HU206708B - Herbicide compositions containing pyrimidine-dion derivatives as active components and for extirpating weeds - Google Patents

Abstract

The invention relates to compounds of formula (I), where R<1>, R<2>, R<3>, R<4>, R<5>, R<6>, R<7>, n and X have the meanings given in the description, as well as to enol ethers and salts thereof and to their preparation. The compounds possess herbicidal properties and are therefore suitable active ingredients for herbicides. The invention also relates to a herbicide containing one or more of these substances and the use of the substances or herbicides for combating weeds. Certain starting materials which also possess herbicidal properties and their preparation are also described.

Description

The present invention relates to heterocyclic compounds of formula I wherein R ^{1 is} hydrogen, C 1-4 alkyl,

R ^{2 is} hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy (C 1 -C 4) alkyl, C 2 -C 5 cyanoalkyl, C 25 alkoxycarbonyl - (C 1 -C 4) alkyl, carbamoyl (C 1 -C 4) alkyl, di (C 1 -C 4) alkylcarbamoyl (C 1 -C 4) alkyl, C 3 -C 4 alkenyl -, C 3 or C 4 alkynyl,

R ^{3 is} hydrogen or C 1-4 alkyl,

R ^{4 is} hydrogen,

R ^{5 is} hydrogen or fluoro,

R ^{6 is} hydrogen, halogen or C 1-4 alkyl,

R ^{7 is C} 1 -C 4 alkyl or C 1 -C 4 haloalkyl, n is 0 or 1 and

X-3-aryl-uracil derivatives represented by oxygen or sulfur, and enol ethers of compounds of formula (I) containing ^{1 to} 4 carbon atoms of R ¹ and salts of compounds of formula (I) containing R ¹ and / or R ² a herbicidal composition and a herbicidal process.

Also included among the enol ethers mentioned above are compounds of formula Ia wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , n and X are as defined above and R ¹ 1-4 represents a C 1 -C 4 alkyl group.

The compounds of the formula I, their enol ethers and their salts are herbicidal and can be used as herbicides. Accordingly, the present invention also encompasses herbicides which contain these compounds as active ingredients, and a process for the preparation of the compounds and the use of the compounds or agents for controlling weeds.

In the compound of formula (I) above, "halogen" means fluorine, chlorine, bromine or iodine. Alkyl, alkenyl and alkynyl groups may be straight or branched, as is the case for any other group containing alkyl, alkenyl or alkynyl moieties. The haloalkyl groups may contain one or more identical or different halogen atoms, and the same applies to haloalkyl groups which form part of a larger group, such as a haloalkoxycarbonylalkyl group. The alkenyl and alkynyl groups may have more than one double or triple bond, depending on the number of carbon atoms they contain.

The salts of the compounds of the formula I are, in particular, their alkali metal salts, for example, their sodium and potassium salts; alkaline earth metal salts such as calcium and magnesium salts; their ammonium salts, i.e. unsubstituted ammonium salts, and mono- or polysubstituted ammonium salts, such as triethylammonium and methylammonium salts, and salts with other organic bases, such as pyridine.

In the case where the compounds of formula I and their enol ethers of formula Ia have at least one asymmetric center, said compounds may exist in the form of their optical isomers. The possible C = C or C = N double bond may also result in geometric isomers. In addition, keto-enol tautomerism [-NH-CO - (-) - N = C (OH) -] may be present in compounds of formula I wherein R ^{1 is} hydrogen. The compounds of formula (I) include all possible isomeric forms and mixtures thereof.

Independently of one another, R ^{1 is} preferably straight-chained C 1 -C 4 alkyl, especially methyl, or C 1 -C 4 haloalkyl, such as difluoromethyl; ^R2 is preferably C1-4 alkyl, C1-4 alkoxy (l-4-szénatomosj cycloalkyl having 3 or 4 carbon atoms, 3 or 4 carbon atoms or alkynyl of 1-4 carbon atoms, a haloalkyl group, especially said first, second, third or fourth group; R ³ and R ⁴ are each hydrogen or C 1-4 alkyl, especially hydrogen; R ^{5 is} preferably hydrogen or fluoro; R ^{6 is} preferably hydrogen, fluoro, chloro; R ^{7 is} preferably C 1-4 alkyl, especially C 1-3 alkyl, such as methyl or ethyl, or C 1-4 fluoroalkyl, especially trifluoromethyl or pentafluoroethyl; and n is preferably 0 when X is sulfur or n is preferably 1 if X is oxygen.

The following compounds of formula (I) are preferred:

6-ethyl-3- [4-allyl-3,4-dihydro-7-fluoro-3-oxo-2H-1,4-benzoxazin-6-yl] -5-bromo-1-methyl-2,4 ( 1H, 3H) -pyrimidinedione,

3- [3,4-dihydro-7-fluoro-3-oxo-4- (2-propynyl) -2H-l, 4benzoxazine-6-yl] -l-methyl-6- (n-propyl) -2, 4 (lH, 3H) -pyrimidinedione,

6-Ethyl-3- [3,4-dihydro-7-fluoro-4-isopropyl-3-oxo-2H-1,4-benzoxazin-6-yl] -1-methyl-2,4 (1H, 3H) -pyr midindion,

6-ethyl-3- [4-sec-butyl-3,4-dihydro-7-fluoro-3-oxo-2H-1,4-benzoxazin-6-yl] -1-methyl-2,4 (1H, 3H) -pyrimidinedione

6-ethyl-3- [3,4-dihydro-7-fluoro-4- (l-methoxy-ethyl) -3-oxo-2H-l, 4-benzoxazin-6-yl] -l-methyl-2,4 ( H, 3H) -pyrimidinedione,

6-ethyl-3- [3,4-dihydro-7-fluoro-4- (1-methoxy-propyl) -3-oxo-2H-1,4-benzoxazin-6-yl] -1-methyl-2,4 ( H, 3 H) -pyrimidinedione,

6-Ethyl-3- [3,4-dihydro-7-fluoro-4- (1-methyl-2-propenyl) -3-oxo-2H-1,4-benzoxazin-6-yl] -1-methyl-2,4 (lH, 3H) -pyrimidinedione,

6-ethyl-3- [3,4-dihydro-7-fluoro-3-oxo-4- (l-methyl-2-propynyl) -2H-l, 4-benzoxazin-6-yl] -l-methyl- 2,4 (lH, 3H) -pyrimidinedione,

6-ethyl-3- [6-fluoro-3-isopropyl-2-oxo-5-benzothiazolinyl] -1-methyl-2,4 (1H, 3H) -pyrimidinedione,

6-ethyl-3- [3-sec-butyl-6-fluoro-2-oxo-5-benzotiazolinil] l-methyl-2,4 (lH, 3H) -pyrimidinedione,

HU 206 708 Β

6-ethyl-3- [6-fluoro-3- (1-methoxyethyl) -2-oxo-5-benzothiazolinyl] -1-methyl-2,4 (1H, 3H) -pyrimidinedione, 6-ethyl- 3- [6-fluoro-3- (l-methoxy-propyl) -2-oxo-5-benzotiazolinil] -l-methyl-2,4 (lH, 3H) -pirimidmdion,

6-ethyl-3- [3-allyl-6-fluoro-2-oxo-5-benzothiazolinyl] -1-methyl-2,4 (1H, 3H) -pyrimidinedione, 6-ethyl-3- [6-fluoro- 3- (1-Methyl-2-propenyl) -2-oxo-5-benzothiazolinyl] -1-methyl-2,4 (1H, 3H) -pyrimidinedione, 6-Ethyl-3- [6-fluoro-2-oxo-3 - (2-propynyl) -5-benzothiazolinyl] -1-methyl-2,4 (1H, 3H) -pyrimidinedione and 6-ethyl-3- [6-fluoro-3- (1-methyl-2-propynyl) - 2-oxo-5-benzothiazolinyl] -1-methyl-2,4 (1H, 3H) -pyrimidinedione.

Preferred compounds of formula I are:

Compounds of formula (I) wherein R ¹ and R ⁷ are both methyl, R ³ , R ⁴ and R ⁶ are hydrogen, R ^{5 is} fluorine, n is 1 and R ^{2 is} ethyl, η-propyl, 2-fluoro ethyl, methoxymethyl, 2-methoxyethyl, methoxycarbonylmethyl, 1-methoxycarbonylethyl,

2-methoxycarbonyl-ethyl, carbamoylmethyl or dimethylcarbamoylmethyl:

3- [3,4-Dihydro-7-fluoro-3-oxo-4- (2-propynyl) -2H-1,4-benzoxazin-6-yl] -1,5,6-trimethyl-2,4 (1H) , 3H) -pyrimidinedione,

3- [3,4-dihydro-2,2-dimethyl-7-fluoro-3-oxo-4- (2-propynyl) -2H-1,4-benzoxazin-6-yl] -1,6-dimethyl- 2.4 (1H, 3H) pyrimidinedione,

3- [2-ethyl-3,4-dihydro-7-fluoro-3-oxo-4- (2-propynyl-2H-l, 4-benzoxazin-6-yl] -l, 6-dimethyl-2,4 (H , 3H) -pyrimidinedione,

3- [3,4-dihydro-3-oxo-4- (2-propynyl) -2H-l, 4-benzoxazin-6-yl] -l, 6-dimethyl-2,4 (lH, 3H) -pyrimidinedione .

3- [7-chloro-3,4-dihydro-3-oxo-4- (2-propynyl) -2H-l, 4benzoxazine-6-yl] -l, 6-dimethyl-2,4 (lH, 3H) -pyrimidinedione, compounds of formula (I) wherein R ¹ is methyl, R ^3, R ⁴ and R ⁶ are both hydrogen, ^R5 is fluorine atom, R ⁷ is trifluoromethyl, n is 1, X is oxygen and R ² ethyl , η-propyl, η-butyl, carbamoylmethyl or allyl;

compounds of formula I wherein R ^{1 is} methyl, R ³ , R ⁴ , R ⁵ and R ⁶ are each hydrogen, R ^{7 is} trifluoromethyl, n is 1, X is oxygen, and R ^{2 is} ethyl, η-propyl -, 2-fluoroethyl, methoxymethyl, 2-methoxyethyl, cyanomethyl, methoxycarbonylmethyl, 1-methoxycarbonyl-ethyl, 2-methoxycarbonyl-ethyl, carbamoylmethyl -, dimethylcarbamoylmethyl, allyl or 1-methyl-2-propynyl;

3- [3,4-Dihydro-2-methyl-3-oxo-4- (2-propynyl) -2H-1,4-benzoxazin-6-yl] -1-methyl-6-trifluoromethyl-2,4 ( 1H, 3H) pyrimidinedione,

3- [7-chloro-3,4-dihydro-3-oxo-4- (2-propynyl) -2H-l, 4benzoxazine-6-yl] -l-methyl-6-trifluoromethyl-2,4 ( H, 3H) pyrimidinedione;

compounds of formula I wherein R ^{1 is} methyl, R ³ , R ⁴ , R ⁵ and R ⁶ are each hydrogen, R ^{7 is} pentafluoroethyl, n is 1, X is oxygen and R ^{2 is} η-propyl, allyl - or propargyl;

compounds of the formula I in which

R ^{1 is} methyl, R ³ , R ⁴ and R ⁶ are each hydrogen, R ^{5 is} fluorine, R ^{7 is} pentafluoroethyl, n is 1, X is oxygen and R ^{2 is} allyl or propargyl and the corresponding 1,4-benzothiazine. derivatives (some of the compounds of formula (I) above wherein the sulfur atom is replaced by an oxygen atom (X));

compounds of formula I wherein R ¹ and R ⁷ are both methyl, R ^{5 is} fluorine, R ^{6 is} hydrogen, n is 0, X is oxygen and R ^{2 is} ethyl,

2-fluoroethyl, 2-methoxyethyl, cyanomethyl, methoxycarbonylmethyl, 1-methoxycarbonylethyl, 2-methoxycarbonylethyl, carbamoylmethyl or dimethyl carbamoyl-methyl;

3- [6-fluoro-2-oxo-3- (2-propynyl) -5-benzoxazolinyl] 1.5.6-2.4 (1H, 3H) -pyrimidinedione,

1.6-dimethyl-3- [2-oxo-3- (2-propynyl) -5-benzoxazolinyl] 2,4 (1H, 3H) -pyrimidinedione,

3- [6-chloro-2-oxo-3- (2-propynyl) -5-benzoxazolinyl] -l, hydroxymethyl-6-2,4 (lH, 3H) -pyrimidinedione;

compounds of formula I wherein R 'is methyl, R ^{5 is} fluorine, R ^{6 is} hydrogen, R ^{7 is} trifluoromethyl, n is 0, X is oxygen, and R ^{2 is} ethyl, n-propyl, η-butyl, , carbamoylmethyl or allyl;

compounds of formula I wherein R ^{1 is} methyl, R ⁵ and R ⁶ are each hydrogen, R ^{7 is} trifluoromethyl, n is 0, X is oxygen, and R ^{2 is} ethyl, η-propyl, 2-fluoroethyl, , methoxymethyl, 2-methoxyethyl, cyanomethyl, methoxycarbonylmethyl, 1-methoxycarbonylethyl, 2-methoxycarbonylethyl, carbamoylmethyl, dimethylcarbamoylmethyl, , allyl or 1-methyl-2-propynyl;

3- [6-chloro-2-oxo-3- (2-propynyl) -5-benzoxazolinyl] -1-methyl-6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione, 1-methyl-3- [ 2-Oxo-3- (2-propynyl) -5-benzoxazotinyl] -6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione is a compound of formula I wherein R ^{1 is} methyl, R ⁵ and R ⁶ hydrogen, ^R7 pentafluoroethyl group, n is 0, X is oxygen and ^R2 is n-propyl, allyl or propargyl;

compounds of formula I wherein R ^{1 is} methyl, R ^{5 is} fluorine, R ^{6 is} hydrogen, R ^{7 is} pentafluoroethyl, n is 0, X is oxygen and R ^{2 is} allyl or propargyl and the corresponding benzothiazoline derivatives [ certain benzoxazoline compounds of formula I wherein the sulfur atom is replaced by an oxygen atom (X).

3-Phenyluracyls acting as herbicides are already disclosed in U.S. Patent No. 195,346. are known from European Patent Application Publication; they are substituted with an ester group at the 3-position of the phenyl group. The compounds of the present invention are disclosed in U.S. Patent No. 195,346. The European patent application published in the European Patent Application Publication No. 4,193,198 discloses that in this situation they contain a characteristic benzanellated heterocyclic group.

The preparation of the compounds of the formula I and their enol ethers and their salts is characterized in that:

(a) compounds of the formula I, and

If desired, for the preparation of their metal salts wherein R 'is hydrogen or (C 1 -C 4) -alkyl and R ^{6 is} hydrogen, a compound of formula (II) wherein

R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , n and X have the meanings given above,

R ⁶ 'is hydrogen and

^Rs C1-4 alkyl under basic conditions known among cyclizing and optionally reacting the uracil derivative of formula (I), optionally resulting metal salt form by treatment with an acid is converted to acid ^(R1 = H), or

b) for the preparation of compounds of formula I and their salts wherein R ^{1 is} hydrogen, R ^{6 is} hydrogen or C 1 -C 4 alkyl and R ^{7 is C} 1 -C 4 alkyl, a compound of formula III in which:

R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ', n and X have the meanings given above,

R ⁷ 'is C 1 -C 4 alkyl, and

R ^{9 is C} 1-4 alkyl ring-protected under basic conditions and optionally converted to an acid form (R ¹ = hydrogen) by treating an optionally formed metal salt of the uracil derivative of formula (I) with an acid, or

c) for the preparation of a compound of formula I wherein R ^{1 is C} 1 -C 4 alkyl, a uracil derivative of formula Γ wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , n and X alkylated with an appropriate alkylating agent having from 1 to 4 carbon atoms as defined above, or

d) for the preparation of compounds of formula (I) wherein R ^{2 is} hydrogen in a uracil slurry of formula (I ') - wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , n and X is as defined above and R ^{10 is C} 1-7 alkyl - R ^{10 is} cleaved, or

e) for the preparation of compounds of formula I in which R ^{2 is} other than hydrogen, a uracil derivative of formula (Γ ”) - wherein R ¹ , R ² , R ³ , R ⁴ , R 1, R ⁶ , R ⁷ , n and X is as hereinbefore defined, or is appropriately alkylated

f) for the preparation of compounds of the formula I in which R ^{6 represents a} chlorine, bromine or iodine atom, a uracil derivative of the formula I "- wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , n and X are chlorinated, brominated or iodinated as defined above, or

g) for the preparation of enol ethers of the formula Ia, a pyrimidinone derivative of the formula IY wherein

R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , n and X are as defined above and

Hal is treated with a chlorine or bromine atom with an alkanol of the formula R ¹ OH in the presence of an organic base, or with the corresponding alcoholate of the formula V where R ¹ is C 1 -C 4 alkyl and M ^{+ is} a metal ion equivalent. Conversion of a compound of formula (Ϊ) wherein R ^{1 is} hydrogen and / or R ^{2 is} hydrogen.

The ring closure reaction of process a) is conveniently carried out by reacting the compound of formula II in an inert polar solvent such as an alcohol such as methanol, ethanol or isopropanol; in an inert, aprotic organic solvent such as an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran or dioxane or an aromatic solvent such as benzene or toluene; in an aprotic aprotic polar solvent such as dimethylformamide or dimethylsulfoxide, such solvents optionally forming a biphasic mixture with a hydrocarbon such as n-hexane or toluene or in water in the presence of a base at a temperature of -78 ° C to the reflux temperature of the reaction mixture. treated. Preferred bases are sodium alcoholates, alkali metal hydroxides, especially sodium hydroxide and potassium hydroxide, alkali metal carbonates, especially sodium carbonate and potassium carbonate, and sodium hydride is preferred. If sodium hydroxide is used as the base, aliphatic or cyclic ether, dimethylformamide or dimethylsulfoxide. Each of these solvents may also be used in the form of a mixture with toluene.

If one of the above bases is used in the ring closure reaction, the product is obtained in the form of the corresponding alkali metal salt. This is isolated and purified in a manner known per se, or the mixture is acidified to give the compound of formula (I) itself. For this purpose, a mineral acid such as hydrochloric acid or a strong organic acid such as acetic acid or p-toluenesulfonic acid is preferably used.

According to process b), the ring closure reaction of the compound of formula III is conveniently carried out in a substantially anhydrous, inert, protic organic solvent such as, for example, a lower alkanol such as methanol or ethanol, a base such as an alkali metal alcoholate that is, in the presence of sodium methylate or ethylate, in a temperature range of from 0 ° C to 70 ° C, preferably from 10 ° C to 70 ° C. In one embodiment of this reaction, the compound of formula (III) is, for example, essentially anhydrous in an inert, aprotic organic solvent such as dimethylformamide, N-methylpyrrolidone, tetramethylurea or hexamethylphosphoric triamide, a metal hydride such as sodium or in the presence of potassium hydride as the base, it is cyclized at a temperature of 0 ° C to 70 ° C, preferably 10 ° C to 30 ° C.

As in Process (a), after completion of the ring closure reaction, using one of the bases mentioned above, the product is obtained in the form of its corresponding alkali metal salt. This can also be isolated and purified by methods well known in the art, or the mixture may be acidified to isolate the compound of formula (I) itself.

In the process (c), the term "alkylation" means that the N 'atom attached to the uracil core is

HU 206,708 Β is replaced by a C 1 -C 4 alkyl group. The alkylating agent is preferably a C 1 -C 4 alkyl halide, in particular the corresponding chloride or bromide or sulfate.

The alkylation is conveniently a mixture of an inert protic organic solvent such as a lower alkanol such as ethanol, optionally in water; an inert, aprotic organic solvent such as an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran or dioxane; a ketone such as acetone or butan-2-one; or an inert, aprotic polar organic solvent such as dimethylformamide, dimethylsulfoxide or acetonitrile, and a base such as sodium hydride, alkali metal hydroxide, especially sodium or potassium hydroxide, alkali metal alcoholate, especially sodium alcoholate or alkali metal carbonate or hydrocarbonate, especially sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate, at a temperature between 0 ° C and the reflux temperature of the reaction mixture, preferably at room temperature. In a preferred embodiment of the reaction, the uracil derivative (Γ) is first treated with a base such as sodium hydride, ethylate or carbonate in a solvent, and after a short reaction, a solution of the halide in the same solvent is added. In another preferred embodiment of the reaction, the uracil derivative (Γ) is reacted with a dialkyl sulfate in the presence of an alkali metal carbonate, especially sodium or potassium carbonate, in a solvent such as acetone at reflux temperature. The reaction is completed in a relatively short time or in a few hours, depending on the solvent used. Depending on the processing of the reaction mixture, the desired final product may be isolated from any starting materials and / or by-products by methods known per se, such as column chromatography and / or fractional crystallization.

For the nitrogen atom of the oxazolinone, thiazolinone or 3,4-dihydro-3-oxo-2H-1,4-oxa / thiazine ring, the R ¹⁰ protecting group may be cleaved according to process d) with a strong, substantially anhydrous, inorganic acid such as sulfuric acid or orthophosphoric acid. treated. Normally, the acid may not only be a reagent but also serve as a solvent, so that no other solvent is required. Preferably, temperatures of from 80 ° C to 160 ° C, in particular from 120 ° C to 150 ° C, are employed.

In process (e), the hydrogen atom to which the heterocyclic nitrogen is attached is a C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy (C 1 -C 4) alkyl, C 2 -C 5 cyanoalkyl -, C 2 -C 5 alkoxycarbonyl (C 1 -C 4) alkyl, carbamoyl (C 1 -C 4) alkyl, di (C 1 -C 4) alkylcarbamoyl (C 1 -C 4) alkyl, C3 or C4 alkenyl or C3 or C4 alkynyl. This "alkylation" can be carried out using a suitable halide, in particular chloride or bromide, in a similar manner to that described in process c). In the case of the reaction of a uracil derivative of the formula (Γ) in which R ^{1 is} hydrogen, it is obvious that the reaction of process c) can also take place and the corresponding mixed alkylated products are formed. Depending on the processing of the reaction mixture, the desired final product may be isolated from any starting materials and / or by-products which are known per se, for example by column chromatography and / or fractional crystallization.

The chlorination or bromination of process (f) is preferably in the presence of an inert organic solvent such as acetic acid or a chlorinated aliphatic hydrocarbon such as methylene chloride, chloroform or carbon tetrachloride, preferably with elemental chlorine or sulfuryl chloride or with elemental bromine or sulfuryl bromide The reaction is carried out at a temperature in the range of from C to 60 ° C, preferably at room temperature. In addition, an acid acceptor may be used to aid the reaction, with sodium acetate and tertiary amines such as triethylamine, dimethylaniline and pyridine being particularly preferred.

For the iodination of process (f), elemental iodine and a low-boiling aliphatic carboxylic acid such as acetic acid are preferably used as the iodinating agent and the reaction is carried out at a temperature of about 0 ° C to 110 ° C, preferably at room temperature. In addition, it has been found convenient to carry out the reaction in the presence of an acid such as fuming nitric acid. After completion of the reaction, saturated aqueous sodium bisulfite solution can be added to remove the excess iodine.

In cases where reaction (I "") uracils of the formula in this procedure, where R ² unsaturated alkenyl or alkynyl, it is also possible that not only the uracil free 5-position halogénezódik but more specifically unsaturated aliphatic also, for example, the allyl group is converted to the 2,3-dibromopropyl group. Such bi-halogenated products are also within the scope of compounds of formula (I). The desired final product is known per se, depending on the processing of the reaction mixture. methods, such as column chromatography and / or fractional crystallization, to isolate any residual starting materials and / or by-products, or isolate two or more halogenated products.

The "metal ion" mentioned in process g) is mainly an alkali metal ion such as sodium or potassium or an alkaline earth metal ion such as calcium or magnesium. Of these, the sodium ion is preferred. A suitable organic base is pyridine.

The reaction is conveniently carried out in excess of the corresponding hydroxyl compound R ¹ 'OH, also used as a solvent at a temperature between 0 ° C and 50 ° C, preferably at room temperature.

If the formula (I) compounds in which ^R1 is hydrogen and / or R ² is hydrogen, salts required do not directly be prepared by cyclisation reaction with the basic conditions referred to above between, it is known per se from these compounds of general formula (I) means, for example, the compound of formula (I) is the appropriate inorganic or organic compound

EN 206 708 Β in solution. Generally, salt formation occurs within a short period of time at room temperature. In one embodiment of the sodium salt formation, the uracil derivative of formula (I) is dissolved in a solution of sodium hydroxide in water at room temperature while using an equivalent amount of uracil derivative and sodium hydroxide. The solid salt may be isolated by separation with a suitable inert solvent or by evaporation of the solvent. In another embodiment, an aqueous solution of the alkali metal salt of the uracil derivative of formula (I) is introduced into an aqueous solution of a salt containing another metal ion as an alkali metal ion, thereby forming a second metal salt of the uracil derivative. This process generally provides uracil metal salts which are insoluble in water.

The resulting compounds of formula (I), enol ethers, and salts may be isolated and purified by known methods. Further, it will be apparent to those skilled in the art that combinations of procedures c) to f) are conveniently performed in order to avoid unwanted competing reactions.

If it is not intended to isolate the pure isomer, the product may be isolated as a mixture of one or more isomers. The individual isomers may be separated by methods known per se. If desired, for example, the pure optically active isomers may be prepared from the corresponding optically active starting materials.

The starting materials (II) are new and can be prepared in a manner known per se, for example according to Scheme 1 (Methods aa and bb). In the Scheme, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁷ ', R ⁸ , n and X are as defined above.

The reaction of method (aa) is conveniently carried out by reacting the compounds of formula (VI) and (VII) in a substantially anhydrous diluent and at an elevated temperature in the presence of an acidic catalyst. Suitable diluents are in particular organic solvents which form an azeotropic mixture with water, such as aromatic solvents such as benzene, toluene and xylenes, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene; aliphatic and cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane; acidic catalysts include, in particular, strong mineral acids such as sulfuric acid and hydrochloric acid; organic acids such as p-toluenesulfonic acid; phosphorus-containing acids such as orthophosphoric acid and polyphosphoric acid; and acidic cation exchangers such as "Amberlyst 15" (Fluka). The reaction is carried out at a temperature between 70 ° C and 120 ° C, preferably at the reflux temperature of the reaction mixture. Under such reaction conditions, rapid removal of water formed during the reaction can be achieved. The reaction according to method bb) is conveniently a substantially anhydrous, aprotic organic solvent such as an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran or dioxane; an aliphatic or aromatic hydrocarbon such as nhexane, benzene, toluene or an xylene; a halogenated aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride or 1,2-dichloroethane, and optionally a base, especially an organic tertiary base such as triethylamine or pyridine, which may also serve as a solvent, or a metal hydride. such as sodium or potassium hydride. The reaction temperature is preferably maintained at about -80 ° C to 50 ° C, most preferably at -30 ° C to room temperature.

The starting materials of formula (III) are also novel. They may be prepared by reacting a compound of formula X wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ ', n and X have the meanings given above, with a carbamic acid of formula XI. with a (lower) alkyl ester wherein R ⁹ is as defined above.

This reaction is conveniently carried out in an essentially anhydrous, inert, aprotic solvent in the presence of an acidic catalyst. The reaction mixture is heated at reflux until water is formed and continuously removed from the reaction mixture. Examples of organic solvents which are azeotropic with water are, for example, aromatic solvents such as benzene, toluene and xylenes; and halogenated hydrocarbons such as chloroform, carbon tetrachloride and chlorobenzene; and acidic catalysts are mainly organic acids such as toluene-4-sulfonic acid; mineral acids such as sulfuric acid, orthophosphoric acid and polyphosphoric acid; and cation exchangers such as "Amberlyst 15" (Fluka). Generally, a temperature in the range of about 70 ° C to about 120 ° C is preferred, preferably at the reflux temperature of the reaction mixture. Under these reaction conditions, rapid removal of the resulting water can be achieved.

The uracil derivatives (Γ), (I ”), (Γ”) and (I ””) used as starting materials in the processes (c) to (f) are subgroups of the compounds of the formula (I) and these compounds are a) or may be prepared according to process b) and, optionally, one or more of processes c) -f).

The compounds of formula (IV) may be prepared by halogenation of new compounds and the corresponding uracil derivatives of formula (Γ). The halogenating agent used for halogenation is mainly thionyl chloride, phosphorus pentachloride or phosphorus oxychloride, or phosphorus pentabromide or phosphoryl bromide. The reaction may optionally comprise a mixture of phosphorus pentachloride and phosphorus oxychloride or phosphorus pentabromide and phosphoryl bromide, in which case an excess of phosphorus oxychloride or phosphoryl bromide may serve as a solvent. The chlorinating or brominating agent is an inert diluent, especially an aprotic organic solvent such as an aliphatic or aromatic hydrocarbon such as n-hexane, benzene, toluene or an xylene; a halogenated aliphatic hydrocarbon such as methylene chloride, chloroform or 1,2-dichloroethane; a halogenated aromatic hydrocarbon such as chlorobenzene or a tertiary amine such as Ν, Ν-dimethylaniline, however, when the halogenating agent used is phosphorus oxychloride or phosphoryl bromide, a separate diluent, and no solvent is required. When thionyl chloride is reacted as a halogenating agent, it is convenient to add a catalytic amount of dimethylformamide to the reaction mixture. The reaction temperature is generally maintained between 0 ° C and the reflux temperature of the reaction mixture, preferably between 80 ° C and 120 ° C.

HU 206 708 Β

The urea derivatives (VII) used as starting materials in Method (aa) are new and can be prepared by reacting an amine of formula (XII) wherein R ² , R ³ , R ⁴ , R ⁵ , n and X have the meanings given above. at room temperature in aqueous acetic acid with isocyanic acid or an aromatic isocyanate of formula IX (see Scheme 1, Method bb) in an inert solvent such as diethyl ether with ammonia. The preparation of aromatic urea derivatives is generally known and there are many references in the literature.

The isocyanates of formula (IX) used as starting materials in process (bb) and used in the preparation of urea derivatives of formula (VII) are also novel and can be prepared by treating an amine of formula (XII) with phosgene. The reaction solvent is preferably ethyl acetate and is carried out at a temperature between room temperature and the reflux temperature of the reaction mixture. It should also be noted that the preparation of aromatic isocyanates is well known in the art and can be found in many places in the literature.

The compounds of formula (X) used in the preparation of compounds of formula (III) are also novel. These can be prepared as described in Scheme 2, Methods cc, dd, and ee. Here, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ', R ⁷ ', R ⁸ , n and X are as defined above and R ^{6 is} hydrogen or C 1-4 alkyl and R ^{11 is} hydrogen or C 1-3 alkyl.

Preferably, process (cc) is carried out by reacting the amine (XII) with diketene (XIII) in the presence of an aprotic solvent such as an aromatic hydrocarbon such as benzene or toluene at about 2050 ° C. The reaction is preferably carried out using a basic catalyst such as 4-pyrrolidinopyridine.

The reaction of method dd is conveniently carried out using an excess of the compound of formula VI at about 60 ° C to the reflux temperature of the reaction mixture. Preferably, the ester of formula (VI) (R ⁸ represents a methyl group) is reacted.

The reaction of method ee is conveniently carried out in an aprotic solvent such as an aromatic hydrocarbon such as toluene or an xylene at a temperature between 100 ° C and 140 ° C.

Starting materials or reagents not specifically mentioned above, such as compounds of formulas (V), (VI), (VIII), (XI), (XII), (XIII) and (XIV), are either known or known per se. may be prepared, see, e.g., Houben-Weyl Methoden Der Organogen Chemie, VIV2a. 492, p. and VIII. 563, I A.C.S. 69, 1819 (1947), J. Org. Chem. 36, 37 (1971), J.A.C.S. 75, 3152 (1953) and J. Org. Chem., 48, 724 (1983) (compounds of formula VI); J. Org. Chem., 14, 807 (1949), Helv. Chim. Acta 25, 1311 (1942), J. Org. Chem. 27, 1358 (1956) and J. Org. Chem., 49, 4780 (1984) (compounds of formula VIH); Japanese Patent Specification 221677 (1987); European Patent Nos. 170191 and 218972 (Compounds of Formula XII); Houben-Weyl Methoden in Organic Chemistry, VH / 4, pp. 223-226. and J.A.C.S. 69, 2446 (Compound (vegyületek)), and J. Org. Chem., 43, 2087 (1972) (compounds of formula XIV).

The compounds of the formula I and their enol ethers and their salts (hereinafter referred to collectively as the compounds or active substances of the invention) have herbicidal properties and weeds, including weeds, such as Abutilon theophrasti, Agropyron repens, Alopecurus myosuroides, retroflexus, Avena fatua, Bromus inermis, Cassia obtusiflolia, Chenopodium album, Chrysanthemum segetum, Cyperus esculentus, Datura stramonium, Digitaria sanguinalis, Echinochloa crus-galli, Galium aparine, Ipomoea purpurea, Matricaria chamilla, Matricaria chamomile halepense, Stellaria media and Xanthium pennsylvanicum in various crops such as cotton, rice, maize, wheat and soybean. The compounds of the invention may also be used as pre-emergence and post-emergence herbicides.

The novel starting materials of formulas (II), (III), (IV), (VII), (EX) and (X) also have herbicidal properties and can therefore be used as herbicides in the same way as the compound of formula (I).

In practice, it is sufficient to apply the compounds of the invention in an amount of 0.03 to 3.0 kg / ha, preferably 0.05 to 2.0 kg / ha, to achieve the desired herbicidal activity.

Further, the compounds of formula I can be used to control unwanted plant growth, for example, in the case of potatoes, cotton, sunflowers, vegetables and aquatic weeds. For example, the compounds of formula I may be used as scorching agents to facilitate the harvesting of potatoes and cotton.

The herbicidal agent according to the invention is characterized in that it contains an effective amount of at least one compound of formula I, as defined above, or an enol ether or a salt thereof, and auxiliaries for formulation. Preferably, the agent comprises at least one of the following formulation aids: solid carriers; solvents or dispersants; surfactants (wetting and emulsifying agents); dispersants (non-surfactant); and stabilizers. While using such and other excipients, these compounds, i.e. herbicidal agents, can be formulated into conventional formulations, dusts, powders, granules, solutions, emulsions, suspensions, emulsifiable concentrates, pastes and the like.

Compounds of formula I and their enol ethers are generally insoluble in water, whereas salts,

In particular, the alkali metal and ammonium salts are water-soluble and can be converted into finished products using conventional formulation aids by conventional methods for processing water-insoluble and water-soluble compounds. The agents may be prepared in a manner known per se. For example, the active ingredient may be admixed with solid carriers, dissolved or suspended in suitable solvents or dispersants, or diluted with other prepared emulsifiable concentrates, with the use of surfactants such as wetting agents or emulsifiers and / or dispersants, and the like being diluted with other solvents or dispersants.

Solid carriers include essentially the following: natural minerals such as chalk, dolomite, limestone, clay and silica, and salts thereof (e.g., silica, kaolin, bentonite, talc, attapulgite and montmorillonite); synthetic minerals such as highly dispersed silica, alumina and silicates; organic materials such as cellulose, starches, urea and synthetic resins; and nutrients such as phosphates and nitrates. These carriers may take the form of, for example, powders or granules.

Suitable solvents and diluents include, in particular, aromatic solvents such as benzene, toluene, xylenes and alkylnaphthalenes; chlorinated aromatic and chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene and methylene chloride; aliphatic hydrocarbons such as cyclohexane and paraffins such as petroleum fractions; alcohols such as butanol and glycol and their ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; highly polar solvents and dispersants, such as dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide, these solvents preferably having a flash point of at least 30 ° C and a boiling point of at least 50 ° C, and water. Suitable solvents or dispersants include so-called liquid gaseous fillers or carriers, which are products that are gaseous at room temperature and pressure. Such products are mainly aerosol propellants such as halocarbons such as dichlorodifluoromethane. The herbicides according to the invention may also be stored in pressurized gas containers, in which case a solvent is preferably used in addition to the propellant gas.

The surfactants (wetting agents and emulsifiers) may be non-ionic compounds such as condensation products of fatty acids, fatty alcohols or fatty-substituted phenols with ethylene oxide; fatty acid esters and ethers of sugars or polyhydric alcohols; condensation products of sugars or polyhydric alcohols with ethylene oxide; block polymers of ethylene oxide and propylene oxide; or alkyldimethylamine oxides.

The surfactants may also be anionic compounds such as soaps; fatty sulfate esters such as dodecyl sodium sulfate, octadecyl sodium sulfate and cetyl sodium sulfate; alkylsulfonates, arylsulfonates and fatty aromatic sulfonates, such as alkylbenzenesulfonates, such as calcium dodecylbenzenesulfonate and butylnaphthalenesulfonates; and complex fatty sulfonates, such as amide condensation products of oleic acid and N-methyl taurine, and sodium sulfonate of dioctyl succinate.

Finally, the surfactants may also be cationic compounds such as alkyldimethylbenzylammonium chloride, dialkyldimethylammonium chloride, alkyltrimethylammonium chloride and ethoxylated ammonium chloride.

Dispersing agents (without surfactant effect) include essentially the following: lignin, sodium and ammonium salts of lignin sulphonic acid, sodium salts of maleic anhydride diisobutylene copolymers, sulphonated polysaccharides and ammonium salts of naphthalene and formaldehyde, and their sulfonated polycondensation products.

Dispersing agents which are particularly useful as concentrating or anti-settling agents are, for example, methylcellulose, carboxymethylcellulose, hydroxylylcellulose, polyvinyl alcohol, alginates, caseinates and blood albumin.

Suitable stabilizers include, for example, acid binders such as epichlorohydrin, phenylglycidether and soy epoxides; antioxidants such as gallic acid ester and butylhydroxytoluene; UV absorbers such as substituted benzophenones, diphenyl acrylonitrile ester and cinnamic acid ester; and deactivators such as ethylenediaminetetraacetic acid salts and polyglycols.

The herbicides according to the invention generally contain from 0.03% to 50%, preferably from 0.5% to 50% by weight, of one or more compounds according to the invention as active ingredient (s). These agents, for example, are in a form suitable for storage or transport. Examples of such formulations are emulsifiable concentrates which normally have a higher active ingredient concentration, preferably between 1 and 50% by weight, in particular between 10 and 20% by weight. These agents may then be diluted with, for example, the same or different inert substances to a concentration suitable for direct use, i.e. preferably from about 0.01% to about 10% by weight, in particular from about 0.5% to about 5% by weight. However, the active ingredient concentration may be lower or higher.

As mentioned above, the preparation of the herbicides according to the invention can be carried out in a manner known per se.

For example, powder formulations may be prepared by mixing the active ingredient, i.e., at least one compound of the invention, with a solid carrier, e.g. or the solid carrier may be impregnated with a solution or suspension of the active ingredient and then the solvent or dispersant removed by evaporation, heating, or suctioning under reduced pressure. By adding surfactants or dispersants, such powdered agents can be readily wetted with water so that they can be converted into aqueous suspensions, for example as sprayers.

The active ingredient may be mixed with a surfactant and a solid carrier which may be wetted with a powder.

EN 206 708 Β which is dispersible in water - or mixed with a solid pre-granulated carrier to form a granular product.

If desired, the active ingredient may be dissolved in a water immiscible solvent, such as a high boiling hydrocarbon, preferably containing dissolved emulsifiers, so that the solution itself emulsifies when water is added. Alternatively, the active ingredient may be mixed with an emulsifier and then diluted with water to the desired concentration. Alternatively, the active ingredient may be dissolved in a solvent and then mixed with the emulsifier. Such a mixture may also be diluted with water to a desired concentration. In this way, emulsifiable concentrates and emulsions for direct use are obtained.

The use of the herbicides according to the invention, which is also a subject of the invention, can be carried out by conventional application methods such as spraying, spraying, dusting, irrigation or spraying. The method of controlling the weeds according to the invention is characterized in that the objects to be protected against the weeds and / or the weeds are treated with a compound produced by the method according to the invention or an herbicide according to the invention.

The following examples further illustrate the invention.

Preparation of the compounds of formula (I) [and (11)] and enol ethers of compounds of formula (I)

Example 1

A solution of 18.51 g of 3-amino-4,4,4-trifluorocrotonic acid ethyl ester in 50 ml of dimethylformamide was stirred at 0 ° C in 4.41 g of 55% sodium hydride dispersion 100 of dimethylformamide (4 ml) was added dropwise and the reaction mixture was stirred at room temperature for 2 hours. The mixture was cooled to -55 ° C and 6.10-fluoro-5-isocyanato-3- (2-propynyl) -2-benzothiazolinone (25.10 g) in dimethylformamide / toluene (1: 1, 200 ml) was added with stirring. prepared solution. During this time, the reaction temperature rises to -15 ° C and is then stirred for one hour at room temperature. The intermediate 5- {3- [2- (ethoxycarbonyl) -1-trifluoromethyl-vinyl] -ureido} -6-fluoro-3- (2-propynyl) -2-benzothiazolinone is isolated.

The reaction mixture was concentrated under reduced pressure at 55 ° C to 200 ml and the residue was poured into a mixture of 700 ml of water and 11 ml of concentrated hydrochloric acid. The aqueous phase is then extracted with 300 ml of ethyl acetate, the insolubles are filtered off, the organic phase is separated off, washed twice with 400 ml each of 400 ml of water and dried over anhydrous sodium sulfate. The solution was crystallized by evaporation and the crystalline material was filtered off and dissolved in ethyl acetate (1 L) at 50 ° C. The insoluble matters are filtered off and the filtrate is concentrated until a viscous oil is obtained, the residue is dissolved in 700 ml of diethyl ether, the solution is treated with carbon and concentrated to 150 ml. Finally, the solution was crystallized by adding n-hexane at 0 ° C with stirring and cooling. The crystalline material is then filtered off, washed with diethyl ether / n-hexane (1: 1) and dried.

The resulting 3- [6-fluoro-2-oxo-3- (2-propynyl) -5-benzothiazolinyl] -6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione is melted at 224-227 ° C.

Example 2

Similarly to the procedure described in Example 1, it is obtained from 3-amino-4,4,4-trifluorocrotonic acid ethyl ester and 3,4-dihydro-7-fluoro-6-isocyanato-3-oxo-4- (2-propynyl) -. Starting from 2H1.4-benzoxazine, 6- {3- [2- (ethoxycarbonyl) -1-trifluoromethyl-vinyl] -ureido} -3,4-dihydro-7-fluoro-3-oxo-4- (2- propynyl) -2H-1,4-benzoxazine (not isolated), and after cyclization of this benzoxazine, 3 [3,4-dihydro-7-fluoro-3-oxo-4- (2-propynyl) -2H-1, 4-benzoxazin-6-yl] -6-trifluoromethyl-2,4 (lH, 3H) -pyrimidinedione.

1 H-NMR (CDCl ₃ , 60 MHz): 7.29 ppm (d, 1H), 6.99 ppm (d, 1H), 6.31 ppm (s, 1H), 4.84-4.61 ppm (m, 4H), 2.35 ppm (t, 1H);

Mass Spectrum: m / e 383 (20) M ⁺ .

Example 3

It is obtained similarly to the procedure described in Example 1

From 3-amino-4,4,4-trifluorocrotonic acid ethyl ester and

Starting from 3,4-dihydro-6-isocyanato-3-oxo-4- (2-propynyl) -2H-1,4-benzoxazine, 6- {3- [2- (ethoxycarbonyl) 1-trifluoromethylmethyl] -ureido } -3,4-dihydro-3-oxo-4- (2-propynyl-2H-1,4-benzoxazine (not isolated)) and after cyclization of this benzoxazine, 3- [3,4-dihydro-3-oxo- 4- (2-propynyl) -2H-1,4-benzoxazin-6-yl] -6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione, m.p.> 250 ° C.

Example 4

A suspension of 8.2 g of 5- [3- (ethoxycarbonylamino) -2-butenoylamino] -6-fluoro-3- (2-propynyl) -2-benzothiazolinone in 100 ml of methanol was stirred at 50 ° C. 11.5 ml of 2N sodium methylate solution are added and the mixture is stirred for 15 minutes. A solution was obtained, which was stirred for 30 minutes and then concentrated under reduced pressure to a volume of 2 ml and the residue was poured into a solution of 20 ml of 2N hydrochloric acid in 500 ml of water. The precipitate formed is filtered off, washed with water and dried. The resulting 3- [6-fluoro-2-oxo-3- (2-propynyl) -5-benzothiazolinyl] -6-methyl-2,4 (1H, 3H) pyrimidinedione (6.1 g) was obtained at 250 ° C. melts at higher temperatures.

5-34. example

In the same manner as in Example 4, the corresponding compound (II) is cyclized to give the compounds (LA) listed in Table 1a and the compounds (IB) listed in Table 1b:

EN 206 708 Β la footprint, general formula (JA)

Example number R ² cr ³ r ⁴ n X Physical data 5 ch ₂ c = ch ch ₂ 1 0 1 H-NMR (CDCl _3> 100 MHz): 7.08 ppm (d, 1H), 6.90ppm (d, 1H), 5.58 ppm (s, 1Η), 4.69-4.64 ppm ( m, 4H), 2.33 ppm (t, 1H), 2.18 ppm (s, 3H); op. 247-249 ° C ⁶ ch ₂ ch = ch ₂ ch ₂ 1 0 1 H-NMR (CDCl ₃ , 400 MHz): 9.89 ppm (s, 1H), 6.98 ppm (d, 1H), 6.82 ppm (d, 1H), 5.83 ppm (m, 1H) ), 5.66 ppm (s, 1H), 5.22 ppm (m, 2H), 4.69 ppm (s, 2H), 4.52 ppm, (m, 2H), 2.14 ppm (d, 2H), 1.69 ppm (s, 1H); op. 141-143 ° C 7 c ₂ h ₅ CH (CH ₃ ) 1 0 op. 147-149 ° C 8 ch ₂ c = ch CH (CH ₃ ) 1 0 op. 227-230 ° C 9 ch ₃ - Zero s mp> 260 ° C 10 c ₂ h ₅ - Zero s mp> 260 ° C 11 ch ₂ ch = ch ₂ - Zero s mp> 250 ° C 12 CH (CH ₃ ) ₂ - Zero s m.p. 193-195 ° C 13 nC ^ H - Zero s mp> 250 ° C 14 CH (CH ₃ ) ₂ - Zero 0 mp> 250 ° C 15 ch ₃ - Zero 0 mp> 250 ° C 16 nC ₃ H ₇ - Zero 0 mp> 250 ° C 17 CH ₂ OCH ₃ - Zero 0 mp> 250 ° C 18 ch ₂ cooc ₂ h ₅ - Zero 0 op. 213-215 ° C 19 ch ₂ ch = ch ₂ - Zero 0 mp> 250 ° C 20 ch ₂ c = ch - Zero 0 mp> 250 ° C 21 Η ch ₂ 1 0 mp> 220 ° C 22 CH ₂ CaCH ch ₂ 1 s 144-147 ° C

Table lb)

Example number R ² cr ³ r ⁴ n X R ⁷ Physical data 23 CH (CH ₃ ) ₂ - Zero s C ₂ H _s op. 237-238 ° C 24 ch ₂ ch = ch ₂ ch ₂ 1 0 C ₂ H ₅ m.p. 193-200 ° C 25 ch ₂ ch = ch ₂ ch ₂ 1 0 nC ₃ H ₇ op. 157-161 ° C 26 ch ₂ c = ch ch ₂ 1 0 C ₂ H ₅ 240 ° C (with decomposition) 27 ch ₂ och ch ₂ 1 0 nC ₃ H ₇ op. 238-239 ° C 28 CH (CH ₃ ) ₂ ch ₂ 1 0 c ₂ h ₅ op. Mp 208-210 ° C 29 CH (CH ₃ ) C = CH ch ₂ 1 0 c ₂ h ₅ Mass Spectrum: m / e 357 (89) M ⁺ 30 CH (CH ₃ ) C ₂ H _s ch ₂ 1 0 c ₂ h ₅ 31 CH (CH ₃ ) OCH ₃ ch ₂ 1 0 c ₂ h ₅ 32 CH (OCH ₃ ) C ₂ H ₅ ch ₂ 1 0 c ₂ h ₅ 33 CH (CH ₃ ) CH = CH ₂ ch ₂ ¹ I ⁰ c ₂ h ₅ 34 ch ₂ ch = ch ₂ - Zero s C2H5

HU 206 708 Β

Example 35

6.45 g of 6- [3- (ethoxycarbonylamino) -2-pentenoylamino] -3,4-dihydro-7-fluoro-3-oxo-4- (2-propenyl) -2H-1,

A suspension of 4-benzoxazine and 3.22 g of sodium methylate in 6.5 ml of methanol was stirred at 62 ° C for four hours. The resulting solution was allowed to stand at room temperature for 64 hours and then poured into a solution of 15 ml of 2N hydrochloric acid in 400 ml of water. The resulting precipitate was filtered, washed with water and recrystallized from acetone / n-hexane. Thus, 6-ethyl-3- [3,4-dihydro-7-fluoro-3-oxo-4- (2-propynyl) -2H-1,4-benzoxazin-6-yl] -2,4 (1H, 3H) ), pyrimidinedione, m.p. 240 DEG C. with decomposition.

Example 36

Similar to the procedure described in Example 35, 6- [3- (ethoxycarbonylamino) -2-pentenoylamino] -4-allyl-3,4-dihydro-7-fluoro-3-oxo-2H-1,4-benzoxazine cyclization to give 6-ethyl-3- (4-allyl-3,4-dihydro-7-fluoro-3-oxo-2H-1,4-benzoxazin-6-yl) -2,4 (1H, 3H) -pyrimidinedione mp 197-200 ° C.

Example 37

Similar to the procedure described in Example 35, the ring closure reaction of 5- [3- (ethoxycarbonylamino) -2-pentenoylamino] -6-fluoro-3- (n-propyl) -2-benzothiazolinone gave the 6-ethyl-3 - [6-Fluoro-2-oxo-3- (n-propyl) -5-benzothiazolinyl] -2,4 (1H, 3H) -pyrimidinedione, m.p.> 250 ° C.

Example 38

27.50 g of 3- [6-fluoro-2-oxo-3- (2-propynyl) -5-benzothiazolinyl] -6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione (see Example 1) 10.80 g of dimethyl sulfate and 9.08 g of sodium carbonate in 250 ml of acetone are refluxed for 1.5 hours. After cooling, the solid ingredients are filtered and washed with acetone. The filtrate was evaporated to dryness under reduced pressure, the residue was dissolved in ethyl acetate (35 mL) and washed with water (3 x 300 mL). The organic layer was then dried over anhydrous sodium sulfate and evaporated to dryness under reduced pressure. The first fraction was recrystallized from ethyl acetate / diethyl ether (1: 1) to give 6-fluoro-5- [2-methoxy-6-oxo-4-trifluoromethyl-1 (6H) -pyrimidinyl] -3 - ( 2-Propynyl) -2-benzothiazolinone is obtained, m.p. 191-192 ° C. The second fraction was recrystallized from diethyl ether / n-hexane (1: 1) to give 3- [6-fluoro-2-oxo-3- (2-propynyl) 5-benzothiazolinyl] -1-methyl-6-trifluoride. methyl methyl 2,4 (1H, 3H) pyrimidinedione is obtained, m.p. 190-192 ° C.

39-72. example

As in Example 38, in each case, the corresponding uracil derivative (Γ) was methylated with dimethyl sulfate to give the 1-methyluracil derivative (Γ "") listed in Table 2 [and in one case also (la '). (enol ether).

Table 2

Example number I 'd. formula. Dry. p »» »» or la '. of formula. r ₂ cr ³ r ⁴ R ⁵ R ⁷ n X Physical data Example number 39 2 i ..... CH ₂ OCH ch ₂ F cf ₃ 1 0 1 H-NMR (CDCl ₃ , 400 MHz): 7.06 ppm (d, 1H), 6.93 ppm (d, 1H), 6.38 ppm (s, 1H), 4.69 ppm (s, 2H) ), 4.64 ppm (q, 2H), 3.57 ppm (t, 3H), 2.29 ppm (t, 1H) 40 3 CH ₂ CsCH ch ₂ H cf ₃ 1 0 op. 216-217 ° C 41 3 la ' ch ₂ c = ch ch ₂ H cf ₃ 1 0 op. 218-220 ° C 42 5 f '' ch ₂ c = ch ch ₂ F ch ₃ 1 0 1 H-NMR (CDCl ₃ , 400 MHz): 7.05 ppm (d, 1H), 6.90 ppm (d, 1H), 5.75 ppm (s, 1H), 4.67 ppm (s, 2H) ), 4.64 ppm (d, 2H), 3.40 ppm (s, 3H), 2.32 ppm (d, 3H), 2.27 ppm (t, 1H) 43 6 i ..... ch ₂ ch = ch ch ₂ F ch ₃ 1 0 1 H-NMR (CDCl ₃ , 100 MHz): 6.88 ppm (d, 1H), 6.81 ppm (d, 1H), 5.82 ppm (m, 1H), 5.72 ppm (d, 1H) ), 5.23 ppm (m, 2H), 4.67 ppm (s, 2H), 4.50 ppm (m, 2H), 3.44 ppm (s, 3H), 2.31 ppm (d, 3H) ) 44 7 i '' ' C ₂ H ₅ CH (CH ₃ ) F ch ₃ 1 0 Mp 211-213 ° C

HU 206 708 Β

Table 2 (continued)

Γ "" of formula. la 't. of formula. r ₂ cr ³ r ⁴ R ⁵ R ⁷ n X Physical data Example number 45 8 ch ₂ c = ch CH (CH) ₃ F ch ₃ 1 0 op. 219-222 ° C 46 9 ch ₃ - F ch ₃ Zero s op. 255-257 ° C 47 10 C ₂ H ₅ - F ch ₃ Zero s op. 235-236 ° C 48 11 ch ₂ ch = ch ₂ - F ch ₃ Zero s op. 210-211 ° C 49 12 CH (CH ₃ ) ₂ - F ch ₃ Zero s op.214-216 C 50 13 - F ch ₃ Zero s op. 222-223 ° C 51 26/35 ch ₂ c = ch ch ₂ F C ₂ H _s 1 0 op. 230 ° C (with decomposition) 52 24/36 ch ₂ ch = ch ₂ ch ₂ F c ₂ h ₅ 1 0 op. 172-174 ° C 53 37 nC ₃ H ₇ - F c ₂ h ₅ Zero s op. 101-102 ° C 54 14 CH (CH ₃ ) ₂ - F ch ₃ Zero 0 op. 143-145 ° C 55 15 ch ₃ - F ch ₃ Zero 0 op. 228-231 ° C 56 16 nC ₃ H ₇ - F ch ₃ Zero 0 op.155-157 C 57 17 CH ₂ OCH ₃ - F ch ₃ Zero 0 mp.200-202 ° C 58 18 ch ₂ cooc ₂ h ₅ - F ch ₃ Zero 0 op. 167-169 ° C 59 19 ch ₂ ch = ch ₂ - F ch ₃ Zero 0 op. 164-166 ° C 60 20 CH ₂ C = CH - F ch ₃ Zero 0 op. 182-184 ° C 61 102 ch ₂ cn ch ₂ F ch ₃ 1 s op. > 230 ° C 62 22 ch ₂ c = ch ch ₂ F ch ₃ 1 s op. 214-217 ° C 63 23 CH (CH ₃ ) ₂ - F C ₂ H _s Zero s op. 176-178 ° C 64 25 ch ₂ ch = ch ₂ ch ₂ F nC ₃ H ₇ 1 0 op. 146-147 ° C 65 27 ch ₂ ocb ch ₂ F nC ₃ H ₇ 1 0 op. 192-193 ° C 66 28 CH (CH ₃ ) ₂ ch ₂ F c ₂ h ₅ 1 0 MS: m / e 361 (67) M ^{@ +} 67 29 CH (CH ₃ ) C = CH ch ₂ F c ₂ h ₅ 1 0 Mass Spectrum m / e 371 (98) M ⁺ 68 30 CH (CH ₃ ) C ₂ H ₅ ch ₂ F C ₂ H ₅ 1 0 69 31 CH (CH ₃ ) OCH ₃ ch ₂ F c ₂ h ₅ 1 0 70 32 CH (OCH ₃ ) C ₂ H ₅ ch ₂ F C ₂ H ₅ 1 0 71 33 CH (CH ₃ ) CH = CH ₂ ch ₂ F C ₂ H ₅ 1 0 72 34 ch ₂ ch = ch ₂ - F c ₂ h ₅ Zero s

Example 73

To a suspension of 0.8 g of a 55 wt% sodium hydride dispersion in ml of dimethylformamide was stirred 6.1 g of 3- [6-fluoro-2-oxo-3- (2-propynyl) 5-benzothiazolinyl] -6 A solution of methyl-2,4 (1H, 3H) -pyrimidinedione (see Example 4) in 50 ml of dimethylformamide was added. After the hydrogen evolution ceased

2.8 g of dimethyl sulfate are added to the reaction mixture and the mixture is stirred for one hour. The reaction mixture was poured into 500 ml of water, the aqueous mixture was extracted with ethyl acetate (3 x 100 ml) and the organic layer was dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure and the resulting residue (7.2 g) was purified on a 350 g alumina (Brockman I) column eluting with 3: 1 methylene chloride / n-hexane. The first fraction (1.5 g) was recrystallized from ethyl acetate to give 1,6-dimethyl-3- [6-fluoro-2-oxo-3- (1,2-propan dienyl) -5-benzothiazolinyl] -2 4 (1H, 3H) -pyrimidinedione, m.p.> 250 ° C, is obtained. Further elution of the column with methylene chloride / ethyl acetate (3: 1) gave a second fraction (4.7 g) which was recrystallized from ethyl acetate. 1,6-dimethyl-3- [6-fluoro-2-oxo-3- (2-propynyl) -5-benzothiazolinyl] -2,4 (1H, 3H) -pyrimidinedione is obtained, m.p. 180-181 ° C. are.

Example 74

A solution of bromine (0.16 mL) in acetic acid (5 mL) was stirred at room temperature for 15 minutes with 1.0 g

HU 206708 Β

3- [3,4-dihydro-7-fluoro-2-methyl-3-oxo-4- (2-propynyl) -2H, 4-benzoxazin-6-yl] -l, 6-dimethyl-2,4 ( Add a solution of 1H, 3H) -pyrimidinedione (see Example 45) in acetic acid (7 mL) and stir at room temperature for 30 minutes. The reaction mixture was concentrated under reduced pressure, the residue was taken up in ethyl acetate, the solution was washed with dilute aqueous sodium bicarbonate solution, the organic phase was dried over anhydrous sodium sulfate and evaporated to dryness. The resulting 5-bromo-3- [3,4-dihydro-7-fluoro-2-methyl-3-oxo-4- (2-propynyl) -2H-1,4-benzoxazin-6-yl] -1,6 -dimethyl-2,4 (1H, 3H) -pyrimidinedione 182-187 ° C.

75-77. example

As in Example 74, in each case, the corresponding uracil derivative (I "") is brominated to provide the compound (XV) listed in Table 3.

Table 3

Example number Γ ''. kepi. DEFAULT. Dry. Example number r ₂ CR ³ R ⁴ R ⁷ Physical data (op.) 75 44 c ₂ h ₅ chch ₃ ch ₃ op. 219-220 'C 76 52 ch ₂ ch = ch ₂ ch ₂ C ₂ H ₅ . op. 215-219'C 77 52 CH ₂ CHBrCH ₂ Br ch ₂ C ₂ H ₅ op. 124-128

Example 78

7.65 g of 6- [2-chloro-6-oxo-4-trifluoromethyl-1 (6H) -pyrimidinyl] -4- (2-propynyl) -2H-1,4-benzoxazine-3 (4H) - A solution of sodium methylate (1.08 g) in methanol (10 ml) was poured into a solution of 300 ml of anhydrous methanol with stirring at 20 'Con. Within 15 minutes a slurry formed and the temperature rose to 30 ° C. The reaction mixture was concentrated under reduced pressure and the residue was dissolved in 500 ml of ethyl acetate. The organic layer was washed with water (2 x 200 mL), dried over anhydrous sodium sulfate and evaporated to dryness under reduced pressure. The crystalline residue was stirred with diethyl ether (20 mL), cooled to 0 ° C, and n-hexane (100 mL) was added. The crystalline material is filtered and dried under reduced pressure at 50 ° C. The resulting 6- [2-methoxy-6-oxo-4-trifluoromethyl-1 (6H) -pyrimidinyl] -4- (2-propynyl) -2H-1,4-benzoxazin-3 (4H) -one 218-220 The C's are.

Example 79

34.94 g of 6-dimethyl-3- (6-fluoro-3-isopropyl-2-oxo-5-benzothiazolinyl) -2,4 (1H, 3H) -pyrimidinedione (see Example 49) under stirring under nitrogen atmosphere in 200 mL of concentrated sulfuric acid and heated at 150 ° C for 45 minutes. The reaction mixture was cooled to 25 ° C and poured onto 1 kg of ice, the precipitated product was filtered and washed with water until neutral. The filtrate was suspended in 500 ml of ethyl acetate at 60 ° C, evaporated to 250 ml, after cooling, the product was filtered off, washed with ethyl acetate and dried at 50 ° C under reduced pressure. The resulting 1,6-dimethyl-3- (6-fluoro-2-oxo-5-benzothiazolinyl) -2,4 (1 H, 3 H) -pyrimidinedione melted above 250 ° C.

Example 80

Similarly to the procedure of Example 79 starting from 6-ethyl-3- (6-fluoro-3-isopropyl-2-oxo-5-benzothiazolinyl) -1-methyl-2,4 (1H, 3H) -pyrimidinedione (see Example 50). 6-ethyl-3- (6-fluoro-2-oxo-5-benzothiazolinyl) -1-methyl-2,4 (1H, 3H) -pyrimidinedione is obtained, m.p.> 250 ° C.

Example 81

3.07 g of 6-dimethyl-3- (6-fluoro-2-oxo-5-benzothiazolinyl) -2,4 (1H, 3H) -pyrimidinedione (see Example 79) and 0.48 g of 55% The sodium hydride dispersion was stirred in 50 ml of anhydrous dimethylformamide for 1 hour at 25 ° C. Chloroacetamide (1.02 g) was then added and stirred at 50 ° C for 6 hours. The reaction mixture was then cooled and water (400 mL) was added. The precipitated product is filtered off, washed with water and the filtrate is suspended in 200 ml of ethyl acetate at 60 ° C. The suspension is concentrated to a volume of about 50 ml, cooled to 25 ° C, the solid filtered and dried at 50 ° C. The resultant 3- (3-carbamoylmethyl-6-fluoro-2-oxo-5-benzothiazolinyl) -1,6-dimethyl-2,4 (1H, 3H) -pyrimidinedione melted at above 260 ° C.

82-101. example

Similar to the procedure described in Example 81, the corresponding uracil derivative (Γ ") is treated with a suitable alkylating agent to provide the compounds (XVI) listed in Table 4 below.

Table 4

Example number Γ ”. DEFAULT. Dry. Example number R ² R ⁷ Physical data (op.) 82 79 IzoC ₄ H ₉ ch ₃ op. 168-171 83 79 sec-C ₄ H ₉ ch ₃ op. 135-137 'C

HU 206 708 Β

Example number Γ ”. start, buy. Example number R ² R ¹ Physical data (op.) 84 80 sec-C ₄ H ₉ c ₂ H ₅ op. 150-152 ° C 85 79 chf ₂ ch ₃ op. 206-208 ° C 86 79 cf ₂ chf ₂ ch ₃ op. 156-158 ° C 87 79 ch ₂ and ₃ ch ₃ op. 243-245 ° C 88 80 ch ₂ and ₃ c ₂ h ₅ op. Mp 198-200 ° C 89 80 CH (CH ₃ ) OCH ₃ C ₂ H ₅ mp 221-222 ° C 90 80 CH (OCH ₃ ) C ₂ H ₅ c ₂ h ₅ op. 232-234 ° C 91 80 CH (CH ₃ ) OC ₂ H ₅ c ₂ h ₅ op. 216-218 ° C 92 79 ch ₂ cn ch ₃ op. 247-250 ° C 93 79 ch ₂ cooc ₂ h ₅ ch ₃ op. 193-195 ° C 94 79 CH ₂ CON (CH ₃ ) ₂ ch ₃ op. 257-258 ° C 95 79 CH ₂ C (CH ₃ ) = CH ₂ ch ₃ op. 203-205 ° C 96 79 CH (CH ₃ ) CH = CH ₂ ch ₃ op. 148-178 ° C 97 80 CH (CH ₃ ) CH = CH ₂ c ₂ h ₅ op.124-134 C 98 79 cinnamylindenyl ch ₃ op.125-160 C 99 80 ch ₂ c = ch c ₂ h ₅ mp> 250 ° C 100 79 CH (CH ₃ ) G = CH ch ₃ op. 184-186 ° C 101 80 CH (CH ₃ ) CCH C ₂ H ₅ m.p. 177-179 ° C

Example 102

Similarly to the procedure of Example 81, 3- (3,4-dihydro-7-fluoro-3-oxo-2H-1,4-benzoxazin-6-yl) -6-methyl-2,4 (1H, 3H) -pyrimidinedione ( see Example 21) alkylated with chloroacetonitrile to give 3- (4-cyanomethyl-3,4-dihydro-7-fluoro-3-oxo-2H-1,4-benzoxazin-6-yl) -6-methyl2 , 4 (1H, 3H) -pyrimidinedione, melting at above 230 ° C.

II. Preparation of Compounds of Formula IX (Intermediates for the Formula I):

Example 103

To a solution of phosgene (60.0 g) in ethyl acetate (300 ml) was added a solution of 5-amino-6-fluoro-3- (2-propynyl) -2-benzothiazolinone (22.5 g) in ethyl acetate (350 ml) at 30 ° C with stirring for 2 hours. ice. The resulting slurry was stirred for 2 hours at 50 ° C and then slowly heated to reflux. The clear solution was evaporated to dryness to give 6-fluoro-5-isocyanato-3- (2-propynyl) -2-benzothiazolinone as a clear crystalline solid. This product serves inter alia as a starting material for 3- [6-fluoro-2-oxo-3- (2-propynyl) -5-benzothiazolinyl] -6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione (see Example 1). example).

Example 104

In a similar manner to that described in Example 103, 6-amino-3,4-dihydro-7-fluoro-3-oxo-4- (2-propynyl) -2H-1,4-benzoxazine was treated with phosgene to afford 3,4 -dihydro-7-fluoro-6-isocyanato-3-oxo-4- (2-propynyl) -2H-1,4-benzoxazine was obtained.

1 H-NMR (CDCl ₃ , 60 MHz): 7.02 ppm (d, 1H), 6.88 ppm (d, 1H), 4.88-4.60 ppm (m, 4H), 2.35 ppm (t, 1H).

Example 105

As in Example 103, 6-amino-3,4-dihydro-3-oxo-4- (2-propynyl) -2H-1,4-benzoxazine was treated with phosgene to give 3,4-dihydro starting material in Example 3. Yield: -6-isocyanato-3-oxo-4- (2-propynyl) -2H-1,4-benzoxazine.

1 H-NMR (CDCl ₃ , 400 MHz): 6.98-6.92 ppm (m, 2H),

6.79 ppm (q, 1H), 4.66 ppm (d, 2H), 4.63 ppm (s,

2H), 2.31 ppm (t, 1H).

III. Preparation of Compounds of Formulas X and 111 [Intermediates for the Preparation of Compounds of Formula I]:

Example 106

A suspension of 4.7 g of 5-amino-6-fluoro-3- (2-propynyl) -2-benzothiazolinone, 1.93 g of diketene and 0.05 g of 4-pyrrolidinopyridine in 250 ml of benzene is stirred for 30 minutes at room temperature and then kept at 50 ° C for 30 minutes. This gives a solution of 5-acetoacetylamino-6-fluoro-3- (2-propynyl) -2-benzothiazolinone, which is used in the next step without isolation of the product.

The clear solution prepared above was heated at reflux for 2.5 hours with 2.85 g of ethyl carbamic acid and 0.2 g of p-toluenesulfonic acid monohydrate in a water separator. Then, 0.2 g of p-toluenesulfonic acid monohydrate was added once more and heated for an additional 2.5 hours. The reaction mixture was evaporated to dryness14

HU 206 708 Β after all. The crude product thus obtained (11.7 g) is slurried with 50 ml of diethyl ether, the insoluble constituents are filtered off and dried. 8.2 g of 5- [3- (ethoxycarbonylamino) -2-butenoylamino] -6-fluoro-3- (2-propynyl) -2-benzothiazolinone are obtained, m.p. 167-169 ° C. . This product is used inter alia as starting material for 3- [6-fluoro-2-oxo-3- (2-propynyl) -5-benzothiazolinyl] -6-methyl-2,4 (1H, 3H) -pyrimidinedione (see Example 4). ).

107-134. example

Similar to the procedure described in Example 106, the corresponding amines of formula XII are reacted with the corresponding diketenes of formula X 'to give the corresponding compounds of formula X' which are reacted with ethyl carbamic acid in Table 5a and Table 5b. The compounds of formula (III) are obtained. These tables also list the respective intermediates [(X '') or (X '') or (IIP) or (III ')] as well as the corresponding final products of formula (I) ) and (III) respectively.

Table 5a

Example number Yeah. Example number R ² (CR ³ R ⁴ ) n X Physical data X ''. Compound of formula (op.) III *. Compound of formula (op.) 107 5 CH ₂ C = CH ch ₂ 1 SHE (not isolated) (not isolated) 108 6 ch ₂ ch = ch ₂ ch ₂ 1 SHE (not isolated) op. 175-177 ° C 109 7 c ₂ h ₅ CH (CH ₃ ) 1 SHE (not isolated) op. 192-194 ° C 110 8 ch ₂ och CH (CH ₃ ) 1 SHE (not isolated) op. 171-173 ° C 111 9 ch ₃ - Zero s op. 150-151 ° C op. 250-251 ° C 112 10 C ₂ H ₅ - Zero s op. 118-120 op. 195-197 ° C 113 11 ch ₂ ch = ch ₂ - Zero s op. 113-115 ° C op. 194-196 ° C 114 12 CH (CH ₃ ) ₂ - Zero s op. 166-167 ° C op. 186-187 ° C 115 13 BC3H-7 - Zero s op. 116-117 ° C op. 203-205 ° C 116 14 CH (CH ₃ ) ₂ - Zero s op. 167-169 ° C op. 186-188 ° C 117 15 ch ₃ - Zero s op. 137-139 ° C op. 200-202 ° C 118 16 - Zero s mp 105-107 ° C op. 159-160 ° C 119 17 ch ₂ and ₃ - Zero s op. 126-128 ° C op. 181-183 ° C 120 18 ch ₂ cooc ₂ h ₅ Zero s op. 143-145 ° C op. 184-185 ° C 121 19 ch ₂ ch = ch ₂ - Zero s op. 106-107 ° C op. 149-151 ° C 122 20 CH ₂ OCH Zero s op. 114-116 ° C op. 199-200 ° C 123 21 H ch ₂ 1 0 mp> 230 ° C 1 H-NMR (CDCl ₃ , 200 MHz): 11.50 ppm (s, 1H), 10.66 ppm (s, 1H), 9.62 ppm (s, 1H), 7.56 ppm (d, 1H) ), 6.96 ppm (d, 1H), 5.30 ppm (s, 1H), 4.57 ppm (s, 2H), 4.30 ppm (q, 2H), 2.26 ppm (s, 3H) ), 1.22 ppm (t, 3H) 124 22 CH ₂ OCH ch ₂ 1 s (not isolated) op. 185-188 ° C

HU 206 708 Β

Table 5b

Example number Example number of final product of formula R ² (CR'R ⁴ ) n X R ⁷ Physical data X ". Compound of formula (op.) III. Compound of formula (op.) 123 23 CH (CH ₃ ) ₂ - Zero S c ₂ h ₅ op. 167-168 ° C op. 150-152 ° C 124 24 ch ₂ ch = ch ₂ ch ₂ 1 SHE c ₂ h ₅ (not isolated) op. 109-115 ° C 125 25 ch ₂ ch = ch ₂ ch ₂ 1 SHE nC ₃ H ₇ (not isolated) op. 86-88 ° C 126 26 ch ₂ c = ch CH ₂ 1 0 c ₂ h ₅ op. 113-115 ° C op. 132-133 ° C 127 27 ch ₂ c = ch ch ₂ 1 SHE nC ₃ H ₇ op. 88-93 ° C op. 143-147 ° C 128 28 CH (CH ₃ ) ₂ ch ₂ 1 0 c ₂ h ₅ (not isolated) (not isolated) 129 29 CH (CH ₃ ) OCH ch ₂ 1 SHE c ₂ h ₅ op. 110-114 ° C (not isolated) 130 30 CH (CH ₃ ) C ₂ H _s ch ₂ 1 SHE c ₂ h ₅ 131 31 CH (CH ₃ ) OCH ₃ ch ₂ 1 0 c ₂ h ₅ 132 32 CH (OCH ₃ ) C ₂ H ₅ ch ₂ 1 0 c ₂ h ₅ 133 33 CH (CH ₃ ) CH = CH ₂ ch ₂ 1 SHE c ₂ h ₅ 134 34 ch ₂ ch = ch ₂ - Zero s c ₂ h ₅

Example 135

A solution of 12.2 g of 6-amino-3,4-dihydro-7-fluoro-3-oxo-4- (2-propynyl) -2H-1,4-benzoxazine in 300 ml of toluene was stirred at 30 ° C. A solution of 2,2-dimethyl-5-propionyl-1,3-dioxane-4,6-dione (11.0 g) in toluene (5 mL) was added dropwise over a minute. The reaction mixture (still solution) is stirred for 4 hours at 124 ° C and then allowed to stand at room temperature for about 16 hours. The precipitated crystalline material is filtered off and dried.

There was thus obtained 3,4-dihydro-7-fluoro-3-oxo-4- (2-propynyl) -6-propioacetylamino-2H-1,4-benzoxazine, m.p. 113-115 ° C.

A suspension of the above prepared intermediate, 6.14 g of ethyl carbamic acid and 0.2 g of p-toluenesulfonic acid monohydrate in 260 ml of benzene is refluxed for 2.5 hours. Then 0.2 g of p-toluenesulfonic acid monohydrate was added once more and refluxed for a further 2.5 hours. The reaction mixture was evaporated to dryness under reduced pressure to give 25.5 g of crude product, slurried with 200 ml of ethyl acetate, washed with 300 ml of water and crystallized from ethyl acetate. 7.2 g of 6- [3- (ethoxycarbonylamino) -2-pentenoylamino] -3,4-dihydro-7-fluoro-3-oxo-4- (2-propynyl) -2H-1,4 Benzoxazine is obtained, m.p. 133 DEG C. with decomposition. This product was used as starting material for 6-ethyl-3- [3,4-dihydro-7-fluoro-3-oxo-4- (2-propynyl) -2H-1,4-benzoxazin-6-yl] 2,4 ( 1H, 3H) -pyrimidinedione (see Example 35).

Example 136

Similarly to the procedure described in Example 135, 4-allyl-6-amino-3,4-dihydro-7-fluoro-3-oxo-2H-1,4-benzoxazine is reacted with 2,2-dimethyl-5-propionyl-1,3 dioxane with 4,6-dione to give 4-allyl-3,4-dihydro-7-fluoro-3-oxo-6-propioacetylamino-2H-1,4-benzoxazine, m.p. (95), M ⁺ . This product is then reacted with ethyl carbamic acid to give 6- [3- (ethoxycarbonylamino) -2-pentenoylamino] -4-allyl-3,4-dihydro-7-fluoro-3 as the starting material in Example 36. oxo-2H-1,4-benzoxazine is obtained, m.p. 115 DEG C. with decomposition.

Example 137

Similar to the procedure described in Example 135, 5-amino-6-fluoro-3- (n-propyl) -2-benzothiazolinone is reacted with 2,2-dimethyl-5-propionyl-1,3-dioxane-4,6-dione. 6-Fluoro-5-propioacetylamino-3- (n-propyl) -2-benzothiazolinone is obtained, m.p. 87-88 ° C. This is then reacted with ethyl carbamic acid to give 5- [3- (ethoxycarbonylamino) -2-pentenoylamino] -6-fluoro-3- (n-propyl) -2-benzothiazolinone as the starting material in Example 37. mp 174-175 ° C.

ARC. Preparation of Compounds of Formula IV:

Example 138

25.55 g of 3- [3,4-dihydro-3-oxo-4- (2-propynyl) -2H-4-benzoxazin-6-yl] -6-trifluoromethyl-2,4 (1H, 3H) To a suspension of pyrimidinedione (see Example 3) and 32.13 g of phosphorus oxychloride in 250 ml of toluene is added 16.61 g of pyridine with stirring at 25 ° C. The reaction mixture was heated at 100 ° C for 6 hours, then cooled to 25 ° C and poured onto 500 g of ice. The aqueous mixture was then extracted with ethyl acetate (3 x 150 mL) and the organic layer was washed with water to neutral, dried over anhydrous sodium sulfate and evaporated to dryness under reduced pressure. The resin product was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1: 3). Finally, the product is recrystallized from diethyl ether / n-hexane. Thus, 6- [2-chloro-6-oxo-4-tri16

708 Β-fluoromethyl-1 (6H) -pyrimidinyl] -4- (2-propynyl) -2H-1,4-benzoxazin-3 (4H) -one is obtained, m.p. 143-145 ° C. example).

V. Formulation Example:

Example 139 To prepare a spray powder by weight, the following ingredients were mixed:

The compound of the present invention is 50 g

Silicic acid, hydrated (carrier, grinding aid) 5 g

Sodium lauryl sulfate (wetting agent) 1 g

Sodium lignin sulfonate (dispersant) 2 g

Kaolin (carrier) 42 g

100 g

The mixture is then finely ground using a rolling mill or other similar grinding equipment.

The resulting spray powder is mixed with water to form a fine suspension which is a spray liquid for direct use.

Compounds of formula I wherein R ⁶ is C 1 -C 4 alkyl may also be prepared according to Scheme 3.

Preparation of 3- [6-fluoro-2-oxo-3- (2-butynyl) -5-benzothiazolinyl] 2,5-dimethyl-6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione

a) 3-Amino-2-methyl-4,4,4-trifluoroacetacetic acid ethyl ester

Ethyl 2-methyl-4,4,4-trifluoroacetic acid ethyl ester (59.4 g) was dissolved in toluene (100 mL) and anhydrous ammonia gas was continuously added to the solution while heating under reflux until completion of the reaction. The solvent was distilled off and the resulting residue was distilled under a pressure of 290 Pa and 132 ° C. This gave 3-amino-2-methyl-4,4,4-trifluoroacetacetic acid ethyl ester; n = 1.4326.

b) 5 - [(2,2,2-trichloroethoxy) carbamino] -6-fluoro-3- (2-propynyl) -2-benzothiazolinone g 6-fluoro-5-amino-3- (2-propynyl) - 2-Benzothiazolinone is dissolved in 200 ml of methylene chloride, 10.5 g of pyridine are added and the mixture is cooled to -50 ° C. A solution of 28.09 g of chloroformate 2,2,2-trichloroethyl ester in 50 ml of methylene chloride is added dropwise. The reaction mixture was stirred for 15 minutes and then poured into 200 ml of water. The organic layer was separated and 50 g of silica gel was added. The silica gel was filtered off and washed with methylene chloride (50 mL). The filtrate and washings were then combined, concentrated and the crystalline product dried under reduced pressure.

Mass Spectrum Data: m / e 402, 400, 360, 358, 252, 2101, 183.

c) 3- [6-Fluoro-2-oxo-3- (2-propynyl) -5-benzothiazolinyl] -5-methyl-6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione

34.2 g of 3-amino-4,4,4-trifluoro-2-methylcrotonic acid ethyl ester are dissolved in 150 ml of dimethylformamide and 20 g of potassium tert-butylate are added under cooling over 10 minutes. After stirring for 60 min, 68.3 g of 5 - [(2,2,2-trichloroethoxy) carbamino] -6-fluoro (2-propynyl) -2-benzothiazolinone, dissolved in 150 ml of dimethylformamide, are added. The reaction mixture was heated to 60 ° C and stirred at this temperature for 2.5 hours. The reaction mixture was poured into water (600 mL), acidified and extracted with ethyl acetate (200 mL x 2). The organic layer was washed with 5% NaCl to neutral and then concentrated. The residue thus obtained was purified by chromatography on silica gel (1000 g), eluting with hexane: ethyl acetate (7: 3). M.p. 201-205 ° C.

d) [6-Fluoro-2-oxo-3- (2-propynyl) -5-benzothiazolinyl] 1,5-dimethyl-6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione

29.6 g of 3- [6-fluoro-2-oxo-3- (2-propynyl) -5-benzothiazolinyl] -5-methyl-6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione 200 ml dissolved in acetonitrile, 9.25 g of dimethyl sulfate and 10.14 g of potassium carbonate were added with stirring and the mixture was stirred at 40 ° C for 90 minutes. The reaction mixture was poured into 200 mL of water and extracted twice with 200 mL of ethyl acetate. The organic phase is then concentrated. The resulting residue was purified by chromatography on 400 g of silica gel using hexane: ethyl acetate (7: 3).

We distinguish two products:

1.6-Fluoro-5- [2-methoxy-5-methyl-6-oxo-4-trifluoromethyl-1 (6H) -pyrimidinyl] -3- (2-propynyl) -2-benzothiazolinone, colorless oil

Mass Spec: m / e 417.375.356.207 1 H NMR (200 MHz, CDCl ₃ ), ppm: 7.34 (d, 1p), 7.3 (d, 3p), 4.5 (m, 1p), 3 , 97 (s, 3p), 2.22 (m, 3p), 1.57 (d, 6p)

2. 3- [6-Fluoro-2-oxo-3- (2-propynyl) -5-benzothiazolidinyl] -1,5-dimethyl-6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione, m.p. 171-173 ° C, from n-hexane / ethyl acetate

Mass Spectrum Data: m / e 417.375,210.43 1 H-NMR (200 MHz, CDCl ₃ ), ppm: 7.34 (d, lp), 7.24 (d, lp), 4.7 (m, lp) , 3.58 (m, 3p), 2.26 (q, 3p), 1.57 (d, 6p)

Preparation of 3- (6-fluoro-2-oxo-5-benzothiazolinyl) -2,5-dimethyl-6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione

5.63 g of 3- [6-fluoro-2-oxo-3- (2-propynyl) -5-benzothiadiazolidinyl] -1,5-dimethyl-6-trifluoromethyl-2,4 (1H, 3H) -pyrimidine -dione for 3 hours at 130 ° C cc. with sulfuric acid. The reaction mixture was poured into 200 mL of ice water, and the precipitated product was suction filtered and washed to neutral.

Mass Spec: m / e 375,210,166.96

1 H-NMR (200 MHz, CDCl ₃ ), ppm: 9.28 (s, D ₂ Oval exchangeable lp), 7.29 (d, lp), 6.80 (d, lp), 3.59 (m , 3p), 2.27 (m, 3p)

e) 3- [6-Fluoro-2-oxo-3- (2-butynyl) -5-benzothiazolinyl] 2,5-dimethyl-6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione 2.5 g 3- [6-Fluoro-2-oxo-5-benzothiazolinyl] -2,5-dimethyl-6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione, 1.42 g

HU 206 708 Β

3-Chloro-1-butine, 0.93 g of potassium carbonate and a catalytic amount of potassium iodide in 10 ml of acetonitrile were stirred at reflux for 8 hours. The reaction mixture was poured into water (50 mL) and extracted with ethyl acetate (2 x 25 mL). The organic phase is washed with neutral and then concentrated. The residue was purified by chromatography on silica gel (30 g) with hexane / ethyl acetate (8: 2) and the product recrystallized from hexane / ethyl acetate.

Mp 188-190 ° C

Mass Spectrum Data: m / e 427, 399, 375,210 1 H-NMR (200 MHz, CDCl ₃ ), ppm: 7.50 (d, lp), 7.36 (d, lp), 5.72 (m, lp), 3.59 (m, 3p), 2.49 (d, lp), 2.26 (m, 3p, 1.66 (d, 3p).

In a manner similar to that described in Example 140 [a-e], the following compounds of formula IA are prepared:

R ² Physical data: CH (CH ₃ ) CH = CH ₂ op. 180-182 ° C CH (CH ₃ ) CH ₂ CH ₃ op. 173-175 ° C CH (CH ₃ ) OCH ₃ mp> 200 ° C (dec.)

VI. Biological examples

]. example

Pre-emergent herbicidal effect

Immediately after planting the experimental plants (monocotyledonous and dicotyledonous weeds) in a greenhouse, the soil surface is sprayed with 3 kg to 30 kg of active ingredient per hectare of active ingredient.

Test substances are preferably formulated in an emulsifiable concentrate (EC) and diluted to the desired concentration in water just prior to use. Insoluble materials are formulated with kaolin as a neutral carrier wettable powder (WP) and suspended in water immediately before use.

Dosage values of "g active ingredient / hectare" are, unless otherwise indicated, the surface of the earth in the pots. The volume of the spray liquid is 100 liters / hectare (corresponding to 100 ml / m ² ).

Seeds of plants are sown in plastic containers of various sizes using heat-sterilized (evaporated) soil (field soil consisting of 2.6% peat, 20% clay, 30% sludge, 47% sand), Plants kept in a greenhouse at medium temperature (17-25 ° C in winter, 18-35 ° C in summer, 30-90% humidity). The length of the light period is 13-16 hours per day; if necessary, artificial light (15,000-18,000 Lux) may be used. Artificial lighting is automatically turned on even when the daylight is not bright enough.

After three weeks, the herbicidal activity was evaluated by a three-step linear grading procedure (necrosis, chlorosis, reduced growth, deformation) against an untreated control group (2: 80-100% damage; 1: 30-79% damage; 0: 0-29% damage).

Table Bi: Pre-emergence herbicidal effect: application rate 3 kg / ha

examples da S SHE R G E C H I THE V E N THE t SHE P C H E N S T E L THE B U T D THE T U M THE T R C THE S s 01 2 2 2 2 2 2 2 2 2 2 02 2 2 2 2 2 2 2 2 2 1 25 2 2 2 2 2 2 2 2 2 2 38 2 2 2 2 2 2 2 2 2 2 39 2 2 2 2 2 2 2 2 2 2 41 2 2 2 2 2 2 2 2 2 2 42 2 2 2 2 2 2 2 2 2 2 43 2 2 2 2 2 2 2 2 2 2 44 2 2 2 1 2 1 2 2 2 2 45 2 2 2 2 2 2 2 2 2 2 46 2 2 2 2 2 2 2 2 2 2 47 2 2 2 2 2 2 2 2 2 2 48 2 2 2 2 2 2 2 2 2 2 49 2 2 2 2 2 2 2 2 2 2 50 2 2 2 2 2 2 2 2 2 2 51 2 2 2 2 2 2 2 2 2 2 52 2 2 2 2 2 2 2 2 2 2 53 2 2 2 2 2 2 2 2 2 2

Table B2: Pre-emergence herbicidal effect: application rate of 30 g / ha

Example S SHE R G E C H I THE V E N C H E N S T E L D THE T U 41 2 2 2 2 2 2 73 2 2 2 2 2 2

Example B2:

Post-emergence herbicide (contact herbicide)

Monocotyledonous and dicotyledonous weeds are treated, after emergence (in the 2-6 leaf stage), with an aqueous dispersion of the active ingredient at a dose of 3 kg / ha.

Test substances are preferably formulated as an emulsifiable concentrate (EC) and diluted with water to the desired concentration just prior to use. Insoluble materials are formulated as kaolin as an inert carrier wettable powder (WP). This is suspended in water just before use.

Dosages per gram of active ingredient per hectare apply to the surface of the soil in the pots unless otherwise stated. The sprayed volume is 500 liters / hectare.

Seeds of plants of different sizes containing plasticized heat-sterilized (steamed) soil1

HU 206 708 ((Optima land: 80% peat, 20% loess). The plants are kept in a greenhouse at moderate temperatures (17-25 ° C in winter, 18-35 ° C in summer, 30-90% humidity). The length of the light period is 1316 hours per day; if necessary, switch on artificial light (1500018000 Lux). The artificial lighting automatically switches on even when the daylight is not sufficient.

After three weeks, the herbicidal activity against an untreated control group (1: 30-79% damage, 0: 0-29% damage) was evaluated on a three-point linear scale (taking into account necrosis, chlorosis, reduced growth, deformity).

Table B3: Post-emergence herbicidal activity:

examples da S SHE R G E C H I THE V E N THE L SHE P C H E N S T E L THE B U T D THE T U M THE T R C THE S S 38 2 2 2 2 2 2 2 2 2 2 39 2 2 2 2 2 2 2 2 2 2 41 2 2 2 2 2 2 2 2 2 1 42 2 2 1 1 2 1 2 2 2 2 43 2 2 1 2 2 2 2 2 2 2 47 2 1 1 1 2 2 2 2 2 1 48 2 2 2 2 2 2 2 2 2 1 49 2 2 2 2 2 2 2 2 2 2 51 2 2 2 2 2 2 2 2 2 2 52 2 2 2 2 2 2 2 2 2 2 53 2 2 2 2 2 2 2 2 2 2

Meaning of abbreviations in the tables:

SORG Sroghum halepense ECHI Echinochloa crus-galli AVEN Avena ALOP Alopecurus myosuroides STEL Stellaria media abut Abutilon theophrasti date Datura stramonium MATR Matricaria chamomilla CASS Cassia obtusifolia PATENT CLAIMS

A process for the preparation of a compound of formula (I) - which

Claims (13)

A process for the preparation of a compound of formula (I) R ^{1 is} hydrogen, C 1-4 alkyl, R ^{2 is} hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy (C 1 -C 4) alkyl, C 2 -C 5 cyanoalkyl, C 25 alkoxycarbonyl - (C 1 -C 4) alkyl, carbamoyl (C 1 -C 4) alkyl, di (C 1 -C 4) alkylcarbamoyl (C 1 -C 4) alkyl, C 3 -C 4 alkenyl -, C 3 or C 4 alkynyl, R ^{3 is} hydrogen or C 1-4 alkyl, R ^{4 is} hydrogen, R ^{5 is} hydrogen or fluoro, R ^{6 is} hydrogen, halogen or C 1-4 alkyl, R ^{7 is C} 1 -C 4 alkyl or C 1 -C 4 haloalkyl, n is 0 or 1 and X is oxygen or sulfur, and the corresponding enol ethers of the compounds of formula (I) wherein R ^{1 is C} 1 -C 4 alkyl, and the salts of the compounds of formula (I), wherein a) for the preparation of compounds of formula I and their alkali metal salts wherein R ^{1 is} hydrogen or C 1 -C 4 alkyl and R ^{6 is} hydrogen, a compound of formula II wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , n and X have the meanings given above, R ⁶ 'is hydrogen and R ^{8 is a C} 1 -C 4 alkyl group which is cyclized under basic conditions and, if desired, the alkali metal salt of the uracil derivative of formula I is converted into an acid form R ¹ = hydrogen, or b) for the preparation of compounds of formula I and their alkali metal salts wherein R ^{1 is} hydrogen, R ^{6 is} hydrogen or C 1 -C 4 alkyl and R ^{7 is C} 1 -C 4 alkyl, a compound of formula III in which R ^{2 is} R ³ , R ⁴ , R ⁵ , R ⁶ ', n and X have the meanings given above, R ^{7 is C} 1-4 alkyl, and R ^{9 is C} 1-4 alkyl ring-protected under basic conditions and, if desired, the alkali metal salt of the uracil derivative represented by formula (I) is converted into the acid form R ¹ = hydrogen, or c) for the preparation of compounds of formula I wherein R ^{1 is C} 1 -C 4 alkyl, a uracil derivative of formula Γ wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , n and X are alkylated with a suitable alkylating agent having from 1 to 4 carbon atoms as defined above, or d) for the preparation of compounds of formula I wherein R ^{2 is} hydrogen in a uracil derivative of formula I 'wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , n and X are as defined above and R ^{10 is C} 1 -C 7 alkyl, R ^{10 is} deprotected, or e) for the preparation of compounds of formula I wherein R ^{2 is} other than hydrogen, a uracil derivative of formula I '- wherein R', R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , n and X are suitably alkylated as defined above, or f) for the preparation of compounds of the formula I in which R ^{6 represents a} chlorine, bromine or iodine atom, a uracil derivative of the formula I "wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , n and X are as defined above EN 206 708 Β - chlorinated, brominated or iodinated, or g) for the preparation of enol ethers of formula Ia, a pyrimidinone compound of formula IV wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , n and X are as defined above and Hal is chloro or bromine atom is treated with an alcohol of formula ^{R 1} OH in the presence of an organic base or the corresponding alcoholate of formula V wherein R ¹ 'is C 1 -C 4 alkyl and M ^{+ is} a metal ion equivalent and optionally treated with a compound of formula I ) compound of formula - wherein ^R1 and / or ^R2 is hydrogen is converted to a salt. 2. An herbicide, wherein the active ingredient is 0.003 to 50% by weight of at least one compound of the formula I in which R ^{1 is} hydrogen, C 1-4 alkyl, R ^{2 is} hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy (C 1 -C 4) alkyl, C 2 -C 5 cyanoalkyl, C 25 alkoxycarbonyl - (C 1 -C 4) -alkyl, carbamoyl (C 1 -C 4) -alkyl, di (C 1 -C 4) -alkylcarbamoyl (C 1 -C 4) -alkyl, C 3 -C 4 or alkenyl -, C 3 or C 4 alkynyl, R ^{3 is} hydrogen or C 1-4 alkyl, R ^{4 is} hydrogen, R ^{5 is} hydrogen or fluoro, R ^{6 is} hydrogen, halogen or C 1-4 alkyl, R ^{7 is C} 1 -C 4 alkyl or C 1 -C 4 haloalkyl, n is 0 or 1 and X is oxygen or sulfur or a compound of formula (I) wherein: ^R1 is a C1-4 alkyl group, an enol ether, or a compound (I) of formula wherein R ^is! hydrogen and / or R ^{2 is} hydrogen, a salt thereof, and formulation aids. The herbicide according to claim 2, wherein the active ingredient is 6-ethyl-3- (4-allyl-3,4-dihydro-7-fluoro-3-oxo-2H-1,4-benzoxazin-6-yl). ) -1-methyl-2,4 (1H, 3H) -pyrimidinedione and / or 6-ethyl-3- [3,4-dihydro-7-fluoro-3-oxo-4- (2-propynyl) -2H-1, Contains 4-benzoxazin-6-yl] -1-methyl-2,4 (1H, 3H) -pyrimidinedione. The herbicide according to claim 2, characterized in that it contains as active ingredient at least one of the following compounds; 6-ethyl-3- (4-allyl-3,4-dihydro-7-fluoro-3-oxo-2H-1,4-benzoxazin-6-yl) -5-bromo-1-methyl-2,4 ( 1H, 3H) -pyrimidinedione, 3- [3,4-Dihydro-7-fluoro-3-oxo-4- (2-propynyl) -2H-1,4-benzoxazin-6-yl] -1-methyl-6- (n-propyl) -2,4 (lH, 3H) -pyrimidinedione, 6-ethyl-3- (3,4-dihydro-7-fluoro-4-isopropyl-3-oxo-2H-l, 4benzoxazine-6-yl) -l-methyl-2,4 (lH, 3H) -pyrimidinedione . 6-ethyl-3- (sec-butyl-3,4-dihydro-7-fluoro-3-oxo-2H-l, 4benzoxazine-6-yl) -l-methyl-2,4 (lH, 3H) -pyrimidinedione . 6-ethyl-3- [3,4-dihydro-7-fluoro-4- (1-methoxyethyl) -3-oxo-2H-1,4-benzoxazin-6-yl] -1-methyl-2,4 ( 1H, 3H) -pyrimidinedione, 6-ethyl-3- [3,4-dihydro-7-fluoro-4- (1-methoxypropyl) -3-oxo-2H-1,4-benzoxazin-6-yl] - l-methyl-2,4 (lH, 3H) -pyrimidinedione, 6-ethyl-3- [3,4-dihydro-7-fluoro-4- (1-methyl-2-propenyl) -3-oxo-2H-1,4-benzoxazin-6-yl] -1-methyl-2, 4 (1H, 3H) -pyridine midindione, 6-ethyl-3- [3,4-dihydro-7-fluoro-4- (1-methyl-2-propynyl) -3-oxo-2H-1,4-benzoxazin-6-yl] -1-methyl-2, 4- (lH, 3H) -pyrimidinedione, 6-ethyl-3- (6-fluoro-3-isopropyl-2-oxo-5-benzotiazolinil) l-methyl-2,4 (lH, 3H) -pyrimidinedione, 6-ethyl-3- (3-sec-butyl-6-fluoro-2-oxo-5-benzotiazolinil) l-methyl-2,4 (lH, 3H) -pyrimidinedione, 6-ethyl-3- [6-fluoro-3- (l-methoxyethyl) -2-oxo-5-benzotiazolinil] -l-methyl-2,4 (lH, 3H) -pyrimidinedione, 6-ethyl-3- [6-fluoro-3- (l-methoxy-propyl) -2-oxo-5-benzotiazolinil] -l-methyl-2,4 (lH, 3H) -pyrimidinedione, 6-ethyl-3- (3-allyl-6-fluoro-2-oxo-5-benzotiazoIinil) -l-methyl-2,4 (lH, 3H) -pyrimidinedione, 6-ethyl-3- [6-fluoro-3- (l-methyl-2-propenyl) -2-oxo-5benzotiazolinil] -l-methyl-2,4 (lH, 3H) -pyrimidinedione, 6-ethyl-3- [6-fluoro-2-oxo-3- (2-propynyl) -5-benzothiazolinyl] -1-methyl-2,4 (1H, 3H) -pyrimidinedione; 6-ethyl-3- [6-fluoro-3- (l-methyl-2-propynyl) -2-oxo-5benzotiazolinil] -l-methyl-2,4 (lH, 3H) -pyrimidinedione. A method for controlling weeds, characterized in that the objects to be protected against weeds and / or the weeds with 30 g to 3000 g / ha of the compound according to claim 1 or 30 g to 3000 g / ha of active ingredient according to claim 2 . 6. The method of claim 5, wherein the objects to be protected against weeds and / or the weeds are treated with an agent according to claim 3 or 4. 7. An agent according to claim 2, wherein R ^{1 is a} methyl group. 8. An agent according to claim 2, wherein R ^{2 in} the active ingredient of formula I is C 1-4 alkyl, C 1-4 alkoxy (C 1-4) alkyl, C 3 or C 4 alkenyl. or C 3 or C 4 alkynyl. 9. An agent according to claim 2, wherein R ^{3 is} H. An agent according to claim 2, wherein R ^{6 in} the active ingredient of formula (I) is hydrogen, fluoro, chloro, bromo or methyl. 11. An agent according to claim 2, wherein R ^{7 in} formula I is methyl, ethyl, trifluoromethyl or pentafluoroethyl. 12. An agent according to claim 2, wherein n is 0 and X is sulfur. 13. An agent according to claim 2, wherein n is 1 and X is O.