FR2516516A1 - THIAZOLO- AND (1,3-THIAZOLO) (2,3-C) (TRIAZINE-1,2,4) -ONES, PROCESSES FOR PREPARING THEM AND HERBICIDAL PRODUCTS CONTAINING SUCH TRIAZINONES - Google Patents

Abstract

THE INVENTION RELATES TO SELECTIVE HERBICIDE PRODUCTS. THEY CONTAIN A THIAZOLO- OR 1,3-THIAZINO 2,3-C TRIAZINE-1,2,4-ONE OF FORMULA: (CF DRAWING IN BOPI) IN WHICH R, REPRESENTS A RADICAL ALKYL POSSIBLY INTERRUPTED BY O OR S, A AN ALKANE CARBOXYLIC ACID RADICAL OR AN ESTER OF SUCH AN ACID, A CYCLOALKYL RADICAL POSSIBLY ALKYL, AN AROMATIC OR AROMATIC-ALIPHATIC HYDROCARBON RADICAL POSSIBLY SUBSTITUTE OR A HYDROCARCLAMIC RADICAL RENTALLY ALKYL, AN AROMATIC OR AROMATIC-ALIPHATIC HYDROCARBON RADICAL POSSIBLY SUBSTITUTE OR A HYDROCARCLAMIC RADICAL RENTEROCYL, AND RENTEROCYL, RENTEROCYL OF OTHERS, HYDROGEN, AN ALKYL OR AN AROMATIC HYDROCARBON RADICAL POSSIBLY SUBSTITUTE, R AND R MAY ALSO REPRESENT A BENZYL OR A HYDROXY AND R WHICH MAY ALSO REPRESENT AN ALCOXY, AND N A IS EQUAL TO AO OR OR.

Description

Thiazolo and /, 3-thiazino / 2,3-c 7 / triazine-1,2,47-ones, methods for

  prepare them and herbicide products containing

such triazinones.

  The invention relates to thiazolo and / 1,3-thiazino / 2,3-c 7 / riazine-1,2, y-ones having a selective herbicidal action, as well as methods for preparing these compounds.

  Triazinones with herbicidal activity are already known

  Cide (patent BE 697 083, patent BE 799 854) Unhappy

  These compounds do not meet the requirements that good herbicides must act effectively against problem weeds and, at the same time, be well tolerated by several major crops.

which are in rotation.

  It was therefore necessary to develop a product that could be used against weeds that were difficult to control in several major crops without causing

damage to these.

  The present invention solves this technical problem by thiazolo and / 1, 3-thiazinyl-2,3-c-riazine-2,4-ones, which have the general formula: R N R 2 R 3 wherein

  R 1 represents a C 1 -C 6 alkyl radical, optionally

  1 or more times, with an oxygen or sulfur atom, an optionally esterified alkane-carboxylic acid radical, a C 3 -C 6 cycloalkyl radical, optionally carrying one or more alkyl radicals, a

  aromatic or aromatic hydrocarbon radical

  aliphatic, optionally carrying one or more substituents taken from the group consisting of C 1 -C 4 alkyls, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, halogens and the like;

  nitro group, or a heterohydrocarbon radical

  cyclic, R 2 represents hydrogen, an alkyl radical C 1 -C 6 or an optionally substituted aromatic hydrocarbon radical, R 3 represents hydrogen, an alkyl radical

  C 1 -C, an aromatic hydrocarbon radical which may be

  substituted, a benzyl radical or the hydroxy group, R 4 represents hydrogen, an alkyl radical

  C 1 -C, an aromatic hydrocarbon radical which may be

  benzyl radical, a C 1 -C 4 alkoxy radical or the hydroxy group, and

n is 0 or 1.

  The compounds according to the invention are excellently suitable for combating problem weeds, while being well tolerated, in particular, by soybeans, potatoes, cotton, maize and wheat, and in this respect they surpass the known products Thanks to

  these properties, they make a great technical progress

  than. For reasons of profitability, the most important plants from the point of view of the agricultural economy are more and more used in a close rotation with respect to each other. As a result, more or less specific flora are developed When there are among these (and this is almost always the case) weeds which, in the current state of the art

  of weed science, are difficult to combat, it appears

  conditions that easily lead to the predominance of

  species of this kind. We are trying to remedy this difficulty.

  for example by applying large doses of herbicides or even excessive doses The cultivated plant is often damaged As the known herbicides can also act, by their residues in the soil, on the following crop, it frequently happens It is also expected that a modern herbicide will have good efficacy against problem weeds and, at the same time, be well tolerated by several major plants that are The compounds in accordance with the invention fulfill these conditions and they are indicated by an extremely good tolerance with respect to the cultures mentioned above, while being able to be applied as well.

  well in pre-emergence than in post-emergence.

  The herbicidal action spreads over many species of weeds As problem weeds, which can thus be easily combated, we can mention Abutilon theophrastii, Ipomoea sp, Solanum sp, Viola sp, Echinochloa crus galli, Setaria

sp and Digitaria sp.

  The application can be made by incorporation into the soil before sowing the cultivated plant, or

pre-emergence or post-emergence.

  For a selective fight, the doses are included

  between about 0.1 and 5 kg of active ingredient per hectare.

  At higher doses, the compounds can also be used to completely destroy the adventitious flora. At lower doses, the compounds according to the invention can also modify the natural development of the plants, which makes it possible to produce different

  properties of interest to the farmer or horticulturist.

  It goes without saying that the effects obtained may vary from

  posed to another, from one type of plant to another and equally

  depending on the mode of application, the timing of the

  cation and dose In general, the control of the natural development of the plant is reflected visually by

251651-6

  changes in the size, shape, color or morpholgy of the treated plant or parts thereof The compounds according to the invention may cause for example the following developmental changes: - inhibition of vertical growth, inhibition of root development, more pronounced brightening of the shade of vegetable dyes,

defoliation.

  Among the compounds in accordance with the invention, some are particularly notable in the field of the described properties: they are in particular those in formula I of which R 1 represents a C 1 -C 6 alkyl radical, for example a radical methyl, trimethylmethyl, ethyl, propyl, isopropyl, 1-methylpropyl, n-butyl, isobutyl, tert-butyl, 2,2-dimethylpropyl, n-pentyl or n-hexyl; a methyl acetate radical; a C 3 -C 8 cycloalkyl radical carrying an alkyl, for example a

  cyclopropyl, cyclopentyl, cyclohexyl, methyl-

  cyclohexyl or cyclooctyl; an aromatic hydrocarbon radical

  optionally substituted, e.g. phenyl, tert-butyl-4-phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 4-fluoro-phenyl, 4-iodophenyl , 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 3-nitro-phenyl, 4-nitro-phenyl, 1-naphthyl or 2-naphthyl; an aromatic-aliphatic hydrocarbon radical, for example

  a benzyl or 4-chlorobenzyl radical; a hydro-radical

  heterocyclic carbon, for example a thienyl or furyl-2 radical; R 2, R 3 and / or R 4 each represent hydrogen, a C 1 -C 6 alkyl, for example a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or dimethyl-2 radical; Propyl, n-pentyl or n-hexyl, an optionally substituted aromatic hydrocarbon radical, for example a phenyl radical, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 4-fluoro-phenyl, 3-chlorophenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 3-nitro-phenyl or 4-nitro-phenyl, and R 3 and / or R 4 may further represent a C 1-4 alkoxy C 4, for example a methoxy, ethoxy, propoxy or n-butoxy radical, or the hydroxyl group, and N is equal to

at O or 1.

  An excellent activity is manifested by those of these compounds in which: R 1 represents a methyl radical, trimethylmethyl,

  m-thylpropyl, n-hexyl, cyclopentyl, cyclohexyl,

  hexyl, phenyl, methylphenyl, tert-butyl-phenyl, methoxyphenyl, fluorophenyl, iodophenyl, chlorophenyl, nitrophenyl, benzyl or thienyl, R 2 represents hydrogen or a methyl or phenyl radical, R 3 R 3 represents hydrogen or a radical methyl or hydroxy, R 4 represents hydrogen or a methyl radical dimethylmethyl (isopropyl), trimethylmithyl (tert-butyl), phenyl, benzyl or hydroxy, and

n is equal to O or a 1.

  The compounds in accordance with the invention may be used alone, as a mixture with one another or as a mixture with

other active ingredients.

  This is how we can associate them, according to

  purpose pursued, eg the herbicidal substances

  which may be added only just prior to the application of the compounds according to the invention substituted anilides of substituted anilines of substituted aryloxycarboxylic acids, and their salts, esters and amides substituted ethers of substituted arsonic acids, as well as their salts, their esters and their amides, substituted benzimidazoies, substituted benzothiazionines substituted benzoxazines substituted benzoxazinones substituted biurets substituted quinolines substituted carbamates substituted aliphatic carboxylic acids, as well as their salts, esters and their amides, substituted N-arylsulfonyl-N'-triazinylureas, substituted aromatic carboxylic acids, and their salts, esters and amides, substituted carbamoylalkyl thiol or dithiophosphates, substituted quinazolines, substituted cycloalkylaminocarbothiolic acids,as well as their salts, esters and amides, substituted cycloalkylcarbonylamino-thiazoles of substituted dicarboxylic acids, as well as their salts, esters and amides, substituted dihydrobenzofuranylsulfonates, substituted disulfides, substituted dipyridylium salts, dithiocarbamates substituted, substituted dithiophosphoric acids, and their salts, esters and amides, substituted ureas, substituted hexahydro-1H-carbothioates, substituted hydantoins substituted hydrazides substituted hydrazonium salts substituted isoxazolepyrimidones substituted imidazoles isothiazole substituted pyrimidones substituted ketones substituted nathtoquinones substituted aliphatic nitriles substituted aromatic nitriles substituted oxadiazoles, substituted oxadiazinone, substituted oxadiazolidinedione substituted oxadiazine substituted diones substituted phenols s, and their salts and esters, substituted phosphoric acids and their salts, esters and amides, substituted phosphonium chlorides substituted phospho-alkyl-glycines substituted phosphites substituted phosphoric substituted acids, and salts thereof, their esters and their amides, substituted piperidines, substituted pyrazoles, substituted pyrazole-alkylcarboxylic acids, as well as their salts, esters and amides, substituted pyrazolone salts of substituted pyrazolium alkylsulfates, substituted pyridazines, substituted pyridazones substituted pyridinecarboxylic acids, as well as their salts, esters and amides, substituted pyridines of substituted pyridine carboxylates, substituted pyridinones, substituted pyrimidines, substituted pyrimidones, substituted pyrrolidinecarboxylic acids and their salts, their esters and their amides, pyrrolidi Substituted, substituted pyrrolidones, substituted arenesulfonic acids, and their salts, esters and amides, substituted styrenes, substituted tetrahydrooxadiazine diones substituted tetrahydrooxadiazole diones substituted tetrahydro-methano-indenes tetrahydro substituted diazole thiones, substituted tetrahydro-thiadiazinethiones, substituted tetrahydro-thiadiazole-diones, substituted thiadiazoles, substituted aromatic thiocarboxamides of substituted thiocarboxylic acids and their salts, esters and amides, substituted thiolcarbamates, thioureas substituted, substituted thiophosphoric acids, as well as their salts, esters and amides, substituted triazines, substituted triazoles, substituted uracils, and

substituted uretin-diones.

  Other substances may be used, for example non-phytotoxic additives which, in the case of herbicides, cause a synergistic increase in activity. These substances are especially wetting agents,

  emulsifiers, solvents and oily additives.

  It is good to apply the active ingredients according to the invention, or mixtures thereof, in the form

  compositions, such as powders, bleaching agents,

  granules, solutions, emulsions or suspensions, containing liquid and / or solid carriers or diluents and possibly wetting agents,

  adhesives, emulsifiers and / or dispersants.

  Suitable liquid carriers are, for example, water, aliphatic or aromatic hydrocarbons,

  such as benzene, toluene, xylenes, cyclo-

  hexanone, isophorone, dimethylsulfoxide, dimethyl-

  formamide, as well as mineral oil fractions.

  The solid supports will be mineral soils, such as Ton Sil, silica gel, talc, kaolin, attapulgite, limestone and silica,

  or plant products, such as flours.

  As surfactants, for example, the

  lignin-calcium sulphonate, poly-

  ethoxylation of alkylphenols, naphthalene

  sulphonic acids and their salts, phenol-sulphonic acids and their salts, condensation products of formaldehyde, sulphates of fatty alcohols, as well as

  substituted benzenesulphonic compounds and their salts.

  The proportion of the active ingredient (s) in the various formulations may vary over extended intervals. Thus the products may contain, for example, from approximately 5 to 95% by weight of active ingredients, from approximately 95 to 5% by weight. liquid or solid carrier weight and, optionally, up to 20% by weight of surfactifso Spreading of the products can be done in the usual manner, for example using: Reading water as a support, under the influence slurries, which are sprayed at doses of about 100 to 5000 liters per hectare It is also possible to apply the products by the so-called "low volume" process and by the so-called "low volume" process.

  "at very low volume", as well as in the form of micro-

  granules. For the preparation of the compositions, the following constituents may for example be used: A wettable powders a) 80% by weight of active ingredient% by weight of kaolin, and% by weight of surfactants based on the sodium salt of N-x-ethyl-N- oleyl-taurine and calcium salt of lignin-sulfonic acid b) 50% by weight of active ingredient% by weight of clay minerals% by weight of pitch from the treatment of cellulose, and% by weight of surfactants based on 'a

  mixture of the calcium salt of lignin

  sulphonic and polyethoxylated products

  alkylphenols; c) 20% by weight of active ingredient% by weight of clay minerals% by weight of cellulosic pitch, and% by weight of surfactants based on a mixture of the calcium salt of lignin-sulfonic acid and polyethoxylation products alkylphenols; d) 5% by weight of active ingredient% by weight of Tonsil 10% by weight of cellulosic pitch, and% by weight of surfactants based on a product

condensation of fatty acids.

  B Emulsifiable concentrate% by weight of active ingredient 40% by weight of xylene% by weight of dimethylsulfoxide, and% by weight of a mixture of a product of poly-

  ethoxylation of nonylphenol and dodecyl-

calcium benzene sulfonate.

  In order to prepare the novel compounds which are the subject of the present invention, it is possible for example: a) to react compounds of general formula:

R N

II

  o 7 SH with compounds of general formula III R -CH-Hal

(R 3 H)

  R 2-C n H-Hal R CH-H-al or with compounds of general formula IV R 4 C = O l (R 3 _CH) n IV /.H Hal R 2 or with compounds of general formula V R 4

3 RC V

  Halogen R 2 in the presence of bases, and, if desired, separating the isomers by column chromatography, or b) reacting compounds of the general formula VI R 1 -C VI with compounds of the general formula VII

H 2 NX

HN

N / A VII

N S

R 4 N

  or c) reacting compounds of general formula VI X Ca

1 CVI

this

RO O

Z 516516

  with thiosemicarbazide, which corresponds to formula VII

H 2 N NH CS NH 2

  VII reaction which leads to compounds of general formula VIII ## STR2 ##

RO O

  VIII and then react these, in the presence of bases, with compounds of general formula III R 4 CH Hal (R 3 H) n R 2 Hal III or with compounds of general formula IV R 4 4

R 4 C = O

  (R 3 CH) n / CH Hal R 2 IV so as to obtain compounds of general formula IX ## STR2 ##

(CH R)

  3 n compounds that are converted, by cyclization in the presence of basic catalysts, the compounds sought IX

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  in the general formula I, or d) in the case where R 9 is a C 1 -C 5 alkane-carboxylic acid radical or an ester radical of such an acid, reacting the acetyl dicarboxylic acid or one of its esters; answering the, formula General X

ROOC 1 C C -C OOR

  with compounds of formula (II) the general genomic reaction which gives rise to cnos of formula xi COOR

HN N = C

N ICF, COOR

N S X

  Rp and convert these by cyclization in the presence of bases, compounds of general formula XII XII '

16516

  that isomerized in order to obtain the desired compounds corresponding to the general formula I. In the various formulas contained in the preceding paragraph, the symbols R 1, R 2, R 3, R 4 and N have the meanings which have been data above and R represents hydrogen or a C 1 -C alkyl. The starting materials used for the preparation of the compounds according to the invention are known or can

  be prepared by known methods.

  The reaction of the reaction partners is

  between 0 and 1200 C, but usually between

  ambient temperature and the reflux temperature of the mixture

corresponding reaction.

  The reaction time is from 1 to 72 hours.

  To synthesize compounds according to the invention, the reaction partners are used in

  approximately equimolar amounts.

  the appropriate solvents include solvents

  inert to the bodies that take part in the reaction.

  The choice of solvents or suspension media depends on the starting materials involved and acid acceptors.

  or bases used as solvents and media of

  For example, ethers such as diethyl ether, di-isopropyl

  tetrahydrofuran and dioxane, aliphatic hydrocarbons

  or aromatic, such as petroleum ether, cyclohexane, hexane, heptane, benzene, toluene and xylenes, carbonitriles, such as acetonitrile,

  and carboxamides, such as dimethylformamide.

  Acid acceptors can be bases

  organic compounds, such as triethylamine, N, N-dimethyl-

  aniline and pyridine bases, or inorganic bases, such as oxides, hydroxides and carbonates of alkaline earth metals or alkali metals. Bases which are liquid, such as pyridine, may be

at the same time serve as solvents.

  The compounds according to the invention which have been prepared by the methods described above can be

  isolated from the reaction mixture by usual methods.

  For example, it is possible to distill off, under normal pressure or under reduced pressure, the solvent

  in play, or precipitate the compounds with water.

  The compounds according to the invention are generally in the form of crystalline products, colorless and odorless, which are sparingly soluble in water and in aliphatic hydrocarbons, and moderately soluble to very soluble in halogenated hydrocarbons, such as chloroform. and carbon tetrachloride, ketones,

  such as acetone, carboxamides, such as dimethyl

  formamide, sulfoxides, such as dimethylsulfoxide, carbonitriles, such as acetonitrile, and alcohols

  such as methanol and ethanol.

  As a solvent for recrystallization it is recommended to use in particular carbon tetrachloride, chloroform, toluene, acetonitrile or

ethyl acetate.

  The following examples illustrate the preparation

  compounds according to the invention.

EXAMPLE 1

  302 g (3.6 moles) of sodium hydrogencarbonate and 137.5 g (0.72 moles) of dibromoethane are introduced into 700 ml.

  of propanol-2 and the suspension obtained is heated to reflux.

  To this boiling mixture is added dropwise a mixture

  consisting of 61 g (0.36 mol) of 3-mercapto (4-methylphenyl).

  6-dihydro-4,5-triazine-1,2,4-one-5, 146 ml of a 10% caustic soda lye and 1500 ml of 60% aqueous propan-2-ol are then heated to reflux temperature.

  for 2 hours, filtered to remove hydrogen carbonate

  undissolved sodium nate and the filtrate is concentrated to dryness under reduced pressure The solid residue obtained is washed with 500 ml of a 5% solution of sodium chloride and is again separated by filtration The product retained by the filter is chromatographed on a column of silica gel with ethyl acetate as eluent. 28.8 g (32% of the theoretical amount) are obtained.

  (4-methyl-phenyl) -3,6-dihydro-4H-thiazolo / 2,3-c-7-riazine

1,2, s-one-4, which melts at 193 C.

EXAMPLE 2

  Under the conditions described in Example 1, 480 g (0.21 mol) of 3-mercapto-4- (4-methoxyphenyl) -5,5-dihydro-1,2,4-triazin-5 and 100 g are reacted. (0.5 moles) 1,3-dibromopropane After separation by chromatography, 7.7 g (14% of the amount obtained) are obtained.

  theoretical) of (4-methoxyphenyl) -3,6,7,8-tetrahydro-4H-

  / 1,3-thiazino / L 2,3-c / riazine-1,2, i-one-4, which melts at

181 C.

EXAMPLE 3

  18.5 g (0.1 mole) of 3-mercapto-6-trimethylmethyl-4,5-dihydro-1,2,4-triazin-5,432 g (0.2 mole) of 2,3-dibromobutane are dissolved. and 258 g (0.2 mole) of ethyl diisopropyl amine in 200 ml of acetonitrile, and

  heated at reflux temperature for 48 hours.

  The mixture is poured into ice water, the precipitate that has formed is filtered off and subjected to chromatography on silica gel using ethyl acetate as eluent. 1 g (34% of the theoretical amount) of trimethylmethyl-3

  dihydro-6,7-dimethyl-6,7 4 H-thiazolo / 2,3-c-7-riazine-1,2,47-

one-5, which melts at 134 C.

EXAMPLE 4

  1 9.8 g (0.1 mol) of 2-hydrazino-4,5-dihydro-thiazole hydrobromide are dissolved in 200 ml of ethanol, 20 ml of an aqueous solution of

  % sodium hydroxide and 23.4 g (0.1 mole) of

  ethyl (4-ethyl-4-phenyl) -glyoxylate, heated for 4 hours at reflux temperature, poured into ice-cold water, the precipitate which

  was formed and recrystallized from ethyl acetate.

  18.5 g (65% of the theoretical amount) of 3- (4-trimethylmethylphenyl) -6,7-dihydro-4H-thiazolo / 2,3-c 7 / 1,2,4-triazine / -one are obtained. -4, melting c 2030 C.

EXAMPLE 5

  Operating as in Example 3, 19.6 g (0.1 mole) of 2 -hydrazino-thiazole hydrobromide and 16.4 g (0.1 mole) of methyl phenylglyoxyate are reacted. 9.8 g are obtained. (43% of the theoretical amount) of 3,4-Dhenyl-thiazolo / 2,3-c- / Ftriazine-1,2,47-o-ne-4, which melts at 1810 C.

EXEIMPLE 6

  By operating as in Example 3, reacting

  12.9 g <0.1 mole) of 2-hydrazino-2,4,5,6-tetrahydro-2H-

  1,3-thiazine and 16.4 g (0.1-mole) of methyl phenylglyoxylate are obtained 18.4 g (75% of the theoretical amount) of 3-phenyl-4-tetrahydro-6,7,8 72-7 Ztriazine-2,47-oxy-4, which melts at 15500 C.

EXAMPLE

  Stir at 600% -1 for 3 hours, 20.5 g

  (0.1 mole) of 3-rhepto-6-phenyl-4,5-dihydro-4,5-triazine

  1,2,4-one-5, 18.4 g (0.2 mol) of water and 80% of a 10% aqueous solution of sodium hydroxide in 250 ml of ethanol is acidified with water. diluted hydrochloric acid and the reaction solution is cooled. The precipitate which has formed is filtered off and chromatographed on a column of silica gel with a mixture of acetone and acetone as eluent. Petroleum ether with equal parts 5 (1) (21% of the theoretical amount) of phenyl-3-methyl-4H-thiazolo [2,3-t] -7-rane are obtained.

1,2,47-one-4, which melts at 1580 C '.

EXAMPLE 8

  Operating as in Example 7, 20.5 g (0.1 mole) of mercapt-o-3-dihydro-475 is reacted.

  1,2,4-triazine one-5 with 39.8 ± 0.2 mol) of bromo-methacrylate;

  phenone After separation by column chromatography, 4.58 g (15% of the amount of the theocaine) of diphenyl-3,6 4 H-thi-azolo / 2-, 3c 7 / triazine-1,2,47 are obtained. one-4, which melts at 1250 C.

EXAMPLE 9

  20.4 g (0.1 mole) of 3-mercapto-6-phenyl-4,5-dihydro-triazine-1,2,4-one-5 are dissolved in a mixture of 100 ml of dioxane and 100 ml of dimethylformamide, 20 ml of a 50% solution of chloroacetaldehyde and stirred for 6 hours at 60 ° C. The reaction mixture is introduced into ice water, separated by

  filtration the precipitate which has formed and

  tography on a column, using as eluent a

  9: 1 mixture of ethyl acetate and methanol.

  3.7 g (amount corresponding to a yield of 15%) of phenyl-3-hydroxy-6-dihydro-6,7 4 H-thiazolo

  / 2,3-c 7 / triazine-1,2,4 / -one-4, which melts at 213 C.

EXAMPLE 10

  15 g (0.073 mol) of 3-mercapto-6-phenyl-4,5-dihydro-triazine1,2,4-one-5 is dissolved in 800 ml of acetonitrile in hot water, 13.5 g (0.15 mol) are added.

  of epichlorohydrin and 14.85 g (0.115 mole) of ethyl diiso-

  propylamine and reacted for 16 hours at 60 ° C.

  The reaction mixture is concentrated under reduced pressure and the residue is subjected to chromatography on a column of silica gel, the eluent used being a 9: 1 mixture of ethyl acetate and ethanol. 6 g (19% of theory) of 3-phenyl-7-hydroxy

  Tetrahydro-4,6,7,8 / Li, 3-thiazino [2,3-c] -triazine-1,2,47-

one-4, which melts at 181 C.

EXAMPLE 11

  15 g (0.1 mol) of phenylglyoxylic acid are dissolved

  In a 1 liter solution of ethanol, a solution of 9.1 g (0.1 mol) of thiosemicarbazide in 500 ml of 5% aqueous acetic acid is added to the resulting solution and this reaction solution is stirred for 15 minutes at 900. C After

  After cooling down, half of the solvent is removed under reduced pressure, the precipitate formed is filtered off,

  washed with water and dried at 50 ° C. Without further purification, the thiosemicarbazone obtained is dissolved in 120 ml of a 5% solution of sodium carbonate, 9.2 g (0.1 mole) of chloroacetone in ml of ethanol and stirred for 2 hours at 60 ° C. It is cooled, acidified with% hydrochloric acid and the precipitate which has formed is filtered off. The latter is dissolved in 200 ml of a mixture of pyridine and acetic anhydride at a ratio of 1: 1 and stirred for 3 hours at 60 ° C. The reaction mixture is poured into 500 ml of ice water, the precipitate which has formed is filtered off, washed with water and recrystallized from ethyl acetate. 12.9 g (53% of the theoretical amount) of 3-phenyl-6-methyl are collected.

  4H-thiazolo / 2,3-c 7 / triazine-1,2,47-one-4, which melts at 158 C.

  By operating as described in the examples and using the appropriate starting bodies, one can

  prepare the compounds listed in the following table.

Name of the compound Physical constant

  trimethyl-3-methyl-6,7-dihydro-4H-

  thiazolo / 2,3-c // triazine-1,2,47-one-4

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

  thiazolo / 2,3-c // triazine-1,2,47-one-4

  (4-chloro-phenyl) -6,7-dihydro-4 H-

  thiazolo / 2,3-c // triazine-11,2,47-one-4-benzyl-3-dihydro-6,7 4 -thiazolo [2,3-c] -triazine-1,2,47-one-4-cyclohexyl 3-dihydro-6,7 4 Hthiazolo / 2,3-c // triazine-1,2,47-one-4-thienyl-3-dihydro-6,7-thiazolof 2,3 c 7 / / 1,2-triazine 47-one-4

F = 122 C

F = 188 C

Mp 184

F = 135C

F = 178C

Mp = 203 ° C

  (4-fluorophenyl) -3,6,7,8-tetrahydro-4H-

  / 1,3-thiazino / 2,3-Z-1,2,4-triazine / -one-4

  (4-nitro-phenyl) -3,6,7,8-tetrahydro-4H-

  F1, 3-thiazin 2 // 2,3-cl / triazine-1,2,4 / -one-4

  cyclopentyl-3-tetrahydro-4,6,7,8 4 H-

  1H-, 3-thiazino-2,3-c-triazine-1,2,47-one-4

  trimethyl-3-methyl-4,6,7,8-tetrahydro-4H-

* / 1,3-thiazino 2,3-c / triazine-1,2,4 -one-4-hexyl-3-tetrahydro-4,6,7,8 4 H -, / 1,3-thiazino / 2 , 3-c // triazine-1,2,4 -one-4 (iodo-4-phenyl) -3-dihydro-6,7 4 H-thiazolo F 2,3-c-, t-riazine-1, 12,47-one-4-cyclopentyl-3-dihydro-6,7 4 H -thiazolo F 2,3 - / - triazine-1, 2,17-7-one-4 (2-methyl-propyl) -3-dihydro-6 , 7 4H-thiazolo / -2,3-di- / Ftriazine-1,2,47-one-4

  trimethylmethyl-3H-thiazolo / 2,3- (7-

  1,2-triazine-1-fluoro-4-fluoro-phenyl-3 H-thiazolo / 2,3-2-triazine-1,2,4 -one-4

  (2-Methylphenyl) -3H-thiazolo /, 3-6 / -

  1,2,4-triazine-4-phenyl-3-phenyl-6-methyl-6,7-dihydro-4H-thiazolo F 2,3 / triazine-1,2,47-one-4

P = 203 ° C

Mp = 2360 ° C

F = 1830 C

F = 1480 C

F = 1210 C

F = 215 ° C

F = 171 ° C

F = 154 ° C

F = & 1510 C

F = 1810 C

F = 1500 C

Mp = 1140 ° C

2516 16

  3-phenyl-6-dimethyl-6,7-dihydro-4H-thiazolo [2,3-f] triazin-1,2,4-4-one-4-phenyl-3-trimethyl-6-ethyl-dihydro-6,7 4 H-thiazolo] 2,3c / 1,2,4-Ztriazine / -one-4-phenyl-6-benzyl-6,7-dihydro-4H-thiazolo-3,7-dihydri-dihydro-6,7 4H-thiazolo F 2,3 1-Trimidine-2,4-benzen-4-phenyl-3-methyl-4,6,7,8-tetrahydro-4H-1,3-triazino [1,2,3-triazin-1]; 4

  cyclohexyl-3 H-thiazolo F 2,3-c 7 it-riazine

  1, 2 4 -one-4-trimethyl-3-methyl-6-methyl-411-thiazolo [2,3-c] -triazine-1,2,4-triton-4-trimethyl-3-methyl-6-diethyl-6,7 411 thiazolo / 2,3c-triazoline-1,2,4 -one-4-ethyl-3-dihydro-6,7 411-thiazolo / 1-,3-c / 2,4-triazin-1,2,4 -one-4 3-isopropyl-6,7-dihydro-4-thiazolo [4,3-c] -triazine-3,2,4 -one-4 (dihydro-6,7-oxo-4H-thiazol) -2,3- 7 / Ftriazine 1,2,3,4-triol-4-yl) -carboxylic acid (6,6-dihydroxy-4-oxo-2,4,4-triazin-1-yl); propionate of - thvie

Mp = 132 ° C

F = 130 ° C

FI = 115 C

Mp = 1240 ° C

  r = 1380 C = 1250 C = 280 C

2 = 1120 C

F = loooc

F = 700 C

F = 1050 C

r = lionc

16516

  3-phenyl-6-ethyl-6,7-dihydro-4-thiazolo [2,3-c]] 1,2,4-trifluoro-4,7-diphenyl-7,7-dihydro-7,4-thiazolo-2 1,2,47-Tri-phenyl-3-phenyl-6,7-dimethyl-6,4-thiazolo [2,3-c] -triazine-1,2,4,4-e-4-fluoro-4 phenyl-3-dihydro-6,7 4 H-thiazolo [2,3-c]] -triazine-1,2,4 -one-4

  (2,4-dichlorophenyl) -3,7-dihydro-4H-

  thiazolo Z 2,3-c / triazine-1,2,47-onie-4 (2,4-dichlorophenyl) -3Hthiazolo [2,3-c] -Ztriazine-1,2,47 -one-4 ( 2,4-dichlorophenyl) -3-methyl-6,7-dihydro-4H-thiazolo [2-,3-c] -7,7-triazine-1,2,47 -one 4

  (5-chloro-2-thienyl) -6,7-dihydro-4 H-

  thiazol / 2,3-c / Ltriazine-1, 2,47 / -one-4 (2,5-dichloro-3-thienyl) -3,7-dihydro-4H-thiazolo [2,3-c] riazine-1,2,47 / -one-4

M = 1790C

M = 1700 C

F = 155 ° C

F 1890 c

Mp = 2420 ° C

F = 1810 C

F = 1560 ° C

F = 19500

M = 1760C

  The preparation of others is described below.

  already known compounds which can be used according to

to the invention.

EXAMPLE 12

  302 g (3.6 moles) of hydrogen are introduced.

  sodium carbonate and 137.5 g (0.72 moles) of dibromoethane in 700 ml of propanol-2 and the suspension is heated

  At this boiling mixture, the reaction mixture is added dropwise.

  dropwise a mixture consisting of 73.8 g (0.36 mol) of 3-mercapto-phenyl-4,5-dihydro-1,2,4-triazin-one, 146 ml of a 10% solution of hydroxide sodium hydroxide and 1500 ml of 60% aqueous propan-2-ol. After heating at reflux temperature for 2 hours, undissolved sodium hydrogencarbonate was filtered off and the filtrate was concentrated to dryness under reduced pressure. solid residue obtained with 500 ml of a

  5% sodium hydroxide solution and filtered again.

  The product retained by the filter is subjected to a chroma-

  Silica gel column chromatography with ethyl acetate as eluent. 28.8 g (34% of the theoretical amount) of 3-phenyl-6,7-dihydro were collected.

  4H-thiazolo / 2,3-c 7 -triazine-1,2,47 / -one-4, which melts at 135 C.

EXAMPLE 13

  By operating as in Example 8, 14.3 g (0.1 mol) of 3-mercapto-6-methyl-4,5-dihydro-1,2,4-triazin-1-one-5 are reacted, and thus 7, 4 g (44%)

  of the theoretical amount) of 3-methyl-6,7-dihydro-4H-

  thiazolo / 2,3-c 7 / triazine-1,2,47-one-4, which melts at 171 C.

EXAMPLE 14

  19.8 g (0.1 mole) of hydrazino-2-dihydro-4,5-thiazole hydrobromide are dissolved in 200 ml of ethanol, 80 ml of an aqueous solution of sodium hydroxide are added successively and 10.2 g (0.1 mole) of methyl pyruvate are boiled once, then cooled. The precipitate which has

  formed and recrystallized from ethyl acetate.

  11.0 g (65% of the theoretical amount) is collected

  3-methyl-6,7-dihydro-4H-thiazolo [2,3,4-tri] -1,2,4-triazine]

one-4, which melts at 171 C.

EXAMPLE 15

  By operating as in Example 10, 16.4 g (0.1 mol) of methyl phenylglyoxylate are reacted with 19.8 g (0.1 mol) of hydrazino-2-dihydro-4,5-thiazole hydrobromide and 13.2 g (yield: 57%) of 3-phenyl-6,7-dihydro-4H-thiazolo [2,3-c] -triazine-1,2,4 -one-4 are obtained.

which melts at 135 C.

EXAMPLE 16

  40 g (0.2 mol) of hydrobromide are dissolved

  of 2-hydrazino-4,5-dihydro-thiazole in 500 ml of a solution of

  2% sodium hydroxide solution, the resulting solution is cooled to 5 ° C., 28 g (0.2 mol) of methyl acetylene dicarboxylate are added dropwise and the mixture is stirred for 2 hours at 25.degree. The precipitate which formed is filtered off, dissolved in 250 ml of methanol, 25 ml of triethylamine are added and the mixture is stirred for one hour at 25 ° C. The precipitate formed is filtered off again. and this time it is boiled under reflux in 500 ml of methanol for one hour. After that, the solvent is removed under reduced pressure and the product which remains is recrystallized from ethyl acetate.

  24.1 g (53% of the theoretical amount) of methoxycarbonyl-

  3-methyl-6,7-dihydro-4H-thiazolo L 2,3-c // 1,2,4-triazine / -one-4,

which melts at 123 C.

  The following examples of execution illustrate the possibilities

  applications of the compounds according to the invention, which are used here in the form of the compositions

which have been described above.

EXAMPLE 17

  In the greenhouse, spray is applied, pre-

  raised and post-levee, the compounds according to the invention which are quoted in the table below, at a dose of kg of active ingredient per hectare, dissolved in 500 liters of water per hectare, on Sinapis, Solanum and Setaria, which serve as test plants. Three weeks after treatment, the results of the treatment are evaluated on a scale in which: O = no action and

4 destruction of plants.

  As we see on the board we reach

  usually a destruction of the test plants.

165 16

  Compound Con P r e l v e e P o S t 1 e form to the invention Se if So 2 e if SO phenyl -3 tetra 4 -1 4 4 4 11, hydro-4,6,7,8

4H- / 1,3-thiazide

No. 7 T 2-, 3 c_ / -

/ Triazine-1,2,4 / -

  one-4 3-di-thienyl dihydro 4 4 4 1 4 6.7 4 li-thiazolo

/ 2,3c 7 / riazine-

  1,2, 1 -one-4-phenyl-3-methyl-4 4 4 4 4

dihydro-6,7 4 H-

  thiazollo F 2,3-c / 1-riazi ne-1,2,47 one-4 (4-chloro-4 4 4 4

nyli'-3 dihydro-

6 7 4 H-thiazolo

9

/ 2,3 c // triazine-

1,2,4 -one-4-methoxycarbonyl 4

methyl-3 dihydro-

6.7 4 H-thiazolo

Z 2,3-c triazine-

  1,2,4-7-one-4-thienyl-4-dihydrate

dro-6.7 4 H-thia-

  zolol 7, -3 = c / rice one-4 (3-methyl-phenyl) 4 4 4 4 4 to 1 l

-11 dihydro-6,7 -

4H-thiazolo / 2,3-c /

/ triazine-1 2,47-

one-4

16516

Compound

  form to the invention P r e le v ee Se si So P os t l e vee Se si SO

<1-methylcyclo

hexyl) -3 dihydro-6,7 4 H-thiazolo

/ 2, 3 C / riazine-

1,2,4 / -one-4

4 4 4

4 4 4

  (2,4-dichlorophenyl) -3 H-thiazolo / 2,3-

/ Triazine-1,2,4 / -

one-4

4 4 4

cyclohexy 11-3 4H-

thiazolo / 2,3-c / _

/ Triazine-1,2,4 / -

  one-4-trimethyl-methyl-6-methyl-6,7-dihydro-2-thiazolo / 2,3 c / _

/ Triazine-1,2,4 / -

one-4

isopropyl-3 dihydro-

6.7 4 H-thiazolo

L 2,3-c / Ltriazine

1,2,4 / -one 4

3-phenyl dimethyl

6.7 4 H-thiazolo

L 2,3-cq // triazine

1,2,4 -one-4 (4-fluorophenyl) -3

dihydro-6,7 4 H-

thiazo 1 o L 2, 3-_cl_

Ztriazine 1,2,4 / -

one-4

(2,4-dichlorophenyl)

  nyl) -3 dihydro-6,7 4 H-thiazolo / 2,3-c /

/ Triazine-I, 2.4 / -

one-4

4 4 4

4 4 4

4 4 4

4 4 4

4 4 4

4 4 4

4 4 4

4 4 4

4 4 4

4 4 4

4 4 4

4 4 4

4 4

'16516

Compound

  Form to the Invention If Se (2-Dichlorophenyl) -3-methyl-6

dihydro-6-7 4 H-

thiazolo / i, 37-c /

/ 1,2-triazine, 47-

one-4

(5-chloro thienyl -

  2) -3-dihydro-6,7-4H-thiazolo / -: i, 3-c /

/ Triazine-1,2,4 / -

one-4

4 4 4

4 4 4

4 4 4

4 4 4

  1- (2,5-Dichloro-3-thienyl-3-yl) dihydro-6,7 4 H-thiazolo [2,3-c] triazin-1,2,47-one

4 4

4 4 4

  trimethylmethyl-3-tetrahydro-4,6,7,8 4 H- / 1,3-thiazino 7

/ 2,3-c // triazine

1,2,47-one-4 cyclopentyl-3

dihydro-6 -7 4 H-

thiazolol / 1, 3 Zc /

/ Triazine-1,2,47-

one-4 trimethylmethyl-3

dihydro-6,7 4 H-

thiazolo / 2,3: 7 c /

Ft.riaziné-1, 2, 47-

one-4 cyclohexyl-3

dihydro-6,7 4 H-

thiazolo / 2,3-c /

/ triazine-1,2 li 7 / -

one-4

4 4 4

4 4 4

4 4 4

4 4 4

4 4 4

4 4 4

4 4 -4

4 4 4

Compound

form to the invention

P re -

  1st grade If So Post 1st grade Se Si So

thienyl-3 dihydro-

6.7 4 H-thiazolo

/ 2,3-c // triazine

  1,2,4-tri-4-trimethylmethyl-4H-thiazolo / 2,3-c /

Ztriazine-1, 2,4 / -

one-4 (2-methylpropyl) -3

dihydro-6,7 4 H-thia-

zolo / 2,3-c // triazine

1,2,4 / -one-4

4 4 4

4 4 4

4 4 4

4 4 4

4 4 4

4 4 4

No treatment

0 O

o O

0 O O

EXAMPLE 18

  The plants mentioned in the table are treated in a greenhouse and treated, before emergence, with a dose of 0.3 or 1 kg / ha of one of the compounds mentioned. For this purpose, the compounds in question are applied regularly. on the soil in the form of an aqueous solution (or suspension) with 500 liters of water per hectare The results show that the compounds according to the invention have, with respect to the comparison compound, a better tolerance.

and a better activity.

A, k "-; *

4-) O

  hereinafter 4) O 'Q O O O (C) W N 4F, O' Q O <F-4cn>; 4 ucn Corrpos according to the invention

1 1 O 1 O 1 O 1 O -

1 1 O 1 O 1 O 1 O -

0 O 00 O

O O 00 O

0 O 0 O

3-phenyl dihydro-

6.7 H-tliiazolo

/ 2,3 = 2H -tiazine-

1,2,4 / -one-4

3-phenyltetrahydro-

dro-4,6,7,8 4 H-

  2 I, 3 thi a z i n U, - / 2,3-c // triazine f, 2, j A-4

  0, 3 1 O 1 O 1 O 1 O 1 O1 O 1 OOO O O O

0 O ph (nyl-, 3 methyl 3

Dihyāro-6.7 4 H-

thiazolo / 2,3-c / -

* F-triazine-1,2,4 / -

one-4

0, 3 1 O 1 O 1 O

O O O O O

O trimethyl-L-hylamide 5- hyl-3

dihidro-6.7 41 i-

a '7

thi'zolo / ', 37 - / -

/ 1,2,41 triazine / -

  one-4 rla LU has a ,. tn 0% Comparison Agent cd rnP, tn 4 j

0 O Q 04 O

U) P 4 <F 4 M

  ## STR2 ## Compound according to the invention trirdethyl-3-methyl-6-methyl-6-dihydro-7H-thiazolo / 2,3-c 7 / triazine1,2, j 7 one-4

0.3 1 O 1 O 1 O

O O

0 O O O O

  w Amino-4-phenyl-4-dihydro-4,5-methyl-3-triazine-1,2,4-one-5 (patent BE 799 854)

1 8 O 7 8

7

0 O 8 1 O 7

0% Ln 0% Ln 0%

EXAMPLE 19

  The plants mentioned, after emergence, are treated with the compounds mentioned at a dose of 0.3 or 1 kg of active ingredient per hectare. For this purpose, the compounds are uniformly sprayed on the plants in the form of a solution. (or suspension) aqueous, with 500 liters of water per hectare Again, it is found, three weeks after treatment, that the compounds according to the invention have a high selectivity while having excellent efficacy against the bad grass The comparison agent

does not have this selectivity.

  0) PPQ) rd 4 y O Mq 0) re r O r 4rd 5 O a) r H (1) e ffi e rd 9 MOG) -P r 4 ffir-i, j rl SH 4-)% a) MN ## EQU1 ## ## EQU1 ## P 11 1-4rd P 4 d (d -4 4 jtp

Q) 1-1

M Q

  Compound according to the invention cyclohexyl-3

dihydro-6,7 4 H-

thiazolo

/ -triazine: 71, 2.147-

one-4

cyclohexyl-3 -

4H-thiazolo / 2,3: c-7

/ Triazine-J, 2.4 / -

one-4

1 1 O 1 O 1 O 10 10 O O

1 10 1 O 10 1 O 10 O O

0 O O O O

  3-cyclopentyl-6-dihydro-4H-thiazolo 1 10 0 10 10 10 O

/ 2, 3 Z: c 7, - / tri a z in e-

   , 2,4 4-one-4-thienyl-3-dihydro-6,7-dihydro-4-thiazol-2-yl-4-thiazol

00 O O O

00 O O O

  M 0% ui 0% Lnen -t of cojEl e Q) 4 p a) 4 j a; "O Q U) ru W> tu u fo 9 O D r Cu r_ Cu r 1-4 8 r o l l n 4O -li O H W> w Ft tu 0 r

IZ 5 1-1

tp C) -Mcd

M 'M

0 z O m a) ul ffi

M 4

1-i (O

$ 44 to

ru -H-P tn 0) 14 m c 1-4 r 11

0 O 4

  ## STR5 ## wherein: embedded image 3-phenyl-6,7-dihydro-4-thiazolo / 2,3-c 7

/ triazine-i, 2, i 7-

one-4

1 1 O 10 10

0 O O O O O O

  3-phenyltetrahydro 1 4,6,7,8 411- / 1,3-thiazino /

Z 2,3-c // triazir E-1,2,4 / -

one-4

1 O 1 () 1 O O O O O O O 1

3-phenyl-6-methyl

dihydro-6,7 4 p-

thiazol o / - 1, 3-c / -

F Eriazin-1,2, l / -one-4

0 3 1 O

10 10 O

0 O O O O O

  4-amino-6-phenyl-4,5-dihydro-3-methyl-1,2,4-triazine 1-5 1 8 8 8 1 3 OO 1 O 1 O 8 r%) One 0% 0% (BE 799 854 patents ) 25165 i 6

Claims (1)

1 selective herbicidal products, characterized in that they contain at least one thiazolo or / 1,3-thiazino // 2,3-c _ // triazine-1,2,4 / -one corresponding to the general formula IR Ité > NIRRR 3 in which R 1 represents an alkyl radical which contains from 1 to 6 carbon atoms and can be interrupted, one or more times, by an oxygen or sulfur atom, an alkane-carboxylic acid radical; C1-C6, an ester radical of such an acid, a cycloalkyl radical which contains from 3 to 8 carbon atoms and which may optionally carry one or more alkyls as substituent (s), an aromatic hydrocarbon radical or-aromatic-aliphatic, optionally carrying one or more substituents taken from the group consisting of CC 4 alkyls, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, halogens and the like; nitro group, or a heterocyclic hydrocarbon radical, R 2 represents hydrogen, a C 1 -C 6 alkyl radical or a optionally substituted aromatic hydrocarbon dicarboxylic acid, - R 3 represents hydrogen, a C 1 -C 6 alkyl radical, an optionally substituted aromatic hydrocarbon radical, a benzyl radical or the hydroxyl group, R 4 represents hydrogen, a C 1 -C 6 alkyl radical, an optionally substituted aromatic hydrocarbon radical, a benzyl radical, a C 1 -C 4 alkoxy radical or the hydroxyl group, and n is 0 or 1. 2 selective herbicidal products according to claim 1, characterized in that: R 1 represents a methyl, dimni: hyl-1,1 ethyl, butyl, nhexyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl, tert-butylphenyl, methoxyphenyl, fluorophenyl, chlorophenyl, iodophenyl, nitrophenyl, benzyl or thienyl, R 2 represents hydrogen or a methyl or phenyl radical, R 3 represents hydrogen or a methyl or hydroxy radical, R 4 represents hydrogen or a methyl radical, methyl-1 ethyl, 1,1-dimethyl-ethyl, phenyl, benzyl E or hydroxy, and n is 0 or 1. A compound according to claim 1, taken from the group consisting of: (4-methyl-phenyl) -3- dihydro-6,7 4 H-thiazolo / 2,3-c- / triazin-1,2,4 / -one-4 trimethyl-3-methyl-dihydro-6,7 4 H-thiazolo / 2,3-c 1,2,4-Triazo-4-one-4-one (4-methoxyphenyl) -6,7-dihydro-4H-thiazolo [2,3-c] -triazine-1,2,47-one 4-chloro-phenyl-3-dihydro-6,7 4 H-thiazolo [2,3-c] -triazine 1,2,47-one-4-benzyl-3-dihydro-6,7 4 H-thiazolo / 2,3-c 7 / triazine-1,2,4-one-4-cyclohexyl-3-dihydro-6,7 4H-thiazolo / 2,3-c // triazine-1,2,4 -one-4-thienyl-3-dihydro-6,74H-thiazolo / 2-,3-c / -Ftriazine-1 , 2, one-4a (4-methoxyphenyl) -3,6,7,8-tetrahydro-4H-1,3-thiazino / 2,3c-triazine-1,2,4 -one 3- (4-Fluoro-phenyl) -4,6,7,8-tetrahydro-4H- [1,3-thiazino] -2,2,3-triazo-1,2,1-triazone-4-one (Nitro-4-phenyl) -3,6,7,8-tetrahydro-4H-1,3-thiazino / 2,3-qH-triazine-1,2,4 -one-4 phenyl- 3-Tetrahydro-4,6,7,8-LH-N-1- (3-thiazolyl) -2- (3-di) -triazine-1,2,47-one-4-cyclopentyl-3-tetrahydro-4 , 6,7,8 4 H 3-thiazino 1 Z 2, 3 e / / triazine-1,2, i / -one-4 trimethylmethyl-3 tetrahydro-4,6,7,8 IH 7/1 -thiaziro 1,2,3-trifluoromethyl-2,3-trifluoromethyl-2,3-trifluoromethyl-2,3-trifluoromethyl-2,3-trifluoromethyl-2,3,7,8-trifluoromethyl-2,3,7,8-trifluoromethyl-2,3-triazo -'tria. 1,2,47-azine-4-one (4-trimethyl-4-phenyl) -6,7-dihydro-4H-thiazolo [2,3-E] -2-triazin-1-ylone (iodine) 4-phenyl) -3-dihydro-6,7 4 H -thiazolo [2- (3H) -tiazine-1,2,7-one-4-cyclopentyl-3-dihydro-6,7 4 H-thiazolo] 2,37 c / Ztriazine-1,2,47-one-4a (2-methylpropyl) -3,6-dihydro-4H-thiazolo / 2,3-c // 1,2,4-triazine / 4-phenyl-3H-thiazolo [2-,3-c] -triazine-1,2,47-one-4-trimethylmethyl-3,4-H-th-Jazolo / 1 3,477-one-4a (2-fluoro-phenyl) -3H-thiazolo [2,3-l] -triazine-1,2,4-a-4a (methyl-2-phenyl) 3,411thiazolo [2,3,4,7-triazine-1,2,4 -one-4 '] trimethyl-3-methyl-6,7-dihydro-6,7 4 H-thiazolo / 2,3- // triazine-1,2,47-one-4-phenyl-3-methyl-6,7-dihydro-4H-thiazolo / 2,37-c 1,2,47-one-4 is 3,7-diphenyl dihydro- 6.7 4 H-thiazolo F 2,3-c ,, 7/7 Eriazine-1,2,4 / -one-4-phenyl-3-methyl-4H-triazolo [3-en] 1,2-1,2,4-triazol-1,2,4-thiazolo-2,3-tri-1,2,4-triazone-4-phenyl-3-hydroxy-6-dihydroxy-1,2-dihydroxy-6-dihydroxybenzoate ydro-6,7 4 H-tl-iiazol OF 2,3-c 7 / - / t-riazine-1,2,47-one-4 phenyl-3-hydroxy-7-tetrahydro-4,6,7 , 8 F 1,3-thiazino / 2,3-c / triazine-1,2,47-one-4-phenyl-3-dimethyl-6-methyl-6,7-dihydroxythiazolo / 3-c / / triazine-1,2,47-one-4-phenyl-3-trimethyl-6-methyl-6,7-dihydro-4 H-thiazo 1 o / 2,3- / Friazine-1,2,47-one-4 phenyl-3 benzy-1-6 dihydro-6,7 411-thiazolo / -3,3-c / - / triazine-1,2,47-one-4 and phenyl-3-methyl-4-tetrahydro-4,6,7 , 8 4 H- / 1,3thiazino / / 2,3-c // 1,2,4-triazine / -one-4. 4 selective herbicidal products according to one of claims 1 and 2, characterized in that they contain at least one compound according to claim 3. Selective herbicidal products according to one of claims 1 and 2, characterized in that they contain 3-phenyl-6,7-dihydro-4H-thiazolo [2,3-c] -triazine-1,2,47-one-4-methyl-3-dihydro-6,7 4 H-thiazolo [2], 3-c // triazine-1,2,47 to one4 and / or methoxycarbonylmethyl-3-dihydro-6,7 4 H-thiazolo / 2,3-c / / triazine-1,2,4 / -one-4 . Products according to any one of claims 1, 2, 4 and 5, which further contain supports and / or adjuvants. Process for the preparation of thiazolo and 1,3-thiazino-7,2,3-c 7 -triazine-1,2,4-7-ones according to claim 1, characterized in that compounds of the general formula II with compounds of the general formula III% -CH-Hal (R 3 CH) n R 2 -CH-Hal or with compounds of the general formula IV o O IV (R 3 Hal or with compounds of general formula VR 4 CH / C Hal R 2 V in the presence of bases, and, if desired, the isomers are separated by column chromatography (in the preceding formulas, the symbols R 1, R 2, R 3, R 4 and N have the meanings given in claim 1 and Hal represents halogen.) 8 Process for the preparation of thiazolo and / 1,3-thiazino / 2,3-c / triazine 1, 2,47-ones according to claim 1, characterized in that compounds of the general formula VI 1- R O are reacted with compounds of the general formula VII with compounds of the general formula VII VI VII R 2 formulas in which R 1, R 2, R 3, R 4 and N have the meanings given in claim 1. 9 Process for the preparation of thiazolo and L / 1,3-thiazino // 2,3-7 L-triazine-1 , 2,47-ones according to claim 1, characterized in that compounds of the general formula VI R 1 OC / VI C RO OO are reacted with the thiosemicarbazide, which corresponds to the following formula: H 2 N NH CS NH 2 VII so as to obtain compounds of the general formula VIII and these are reacted, in the presence of bases, with compounds of the general formula III R 1 CH Hal III ( R 3 CH) R 2 CH Hal or with compounds of general formula IV R 4 RX-C = O (R 3 CH) n IV / CH Hal reaction which gives rise to compounds of general formula IX RRCN CH R 3) n IX IR 0% o which is converted, by cyclization, in the presence of basic catalysts, the compounds of general formula i vculus (in the above formulas, the symbols R 1 i Roy R 3, R 4 and N have the meanings given in claim 1 and Hal represents a halogen atom). Process for the preparation of thiazolo and /, 3-thiazino / 2,3-c 7 / triazine-1,2,4 / -ones according to claim   1 in which R 1 represents an alkane-acid radical   C 1 -C 6 carboxylic acid or ester of such an acid,   characterized in that the acetylene acid is reacted   dicarboxylic acid or one of its esters corresponding to the general formula X ROOC -C C COOR X   in which R represents hydrogen or a C 1 -C 4 alkyl radical, with compounds corresponding to the general formula VII N HN N / "'VII R 4 (CH) n 2 R-   in which R 2, R 3, R 4 and N have the meanings given in claim 1, which reaction gives compounds of general formula XI C 00 R HN N = C CH COOR N S   Embedded image The latter are converted by cyclization in the presence of bases to compounds of the general formula XII ## STR1 ## finally we areomerize these in order to obtain the compounds of general formula I desired.