DD204024A5 - SELECTIVE HERBICIDES MEDIUM - Google Patents

Abstract

The invention relates to selective herbicidal compositions based on new triazinones, which can be used successfully in agriculture. The aim of the invention is to increase the compatibility of the agents with crops with good herbicidal activity. The object of the invention is the provision of new selective herbicidal agents. According to the invention these are thiazolo or (1,3) thiazino (2,3-c) (1,2,4) triazinones of the general formula I, wherein R deep 1 to R deep 4 and n have the meaning given in the description.

Description

-ή-

Selective herbicidal agents Field of application of the invention

The invention relates to thiazole and / * 1, ЗЗ thiazino / * 2,3-c₃ £ l, 2,43Triazinone containing selective herbicidal agents,

Characteristic of the known technical solutions

Triazinones with herbicidal activity are already known (BE-PS 69 70 83j BE-PS 79 98 54). However, the problem of a good herbicidal action against problem weeds while being well tolerated against several main crops that are in crop rotation does not solve these herbicides »

Object of the invention

It is an object of the invention to increase the tolerance to crops with good herbicidal activity,

Explanation of the invention of the invention

The object of the present invention is the development of an agent which can be used against hard to control weeds in several major agricultural crops without their damage.

This object is achieved according to the invention by means of

holding thiazolo- and £ l, 3} thiazino £ 2 _# 3 ~ сД £ і, 2,4] тгіа zinone of the general formula

in the

R _{1 is} an optionally mono- or polysubstituted by oxygen or sulfur atoms interrupted C ₁ -Cg-alkyl radical, a C ^ -Cg-alkylcarboxylic acid or ester radical, an optionally mono- or polysubstituted by alkyl Cj-Cg-cycloalkyl, optionally - or more than once by C ₁ -C ₄ alkyl and / or C ₁ -C ₄ -alkoxy and / or Qj-C-alkylthio and / or halogen and / or the nitro group substituted aromatic or Aroraatischaliphatischen hydrocarbon radical or a heterocyclic hydrocarbon radical .

Rp is hydrogen, a C ₁ -C -alkyl radical or an optionally substituted aromatic hydrocarbon radical,

R_ is hydrogen, a C ₁ -C -alkyl radical, an optionally substituted aromatic hydrocarbon radical, a benzyl radical or the hydroxyl group,

R ₄ "Hydrogen f, a C ^ C. alkyl radical, an optionally substituted aromatic hydrocarbon radical, a benzyl radical, a C ₁ -C alkoxy radical or the hydroxyl group and

η represents 0 or 1, in admixture with carriers and / or excipients,

Surprisingly, the compositions according to the invention are outstandingly suitable for controlling problem weeds with a compatibility, in particular for soybeans, potatoes, cotton, maize and wheat, which exceed the known compositions. These properties combine great technical progressiveness.

It is well known that, for economic reasons, the most important agricultural crops are more and more closely cropped together. As regards the weed flora, this causes more and more specific accompanying flora to develop. When, as is almost always the case, weeds conditions that are difficult to combat with the current state of the art in the field of weed control, thus creating conditions that easily lead to the dominance of such species. For example, one tries to address the problem by trying to combat it with full or even excessive amounts of herbicides. "This often causes damage to the culture. Since the known herbicides can also have a residual effect on the subsequent cultures via the soil, damage often occurs there as well. Therefore, an advanced herbicide is desired to have good activity against problem weeds while being well tolerated against several major crops in crop rotation.

The erfindungsgeraäßen agent meet these requirements and are characterized by a surprisingly good compatibility with the above cultures, where they can be used both in the pre-emergence and postemergence process.

The herbicidal action extends to many weed species. Abutilon theophrastii, Ipomoea ssp, Solanura ssp, Viola spp., Echinochloa crus galli, Setaria spp., Are well combated problem weeds. and Digitaria ssp · called «

The application can be carried out by incorporation into the soil prior to culturing or pre- or postemergence.

The application rates are approximately 0.1 to 5 kg of active ingredient / ha for selective weed control.

In higher application rates, the funds can also be used for total weed control «

The erfindungsgeraäßen means can change the natural development of the plants in low application rates to achieve various agricultural or horticultural noticeable properties. It will be understood that not every compound causes the same regulatory effects on each plant species and on the type of application, date of application or concentration of use. In general, the control of the natural Pflanzenwachsturas is visually recognizable by changes in GcöS) e _t shape, color or texture of the treated plant or its parts "following, caused by the compounds of this invention developmental changes of the plants can be exemplified:

Inhibition of vertical growth,

Inhibition of root development,

Intensification of the revitalization of plant pigments, defoliation *

Of the compounds to be used according to the invention, the properties described in particular include those in which, in the abovementioned general formula I, R.sup.1 denotes a C 1 -C 4 -alkyl radical, such as, for example, methyl, trimethylmethyl, ethyl, propyl, isopropyl, methylpropyl, η-butyl, isobutyl, tert-butyl, 2,2-dimethyl-1-propyl, n-pentyl or n-hexyl, a methyl acetate residue; optionally alkyl-substituted C ₃ -C ₃ -cycloalkyl radicals, such as, for example, cyclopropyl, cyclopentyl, cyclohexyl, methylcyclohexyl or cyclooctyl; optionally substituted aromatic hydrocarbon radicals, such as, for example, phenyl, 4-trimethylmethylphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 4-fluorophenyl, 4-iodophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 3-nitrophenyl, 4-nitrophenyl, 1-naphthyl or 2-naphthyl, an aromatic-aliphatic hydrocarbon radical such as benzyl or 4-chlorobenzyl, a heterocyclic hydrocarbon radical such as thienyl or 2-furyl; R ₂ , R ₃ and / or R _{4 is} hydrogen, a C 1 -C -alkyl radical, such as, for example, methyl, ethyl, propyl, isopropyl, n-8-butyl, isobutyl, tert-butyl, 2,2-dimethyl-1 Propyl, n-pentyl or n-hexyl, an optionally substituted aromatic hydrocarbon radical, such as, for example, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-methoxyphenyl,

4-methoxyphenyl, 4-fluorophenyl, 2-chlorophenyl, _f- 3-chlorophenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 3-nitrophenyl or A- nitrophenyl; and R, and / or R ₄ additionally have a C.C.-alkoxy radical , such as methoxy, ethoxy, propoxy or n-butoxy, or the hydroxyl group and η is zero or 1 »

Outstanding compounds of these compounds are those in which R _{1 is} methyl, trimethylmethyl, methylpropyl, n-hexyl, cyclopentyl. Cyclohexyl, phenyl, methylphenyl, trimethylmethylphenyl, methoxyphenyl, fluorophenyl, oodophenyl, chloro

phenyl, nitrophenyl, benzyl or thienyl, R _{2 is} hydrogen, methyl or phenyl, R _{4 is} hydrogen, methyl or hydroxyl, R is hydrogen, methyl, dimethyl-ethyl, tri-methylethyl,

Phenyl, benzyl or hydroxyl and η represents 0 or 1.

The compounds of the invention may be used either alone, in admixture with each other or with other active ingredients.

De for the desired purpose, for example, offer the following herbicidal active ingredients, which may also be added to the compounds of the invention only immediately before use:

substituted anilides substituted anilines

substituted aryloxycarboxylic acids and their salts, esters and amides

substituted ether substituted arsenic acids and their salts, esters and amides substituted benzimidazoles substituted benzthiadiazinonedioxides substituted benzoxazines substituted benzoxazinones substituted biurets substituted quinolines substituted carbamates substituted aliphatic carboxylic acids and their salts,

Esters and aroids

substituted N-arylsulfonyl-N'-triazinyl-urea derivatives substituted aromatic carboxylic acids and their salts,

Esters and amides

substituted carbamoylalkyl-thiol or dithiophosphates substituted quinazolines substituted Cycloalkylaraidocarbonthiolsäuren and their

Salts, esters and amides

substituted Cycloalkylcarbonamide-thiazoles substituted dicarboxylic acids and their salts, esters and

amides

substituted dihydrobenzofuranylsulfonates substituted disulfides substituted dipyridylium salts substituted dithiocarboxylates substituted dithiophosphoric acids and their salts, esters

and amides

substituted ureas substituted hexahydro-1H-carbothioates substituted hydantoins

substituted hydrazides substituted hydrazonium salts substituted isoxazole pyriraidones substituted imidazoles substituted isothiazolepyrimidones substituted ketones substituted naphthoquinones substituted aliphatic nitriles substituted aromatic nitriles substituted oxadiazoles substituted oxadiazinones substituted oxadiazolidinediones substituted oxadiazinediones substituted phenols and their salts and esters substituted phosphoric acids and their salts, esters and

Amides substituted aromatic carboxylic acids and their salts,

Esters and amides

substituted carbamoylalkyl-thiol or dithiophosphates substituted quinazolines substituted Cycloalkylamidocarbonthiolsäuren and their

Salts, esters and amides

substituted Cycloalkylcarbonamido-thiazoles substituted dicarboxylic acids and their salts, esters and

amides

substituted dihydrobenzofuranylsulfonates substituted disulfides substituted dipyridylium salts substituted dithiocarbamates substituted dithiophosphoric acids and their salts, esters

and amides

substituted ureas substituted hexahydro-1H-carbothioates substituted hydantoins substituted hydrazides substituted hydrazoniurase salts substituted isoxazolepyrimidones substituted imidazoles substituted isothiazolopyriraidones substituted ketones substituted ^ 4-naphthoquinones substituted aliphatic nitriles substituted aromatic nitriles substituted oxadiazoles substituted oxadiazinones substituted oxadiazolidinediones substituted oxadiazinediones substituted phenols and their salts and esters substituted phosphoric acids and theirs Salts, esters and

amides

Substituted Phosphonium Chlorides Substituted Phosphonalkylglyzine substituted phosphite substituted phosphoric acids and their salts, esters and

amides

substituted piperidines substituted pyrazoles substituted pyrazolalkylcarboxylic acids and their salts,

Esters and Amides substituted Pyrazoliumsalze substituted Pyrazoliuraalkylsulfate

substituted pyridazines substituted pyridazones

substituted pyridinecarboxylic acids and their salts, esters and amides

substituted pyridines substituted pyridinecarboxylates substituted pyridinones substituted pyrimidines substituted pyrimidones substituted pyrrolidinecarboxylic acids and their salts,

Esters and amides substituted pyrrolidines substituted pyrrolidones substituted arylsulfonic acids and their salts, esters

and amides

Substituted styrenes Substituted tetrahydrooxadiazinediones Substituted tetrahydrooxadiazolediols Substituted tetrahydahydrotnethanoindenes Substituted tetrahydrodiazole thiones Substituted tetrahydro thiadiazine thiones Substituted tetrahydro thiadiazole diones Substituted thiadiazoles Substituted aromatic thiocarboxylic acid substituted thiocarboxylic acids and their salts, esters

and amides

substituted thiocarbamates substituted thioureas substituted thiophosphoric acids and their salts, esters

and amides

substituted triazines substituted triazoles substituted uracils substituted uretidinediones.

In addition, other additives may also be used, for example non-phytotoxic additives which give a synergistic increase in herbicides, such as wetting agents, emulsifiers, solvents and oily additives.

Appropriately inventive compositions or mixtures thereof in the form of preparations ·, such as powders, Streuraitteln, granules, solutions, emulsions or suspensions with the addition of liquid and / or solid carriers or diluents and optionally of wetting, tackifying, emulsifying and / or Qispergierhilfsraittel, applied.

Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulfoxide, dimethylformamide, furthermore mineral oil fractions,

Suitable solid carriers are mineral earths, for example, tonsil, silica gel, talc, kaolin, attapulgite, limestone, silicic acid and vegetable products, for example flours.

Surfactants include, for example, calcium lignosulfonate, polyoxyethylene alkylphenol ether,

Naphthalenesulfonic acids and their salts, phenolsulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates and substituted benzenesulfonic acids and their salts

The proportion of or of the active substances (s) in the various preparations can vary within wide limits. For example, the compositions contain about 5 to 95 percent by weight of active ingredients, about 95 to 5 percent by weight of liquid or solid carriers and optionally up to 20 percent by weight of surface-active substances,

The application of the agents can be carried out in the usual manner, for example with water as a carrier in Spritzbrühraengen of about 100 to 5000 liters / ha. An application of the means ira so-called low-volume and ultra-low-volume methods is just as possible as their application in the form of so-called microgranules «

For the preparation of the preparations, for example, the following constituents are used:

A «spray powder

a) 80 weight percent active ingredient 15 weight percent kaolin

5% by weight of surfactants based on the sodium salt of N-methyl-N-oleyl-taurine and the calcium salt of lignosulfonic acid.

b) 50% by weight of active ingredient

40% by weight of toners

5% by weight cell pitch

5% by weight of surfactants based on a mixture of the calcium salt of lignin sulfonic acid with alkylphenol polyglycol ethers *

c) 20% by weight of active ingredient

70 weight percent clay minerals 5 weight percent cell pitch

5% by weight of surfactants based on a mixture of the calcium salt of lignin sulfonic acid with alkylphenol polyglycol ethers,

d) 5% by weight of active ingredient 80% by weight of tonsil

10% by weight cell pitch

5% by weight of fatty acid condensation product surfactants ·

B emulsion concentrate

20% by weight of active ingredient 40% by weight of xylene 35% by weight of dimethyl sulfoxide 5% by weight mixture of nonylphenylpolyoxyethylene or calcium dodecylbenzenesulfonate.

The novel compounds to be used in the invention can be prepared, for example, indera man

a) compounds of the general formula

II O SH

with compounds of the general formula

R ₄ -CH- Hal

R ₃ - CH) _n in

R ₂ -CH- Hal

or rait compounds of the general formula

C = O

(R ₃ - CH) _n IV

CH - Hal

or with compounds of the general formula

CH

CH - halogen

in the presence of bases and if desired separated by column chromatography in the isomers or

b) compounds of the general formula

RO

with compounds of the general formula

H ₉ N

² \

HN

VII

to react or

c) compounds of general formula R.0

I vi

RO 0

with thiosemicarbazide of the formula

- NH - CS - NH ₂ VII

to compounds of the general formula R ₁ N - NH - CS - NH ₂

VIII

RO O

and then these in the presence of bases with compounds of the general formula

R-CH shark

(R ₃ - CH) _n III

R ₂ -CH- shark

or with compounds of the general formula

C = O - CH) _n IV

CH - shark

with formation of compounds of the general formula

^R 2

Ro ..

/ 4

brings to the reaction which cyclized in the presence of basic catalysts to the desired process products of general formula I or that

d) - if R. is a C ₁ -C_-Alkylcarbonsäurerest or a C. -Cg-Alkylcarbonsäureesterrest represents acetylenedicarboxylic acids or their esters of the general formula

ROOC - C s C - COOR X

with compounds of the general formula

HN

VII

J <

^R 3 to form compounds of the general formula

COOR HN - N = С

COOR

XI

reacts, these in the presence of bases to compounds of the general formula

COOR

XII

cyclized, which are iseraerized to the desired process products of the general formula I, in which R 1, R ₂ , f, R 31 and R _{4 have} the abovementioned meaning and R is hydrogen or C 1 -C -alkyl,

The starting materials for the preparation of the novel compounds are known per se or can be prepared by processes known per se.

The reaction of the reactants is carried out between 0 and 120 ⁰ C ₄ but generally between room temperature and reflux temperature of the corresponding reaction mixture *

The reaction time is 1 to 72 hours «

For the synthesis of the new compounds, the reactants are used in approximately equimolar amounts. Suitable reaction media are inert solvents to the reactants. The choice of solvents or suspending agents depends on the use of the corresponding starting compounds and the acid acceptors or bases used. Examples of solvents or suspending agents include ethers, such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane, aliphatic and aromatic hydrocarbons, such as petroleum ether, cyclohexane , Hexane, heptane, benzene, toluene and xylene, carbonitriles such as acetonitrile, and carboxylic acid amides such as dimethylformamide.

Suitable acid acceptors are organic bases, such as, for example, triethylamine, N, N-dimethylaniline and pyridine bases or inorganic bases, such as oxides, hydroxides and carbonates of alkaline earth and alkali metals. "Liquid bases, such as pyridine, can be used simultaneously as solvent.

The novel compounds prepared by the abovementioned processes can be isolated from the reaction mixture by customary processes, for example by distillation.

distilling the solvent used at normal or reduced pressure or by precipitation with water,

The novel compounds are generally colorless and odorless crystalline bodies that are sparingly soluble in water and aliphatic hydrocarbons, moderately to readily soluble in halogenated hydrocarbons such as chloroform and carbon tetrachloride, ketones such as acetone, carboxylic acid amides such as dimethylformamide, sulfoxides such as Dimethylsulfoxide, carbonitriles, such as acetonitrile, and lower alcohols, such as methanol and ethanol,

The solvents used for recrystallization are in particular carbon tetrachloride, chloroform, toluene, acetonitrile and ethyl acetate.

The following examples illustrate the preparation of the compounds to be used according to the invention,

example 1

302 g (3.6 mol) of sodium bicarbonate and 137.5 g (0.72 mol) of dibromoethane are introduced into 700 ml of 2-propanol, and this suspension is heated to reflux. To this boiling mixture is added a mixture consisting of 61 g (0.36 mol) of 3-mercapto-6- (4-raethylphenyl) -4,5-dihydro-1-l, 2,43-triazin-5-one, 146 ml of 10 % sodium hydroxide solution and 1500 ml of 60% aqueous 2-propanol added dropwise. The mixture is then heated for 2 hours at reflux temperature, filtered from undissolved sodium bicarbonate and concentrated in vacuo to dryness. The resulting solid residue is mixed with 500 ml

Washed 5% sodium hydroxide solution and filtered again. »The residue is separated by column chromatography on silica gel, eluent ethyl acetate. This gives 28.8 g (32 % of theory) of 3- (4-methylphenyl) -6,7-dihydro-4H-thiazolo-2,3,3-celium, 2,43-triazin-4-one.

Mp .: 193 ⁰ C

Example 2

48.0 g (0.21 mol) of 3-mercapto-6- (4-raethoxyphenyl) -4,5-dihydro-1-l, 2,43-triazin-5-one and 100 g (0.5 mol) of 1,3 -Oibroropropane be implemented analogously to the reaction conditions listed in Example 1. After chromatographic separation 7.7 g (14 % of theory) of 3 ~ (4-methoxyphenyl) -4,6,7,8-tetrahydro-4H- £ 1.3 } thiazines £, 3-c3-l, 2,43triazin-4-one were obtained.

Mp .: 131 ° C

Example 3

18.5 g (0.1 mol) of 3-mercapto-6-triniethyl-ethyl-4,5-dihydro-1, 2,4} -triazin-5-one, 432 g (0.2 mol) of 2,3-dibrofflbutane and 258 g (0.2 mol) of ethyldiisopropylamine are dissolved in 200 ml of acetonitrile and heated to reflux for 48 hours. It is poured into ice-water and the precipitate is filtered off and separated by chromatography on silica gel, mobile phase ethyl acetate. This gives .1 g (34 % of theory) of 3-trimethyl-ethyl-6,7-dihyro-6- _t- 7-dimethyl-4H-thiazolo-2,3,3-cis-2,43-triazin-4-one _a

Mp .: 134 ^° C

Example 4

19.8 g (0.1 mol) of 2-hydrazino-4,5-dihydro-thiazole hydrobromide are dissolved in 200 ml of ethanol, successively with 20 ml of 10% aqueous sodium hydroxide solution and 23.4 g (0.1 mol) of 4-trimethyl · Methylphenyl-glyoxylsäureethylester, heated for 4 hours at reflux temperature, poured into ice water ¹ , the precipitate filtered off and isk-crystallized from ethyl acetate. This gives 18.5 g (65 % of theory) of 3- {4-trimethylmethylphenyl) -6,7-dihydro-4H-thiazolo ¥ 2,3-c3 ІХ , 2,4'-t riazin-4-one ♦

Mp .: 203 ⁰ C

Example 5

19.6 g (0.1 mol) of 2-hydrazinothiazole hydrobroraid and 16.4 g (0.1 mol) of methyl phenylglyoxylate are reacted analogously to Example 3, giving 9.8 g (43 % of theory) of 3-phenyl-4H -thiazolo 2,3-c3 Cl , 2,4-triazin-4-one.

Mp .: 181 ⁰ C

Example 6

12.9 g (0.1 mol) of 2-hydrazino-2,4,5,6-tetrahydro-2H-l, 33 thiazine and 16.4 g (0.1 mol) phenylglyoxylic acid ethyl ester are reacted analogously to Example 3. Obtained are 18.4 g (75 % of theory) of 3-phenyl-4,6,7,8-tetrahydro-4H-1-l, 33thiazine l2,3-c3-l, 2,4-triazin-6-one .

Mp: 155 ^° C

Example 7

20.5 g (0.1 mol) of 3-mercapto-6-phenyl-4,5-dihydro- £ i _f 2 _# 47-triazin-5-one, 18.4 g (0.2 mol) of chloroacetone and 80 10% aqueous sodium hydroxide solution is stirred in 250 ml of ethanol at 60 ° C. for 3 hours. It is acidified with dilute hydrochloric acid and the reaction solution is cooled. The resulting precipitate is filtered off and separated by column chromatography on silica gel, eluent acetone / petrol ether (1: 1) »There are 5.10 g (21 % of theory) of S-phenyl-e-methyl- ^ H-thiazolo £ 2.3 -е} [l , 2,4} triazin-4-one.

Mp .: 158 ⁰ C

Example 8

20.5 g (0.1 mol) of S-mercapto-phenyl-4,5-dihydro-1,2,4-triazin-5-one are reacted with 39.8 g (0.2 mol) of bromoacetophenone analogously to Example 7 column chromatography separation gives 4.58 g (15 % of theory) of 3,6-oiphenyl-4H-1hiazolo-2,3,3-c3-Cl, 2,4,2-t-riazin-4-one,

Mp: 125 ⁰ G

Example 9

20.4 g (0.1 mol) of 3-mercapto-6-phenyl-4,5-dihydro-1,4-triazin-5-one are dissolved in 100 ml of dioxane plus 100 ml of dimethylformamide, with 20 ml added to a 50% solution of chloroacetaldehyde and stirred for ⁶ hours at 60 ° C. The reaction

tion mixture is added to ice water, the precipitate separated by column chromatography, mobile phase ethyl acetate / methanol (9: 1), separated. This gives 3.7 g (15 % of theory) of S-phenyl-6-hydroxy-e ^ -dihydro ^ H-thiazolo CZ1 3-cJ fl, 2,4) t riazin-4-one.

Mp: 213 ⁰ C

Example 10

15 g (0.073 mol) of 3-mercapto-6-phenyl-4,5-dihydro-Ü, 2,4j triazin-5-one are dissolved in the heat in 800 ml of acetonitrile, with 13.5 g (0.15 Mol) epichlorohydrin and 14.85 g (0.115 mol) of ethyl diisopropylamine and 16 hours at 60 ⁰ C reacted. The reaction mixture is concentrated under reduced pressure and the residue is separated by column chromatography on silica gel (system ethyl acetate / ethanol 9: 1). 3.5 g (19 % of theory) of З-Рпепуі-7-hydroxy-4,6,7,8-tet rahydro l l, ъ) thiazino-2,3 2,3-cJ ≦ l, 2 , 4 are obtained. triazin-4-one with m.p. 181 ⁰ C.

Example 11

15 g (0.1 mol) of phenylglyoxylic acid are dissolved in 1 liter of ethanol. For this purpose, a solution of 9.1 g (0.1 mol) of thiosemicarbazide in 500 ml of 5% aqueous acetic acid is added and stirred this reaction solution at 90 ⁰ C for 15 minutes. After cooling, half of the solvent is removed under reduced pressure, the precipitate which has precipitated is filtered off, washed with water and dried at 50.degree. The thiosemicarbazone obtained is then without further purification in 120 ml

a 5% sodium carbonate solution, treated with 9.2 g (0.1 mol) of chloroacetone in 50 ml of ethanol and stirred at 60 ⁰ C for 2 hours. E _s is cooled, acidified with 10% hydrochloric acid and filtered the precipitate. The precipitate is dissolved in a mixture of 200 ml of pyridine / acetic anhydride (1: 1) and stirred at 60 C for 3 hours. The reaction mixture is poured into 500 ml of ice-water, the precipitate which has precipitated is filtered off, washed with water and recrystallised from ethyl acetate. 12.9 g (53 % of theory) of 3-phenyl-6-ethyl-4H-thiazolo are obtained -c3 (l, 2,4-triazin-4-one with m.p. 158 ⁰ C.

In an analogous manner as described in the examples, the following compounds can be prepared using appropriate starting materials.

Name of the connections Physical

constant

3-Trimethylmethyl-6,7-dihydro-4H thiazolo ~ £ 2,3-c? £ L, 2.4} triazin-4-one M.p .: 122 ⁰ C.

3- {4-Me th oxyphe nyl) -6,7-d ihyd ro-4H-1 h iazolо £ 2,3-c] £ l, 2,4} triazin-4-one M.p .: 188 ⁰ C.

3- (4-chlorophenyl) -6,7-dihydro-4H-thiazolo £ 2,3-cJ (: L # 2.4} triazin-4-one M.p .: 184 ⁰ C.

3-benzyl-6,7 ~ dihydro-4H-thiazolo - £ 2 * 3-е} £ l, 2,4jtriazin-4-one M.p .: 135 ⁰ C.

3-Cyclohexyl-6,7-dihydro-4H-thiazolo - £ .2,3'-ileol _# 2,43triazin-4-one M.p .: 178 ⁰

Name of the connections Physical

constant

3-thienyl-6,7-dihydro-4H-thiazolo-C2,3-c3

Cl, 2 »4} triazine-4-one M.p .: 203 ^° C.

3- (4-fluorophenyl) -4,6,7,8-tetrahydro-4H- £ і, 3 ^! Ііагіпо £ 2,3-сДСі, 2,4 ^ гіагіп-4-оп Fp ,: 203 ⁰ C

3- (4-nitrophenyl) -4,6,7,8-tetrahydГ0-4Н-

£ £ 1,3Jthiazino- 2,3-c3 Cl, 2.4} triazin-4-one mp * 236 ⁰ C.

In an analogous manner as described in the examples, the following compounds can be prepared using appropriate starting materials. «

Narae of the compounds Physical

constant

3-Trimethylraethyl-6,7-dihydro-4H-thiazolo

2,3 2,3-е l l, 2,4} triazin-4-one m.p .: 122 ^° C

3- (4-methoxyphenyl) -6,7-dihydro-4H-thiazoles

2, 3-е, 2,4) triazin-4-one mp *: 188 ^° C

3- {4-Chlorophenyl) -6,7-dihydro-4H-thiazoloC2,3-cCl, 2,4} triazin-4-one

3-Benzyl-6,7-dihydro-4H-thiazolo-iC2,3-c ^

, 2,4} triazin-4-one M.p .: 135 ^° C.

3-Cyclohexy1-6,7-dihydr0-4H-thiazole- £ 2.3 ~ c3

, 2,4} triazin-4-one M.p .: 178 C

Name of the connections Physical

constant

3-thienyl-6,7-dihydro '-4H-.thiazolo- £ 2.3 cJ ~ £ l, 2 _f 4 ^ triazin-4-one mp 203 ,: ⁰ C

3- (4 ~ fluorophenyl) -4,5,7,8-tetrahydro-4H-£ l, 3) thiazino- £ 2 _# 3-c7Cl, 2,4 ^ triazine-4-one mp *: 2C3 ⁰ C

3- (4 ~ nitrophenyl) -4,6,7,8-tetrahydro-4H-

Mp .: 236 ° C

3-Cyclopentyl-4,6,7,8-tetrahydro-4H-l £, thiazino-C2,3-c ^ * D. 2,4j-triazin-4-one mp 183 ,: ⁰ C

3-Trimethylmethyl-4,6,7,8-tetrahydro-4H-£ l, 35-thiazino-C2,3-C3c ¹ * ² * 3 ^{4-triazin-4-one 0} C Fp.:148

3-hexyl-4,6,7,8-tetrahydro-4H-l £, 3J

thiazino- £ £ l 2,3-cJ, 2,4j-triazin-4-one M.p .: 121 ⁰ C.

3- {4-Oodphenyl) -6,7-dihydro-4H-thiazoIo

4-on mp .: 215 ° C

3-cyclopentyl-6,7-dihydro-4H-thiazolo C2,3-c ^ Cl, 2 _t 47-triazin-4-one mp ": 171 ⁰ C.

3- (2-methylpropyl) -6,7-dihydro-4H-thiazolo

, 3-cJ CL, 2.43-triazin-4-one M.p .: 154 ⁰ C.

3-Trimethylmethyl-4H-thiazolo -QZ, 3-c3 £ l, 2,43triazin-4-one M.p .: 151 ⁰ C.

3- (2-Fluorophenyl) -4H-thiazolo - £ 2,3-с ^ £ l, 2,4} triazin-4-on _e, mp 181 ⁰ C.

Name of the connections Physical

constant

3- (2-Methylphenyl) -4H-thiazolo 2,3-£ c3 Cl, 2 _t 43 ^triazi n-.4-one M.p .: 150 ⁰ C.

3-phenyl-6-raethyl-6,7-dihydro-4H - thiazolo £ 2 _# 3-c3Cl, 2 _t 4 triazin-4-one M.p .: 114 ⁰ C?

S-phenyl-ö-dimethylmethyl-ö ^ -dihydro-4H-thiazoloC2,3-c ^ £ l, 2,4jtriazin-4-one mp *: 132 ⁰ C.

3-phenyl-6 ~ trimethylmethyl-6,7-dihydro-4H-thiazolo 2,3-c3 £ £ l _f 2 _f 4} triazin-4-one M.p .: 130 ° C

3-phenyl-6-benzyl-6- _t- 7-dihydro-4H-thiazolo-2,3-c3Cl, 2,43-triazin-4-one m.p .: 115 ° C

3 _# 7-Oiphenyl-б, 7-dihydгo-4H-thiazolo £ _t 2 3-c ^ Cl "2,43triazin-4-one ⁰ C Fp.:124

3-Phenyl-7-methyl-4,5 _# 7,8-tetrahydro-4H-fl, _3-i 3ÜthiazinoC2 c3Cl, 2 _l 43triazin-4-.on Mp .: 133 ⁰ C.

3-cyclohexyl-4H-thiazolo [2,3-C ^ Сі # 2,4Э-

triazin-4-οπ m.p .: 125 ⁰ C.

ö-Trimethylraethyl-e-methyl ^ H-thiazolo £ 2,3-cJ ([l, 2,47triazin-4-one mp .; 128 ⁰ C.

S-Trimethylraethyl-ö-methyl-e ^ -dihydro-4H-thiazoloC2,3-c ^ tl * 2,4] triazin-4-one M.p .: 112 ⁰ C.

3-Ethyl ~ 6,7-dihydro-4H-thiazolo [2,3- £ l, 2,4] 3triazin-4-one M.p .: 100 ⁰ C.

Name of the connections Physical

constant

3 ~ ~ isopropyl 6,7-dihydro-4H-thiazolo

[Z, 3-е} Cl # 2.43 triazin-4-οπ m.p .: 70 ⁰ C

1- (6,7-dihydro-4-oxo-4H-ihiazolofc, 3-c ^ £ l _i 2 _i 4 ^ triazxn-3-yl) -ameisensäure-ethyl-- m.p .: 105 C ester

2- (6.7-0 ihyd ΓΟ-4-ΟΧΟ-4Η-1 h iazolo £ 2,3-сД Cl, 2 43triazin _f ~ 3-yl) -propionic acid ethyl mp;. 110 ⁰ C ester

3-phenyl-6-ethyl-6,7-dihydro-4H-thiazolo £ 2,3-c? _I £ l 2,4jtriazin-4-one M.p .: 179 ⁰ C.

3 _# 7-diphenyl-6,7-dihydro ~ 4H-thiazolo 2,3-c3 £ £ l / 2,43triazin ~ 4-one mp: 170 ⁰ C.

3-phenyl-6 _# 7-dimethyl-4H-thiazolo

4-on mp: 155 ⁰ C

3_ (4-fluorophenyl) -6,7-dihydro-4H-thiazolo £ ₁ 2 3-c ^ | £ l, 2,4] ltriazin-4-one mp _#: 139 ⁰ C.

3- {2,4-dichlorophenyl) -6,7-dihydro-4H-thiazolo £ 2 _# 3-c7 £ l, 2,4> ltriazin-4-one ⁰ C Fp.:242

3- (2 _i 4 ° ichlorphenyl) -4H-thiazolo-r2,3-c3 £ l, 2,45triazin-4-one m.p.? 131 ⁰ C

3- (2 _i 4- ^D ichlorphenyl) -6-raethyl-6 _J 7-dihydro-4H-thiazolo ~ £ £ l 2,3-c3, 2.43 ^triazin - ^{4 "on} Fp.:156 ⁰ C

Name of the connections Physical

constant

3- (5-chloro-2-thienyl) -6,7-dihydro-4H-2,3-c-1 L, 2,4-triazin-4-one Fp ♦: 195 ^° C

3- (2,5-dichloro-3-thienyl) -6,7-dihydro-4H-2,3-thiazoio £ £ l c3, 2,4jtriazin-4-one M.p .: 176 ⁰ C.

The following describes the preparation of further compounds which are already known per se and which can be used according to the invention.

Example 12

302 g (3.6 mol) of sodium bicarbonate and 137.5 g (0.72 mol) of dibromoethane are introduced into 700 ml of 2-propanol, and this suspension is heated to reflux. Into this boiling mixture is added a mixture consisting of 73.3 g (0.36 mol) of 3-mercapto-6-phenyl-4,5-dihydropoyl, 2,4,5-triazin-5-one, 146 ml 10% sodium hydroxide solution and 1500 ml of 60% aqueous 2-propanol was added dropwise. The mixture is then heated to reflux for 2 hours, filtered from undissolved sodium bicarbonate and concentrated in vacuo to dryness. The resulting solid residue is washed with 500 ml of 5% sodium hydroxide solution and filtered again. The residue is separated by column chromatography on silica gel, eluent ethyl acetate. This gives 28.3 g (34 % of theory) of 3-phenyl-6,7-dihydro-4H-thiazolof2,3-c ^ fl, 2,4jtriazin-4-one

Mp: melting point 135 ^° C.

Seismic Example 13

Analogously to Example 8 14.3 g (O _# l mol) З-Мегсарго-б-raethyl-4,5-dihydro £ i _f 2 _J 4! Jtriazin-5-one 7.4 g (44% of theory) 3-methyl-6,7-dihydro-4H-thiazolo £ 2,3-е} £ l, 2, 4} - triazin-4-one is reacted.

Mp: 171 ⁰ C

Example 14

19.8 g (0.1 mol) of 2-hydrazino-4,5-dihydrothiazole hydrobroraid are dissolved in 200 ml of ethanol, admixed successively with 80 ml of 10% aqueous sodium hydroxide solution and 10.2 (0.1 mol) of pyruvic acid ethyl ester, once boiled and then cooled. The resulting precipitate is filtered off and uracilcrystallized from ethyl acetate. Obtained is 11.0 g (65 % of theory) of 3-methyl-6,7-dihydro-4H-thiazolo 2,32,3-c3 l1,2,4 * -. triazin-4-one,

Mp: 171 ^° C. Example 15

Analogously to Example 10, 16.4 g (0.1 mol) phenylglyoxylic acid ethyl ester with 19.8 g (0.1 mol) of 2-hydrazino-4,5-dihydro-thiazole-hydrobroraid to 13.2 g (57 % of theory) 3-? -Enyl-6,7-dihydro-4H-thiazolo? 2,3-c3? L, 2,4] triazin-4-one reacted.

Mp .: 135 ° C

Example 16

40 g (0.2 mol) of 2-hydrazino-4,5-dihydro-thiazole hydrobromide are dissolved in 500 ml of a 2% sodium hydroxide solution, this solution is cooled to 5 ° C, dropwise with 28 g (0.2 mol Acetylendicarbonsäureraethylester and stirred at 25 ⁰ C for 2 hours. The deposited precipitate is filtered, dissolved in 250 ml of methanol, treated with 25 ml of triethylamine and stirred at 25 ⁰ C for 1 hour. Dor deposited precipitate is filtered again and then boiled in 500 ml of methanol for 1 hour reflux. Thereafter, the solvent is removed in vacuo and the remaining residue is recrystallized from ethyl acetate. This gives 24.1 g (53% of theory) of S-carbomethoxy-raethyl-EJY-dihydro-4H-thiazoloC2,3-c3fl, 2.4X-triazin-4-one with melting point of 123 ⁰ C.

The following embodiment serves to explain the applications of the compositions of the invention, which takes place in the form of the above-mentioned preparations.

Example 17

In the greenhouse, the compounds listed in the table at a rate of 5 kg of active ingredient / ha were dissolved in 500 liters V / asser / ha, sprayed on Sinapis, Solanum and Setaria as test plants in the pre- and post-emergence. 3 weeks after the treatment, the treatment result was scored, with

O = no effect and

4 = destruction of the plants

As the table shows, destruction of the test plants was generally achieved

Connections Pre-emergence post-emergence

Se Si So Se Si So

3-phenyl-4,5,7,8-

tetrahydro-4H-1, 33 ~ 4 4 4 4 4 4

thiazino- £ 2,3-cJ

£ l, 2 _# 4l-triazine-4-one

3-phenyl-6,7-dihydro ~

4H-thiazolo-C2.3~c) - 4-4 4 4 4 4

£ 4y 1.2 _f-1 riazinetrione-4-one

3-phenyl-6 ~ methyl-6,7-

dihydro-4H-2,3-c3- 4 4 4 4.4 4

D-f2,43-1 riazin-4-one

3- (4-chlorophenyl) -6,7-

dihydro-4H-thiazolo- 4 4 4 4 4 4

£ 2,3-cl Cl, 2,4} t riazin-4-one

3-carboinethoxy-ethyl-5,7-dihydro-4H-thia-4 4

zolo- £ 2 _t 3-c £ l, 2,4} -triazin-4-one

y ^ y

4H-thiazolo-C, 2, 3 ~ c} - 4 4 4

Ц1 # 2,4jtriazin-4-one

3- (3-methylphenyl) -6,7-dihydro-4H-thiazolo 4, 2, 3, 3, 4, 4-riazin-4-one

3- (1-methylcyclohexyl) -6,7-dihydro-4H-thia-4 £ ЗC3

triazin-4-one

3- (2,4-і-пппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппппп

triazin-4-one

Connections Pre-emergence post-emergence

Se Si So Se Si So

S-Trimethylmethyl-ö-

Rethyl-6,7-dihydro- 4 4 4 4 4

4H-thiazolof2,3-c3-1,2,4-yliazin-4-one

3-isopropyl-6,7-di-

hydro-4H-thiazolo- 4 4 4 4 4

£ 2,3-е3Cl, 2.43-triazin-4-one

3-phenyl-6,7-di-

methyl-4H-thiazolo- 4 4 4 4 4

triazin-4-one

3- (4-fluorophenyl-6,7-dihydro-4H-thiazolo- 2,3-C] JCl, 2,4} -triazin-4-one

3- (2 _# 4-dichlorophenyl) -6,7-dihydro-4H-thia-3f3

triazin-4-one

3- (2,4-dichlorophenyl) -6-methyl-6,7-dihydro-4H-thiazolo-2,3,3-C10- Cl , 2,431-riazin-4-one

3- {5-Chloro-2-thienyl) -6,7-dihydro-4H-f2,3-c3 [ 1,2,4,3-triazin-4-one

3- (2,5-Oichlor-3-thienyl) -6,7-dihydro-4H-th iazolof2,3-c3 £ 1.2, 4} triazin-4-one

3-trimethylmethyl-4,6,7,8-tetrahydro-4H-Cl.3j-thiazino-Z 2 , 3-C 1 Cl, 2,4-jtriazin-4-one

Connections Pre-emergence post-emergence

Se Si So Se Si So

3-Cyclopentу1-6,7-

dihydro- ^ H-thiazolo- 4 4 4 4 4

3-trimethylmethyl-6,7-dihydro-1H-thiazolo- K3

triazine ~ 4 ~ on

3-cyclohexyl-6,7 ~ dihydro-4H-thia2olo-3C}

triazin-4-one

3-Thienyl-6,7-dihydro-4H-thiazolo-4 4 4

£ 2,3-O Cl, 2,4> triazine-4-one

3-Triraethylmethyl-

4H-thiazolo-C2,3-cJ 4 4 4 ti, 2., Altriazin-4-o

3- {2-Methylpropyl) -6 _# 7-dihydro-4H-thia-4 4 4

zolof2,3-ee IX214> triazine-4-one

Untreated 0 0 0

Example 18

In the greenhouse, the listed plants were treated prior to emergence with the compounds in a Mindestaufwandnenge of 0.3 or 1 kg of active ingredient / ha. The compounds were applied evenly to the soil as an aqueous solution or suspensions containing 500 liters of water / ha for this purpose. The results show that, in contrast to the comparison compound, the agents according to the invention have a better compatibility or better effect.

co о

ri 0) t-i га

to ωr \ с jz-H

<C Ч- rH OEUCOL-

ч- OCCO ιΗ СО 3 О -rl СО

CO О δ (D JJ · Η <D C (О С I- 4- »

je га -м о) ε ν <л «> - ^ ε го гч -н · <п -n

N. · «"> t_ H 3 • HL.-HSOrHOJCDJ + JD)

D) O co co co οβ) θ.οο_.ο · Ηθ · © · Η i 'ш 2 Σ ω аоа; <нсл> шоо5сі connections

S-phenyl-δ-dihydro- 1 10 10 10 10 --- 000OO OO 4H-thiazolo ~ C2,3-c3 ~

£ l _t 2,4) * - triazin-4-one

3-phenyl-4,6,7,8- 1 10 10 10 10 --- 000OO OO

te rahyd ro-4H-.fl, Ъ ") -thiazino-f2,3-ee ) 1,2,2,4-triazin-4-one

3-phenyl-6-methyl-6,7-0,3 10 10 10 10 10 10 Ю 0 0 0 0 0 0 0 dihydro ~ 4H-thiazolo-

3-trimethylmethyl 0.3 10 10 10 --- 00000 00

6,7 ~ dihydro ~ 4H-thia ~

triazin-4-one

3-trimethylmethyl 0.3 10 10 10- --- 00000 00 6 ~ methyl ~ 6.7 ~ di-

hydro ~ 4H-thiazolo

triazin-4-one

Le icjism it t el

4-amino-6-phonyl-4,5 ~ 18 0 78 --- 57008 10 7 dihydro-3-mothyl-l, 2,4-

triazine ~ 5 ~ on

Example 19

In the greenhouse, the plants listed were treated after emergence with the listed compounds in an application rate of 0.3 or 1 kg of active ingredient / ha. The compounds were sprayed for this purpose as an aqueous solution or suspension with 500 liters of water / ha evenly over the plants. Again, 3 birds after treatment, the agents of the invention show a high selectivity with excellent activity against the weed, The comparison means did not show this selectivity.

η ι- ι

H- 3 *> O * <3 N Q. H-H- -5 3 O! I

on w σ>

I!

O 3 "D

DOT

ГО H- I

t

Men

 vl

OD I

W O O

H"

cn

3 - D Wv <3 "I CO O -i 3

rt W

-ш ι

H- rf -D

1 I M

• t Ϊ

ГО it 3 • 3 "O 4> H- it V-» D 3Γ it N * <TOM H- H ¹ I

в о σ

N I Hvj 3 I

O Ы

O 1

O O

O O O O O O

H-

D) (C

3-3

I O Q <t I τ

η-ro 1

D · ^ NW ZZ !

CD I

O o t i

O O O O O O

H * XI »i Tl WrtT. ZT Q £> H-3

t- ¹

H-O-

0 1 vj N »l

η · ro с 3 · H-

1 W ZT. &. I <J O C о \ -L 3 I O

O T (T H-

3 CL C 3 CD O 3

kg / ha AS

O soy O potato O Corn I cotton 1 wheat I barley 1 rice O Abutilon O Ipomea O solarium O viola O Echinochloa O Setaria O Digitaria

1'-i

1 * 0 rt 3 *

. · £ ". H- CD Wu) 3 <t Ν · <"5 O tJ H-HJ I O O CTi N 1 *

3 r? I

§wl

O I

ъг \ о.ы

! ГО η · I

2 ~

ϊ C

Where f »J -D

Г0

si-

D · <N O

M-OM N Η · t

O O

O O O

^ O D-

N Ы μ H. 1 J 3 O ^

2.П O -j μ

woo

»- * β) ·" JN si H-OIO) H- ¹ NO H- 1

μ.

с.

H.

S i

as

soy

potato

Corn

Cotton wheat

barley

rice

Abutilon

Iporaea

Solanuro

viola

Echinochloa

° igitaria

Claims (3)

Erfindunqsanspruch 1, Selective herbicidal compositions, characterized by a content of at least one thiazolo or l, 33Thiazino · the general formula in the R _{1 is} an optionally mono- or polysubstituted by oxygen or sulfur atoms interrupted C ₁ -C alkyl radical, a C.-Cg-Alkylcarbonsäurerest, a ^с С " ^с _б ~ Alkylcarbonsäureesterrest, an optionally mono- or polysubstituted by alkyl C -Cg -Cycloalkyl radical, an optionally mono- or polysubstituted by C ^ -C. alkyl and / or C ₃ -C ₄ -alkoxy and / or C.-C.-alkylthio and / or halogen and / or the nitro group substituted aromatic or aromatic-aliphatic Hydrocarbon radical or a heterocyclic hydrocarbon radical, Rp is hydrogen, a C ^ -C alkyl radical or an optionally substituted aromatic hydrocarbon radical _t R _{3 is} hydrogen, a C 1 -C -alkyl radical, an optionally substituted aromatic hydrocarbon radical, a benzyl radical or the hydroxyl group, R ₄ is hydrogen, a C.-Cg-alkyl optionally substituted зіпеп агояаtischen Kohlemvasssrstcf ^f rust, a benzyl radical, a C _- -C.-alkoxy radical or hydroxyl group and dia η represents O or 1, in admixture with excipients and / or excipients. 2. Selective herbicidal compositions according to item 1, wherein R _{1 is} methyl, triethylmethyl, methylpropyl, n-hexyi, cyclopentyl, cyclohexyl, phenyl ^ methylphenyl _: tri-ethyl-ethylphenyl, methoxyphenyl , fluorophor / 1, chlorophenyl, dodphenyl, nitro-phenyl, benzyl or thienyl, Яр is hydrogen, methyl or phenyl, R _{7 is} hydrogen, methyl or hydroxyl, R 'is hydrogen, methyl, dinethylroethyl, tri.T. ethyline, hyl, phenyl, benzyl or hydroxyl and η represent 0 or 1, 3. Selective herbicidal compositions according to items I and 2, marked by зіпеп salary 3-phenyl-6,7-dihydro-4H-thia2: oloi2,3-c1 fl _f 2,4J | -trxazir, -4-one, 4-one and or 3 ~ Ca rbome t лохуяе thy 1-6,7-dihydro-4H - *: hiazoi о- £ 2,3-cJ fl, 2,4-triazine ~ 4-one «