DE1770236A1 - 1,3,4-thiadiazolon- (5) -yl- (2) -ureas - Google Patents

Description

FARBENFABRIKEN BAYER AG Π70236 LEVERKUSEN-Bayerwerk

ΓΑΤΕΝΤ-AHERUNC

April 18, 1968

1.3.4-3? Hladiazolon- (5) -yl- (2) -uratoffe

The present invention relates to new 1,3,4-3hiadiazolon- (5) -yl- (2) -ureas, which have herbicidal properties and processes for their preparation.

It has already become known that 1,3-thiazolyl- (2) -ureas, z. B. the i- / 5-methyl-i, 3-thiazolyl ~ (2) -7-3-methyl-urea, can use as herbicidal active ingredients (see Belgian patent 679 138).

It has been found that the new 1,3,4-thiadiazolonylureas the Pormel

^N R "·

(D

in which

R represents hydrogen, alkyl having 1 to 13 carbon atoms which is optionally substituted by alkoxy; for cycloalkyl with 3 to 12 ring members,

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109841/1887 _{BAD 0RIGlNAU}

which optionally contains olefinically unsaturated and optionally condensed rings and is optionally substituted by halogen and / or alkyl having 1 to 4 carbon atoms; for aralkyl with 1 to 4 carbon atoms in the alkyl radical and 1 to 3 arylreaten as substituents, for aryl, where the aryl of the last two radicals mentioned is optionally replaced by alkyl with 1 to 4 carbon atoms, alkoxyl with 1 to 4 carbon atoms, halogen, cyano, nitro , Trifluoromethyl and / or dialkylamino can be substituted with 1 to 4 carbon atoms in the alkyl radicals, or stands for furfuryl,

R ^{1 represents} hydrogen, alkyl with 1 to 4 carbon atoms, alkenyl with 2 to 4 carbon atoms, alkoxyalkyl with 1 to 4 carbon atoms in the alkyl radical and 1 to 4 carbon atoms in the alkoxyl radical,

R "represents hydrogen or an aliphatic hydrocarbon radical having 1 to 3 carbon atoms stands and

R "'for an aliphatic hydrocarbon radical with 1 to 4 carbon atoms or alkoxyl with 1 to 4 carbon atoms,

have strong herbicidal properties.

It has also been found that the 1,3,4-thiadiazol'onyl ureas can be used (I) get when one

(a) Carbamic acid halides of the formula

^V NNR ¹ O

C "L ι» O ^A S ^ N-C-HaI

(II) Le A 11424 - 2 -

100841/1887

BATH ORIGINAL

in which

R and R ^{1 have} the meaning given above and Hal stands for chlorine or bromine, '· ■ ·.' ·,

with amines of the formula

(III)

in which

R "and R" 'have the meaning given above,

umeetat, or
(b) 2-Amino-1,3,4-thiadiazolone- (5) of the formula

- R

^ NNR ¹

O ^ S ^ NH (IV)

in which

R and R ^{1 have} the meaning given above,

with isocyanates of the formula

0 C = NR "·

(V)

in which

R " ^{1 has} the meaning given above,

implements. 109841/1887

Le A 11 424 - 3 -

BAD ORiGINu

Surprisingly Beiges ureas according to the invention (I) is considerably stronger and more selective herbicidal properties than the previously known from the prior art ureas, which are the active ingredients chemically closest Wirkungeart same. Pie substances according to the invention thus represent an enrichment of technology.

The course of the reaction in process (a) can be adjusted as if one of 2- (N-methyl-N-chlorocarbonyl-amino) - ^ - cyclohexyl-i, 3 »4-thiadiazoHnon- (5) and methylamine runs out:

N CH ₃ (j * y ^V - ^{W CH} 3

^ N-CO-Cl + HKHQH ₃ '-> ₀ *' S ^ H-CO-IfHCH ₃

(VI)

The carbamic acid halides to be used are through clearly characterizes the formula (III) given above. In this formula, R preferably represents hydrogen, Alkyl with 1 to 13 carbon atoms, preferably with 1 to 8 carbon atoms, where the alkyl radical is straight or can be branched and also with alkoxyl radicals Contain 1 to 4 carbon atoms as substituents can.

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109841/1887

Furthermore, R eteht for cycloalkyl with 5 to 12 ring members. The remainder can contain olefinic double bonds or fused rings, in particular aromatic and hydroaromatic rings. The cycloalkyl radical can be substituted by alkyl having 1 to 3 carbon atoms and / or chlorine, fluorine and bromine .

Finally , R preferably also stands for aralkyl with 1 to 3 carbon atoms in the alkyl radical and 1 to 2 aromatic rings, in particular phenyl and naphthyl, and also for aryl, in particular phenyl and naphthyl. In both cases, the aryl radicals can contain the following substituents: alkyl with 1 to 3 carbon atoms, alkoxyl with 1 to 2 carbon atoms, halogen, bromine, fluorine, cyano, nitro, trifluoromethyl and dialkylamino with 1 to 2 carbon atoms in the alkyl radicals. R also stands for furfuryl.

R ^f preferably represents hydrogen, alkyl with 1 to 4 carbon atoms, alkenyl with 3 to 4 carbon atoms, alkoxyalkyl with 1 to 4 carbon atoms in the alkoxyl radical and 1 to 2 carbon atoms in the alkyl radical.

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The carbamic acid halides (II) have not yet become known. However, they can be prepared in a simple catfish, when corresponding 1,4-disubstituted Thiο semicarba "lde in inert organic solvents such as hydrocarbons or chlorinated hydrocarbons, with at least 2 moles Fhosgenpro Thiοsemicarbazid moles, preferably 2 to 4 mol of phosgene, at temperatures between -20 and +200 ⁰ G implemented (see German patent application P 54 220 IVd / i2p).

Two examples for the preparation of carbamic acid chlorides according to formula (II) are given below.

Preparation of 2- (N-chlorocarbonyl-N-methyl-amino) -4-phenyl-1.3t4-thiadiazole-5-one

181 g (1 mol) of i-phenyl ^ -methyl-thiosemicarbazide are suspended in 700 ml of chlorobenzene. Phosgene is gradually passed in at room temperature, the temperature rising to 40 to 45.degree. At the same time, the suspension is initially thickened and later diluted. After the self-heating has subsided, it is heated from the outside in order to maintain a temperature of 40 to 45 ^° C. After about 220 g of phosgene (2.2 mol) have been introduced, a clear solution has formed. Mail slowly warms up in a weak stream of phosgene

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BAD ORJGiNAi.

further bia to 100 ° C and maintains this temperature for another hour. The solution is evaporated in vacuo. As a residue, the 2- (N-chlorocarbonyl-N-iaethyl-amino) -4-phenyl-1,3,4-thiadiazolin-5-one remains. in practically quantitative yield. Recrystallized from carbon dioxide, the purified product is obtained in a yield of 825%. F .: 105 ° C

Preparation of 2- (N-chlorocarbonyl-N-methyl-amino) -4-propyl-t.3 «4-thiadiagolin-5-one

147 g (1 mol) of i-propyl-4-methyl-thiosemicarbazide are dissolved in 600 ml of chloroform. At room temperature, passing an about 220 g (2.2 Hol) phosgene, the temperature to about 4O ⁰ C increases. A temporarily occurring colorless precipitate goes back into solution in the further course of the reaction. After the self-heating has subsided, the solution is heated to boiling in a weak stream of phosgene for about 1 hour and then evaporated in vacuo. A gradually crystallizing residue remains in a practically quantitative yield, from which 2- (N-chlorocarbonyl-N-methyl-amino) -4-propyl-1,3,4-thiadiazolin-5-one in oil by recrystallization from ligroin Yield is obtained in pure form. P. 34-36 ° C.

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109841/1887

The amines to be used are clearly defined by the formula (III). In this formula, R "preferably stands for hydrogen, alkyl with 1 to 2 carbon atoms, allyl and propynyl. R ¹¹¹ preferably stands for alkyl with 1 to 4 carbon atoms, alkenyl with 3 to 4 carbon atoms, propynyl and alkoxyl with 1 to 4 carbon atoms .

The following functional conditions arise for carrying out the process (a):

The reaction can be carried out in the presence of diluents. All of them come as a diluent inert organic solvents in question. These essentially include aliphatic and aromatic, optionally chlorinated hydrocarbons, such as benzene, toluene, chlorobenzene, methylene chloride, chloroform and Carbon tetrachloride; Ketones such as acetone and cyclohexanone; Ethers such as diethyl ether, dioxane and tetrahydrofuran; and mixtures of these diluents. However, it is also possible to work in aqueous suspensions be that either only water, water and a water-soluble solvent or water and contain a water-insoluble solvent.

To bind the split off hydrogen halide acid-binding agents added. The amines used for the reaction can act as such if one twice the equiraolar amount, based on the acid

Le A 11 424

1 0 9 8 A 1 / f8 8 f

BATH ORIGINAL

halide, uses. However, other acid-binding agents can also be used, e.g. B. inorganic bases such as alkali and alkaline earth metal hydroxides, alkali and alkaline earth metal carbonates, or organic bases such as tertiary amines, e.g. B. triethyl amine, Ν, Ν-dimethyl aniline and pyridine.

The reaction temperatures can be varied over a wide range. In general, the reaction is preferably carried out at between O and 10O ⁰ C, between 10 and 40 ⁰ C.

When carrying out process (a), it is expedient to use equimolar amounts of the reactants. The implementation is carried out in the usual way carried out, as well as the work-up, z. B. by filtering off, evaporation and recrystallization.

The course of the reaction in process (b) can be represented by the following equation: if you think of 2-methyl-amino-4-phenyl-1,3,4-thiadiazolon- (5) and methyl isocyanate runs out:

/ -NN CH-, O - _r NN CH * / I ι> 5 ti -Vi ι ι ->

Q - S - NH t C = NCH ₃ ^ 0 ^S '" ^N - ^G ° - ^NHCH 3

(VII)

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109841/1887

The 2-amino-1,3,4-thiadiasölones required are clearly characterized by the above formula (IY). In this formula, R and R * have the same Yorsuge white meanings as given above.

You Amino-1,3,4-thiadiazolone Bind only to a «small one Part known. The still new thiadlazolones can be produced in an analogous manner.

1) They can be obtained if aan 1,4-disubstituted thiosemicarbazide reacts with about 1 mole of phosgene (see e.g. Five-Merabered Heterocyclic Compounds with Nitrogen and Sulfur or Hitrogen, Sulfur and Oxygen, pages 153-173 (19 ), in the series: A. Weissberger, The Chemistry of Heterocyclic Compounds, Interscience Publishers, Hew York).

2) Bas in the 5-position unsubstituted ^ - diazolon- (5) can be prepared by heating i-carbamoyl-2-thiocarbamoyl-hydraein in concentrated hydrochloric acid (Chem. Ber. ^ A, 2506 (iöS6); J. Ind. Inst. Sci. 16 A , 11 (1933); J. Phare. Soc. Japan 72, 1533 (1952)).

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109841/1187

3) This substance can also be produced by reacting 2-thiocarbamoylhydrazinecarboxylic acid ethyl ether with acetic anhydride and subsequent acidic cleavage of the acetyl derivative initially formed (cf. Soc. 1958 , 1508).

4) A very general process for the preparation of 2-amino-1,3,4-thiadiazolones (5) is that the corresponding 2-halocarbonylamino compounds (II) in the presence of inert organic solvents, eg. B. acetone, at low temperatures, e.g. B. between -10 and + 2O ⁰ C, with aqueous alkali, z. B. aqueous sodium hydroxide solution, treated, wherein the chlorocarbonyl residue is split off.

The isolation is carried out in the usual way, for. B. by neutralizing the reaction mixture and filtering off of the reaction product.

Preparation of 2-allylamino-4-phenyl-1, j, 4-thiadiazolon- (5)

45 g of 2- (N-allyl-N-chlorocarbonyl-amino) -4-phenyl-1,3,4-thiadiazolon- (5) are dissolved in 250 ml of acetone. The solution of 1b g of sodium hydroxide in 100 ml of water is added dropwise with cooling (temperature 20 ^{° C.).} The mixture is stirred for 1 hour at room temperature. More are added

Le A 11 424 -11-

109841/1887

¹ SAT ORIGINAL

500 ml of water and neutralized by adding small amounts of hydrochloric acid. The deposited reaction product is filtered off with suction, dried and crystallized from white spirit. Yield: 30 g, P .: 1O3-1O5 ° C.

The isocyanates also used for reaction (b) are clearly characterized by the formula (V) given above. In this formula, R ^{HI has} the same preferred meanings as given above. These isocyanates are already known.

The conditions for implementation (b) are as follows:

The reaction can be carried out in the presence of diluents. In this case, the same diluents are used as indicated above for reaction (a). However, it is also possible to carry out the reaction in the melt without a diluent.

The reaction temperatures can be varied over a wide range. They are generally between 0 and 150 ⁰ C.

Tertiary amines such as triethylamine, tributylamine or bis-ethylenediamine can be used to accelerate the reaction add in small amounts.

Le A 1 ι 424 - 12 -

109841/1887

When carrying out method (b), one sets expediently about equimolar amounts of the starting materials. Working up is carried out in the usual way Way.

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109841/1887

Examples of the ureas according to the invention are called:

1- / T, 3,4-thiadiazolon- (5) -yl- (2) J7-3-methyl-urea

1- / ~ "» "_7-1,3-dimethyl-"

i- / 4-methyl-1,3,4-thiadiazolon- (5; -yl (2) _7-3-methyl-urea ^"lf _7-1,3-dimethyl-"

"" _7-1,3,3-trimetliyl ~ ··

1- ^ 4-ethyl- " _7-1,3-dimethyl-urate

1- ^ T-Jutyl- "_7-1,3-dimethyl-"

1- / 4-heptyl- ·· J7-1.3- ""

1- / 4- (1-propyl-butyl-1,3,4-thiadiazolon- (5) -yl- (2) _7-1,3-dimethyl

urea

1 -SS- (2-ethyl-hexyl) -1,3,4 "_7 ~ ^1» 3- ^H

urea

1- / 4 "- (1-methyl-dodecyl) -1,3,4-" _7 ~ 1,3- "

urea

1- / 4 "-Butoxy-ethyl-1,3,4-thiadiazoIon-l5) -yl-l2) __ 7 ~ 1,3-dimethyl-

urea 1 - /, T-Benzyl-1,3,4-thiadiazole £> n- (i>) - yl- (2) _7_i, 3-dimethylurea

1 - ^ / 4-chloro-benzylj-1,3, 4-tiiiadiazolon-l5) -yl- (2) _7-1,3-diaethyl-

urea 1- β- { 4 -kethoxy-benzyl) -1,3,4- "urea

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109841/1887

1- ^ 4- (4-butyl-benzyl) -1,3,4-thiadiazolon- (5) -yl- (2) _7-1,3-dimethyl-

urea

1- / 4- (2,4,5-trichlorobenzy: U-1,3,4- "_7-1» 3- "

urea

1- / 4 ~ - (3-nitro-benzyl) -1,3,4- "_J7-1,3-"

urea

1- / 4 "- (4-cyano-benzyl) -1,3, 4-" J- 1,3- "

urea

1- / 4 "- (4-x ¹ rifluoromethyl-benzyl) -1,3,4" _7-1,3- "

urea

1- / 4- (1-l> henyl-ethyl) -1,3,4- "_J7-1,3-"

urea

1- / T-i) iphenylmethyl-1,3,4- "J7-1,3"

urea

1- / 4-rriphenylmethyl-1,3,4- "J ⁷ -1>3-"

urine

I- / J- (2- (4 - «- ethyl-phenyl) -ethylJ-1, 3,4" J7-1,3- "

urea

urea

1-./4-(1-waphohyl-(1)-kthylj-1 _f 3,4- " J-Λ , 3-"

urea

1- / 4-Furfury.-1,) ₁ 4-thiaüxazolori- (5) -yl- ' _v 2) J7-1, 3-dimethyl-urea f

1- / 4 "-Oy (; lopropyl-1, ί, 4- '· Le A 1 1 ' \ / 4

1098 Al / 1887

BATH

-1,3,4-thiadiazolon- (5) -yl- (2) J7-1,3-d im ethyl urea 1- ^ r-cyclododecyl-i, 3,4- "_7 ~ 1,3-""

1- / 4- (4-methyl-cyclohexyl) -1,3,4- "_7 ~ 1,3-" "

1- / 4- (3,4,5-trimethyl-cyclohexen- (2) -yl) -1,3,4-thiadiazolon- (5) -yl- (2) _7-1,3-dimethyl-urea

1- / 4-pluorenyl (9) -1,3,4-thiadiazoloxy (5) -yl- (2) J7-1,3-dimethylurea

1- / 4 ~ -i'etrahydronaphthyl- (1) -1 , 5 , 4-thiadiazolon- (5) -yl- (2) _7_i, 3-dimethyl urea

1- / 4-Phenyi-1,3,4-thiadiazolon- (5) -yi- (2) _7-1,3-dimethyl-urea 1- / 4-phenyl-1,3,4-thiadiazolon- (5 ) -yl- (2) __ 7-1 _t 3,3-trimethyl-urea £ f 1- / 4- (4-chloro-phenyl-) - 1 , 5 , 4-thiadiazolon- (i?) - yl- ( 2) J7-1 _t 3-dimethylurea

1- / 4 "- (3,4-iichloro-phenyl) -1, ^, 4-thiadiazolon- ^ 5) -yl- (2) _7-1, 3-dimethyl-urea

1- / 4- (4-Bromo-phenyl) -1,;>, 4- "_J7-1,3-

dimethyl urea 1- / T- (4-iluoro-phenyl-) ~ 1,;, 4- " dimethyl urea 1- / 4- (4-iodine-pheny]) - 1, ^, 4- » dimethyl urea 1- / T-methyl 1-phenyl) -1,3,4- " dimethyl urea 1- / T- (4-i'rifiuoriaethyl-phonyl) -1, 5, Ί- " dimethyl urea

Le A 11 4 ^ 4 - 16 -

109841/1887

1- / T- (2-chloro-4-trifluoromethyl-phenyl) -1,3,4-thiadiazolone-

(2) _7-1,3-dimethyl-urine-off

1 _ ^ _ (2-nitro-phenyl) -1,3,4-thiadiazolon- (5) -yl- (2) _7-1,3-dimethyl-

urea

1- / 2T_ (4-uyanophenyl) -1,3,4- " .7-1,3- "

urea

1- / 4-naphthyl- (1) -1,3,4- ".7-1,3-"

urea

1- / J-lMaphthyl- (2) -1,3,4- "_7 ~ 1,3-"

urea

! - / i-Ethyl-1,3,4- ^lf J7-1-ethyl-3-

methyl urea

1- / 4-isopropyl-1,3,4-thiadiazolon- (5) -yl- (2) _7-1-allyl-3-methyl-

urea

1- / 4-Butyl-1,3,4-thiaaiazoIon- (5) -yl-l2) _7_i- (2-methoxy-ethyl) -3-

methy! urea

^ - / T-troρyl- ^ , 3,4-thiadiazolon- (5) -yl- (2) J7-1-ynethyl-3-ethyl-

urea

1- / 4-i ^ ropyI-1,3, 4-thiadiazolon- (5) -yl- (2) JZ-i-methyl ^ -allyl-

urea

i- ^ T-iropyl-i ^, 4-thiadiazolon- (b) -yl (2) _J7_i_ _me thyl-3-propynyl

urinate / Oli

1- ^ Τ-ΐΊιί; Γ ^ 1-1,3,4 "_7-1,3-dimethyl-3-butyl-

urea

1- / 4 "-ihenyl-1, 5,4-" _7 ~ 1, j-aimethyl-j-propynyl-

hurriBtof f

l- ^ J-l'henyL-1, 5.4- "__7-1, i-diraethyl-3-methoxy-

hurrii; toff

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109841/1887

The thiadlazolonylureas have a strong herbicidal potency and can therefore be used as weed killers . Weeds in the broadest sense are to be understood as meaning all plants which grow in locations where they are undesirable. Whether the agents erfinduogs contemporary act as total- or selelrtiv-herbicidal agents depends on the amount of time spent workest off amount from.

The active ingredients according to the invention can, for. B. be used in the following plants : Dicotyls, such as mustard (Sinapis), cress (Lepidium), burdock (GaIium), chickweed (Stellaria), chamomile (Matricaria), French herb (Galinsoga), goose foot (Chenopodium), nettle (Urtica ), Ragwort (Senecio), cotton (Gossypium), beets (Beta), carrots (Daucus), beans (Phaseolus), potatoes (Solanum), coffee (Coffea); Monocots, such as timothy (Phleum), bluegrass (Poa), fescue (Festuca), Eleusine (Eleusine), Fennich (Setaria), Raygrass (Lolium), Trespe (Bromus), barn millet (Echinochloa), maize (Zea), rice ( Oryza) oats (Avena), barley (Hordeum), wheat (Triticum), millet (Panicum), sugar cane (Saccharum).

The thiadiazolonylureas are preferably used as selective herbicides. You have z. B. good selectivity in cotton, grain and carrots

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109841/1887

The active compounds according to the invention can be converted into the customary Formulations are transferred, such as solutions, emulsions, suspensions, powders, fasts and granules. These are made in a known manner, e.g. B. by mixing the active ingredients with extenders, ie liquid solvents and / or solid carriers, optionally using surface-active substances Agents, that is to say emulsifiers and / or dispersants. In the case of using water as an extender can e.g. B. organic solvents can also be used as auxiliary solvents. As a liquid Solvents are essentially possible: aromatics such as xylene and benzene, chlorinated aromatics such as chlorobenzenes, Baraffins such as petroleum fractions, alcohols such as methanol and butanol, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, as well Water; as solid carrier materials: natural rock flour, such as kaolins, clays, talc and chalk, and synthetic minerals such as fumed silica and silicates; as emulsifier: non-ionic and anionic emulsifiers, such as polyoxyäthyIeτι fat acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. Alkylaryl polyglycol ethers, alkyl sulfonates and aryl sulfonates, as a dispersant: e.g. B. lignin, sulphite waste liquors and methyl cellulose.

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1098A1 / 1887

The active compounds according to the invention can be present in the formulations as a mixture with other known active compounds.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. It is used in the usual way, for. B. by dusting, atomizing, splattering, pouring and scattering.

The amount used can fluctuate in larger areas. It essentially depends on the type of thing you want Effect. In general, the application rates are between 0.5 and 20 kg of active ingredient per hectare, preferably between 1 and 10 kg per hectare.

The active ingredient concentration is in the usual aqueous preparations and in the application according to the Emergence generally between 0.005 and 1.0 percent by weight, preferably between 0.01 and 0.5 Weight sprο ζ ent

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Example 1:

₀ - -u rv. _H - S - NH - CH ₃

20.7 g (0.1 mol) of 2-methylamino-4-phenyl-1,5,4-thiadiazolon- (5) are dissolved in 120 ml of dimethylformamide. After adding a catalytic amount of triethylenediamine , 5.7 g (0.1 mol) of methyl isocyanate are added dropwise at room temperature. The mixture is stirred for 1 hour at room temperature, 1 hour at 35-40 ° and 1 hour at 70-75 °, cooled to room temperature and the reaction product is precipitated by adding water / water. This is dried and recrystallized from butanol.

Yield: 25.2 g (88 i ° of the 'iheorie) of 1- / T-phenyl-1,3,4-thiadiazolon- (5) -yl (2) _7-1,3-dimethyl-urea. P: 197-198 °.

Example 2:

·. H / -N N

0 NC-NH-CH ₃ 26 g (U, 1 itaol) 2 ~ (N-methyl-N-chloroarbonyl-amino) -4-

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109841/1887

cyclohexyl-1,3,4-thiadiazolinon- (5) are in 125 ml Dissolved acetone. 17 g (0.22 mol) of a 40 # strength aqueous solution are left at room temperature with stirring and cooling Add methylamine solution dropwise. The mixture is stirred for 1 hour at room temperature, 250 ml of water are added and suction is carried out the failed product. After drying, 24.8 g (92 l of theory) of i - ^ - cyclohexyl-1,4-thiadiazolon- (5) -yl- (2) -7-1,3-dimethylurea are obtained. P: 196-198 °.

Example 3:

O 3 "^ CH,

• - ° ■ ν:

Into a solution of 22.2 g (0.1 mol) of 2- (N-methyl-N-chlorocarbonyl-amino) -4-ethyl-1,3,4-thiadiazolinon- (5) in 125 ml of benzene is passed under Cooling at 20-25 ° 9.9 g (0.22 mol) of dimethylamine. The mixture is stirred at room temperature for 1 hour, then washed twice with water and the benzene solution is evaporated in vacuo. The residue remains

trimethyl urea in practically quantitative yield. Recrystallized from Vi'aschbenzin, it melts at ü ^l : 60 - 62 °.

The following connections of the iorinei (1) are obtained in a corresponding manner: Le A 11 424

No.

Tabel

R "

R "

F ( ⁰ C)

uncrystallized a \; s

4) -CH ₃ CH ₃ H H H CH ₃ 214-215 Butanol 5) -CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ 111-112 water 6) -C ₂ H ₅ CH ₃ H . OH, 175-177 toluene 7) -C ₃ H ₇ CH ₃ H · CH ₃ 135-136 toluene O 8th) -C ₃ H ₇ CH ₃ H CH ₃ 69 Petroleum ether CO
OO
^ * 9) -CH (CH ₃ ) ₂ CH ₃ CH ₃ CH ₃ 163-165 toluene 10) -CH (CH ₃ ) ₂ CH ₃ C ₂ H ₅ C ₂ H ₅ 146-147 Petroleum ether _ »
OO 11) -CH (CH ₃ ) ₂ CH ₃ CH ₂ -CH = CH ₂ 126-127 Petroleum ether OO
-3 12) -CH (CH ₃ ) 2 CH ₃ CH ₃ 68-70 Petroleum ether 13) -CH (CH ₃ ) 2 CH ₃ C ₂ H ₅ 45-46 Ligroin

Le A 11 424

- 23 -

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109841/1887

Table 1 (port setting)

O CO OO JE-

No.

R '

F ( ⁰ C)

-CH,

-CH,

23) 24)

25) 26)

27) 28)

29)

Le A 11

" ^CH 2A V ^C1

CH,

CH,

CH

CH

CH,

CH,

CH,

CH,

CH,

CH-

CH,

CH-CH ₃

- 25 -

time crystallizes out

71-72 Petroleum ether 235-236 Glycol Monitors oil - 200 Butanol 75-77 Petroleum ether 221 Butanol 117-119 Petroleum ether

Table 1 (port setting)

No.

R "R" F ( ⁰ C)

recrystallized from

30)

CH, 148-150

toluene

31) -CH ₂ -CH ₂ - /> CH ₃ CH ₃ CH ₃ CH ₃ 106-107

Petroleum ether

32) 33) 34)

CH ₃ H

CH ₃ H

CH ₃ CH ₃ CH

121-123

62

197

Tetra / ligroin

Petroleum ether

Ethanol

35)

CH ₃ CH ₃ CH ₃ 90-92

Petroleum ether

Le A 11 - 26 -

τ- II Il Il Il

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H Il Il

H Il Il

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fit Il Il

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O to O to W. W. te CVJ to "w O O O O O O I.

to to to to to to to to K ! Xi do Ä W. O O O O O O O

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109841/1887

Tabel

1 (port setting)

Mr.

R ¹

R "

P ( ⁰ C)

recrystallized from

44) 45) 46) 47) 48) 49) 50) 51) 52) 53) 54)

Lt A 11

CH, CH, CH, CH,

CH (CH ₃ ) ₂ CH ₂ -CH (CH ₃ ) ₂ CH ₂ -CH (CH ₃ ) ₂

H CH.

C ₂ H ₅

CH,

CH,

CH,

-CHp-CH = CHp 169-170 Ethanol OH, 103 Petroleum ether C ₂ H ₅ oil - -CHp-CH = CHp 66-67 Petroleum ether CH ₃ 194-195 Methanol CH ₃ 78-80 Methanol CH ₃ 167-168 Ethanol CH ₃ 47 'Petrol CH ₃ 162-164 toluene CH ₃ 158-160 Ethanol CH, 48-50 Petroleum ether

- 28 -

Tabel

1 (continued)

Mr.

H"

F ( ⁰ C)

recrystallized from

57)

58)

CH ₂ -CH = CH ₂ CH ₂ -CH = CH ₂

CH,

O
ts>
OO 59) Cl Cl CH ₃ * ~
'S * 60) ς} CH ₃ 1887 Cl ^ - ^ ~ Vci 61) -O- ⁰¹ CH ₃ 62) -Q.01 CH ₃ 63) 11 424 CH ₃ 64) CH ₃ Le k

H H

CH, H

CH,

CH, CH,

CH

CH ₅

CH, CH-, C ₂ H ₅

H4-U5 48 54-56

258

178 209-210

90

163-165 188

Carbon tetrachloride

Ligroin

Petroleum ether

Dioxane

Butanol Butane I.

Ethanol

Ethyl acetate

Butanol

CH (CH ₅ ) ₂ 173-174 butanol

- 29 -

Table 1 (continued)

Mr.

F ( ⁰ C)

recrystallized from

65) 66) 67)

68) 69) 70)

Cl

Cl

Cl

CHj

CH,

fit fr ^CH 3

CH,

Cl

71) 72) 73 -O ^ ^F 3

74) _C1 ^> ^CP 3 Le A 11

CH,

CH,

CH,

CH,

CH,

CH,

CH,

CH,

CH,

CH,

CHj

CH, H

CH, H

CH,

H H

CH ₂ -CH = CH ₂ 157 CHj 128-130 CHj 210 CHj 136-138 CHj 188-189 CH, 93-95 CH, 223-225

105-107

270

212-214

Ethanol

Petroleum ether ethanol

Ethanol ethanol

Petrol Butane I.

Ethanol

Butanol ethanol

Table 1 (continued)

No.

R "

R "

P ( ⁰ C)

recrystallized from

l ^

75) 76)

77) 78)

79) C ₃ H ₇ 80)

⁸¹ ) (CH ₃ J ₂ CH-CH

CH,

CH,

CH.

C ₂ H ₅

CH,

CH ₃

H H H

CH

CH ₃

CH ₃ CH ₃ CH,

CH

145-146 ethanol 218 butanol 155 butanol

138-140 ethyl acetate / ligroin

146-148 methanol

140 mineral spirits 138-140 carbon tetrachloride

L e A 11

- 31 -

Table 1 (continued)

R "

F ( ⁰ C)

recrystallized from

84) (CH ₃ J ₂ CH-

? 2 «5 87) C ₄ H ₉ -CH-CH ₂

C ₂ H ₅ H CH ₃ 159 Ethanol C ₂ H ₅ CH ₃ CH ₃ 68-70 Petroleum ether C ₂ H ₅ H CH ₃ 168 Toluene / ligr C ₂ H ₅ H . ^CH 3 223-225 Petroleum ether C ₂ H ₅ CH ₃ CH ₃ 77-78 Ligroin

CH

Petroleum ether

Cj

CH,

CH

167-169

toluene

Le A 11

- 32 -

Table 1 (continued)

Mr. R.

R ^r R "R ^M

recrystallized from

CH ₃ CH ₃ 60-62

Petroleum ether

CH ₃ CH ₃

90) CH _x -C- CH-

J 1

CH,

CH ₃ H CH ₃ 164-166 carbon tetrachloride

CH ₃ H CH, 224-226 butanol

^X 3

CH ₃ CH ₃ CH ₃

Petroleum ether

CH

CH

CH, H

CH,

184-185 butanol

Le A 11 424 CD KJ CO

Table 1 (port setting)

Mr.

R "

/O

rc)

recrystallized from

94) (CH

CH ₅ H

212

Butanol

95)

CH,

CH,

100

Ethanol

96) (CH ₂ )

CH,

CH, 207-209 butanol

97)

CH,

CH,

107-108 petroleum ether

98) Cl - /> - CH

CH ₅ H CH ₅ 214-215 butanol

99)

Le A 11 424

Cl

CH,

CH ₅ CH ₅

- 34 - 117-119 petrol

Table 1 (continued)

No.

R "R"

( ⁰ C)

recrystallized from

1CO)

101) ICJ)

1 04)

""

CH,

: h ₃ - <

GH,

CH,

CH,

CU

CH

CH

CH, 112

CH, 194

CH ₃ CH ₃

CH, CH,

104

CH, 205

91

Petroleum ether

Butanol

Petroleum ether

Butanol

Petroleum ether

Le A 11

- 35 -

CjJ CD

example A.

Pre-emergence test

Solvent: (parts by weight of emulsifier: parts by weight

To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amount Solvent, add the specified amount of emulsifier and dilute the concentrate with water to the desired concentration

Seeds of the test plants are sown in normal soil and, after 24 hours, watered with the preparation of the active compound. Included the amount of water per unit area is expediently kept constant. The concentration of active ingredients in the preparation plays a role Doesn't matter, only the amount of active ingredient applied per unit area is decisive. After three weeks, the degree of damage will be of the test plants and designated with the code numbers 0-5, which have the following meaning:

0 no effect

1 slight damage or growth retardation

2 significant damage or stunted growth

3 serious damages and only poor development or only 50 i » accrued

4 plants destroyed after germination partially OAER accumulated only 25 i>

5 plants completely dead or not emerged

Active ingredients, application rates and results are based on the following Table out *

Le A 11 424 - 36 -

109841/1887

ύ ta ν •egg Φ

03 H H

al pq ι. · fa

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CQ

OOO HOO OOO H

OO HOO OOO J

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1 098-1 / 188

BATH ORIGINAL

T a be 1 1 e 2 (Continue.)

Active ingredient active ingredient- Echino- Cheno- Sina- oat cotton wheat

effort chloa podium pis
kg / na

10 5 5 5 4-5 5 5

5 555444

2.5 5 5 5 3 3 3

16: ID 5 5 5 4-5 0 4

5 4-5 5 5 3-4 0 3

0 3

10 5 5 5: 1 1 1

5 4-5 5 4-5 0 0 0

2.5 4 5 4 0 0 0

10 5 5 5: 1 1 1

5 4 * 5 5 4-5 0 0 1

2.5: 4 ^ 5 3 * 0 0 0

10 5 "53 5:. Z- 0 2

0 1,

; 53 4 ^ 5S 53 4 * O 0 0

15) ΙΟ) 4 * 5 ^; 53 5- 22 O 2:

5 4 ^; 5j 4-5 "0; 0 1:

0 0

O 188 100 53 53 53 4 ^ 2 4 <

= 53 44 53 53 4-J- 2 3

1 2Λ

5
5 UNUNUN vnvnvji 4-5
4th
3 5
4-5
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4-5
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0
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4-5 1
0
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53 53 4-5; Z-
1.
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5: # 22nd
0;
0 53 53
4 * 53
4 < 2 5 ^r
53
4-5 53
5- 53 ·
53 5
5
4th

1OC 5 ^r 53 53 5 5 5 - <ΐ

53 53 53 % - 5 4-5: 4 σ

3 3 ro

• 386 - ·

Table 2 (continued)

Active ingredient

58

74

Active ingredient Echino Cheno- Sina- oats Cotton 1 fei expenditure
kg / ha chloa podiua pis 10 4-5 5 5 1 3 1 5 4th 5 4-5 0 2 0 2.5 4th 4-5 4th 0 1 0 10 4-5 5 4-5 0 0 0 5 4th 5 4th 0 0 0 2.5 4th 4-5 3-4 0 0 0 10 5 5 5 1-2 0 1 5 4-5 5 0 0 0 2.5 4th 5 4th 0 0 0

Le A 11 424 - 39 - O

NJ GJ CD

Example B. Post-emergence test

Solventi parts by weight Emulsifier parts by weight

To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amount Solvent »adds the specified amount of emulsifier and then dilutes the concentrate with water to the desired concentration.

Test plants, which have a height of about 5-15 cm, just dewy. Haoh three Weeks, the degree of damage to the plants is determined and with denoted by the code numbers 0-5, which have the following meaning:

0 no effect

1 single light burn marks

2 distinct leaf damage

3 individual leaves and stem parts partly dead

4 plant partially destroyed

5 plant totally dead

Active ingredients, active ingredient concentrations and results run out the table below

Le A 11 424 - 4ü -

109841/1887

BATH ORIGINAL

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U.N.
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109841/1887

Claims (6)

R represents hydrogen, alkyl having 1 to 13 carbon atoms which is optionally substituted by alkoxy; for cycloalkyl with 3 to 12 ring members, which is optionally olefinically unsaturated and optionally contains fused rings and is optionally substituted by halogen and / or alkyl with 1 to 4 carbon atoms; for aralkyl with 1 to 4 carbon atoms in the alkyl radical and 1 to 3 aryl radicals as substituents; for aryl, where the aryl of the two last-mentioned radicals can optionally be substituted by alkyl with 1 to 4 carbon atoms, alkoxyl with 1 to 4 carbon atoms, halogen, cyano, nitro, trifluoromethyl and / or Malkylamino with 1 to 4 carbon atoms in the alkyl radicals , or stands for furfuryl, R ¹ for hydrogen, alkyl with 1 to 4 carbon atoms, alkenyl with 2 to 4 carbon atoms, alkoxyalkyl with 1 to 4 carbon atoms im Alkyl radical and 1 to 4 carbon atoms in the alkoxyl radical , R "represents hydrogen or an aliphatic hydrocarbon radical having 1 to 3 carbon atoms stands and Le A 11 424 - 43 - ^iiS - ^jL - ^u - "109841/1887 BATH ORIGINAL R " ^{1 stands} for an aliphatic hydrocarbon radical with 1 to 4 carbon atoms or alkoxy1 with 1 to 4 carbon atoms. 2) Process for the preparation of 1,3,4-thaladiagolonyl-barn-8toffen, characterized in that one (a) Carbamic acid halides of the formula R ^N HNR · O -Hal (II) in which R and R ^{1 have} the meaning given above and Hal stands for chlorine or bromine, with amines of the formula . HH (III) ^ R " ¹ in which R "and R" ^{1 have} the meaning given above, umeetst or (b) 2-Amino-1,3,4-thiadia «olone- (5) of the formula Le A 11 424 - 44 - 109841/188? hg * 177Ü236 in which R and R ^{1 have} the meaning given above, with isocyanates of the formula C = NR " ¹ (V) in which R "'has the meaning given above, implements. 3) Herbicidal agents »characterized by a content of 1,3,4-thiadiazolonyl ureas according to claim 1. 4) A method for combating unwanted plant growth, characterized in that 1,3,4-thiadiazolonyl ureas according to claim 1 can act on the unwanted plants or their habitat. 5) Use of 1,3,4-thiadiazolonyl ureas according to Claim 1 for combating undesirable plant growth. 6) Process for the preparation of herbicidal agents, thereby characterized in that one 1,3,4-thiadiazolonylureas according to claim 1 mixed with extenders and / or surface-active agents. Le A 11 424 - 45 - 108841/1887