solvent has been distilled off, the residue becomes fractionated. The 3-trifluoromethyl-S-trichloromethyl-l ^^ - oxadiazole has the bp: 42-44 ° / 14 Torr.

A solution of 29.3 g of ammonia in 500 ml of methanol is added dropwise to a solution of 200 g of S-trifluoromethyl-S-trichloromethyl-l ^^ - oxadiazole in one liter of benzene. After the exothermic reaction has subsided, the mixture is stirred for 16 hours at room temperature and the solvent mixture is then distilled off in vacuo. The crystalline residue is made into a paste with a little water and washed. That
diazol has the melting point: 103-105 °.

Example G

110 g of S-trichloromethyl-S-amino-l ^^ - thiadiazole are in 2.5 1 of pure methanol, dissolved and in the presence of 25 g of palladium-charcoal 5% at room temperature and normal pressure with Hydrogen treated. The hydrogenation comes to a standstill after about 20 hours. The catalyst is filtered off, the filtrate evaporates to dryness in vacuo and the residue recrystallizes from alcohol / water. Obtain 59 g of 3-dichlorinethyl-5-amino-1,2,4-thiadiazole with a melting point of 164 ° -166 °.

109840/1833

The following is obtained analogously:

a-Dichloromethyl-S-methylamino-l ^^ - thiadiazole. Mp: 122-126 ° (Methanol / water).

The intermediates recorded in the table below were prepared analogously to Examples A-G.

109840/1833

CO OO • Ρ *

Links :

3-trifluoromethyl 1-5-amino-1,2,4-thiadiazole

3-trifluoromethyl-5-methylamino-1,2,4-thiadiazole

S-trichloromethyl-S-amino-1,2,4-thiadiazole

3-Trichlorotinyl-5-methylamino-1,2,4-thiadiazole

N-13-trifluoromethyl-1,2,4-thiadiazole (5) 1-N-methyl-carbamoyl chloride N-13-Trichloromethyl-1,2,4-thiadiazole (5)] -N-methyl-carbamic acid phenyl

ester N-13-trichloromethyl-1,2,4-thiadiazole (5)] -carbatinic acid peptenyl ester 3-Trichloromethyl-1,2,4-thiadiazolyl (5) -N-ethyl-carbamoyl chloride 3-trifluoromethyl-1,2,4-thiadiazolyl (5) -N-methyl-carbamoyl chloride

N- [3-dichloromethyl-1,2,4-thiadiazolyl (5) 1 -N-methyl-carbatnoyl chloride N- [3-dichloromethyl-1,2,4-thiadiazolyl (5)] -carbamic acid phenyl ester

Fp:

188 - 190 ° 124 - 125 ° 195 - 197 ° 198 - 200 ° 43 - 45 ° 85 - 87 ° 167 - 169 ° 23 - 25 ° 28 - 30 ° 64 - 66 ° 168 - 170 °

ro

co

CD CO

co

00 Ca) CkJ

Links : Fp: S-trichloromethyl-S-methylamino-1,2,4-oxadiazole 142-144 ° 3-trifluoromethyl-5-methylamino-1,2,4-oxadiazole 68-70 ° N- [3-trifluoromethyl 1-1, 2,4-oxadiazole (5)] -N-methylcarbamic acid phenyl ester 66-68 ° N- [3-Trichloraethyl-1,2,4-oxadiazole (5)] - N-methyl-carbamic acid- phenyl ester 108-110 ° N- [3-Trichloromethyl-1,2,4-oxadiazole (5)] -carbamic acid phenyl ester 163-166 ° N- [3-trichloromethyl-1,2,4-oxadiazolyl (5)] - N-methyl-carbamoyl- chloride 49- 50 ° '

CO CD CO CO

The preparation of herbicidal compositions according to the invention takes place in a manner known per se by intimately mixing and grinding active ingredients of the general formula I with suitable carriers, optionally with the addition of Dispersants or solvents which are inert towards the active ingredients. The active ingredients can be used in the following processing forms are available and used:

Solid forms of processing: dusts, grit, granulates , Coating granules, impregnation granules and Hcmogen granules;

Active substance concentrates dispersible in water: wettable powder,

(wettable powder), pastes, emulsions;

liquid forms of preparation: solutions.

For the production of solid processing forms (dusts, grit, granulates), the active ingredients are used with mixed solid carriers. Carriers include kaolin, talc, bolus, loess, chalk, limestone, Lime grit, ataclay, dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminum silicates (Feldspars and mica), calcium and magnesium sulfates, magnesium oxide, ground plastics, Fertilizers, such as ammonium sulfate, ammonium phosphate, Ammonium nitrate, urea, ground vegetable products such as grain flour, tree bark flour, wood flour, nutshell flour, Cellulocepvlver, residues from plant extractions, activated charcoal etc., each individually or as mixtures with one another.

The grain size of the carrier substances is for dusts practical up to approx. 0.1 mm, for grit approx.

109840/1833

0.075 to 0.2 mm and for granules 0.2 mm or more.

The active ingredient concentrations in the solid preparation forms are 0.5 to 80 %.

These mixtures can also stabilize the active ingredient Additives and / or non-ionic, anion-active and cation-active substances are added, for example improve the adhesion of the active ingredients to plants and parts of plants (adhesives and adhesives) and / or ensure better wettability (wetting agents) and dispersibility (dispersants). As an adhesive For example, the following are possible: olein-lime mixture, cellulose derivatives (methyl cellulose, carboxymethyl cellulose) , Hydroxyethylene glycol ethers of mono- and dialkylphenols with 5-15 ethylene oxide residues per molecule and 8-9 carbon atoms in the alkyl radical, lignin sulfonic acid,

their alkali and alkaline earth salts, polyethylene glycol ethers (Carbowaxe), Fatty alcohol polyglycol ether with 5-20 ethylene oxide residues per molecule and 8-18 carbon atoms in the fatty alcohol part, Condensation products of ethylene oxide, propylene oxide, Polyvinylpyrrolidones, polyvinyl alcohols, condensation products of urea-formaldehyde and latex " Products.

Active substance concentrates which are dispersible in water, ie wettable powders, pastes and emulsion concentrates, represent agents which can be diluted with water to any desired concentration. They consist of active ingredient, carrier, optionally additives stabilizing the active ingredient, surface-active substances and antifoams and optionally solvents. The concentration of active ingredients in these agents is 5-80%.

109840/1833

The wettable powders and pastes are obtained by mixing the active ingredients with dispersants and powdery carriers mixed and ground in suitable devices until homogeneous. As carriers For example, there are those above for the solid work-up forms mentioned in question. In some cases it is advantageous to add mixtures of different carriers use. Examples of dispersants that can be used are: condensation products of sulfonated naphthalene and sulfonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acids with phenol and formaldehyde as well as alkali, ammonium and alkaline earth salts of lignin sulfonic acid, further Alkylarylsulfonates, alkali and alkaline earth metal salts of dibutylnaphthalene sulfonic acid, fatty alcohol sulfates, such as Salts of sulfated hexadecanols, heptadecanols, octadecanols and salts of sulfated fatty alcohol glycol ethers, the sodium salt of oleyl methyl tauride, ditertiary acetylene glycols, Dialkyldilaurylammonium chloride and fatty acid alkali and alkaline earth salts.

Silicones, for example, can be used as antifoam agents Question.

The active ingredients are made with the additives listed above mixed, milled, sifted and passed in such a way that the solid part of the wettable powders has a grain size from 0.02 to 0.04 and not exceeding 0.03 mm for pastes. For the production of emulsion concentrates and pastes become dispersants as listed in the previous sections, organic solvents and water used. As solvents, for example, the following are possible: alcohols, benzene, Xylenes, toluene, dimethyl sulfoxide and in the range of

109840/1833

Mineral oil fractions boiling at 120 to 350 °. The solvents must be practically odorless, not phytotoxic, inert to the active ingredients and must not be easily flammable.

The agents according to the invention can also be used in the form of solutions. For this purpose, the active ingredient or several active ingredients of the general formula I are dissolved in suitable organic solvents, solvent mixtures or water. Aliphatic and aromatic hydrocarbons, their chlorinated derivatives, alkynaphthalenes, mineral oils, alone or as a mixture with one another, can be used as organic solvents. The solutions should contain the active ingredients in a concentration range of 1 to 20 %.

Leave the described agents according to the invention other biocidal active ingredients or agents are mixed in. So the new agents can be used in addition to the compounds mentioned of the general formula I, for example insecticides, fungicides, bactericides, fungistats, bacteriostats or Contains nematocides to broaden the spectrum of activity. The agents according to the invention can furthermore also contain vegetable oils Contain fertilizer, trace elements, etc.

The following are processing forms of the new Urea described. Parts mean parts by weight.

109840/1833

granules

For the production of 5 xlgen granules the following substances are used:

5 parts N-ia

* olyl (5) l-K, M'-0.25 parts epichlorohydrin, 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethyleneglycol, 91 parts of kaolin (grain size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved in 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The solution obtained in this way is sprayed onto kaolin and then evaporated in a vacuum.

Wettable powder

The following ingredients are used to produce a) 50%, b) 25% and c) 10% wettable powder :

a) 50 parts of N- {3-trifluoromethyl-1,2,4-thiadiazolyl (5) J

N ', N'-dimethyl urea,

5 parts of sodium dibutylnaphthalene sulfonate, 3 parts of naphthalenesulfonic acids-phenolsulfonic acids-

Formaldehyde condensate 3: 2: 1, 20 parts of kaolin, 22 parts of Champagne chalk;

109840/1833

b) 25

p |

2,5 'ilifci ^ !! W ^ illiiilliplföttiliuren-Fornjaldehyde-Condens-

TtUt IUoiin;

c) 10 parts M-i3-Trlchloromethyl-l, 2,4-thiadiazolyl (5)] H-methyl-N'-cyclopropyl urea, Share Geroic of the sodium salts of saturated Fatty alcohol sulfates, Parts of naphthalenesulfonic acid-formaldehyde condensers eat, Share kaolin.

The specified active ingredient is applied to the appropriate carriers (kaolin and chalk) and then mixed and wedded. A wettable powder with excellent wettability and suspension properties is obtained. From such Wettable powders can be diluted with water to obtain suspensions of any desired active ingredient concentration. * Such suspensions are used to control weeds and grass weeds in culture plantings.

BATH ORIGINAL 109840/1833

paste

The following substances are used to produce a paste:

45 parts of N-13-trifluoromethyl-1,2,4-thiadiazolyl (5)] -

N, N ^f -dlmethyl urea, 5 parts of sodium aluminum silicate,

14 parts of cetyl polyglycol ether with 8 moles of ethylene

oxide,

1 part oleyl polyglycol ether with 8 moles of ethylene

oxide,

2 parts spindle oil,

10 parts of polyethylene glycol, 23 parts of water.

The active ingredient is added to this with the additives suitable equipment intimately mixed and ground. A paste is obtained which can be diluted with water Prepare suspensions of any desired concentration. The suspensions are suitable for the treatment of Vegetable plantings.

• Emulsion concentrate -

To make a 10 Xiger. Emulsion concentrates will

10 parts of N-l3-trifluoromethyl-l, 2 _f 4-thiadiazolyl (5) JN, N'-dimethyl urea,

15 parts of oleyl polyglycol ether with 8 moles of ethylene

oxide, 75 parts isophorone

mixed together. This concentrate can be diluted to suitable concentrations _{with water / to emulsions.} Such emulsions are suitable for combating

Weeds in crops such as s.B. Cotton, Mals »etc.

109840/1833

Claims (18)

Claims 1. New ureas of formula I: »• 1 ι ' η R ^(I) C - NCT '"* I 8 ^ ^R 4 R ₂ O in which R, a lower α-haloalkyl radical, R and R. independently of one another are each hydrogen or a lower alkyl radical, R, one optionally by cyano or Alkoxy substituted lower alkyl radical, a cycloalkyl radical, an alkoxy radical, an alkenyl, haloalkenyl or alkynyl radical, X represent oxygen or sulfur. 2. The new ureas of the formula defined in claim 1 I in which X means sulfur. 3. N-13-Trifluoromethyl-1,2,4-thiadiazolyl (5)] - N, N'-dimethylurea. 4. N-13-Trifluoromethyl-1,2,4-thiadiazolyl (5)] - N * N ¹ -dimethylurea. 5. N-ί 3-trifluonaethyl-1,2,4-thiadiazolyl (5)] - N'-methy1-urea. 6. N-ί 3-trifluoromethyl-1,2,4-thiadiazoly1 (5)] - N-ethy1-N'-methy! -Urea. 109840/1833 7.. N-13-Trifluoromethyl-1,2,4-oxadiazolyl (5)] - N ¹ -raethyl-N ¹ methoxy urea. 8. N- [3-dichlorotethyl-1,2,4-thiadiazoly 1 (5) J-N ', N ¹ -dimethylhammer. 9. N- [3-dichloromethyl-1,2,4-thiadiazoly1 (5)} - N'-methylurea. 10. N- [3-dichloromethyl-1,2,4-thiadiazolyl (5) JN, N ¹ -dimethylurea. 11. The new ureas of the formula I defined in claim 1 in which X is oxygen. 12. N- [3-Trifluoromethyl-1,2,4-oxadiazolyl (5) JN ¹ N'-dimethyl urea. 13. A process for the preparation of ureas of the formula I of claim 1, characterized in that an amine is used Formula II: l (ι Μ ¹ LJ- (U) y ^ y NHR ₂ in which R-, »Ro ^{and x have the} meanings given under formula I, either with a halocarbonic acid ester or with phosgene in the presence of an acid-binding agent in a carbamic acid derivative and this is converted with an amine of the formula III: in R ~ and R, the meanings given under formula I have 1098 AO / 1833 14. The method according to claim 11, characterized in that that the halogenated carbonic acid ester used is chlorocarbonic acid or chlorothiocarbonic acid phenyl ester. 15. A process for the preparation of ureas of the formula I in which R, denotes hydrogen *, characterized in that an amine of the formula IX of claim 13 with an isocyanate of formula IV: R ₄ - NGO (IV) converts * in the R, the meanings given under formula I. Has. 16. Herbicidal agent, characterized in that there is at least one urea of the formula I des as the herbicidal active ingredient Claim 1, together with distribution means suitable for combating grass-like and dicotyledonous weeds and / or carriers and optionally other herbicidal and biocidal active ingredients. 17. Methods of controlling grassy and dicotyledonous Weeds characterized by the use of . herbicidal ureas of the formula I of claim 1, or of * agents according to claim 14. FO 3.35 / Nu / kö 109840/1833 February 18, 1971