DE2614762A1 - HERBICIDES AND METHOD FOR MANUFACTURING THEM - Google Patents

Description

The invention relates to herbicides and growth regulators for plants and the like, and in particular to s-triazine compounds having these properties and processes for their preparation and the use of these compounds.

The invention relates to s-triazine compounds of the general formula wherein R [deep 1] is a methyl or ethyl group;

R [deep 2] is a methyl group;

R [deep 3] is hydrogen or an alkyl radical having 1 to 4 carbon atoms;

R [deep 4] is an alkyl radical having 1 to 4 carbon atoms;

X chlorine, the group wherein R [deep 5] is hydrogen or an alkyl group having 1 to 4 carbon atoms and R [deep 6] is an alkyl group having 1 to 4 carbon atoms, or the group S - R [deep 7], wherein R [deep 7] is an alkyl group having Is 1 to 4 carbon atoms.

The invention furthermore relates to a process for the preparation of the compounds mentioned, which is characterized in that cyanuric chloride is mixed with a 2-hydroxy-2-alkylnitrile in the presence of an acid acceptor (B) to form 2,4-dichloro-6- (2 -cyano-2-alkoxy) -s-triazine and a salt according to the following reaction equation: and then the 2,4-dichloro-6- (2-cyano-2-alkoxy) -s-triazine in the presence of an acid acceptor (B) is reacted with an aliphatic amine, a 2-chloro-4-alkylamino-6- (2-cyano-2-alkoxy) -s-triazine and a salt according to the following reaction equation is obtained:

According to a first modification of this process, the 2-chloro-4-alkylamino-6- (2-cyano-2-alkoxy) -s-triazine is then reacted with an aliphatic amine in the presence of an acid acceptor (B), whereupon a 2, 4-bis-alkylamino-6- (2-cyano-alkoxy) -s-triazine and a salt according to the following reaction equation is obtained:

According to a further modification of the process according to the invention, the 2-chloro-4-alkylamino-6- (2-cyano-2-alkoxy) -s-triazine is then reacted with an alkyl mercaptan in the presence of an acid acceptor (B), whereupon a 2- Alkylthio-4-alkylamino-6- (2-cyano-2-alkoxy) -s-triazine and a salt according to the following

Reaction equation gets:

The reaction (1) is preferably carried out in a mixture of water and acetone or water and methyl ethyl ketone at temperatures between -7 and + 7 ° C in the presence of a strong base (sodium or potassium hydroxide or the like), with the Maintains pH in a range between 9 and 11. At lower pH values, the reaction proceeds much more slowly, while at higher pH values a decrease in the yield is observed as a result of decomposition phenomena.

A 2,4-dichloro-6- (2-cyano-2-alkoxy) -s-triazine is obtained in which the (2-cyano-2-alkoxy) group gives the triazine nucleus a particular reactivity. As a result, the reaction temperature is lowered for the conversion of the remaining chlorine atoms.

The reactions (2), (3), (4) are carried out in a conventional manner: the reaction (2) is carried out at a temperature between -7 and + 7 ° C., the reactions (3) and (4) are carried out at temperatures between +30 and + 100 ° C.

The above three reactions can be carried out in a single step without isolation of intermediates.

The compounds according to the invention are particularly effective for use as weedkillers, both for selective weed control in a wide variety of agricultural crops and for complete weed control on non-agricultural areas. In addition, they are effective as growth regulators for plants, with - in general with reduced doses compared to their use as herbicides - particularly desired effects on useful or ornamental plants are achieved, such as greater productivity, an increase in the protein content of the crop, a Reduction in plant size and other desired or beneficial effects.

The compounds according to the invention can also be used for the destruction of algae and aquatic plants in canals, lakes, water courses, swimming pools and industrial water systems.

Among the compounds according to the invention which correspond to the abovementioned general formula, those which are listed in Table I below with their melting points are of particular interest. The compounds 1, 4 and 7 are particularly noteworthy.

Table I.

The compounds according to the invention can be used in a particularly advantageous manner for the selective destruction of weeds in agricultural crops, in particular in crops of maize, peanuts, soybeans, sunflowers, potatoes, peas, beans, wheat, barley and rice.

Under some climatic and soil conditions, the compounds according to the invention can also be used for selective weed control in stands of cotton plants, pineapples and sugar cane.

The activity of the compounds according to the invention is evident in relation to a large number of infested plants. The grass-like infestation plants include the following: Echinochloa crus-galli, Setaria viridis, Digitaria sanguinalis, Avena ludoviciana and Avena fatua, Alopecurus myosuroides,

Lolium italicum and Poa annua.

Among the dicotyledonous infestation plants, inter alia, the following compounds are destroyed by the compounds according to the invention: Amaranthus retroflexus, Chenopodium album, Polygonum persicaria, Polygonum convolvulus and Polygonum aviculare, Papaver rhoeas, Stellaria media, Portulaca oleracea, Capsella bursa pastoris, Sinistrapis alba and Raphanus.

The compounds according to the invention are therefore of particular importance for the selective weed killing in agricultural Union crops because they do not stay long in the ground, whereby the remains that are present at the end of a cultivation cycle of the treated crops are very little or not at all detectable, so that there is no danger for possible successor crops that are attacked by the compounds according to the invention themselves would.

With regard to the use of the compounds mentioned as complete herbicides, it suffices to state that they can advantageously be used on non-agricultural areas, such as industrial areas, railways and banks, as well as roads and the like.

The compounds according to the invention can be used both as weedkillers and as growth regulators: they can be brought to the ground before sowing, whereupon, if necessary, they can be dug into the ground using suitable equipment such as toothed or disc harrows or harrows with rotating blades can be introduced. Another application is to apply the compounds after sowing, but before the plants emerge from the ground. The herbicides or growth-regulating or preventing products according to the invention can moreover also be used after the plants and weeds have emerged from the soil, if the

Plants or weeds are more or less developed.

The doses in which the various compounds can be used vary within relatively wide limits, but are kept in a range from 0.1 to 10 kg / ha when used as selective weedkillers for various crops or between 1 and 40 kg / ha. ha when used as a complete weedkiller for non-agricultural areas.

The compounds according to the invention can be used as herbicides or growth regulators after they have been suitably processed into a preparation so that they can be distributed on the soil or on the useful plants or weeds or grasses to be treated.

The most common method of processing the compounds into a preparation, namely the production of a wettable powder, is carried out by mixing the compounds with suitable surface-active and suspending agents already in powder form and with inert carrier materials such as kaolin, various clays, carbonates and silicates as well as by Milling of the mixture obtained in mechanical mills or with the aid of air jets, so that formulations are obtained which are identical are moderate and of a high degree of fineness, for example between 0.1 and 100 microns.

Pastes which can be suspended in water can also be obtained by adding the compounds according to the invention in powder form with surface-active, suspending, anti-foaming and thickening agents and, if possible, also with antifreeze liquids and liquid carriers, such as water, glycols, various oils and hydrocarbons, as well as under Under certain circumstances mixed with smaller amounts of solid, inert carriers of the aforementioned type. In this case, the mixture is then ground in suitable colloid, ball or liquid jet mills so that a degree of division of the solid particles between 0.1 and 100 μm is obtained.

A special formulation, which is less common, but is also possible, consists of granules which contain granular solid inert carriers (which can also be chemical or natural fertilizers) with which the compounds according to the invention and possibly auxiliaries or binders are mixed either by granulating the particles (by spray drying or extruding liquid pastes) or by coating the particles themselves; the fineness of these granules is between 0.1 and 4 mm or more. Powdery formulations are also possible, which are obtained by dry pulverization and from a finely ground mixture of the compounds according to FIG of the invention with inert solids, among which in particular talc and kaolin as well as various clays and silicon dioxide exist.

Formulations in the form of liquid solutions are also possible, both as aqueous solutions of salts and the compounds according to the invention (hydrochlorides, acetates and others) with excess acid, and as solutions of the compounds in suitable organic solvents with the addition of emulsifiers so that stable emulsions can be formed in water.

Surfactants or dispersants or emulsifiers which are suitable for use in the formulations of the compounds according to the invention are those described in McCuctheon's Detergents and Emulsifiers - North American and International Editions - 1975-Annual, Ridgewood, N.J. (USA) are listed.

The compounds according to the invention can be used alone or, depending on the most varied of requirements, in a mixture with other herbicides or active substances which regulate or prevent vegetation. The following is a list of active herbicides or growth-regulating compounds which can be used in a mixture with compounds according to the invention.

2-chloro-N- (2-ethyl-6-methylphenyl) -N- (1´-

methyl-2´-methoxyethyl) acetanilide (Metetilachlor)

2-chloro-N- (2,6-diethylphenyl) -M- (methoxy-

methyl) acetanilide (alachlor)

small alpha-chloro-N-propyl acetanilide (propachlor)

3-amino-2,5-dichlorobenzene acid (chloramben)

2- (3,4-dichloro-phenyl) -4-methyl-1,2,4-

oxydiazolidine -3,5-dione (metazole)

3- (4-bromo -3-chloro-phenyl) -1-methoxy-1-

methylurea (Chlorbromuro)

3- (3-chloro-p-toluyl) -1,1-dimethylurea (chlorotoluron)

3- (4- (4-chloro-phenoxy) phenyl) -1,1-

dimethylurea (chloroxuron)

3- (3,4-dichloro-phenyl) -1,1-dimethylurea (diuron)

3-phenyl-1,1-dimethylurea (fenuron)

3- (3-trifluoro-methylphenyl) -1,1-dimethylurea (Fluometuron)

3- (3,4-dichloro-phenyl) -1-methoxy-1-methylurea (Linuron)

3- (4-bromo-phenyl) -1-methoxy-1-methylurea (metobromuron)

3- (3-chloro-4-methoxyphenyl) -1,1-dimethyl urea (metoxuron)

3- (4-chloro-phenyl) -1-methoxy-1-methyl-urea (monolinuron)

3- (4-chloro-phenyl) -1,1-dimethylurea (Monuron)

3- (3,4-dichloro-phenyl) -1-butyl-1-methylurea (Neburon)

2-chloro-4-ethylamino-6-isopropylamino-s-triazine (atrazine)

2- (Methylthio) -4-ethylamino-6-isopropylamino-s-triazine (Ametryn)

2-methoxy-4-ethylamino-6-isopropylamino-s-triazine (Atraton)

2-methylthio-4-azido-6-isopropylamino-s-triazine (Aziprotryn)

2-chloro-4- (1-cyano-1-methylethylamino) -6-

thylamino-s-triazine (cyanazine)

2-chloro-4-cyclopropylamino-6-isopropylamino-s-triazine (cyprazine)

6-methylthio-4-methylamino-6-isopropylamino-s-triazine (Desmetryn)

2-ethylthio-4,6-di- (isopropylamino) -s-triazine (Dipropetryn)

2-methylthio-4- (3-methoxypropylamino) -6-

isopropylamino-s-triazine (Metoprotryn)

2-methylthio-4,6-di- (isopropylamino) -s-triazine (Prometryn)

2-methoxy-4,6-di- (isopropylamino) -s-triazine (Prometon)

2-chloro-4,6-di- (isopropylamino) -s-triazine (propazine)

6-methoxy-4-ethylamino-2-sec.butylamino-s-triazine (secbumetone)

2-chloro-4,6-bis- (ethylamino) -s-triazine (simazine)

2-methylthio-4,6-bis- (ethylamino) -s-triazine (Simetryn)

2-methoxy-4,6-bis- (ethylamino) -s-triazine (simetone)

2-methoxy-4-ethylamino-6-tert-butylamino-s-triazine (terbumetone)

2-methylthio-4-ethylamino-6-tert-butylamino-s-triazine (terbutryn)

2-chloro-4-ethylamino-6-ter-butylamino-s-triazine (terbuthylazine)

2-chloro-4-diethylamino-6-ethylamino-s-triazine (trietazine)

S-ethyl diisobutylthio carbamate (butylate)

Ethyl dipropylthio carbamate (EPTC)

NN-diallyl dichloroacetamide

S-ethyl diethylthio carbamate (Etiolate)

S-propyl butylethylthiolcarbamate (Pebulate)

S-propyl-dipropylthiocarbamate (vernolate)

N, N-Dipropyl-2,6-dinitro-4trifluoro methyl-aniline (trifluralin)

N-butyl-N-ethyl-2,6-dinitro-4-trifluoro-methylaniline (benfluralin)

N, N-diethyl-2,6-dinitro-4-trifluoro methyl-m-

phenylene diamine (dinitramine)

N-Cyclopropylmethyl-2,6-dinitro-N-propyl-

trifluoro methyl-aniline (Profluralin)

N- (1-ethylpropyl) -2,6-dinitro-3,4-xylidine (Penoxyn)

4-isopropyl-2,6-dinitro-N, N-dipropylaniline (isopropaline)

4-methylsulfonyl-2,6-dinitro-N, N-dipropylaniline (nitralin)

3,5-Dinitro-NN-dipropyl sulf anilamide (oryzalin)

4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-

1,2,4-triazin -5-one (metribuzin)

Isopropyl phenyl carbamate (Propham)

3,4-dichlorophenyl carbamate (Swep)

Isopropyl 3-chloro phenyl carbamate (chlorpropham)

3- (3,3-Dimethylureido) -phenyl-tert-butylcarbamate (carbutylate)

2-amino-1,2,4-triazole (aminotriazole)

2,2-dichloropropionic acid (Dalapon)

4-amino-3,5,6-trichloropicolinic acid (picloram)

2,3,5,6-Tetrachloro terephthalic acid - dimethyl ester (Chlortal-dimethyl)

3,4-dichloropropionanilide (propanil)

3,5-dichloro-N- (1,1-dimethylpropynyl) -benzamide (propyzamide)

5-bromo-3-sec-butyl-6-methyluracil (Bromacil)

5-chloro -3-tert-butyl-6-methyluracil (Terbacil)

1-naphthylphthalamic acid (naptalam)

3,6-dichloro -2-methoxybenzoic acid (Dicamba)

Monosodium methyl arsonate (MSMA)

Disodium methylarsonate (DMSA)

Cacodylic acid

Potassium cyanate

2,4-dichloro-phenoxyacetic acid (2,4-D)

2,4-dichlorophenoxybutyric acid (2,4-DB)

2,4-dichlorophenoxypropionic acid (diclorprop)

2-chloro-4-methylphenoxyacetic acid (MCPA)

2-chloro-4-methylphenoxybutyric acid (MCPB)

2-chloro-4-methylphenoxypropionic acid (mecoprop)

2,4,5-trichlorophenoxy acetic acid (2,4,5-T)

2,4,5-trichlorophenoxy acid (fenoprop)

Trichloroacetic acid (TCA)

4,6-dinitro-o-cresol (DNOC)

2-sec-butyl-4,6-dinitrophenol (Dinoseb)

2-sec-butyl-4,6-dinitrophenol acetate (dinoseb acetate)

2-tert-butyl-4,6-dinitrophenol (Dinoterb)

6-tert-butyl-2,4-dinitro-m-cresol acetate (Medinoterb acetate)

2,3,6-trichlorophenylacetic acid (Clorfenac)

2,6-dichlorobenzonitrile (dichlobenil)

2,6-dichloro-thiobenzamide (chlorotiamide)

N-phosphonomethylglycine (glyphosate)

3,5-dibromo-4-hydroxybenzonitrile (bromoxinil)

3,5-diode-4-hydroxybenzonitrile (Joxinil)

3-isopropyl- (H) -benzo-2,1,3-thiadiazine -4-

on -2,2-dioxide (bentazone)

N, N-dimethyldiphenylacetamide (difenamides)

1,1-ethylene -2,2´-dipyridyl (Diquat)

1,1-dimethyl-2,2´-dipyridyl (paraquat)

4-nitrophenyl-2-nitro-4-trifluoro methylphenyl ether (fluorodifen)

2,4-dichloro-phenyl-4´-nitrophenyl-ether (nitrofen)

2,4,6-Trichlorophenyl-4´-nitrophenyl ether (CNP)

2,4-dichloro-phenyl-3´-methoxy-4´-nitrophenyl ether (X 52)

Methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate (Bifenox)

The following products are particularly suitable for use in admixture with compounds according to the invention.

2-chloro -4-ethylamino-6-isopropylamino-s-triazine (atrazine)

2-chloro -4,6-bis (ethylamino) -s-triazine. (Simazine)

2-chloro -4-ethylamino-6-tert-butylamino-s-triazine (terbutil-azine)

2-chloro -N- (2-ethyl-6-methylphenyl) -N´- (1´-methyl-2´-

methoxy-ethyl) acetanilide (Metetilachlor)

2-chloro -N- (2,6-diethylphenyl) -N- (methoxymethyl)

acetanilide (alachlor)

-Chlor -N-propyl acetanilide (propachlor)

3- (3,4-dichlorophenyl) -1-methoxy-1-methylurea (Linuron)

3- (4-bromo -3-chlorophenyl) -1-methoxy-1-methylurea (Chlorbromuron)

N, N-Dipropyl-2,6-dinitro-4-trifluoro methylaniline (trifluralin)

2,4-dichlorophenoxyacetic acid (dichloroprop)

2-chloro -4-methylphenoxyacetic acid (mecoprop)

4,6-dinitro-o-cresol (DNOC)

2-sec-butyl-4,6-dinitrophenol (Dinoseb)

2-tert-butyl-4,6-dinitrophenol (Dinoterb)

Mixtures of these compounds and numerous compounds according to the invention are particularly useful for selective weed control in maize crops and also, for some compounds, for selective weed control in crops of soybeans, cotton plants, peanuts and cereals (wheat, barley, rye, oats and

Rice).

The following examples serve to further illustrate the invention.

Examples 1 to 5 serve to illustrate manufacturing processes for the compounds according to the invention, while Examples 6 to 10 relate to the formulation of herbicidal products or plant growth regulators or destructive agents, while Examples 11 to 15 are directed to the use of herbicides or plant growth regulators which with compounds according to the invention.

example 1

100 g of cyanuric chloride are quickly added with stirring to a solution of 650 ml of acetone and 200 ml of water, which has been cooled to 0 ° C. After about three hours, a solution of 71.1 g of 2-methyllactonitrile in 100 ml of water is added to the whole, while the temperature is kept between -5 and 0 ° C. and the pH value between 7 and 9, with 100 to 120 g at the same time 5 to 6% sodium hydroxide solution can be added.

In a further two hours or so, 320 to 340 g of 5 to 6% strength sodium hydroxide solution are added dropwise, the pH being kept between 10 and 10.5 and the temperature between -5 and 0 ° C. Then 800 ml of water added and the mixture cooled to a temperature between -5 and -10 ° C for half an hour with vigorous stirring.

A white, crystalline product is obtained as a precipitate, which is filtered and washed with cold water.

105 to 108 g of 2,4-dichloro-6- (2-cyano-2-propoxy) -s-triazine with a melting point of 83.5 to 86 ° C. and a yield of 83 to 87% of theory were obtained .

23.3 g (0.1 mol) of 2,4-dichloro-6- (2-cyano-2-propoxy) -s-triazine, which had been obtained as described above, are in a solution of 180 ml of acetone and 20 ml of water, which had previously been cooled to 0 ° C, dissolved. While maintaining the temperature between 0 and + 5 ° C, 0.1 mol of monoethylamine are added dropwise and then 0.1 mol of 15% sodium hydroxide solution. After the addition is complete, the mixture is stirred for about an hour at 5 ° C.

The solvent is then distilled off under reduced pressure of 20 mm Hg, with water being added at the same time; finally it is cooled and filtered.

23 to 23.5 g of 2-chloro-4-ethylamino-6- (2-cyano-2-propoxy) -s-triazine with a melting point of 95 to 97 ° C., a purity of 98 to 99% and in a yield of

96 to 98% of theory. Analogously, starting from a corresponding amount of isopropylamine, 2-chloro-4-iso-propylamino-6- (2-cyano-2-propoxy) -s-triazine with a melting point of 72 to 75 ° C. is obtained.

Example 2

23.3 g (0.1 mol) of 2,4-dichloro-6- (2-cyano-2-propoxy) -s-triazine obtained according to Example 1 are dissolved in a solution of 180 ml of acetone and 20 ml of water, the had previously been cooled to 0 ° C, dissolved.

0.1 mol of isopropylamine is then added dropwise between 0 and 5 ° C. and then 0.1 mol of 15% strength sodium hydroxide solution.

The temperature is kept at + 5 ° C. during the subsequent one-hour stirring and then increased to + 20 ° C., 0.1 mol of 70% monoethylamine is added dropwise and then 0.1 mol of 15% sodium hydroxide solution.

The whole is refluxed for two hours, the solvent is then evaporated off while water is added at the same time.

It is then cooled with vigorous stirring, and then filtered and washed.

25.3 to 25.8 g of 2-ethylamino-4-isopropylamino-6- (2-cyano-2-propoxy) -s-triazine of melting point 122 to 126 ° C., a purity of 95 to 97% and in a yield of 96 to 98% of theory.

Using appropriate amines and the corresponding 2,4-dichloro-6- (2-cyano-2-alkoxy) -s-triazine as starting materials, the s-triazine derivatives given in Table II below with the yields also given and in obtained the purity also indicated.

Example 3

60 g of cyanuric chloride are added to a solution of 500 ml of water and 50 ml of methyl ethyl ketone, which has been cooled to 0 ° C., with vigorous stirring. Then 50 g of 2-hydroxy-2-methylbutyronitrile are added dropwise over the course of one and a half hours, the temperature between 0 and + 3 ° C. and the pH being kept between 9 and 10 by the simultaneous addition of about 100 g of 5 to 6% sodium hydroxide solution . After a further two hours, about 300 g of 5 to 6% sodium hydroxide solution are added dropwise, thereby keeping the pH between 10 and 10.5.

After filtering, washing and drying, 56 to 60 g of 2,4-dichloro-6- (2-cyano-2-but oxy) -s-triazine are obtained in a yield of 70 to 75% of theory and with a melting point of 65 to 68 ° C.

24.7 g (0.1 mol) of the 2,4-dichloro-6- (2-cyano-2-butoxy) -s-triazine obtained are dissolved in a solution of 180 ml of acetone and 20 ml of water, which has previously been heated to 0 ° C has been cooled. While maintaining the temperature between 0 and 5 ° C, 0.1 mol of 100% isopropylamine are added dropwise between 0 and 5 ° C and then 0.1 mol of 15% sodium hydroxide solution. The temperature is kept at + 5 ° C for one hour while stirring and then then increased to + 20 ° C, and 0.1 mol of 70% monoethylamine are added dropwise and then 0.1 mol of 15% sodium hydroxide solution. The mixture is refluxed for about two hours and the solvent is then evaporated while adding water. It is then cooled, filtered and washed with vigorous stirring. 27 to 27.5 g of 2-ethylamino-4-isopropylamino-6- (2-cyano-2-butoxy) -s-triazine with a melting point of 110 ° to 114 ° C. are obtained in a purity of 95% and with a yield of 96 up to 98% of theory.

Using the corresponding starting amines, the compounds given below are obtained analogously with the corresponding yields and the corresponding purity:

Designation Educ. Reinh.

2,4-bis-isopropylamino-6-

(2-cyano-2-butoxy) -s-triazine 95 to 97% 95%

2,4-ethylamino-4-tert-butyl-

amino-6- (2-cyano-2-butoxy) -

s-triazine 96 to 98% 98%

Example 4

The procedure is as described in Example 1, with the difference that instead of adding water and cooling to precipitate the 2,4-dichloro-6- (2-cyano-

2-propoxy) -s-triazines 26.86g of 100% isopropylamine are added over 30 minutes, the temperature being kept between 0 and 5 ° C. A solution of 18.2 g of sodium hydroxide in 180 ml of water is then added over the course of about an hour, the temperature being kept between +5 and + 6 ° C. The mixture is kept stirring for one hour at 5 ° C. and then heated to 10 ° C. and an excess (about 70 g) of 70% monoethylamine is added.

The mixture is refluxed for about three hours, then 300 ml of water are added and the mixture is cooled to 0 ° C. with vigorous stirring. 2-Ethylamino-4-isopropylamino-6- (2-cyano-2-propoxy) -s-triazine, a white, crystalline product, is precipitated, which after filtering, washing and drying in a yield of 125 g, corresponding to 90% of theory, and with a melting point of 124 to 126 ° C and in a purity of 98%.

The 2-cyano-2-alkoxy-s-triazine derivatives mentioned in Example 2 are obtained in an analogous manner.

Example 5

0.1 mol of 2-chloro-4-isopropylamino-6- (2-cyano-2-propoxy) -s-triazine, which has been prepared as described in Example 1, is dissolved in 20 ml of 90% strength tert-butyl alcohol solved. To the solution obtained 0.15 mol

Sodium thiolate (CH [deep 3] SNa) in 10% aqueous solution was added, followed by heating under reflux for five hours.

The lower phase is separated off and 100 ml of solvent are distilled off under reduced pressure.

Then water and ice are added and the resulting precipitate is filtered off.

2-Methylthio-4-isopropylamino-6- (2-cyano-2-propoxy) -s-triazine is obtained in a yield of 93 to 95% of theory.

The white, crystalline product has a purity of 96 to 97% and a melting point of 98.5 to 102 ° C.

Analogously, 2-methylthio-4-monoethylamino-6- (2-cyano-2-propoxy) -s-triazine is used in a yield of 94 to 96% of theory. obtained in a purity of 95 to 97% and with a melting point of 92.5 to 95.5 ° C.

Example 6

The following substances are placed in a powder mixer.

Compound 1 (Table I), purity 96%,

in the form of a fine powder 50 kg

Sodium dibutylnaphthalene sulfonate 3 kg

Condensate from sodium naphthalenesulfonate and formaldehyde 2 kg

Kaolin in the form of a very fine powder 45 kg

All ingredients are mixed for 30 minutes and then ground in a pin mill, after which they are mixed for an additional twenty minutes.

A water-dispersible powder with particles between 1 and 20 microns in diameter, which is suitable as a herbicide or herbicide, is obtained.

Example 7

The following substances are placed in a powder mixer:

Compound 1 (Table I), purity 96%, in the form of a

fine powder 40 kg

2-chloro-4-ethylamino-6-isopropylamino-s-triazine,

Purity 97%, in the form of a fine powder 40 kg

Sodium dibutylnaphthalene sulfonate 3 kg

Condensate from sodium naphthalenesulfonate and formaldehyde 2 kg

Synthetic colloidal silicon dioxide 5 kg

Kaolin as a fine powder 10 kg

The ingredients are mixed for 30 minutes, then ground in an air jet mill and then mixed again for 15 minutes.

A water-wettable powder with a particle size between 0.5 and 15 μm, which is suitable as a herbicide, is obtained.

Example 8

The following ingredients are intimately mixed with one another in a screw homogenizer to produce a paste:

Deionized water 40 kg

Ethylene glycol 7 kg

Polycondensate of nonylphenol and 9 moles of ethylene oxide 1 kg

9 moles of ethylene oxide 1 kg

Polyethoxylated stearyl alcohol 1 kg

Formaldehyde 0.3 kg

Carboxymethyl cellulose 0.5 kg

Dimethylpolysiloxane 0.2 kg

Compound 4 (Table I), purity 92%, as a fine powder 50 kg

The solid particles are then ground in a sand-type colloid mill.

A paste is obtained which is dispersible in water and has solid particles with a diameter of 0.1 to 10 μm, which is extremely active as a herbicide.

Example 9

The following ingredients are intimately mixed with one another in a screw homogenizer to produce a paste:

Deionized water 40 kg

Ethylene glycol 7 kg

Polycondensate from nonylphenol and

9 moles of ethylene oxide 1.3 kg

Polyethoxylated stearyl alcohol 1.0 kg

Colloidal silica 1.0 kg

Carboxymethyl cellulose 0.5 kg

Dimethylpolysiloxane 0.2 kg

Compound 1 (Table I) purity 96%,

as a fine powder 25 kg

2-chloro-4-ethylamino-6-isopropylamino-s-triazine,

Purity 97%, as a fine powder 25 kg

After the homogeneous paste is prepared, the solid particles are ground in a sand-type colloid mill.

A paste is obtained which is dispersible in water and has solid particles with a diameter of 0.1 to 10 μm and is extremely active as a herbicide.

Example 10

The following ingredients are placed in a mixing vessel for liquids equipped with a stirrer:

Water 50 kg

Technical 2-chloro-4-methyl-phenoxyacetic acid, purity 85% 40 kg

Dimethylamine, 40%, in water 3 kg

These ingredients are homogenized in a paste disperser together with the following ingredients:

Compound 7 (Table I), purity 98%, as a fine powder 6 kg

Condensate of nonylphenol and 9 moles of ethylene oxide 0.3 kg

Ethoxylated stearyl alcohol 0.2 kg

Methyl polysiloxane 0.1 kg

Carboxymethyl cellulose 0.4 kg

The obtained homogeneous paste is ground in a sand-type colloid mill to obtain a water-dispersible paste which can be used as a weed killer.

Example 11

In a greenhouse that is kept at 24 ° C during the day and 18 ° C at night with a relative humidity of 70% is air-conditioned, cultivation vessels are filled with arable soil, which consists of 74% sand, 17% mud and 9% clay, after which the following plants are sown in the vessels:

Corn (Varietas Funk's G 99)

Wheat (Varietas Marzotto)

Barley (Varietas Perga)

Beetroot (Varietas KHS Monogerm)

The following infested plants are sown in other culture vessels:

Avena ludoviciana

Alopecurus myosuroides

Echinochloa crus galli

Setaria viridis

Digitaria sanguinalis

Matricaria chamomilla

Stellaria media

Amaranthus retroflexus

Before sowing the useful plants and weeds, an aqueous suspension of the compounds 1 to 9 according to the invention according to Table I, which have been formulated according to one of the methods given in Examples 5 to 9, is applied to the surface of the arable soil in an amount of 8, 2, 0.5 or 0.125 kg of active substance per hectare sprayed on, with the comparison substances the following, already known weedkillers or herbicides were used in the same doses:

2-chloro-4-ethylamino-6-isopropylamino-s-triazine (atrazine)

2-chloro-4-ethylamino-6- (1-cyano-1-methylethylamino) -s-triazine (cyanazine)

2-methylthio-4-ethylamino-6-tert-butylamino-s-triazine (terbutryn)

2-methoxy-4-ethylamino-6-tert-butylamino-s-triazine (terbumetone)

After these compounds have been sprayed on, it is ensured that they are introduced into the soil to a depth of 5 cm by carefully mixing the surface of the soil in the vessels and only then sowing the useful plants and weeds.

About 30 days after sowing, the results are evaluated by determining the phytotoxicity of both the useful plants and the weeds using the following rating scale.

0 = 0% phytotoxicity

1 = 10% "

2 = 20% "

3 = 30% "

4 = 40% "

5 = 50% "

6 = 60% "

7 = 70% "

8 = 80% "

9 = 90% "

10 = 100% "

The results are summarized in Table III below:

Example 12

Another greenhouse experiment was carried out as described in the previous example, using the same herbicidal products in the same doses, but applying them to the surface of the soil after the crops and weeds were sown and before they appeared on the surface.

In this experiment, the following useful plants were used in addition to those mentioned in Example 11:

Soybeans (Varietas Clay) and

Cotton plants (Varietas Syracuse).

Papaver rhoeas of the weeds were also tested.

About 30 days after the application of the herbicides, the phytotoxicity of the various compounds was determined analogously to Example 11 using the same evaluation criteria; the results are summarized in the following Table IV:

Example 13

Another experiment was carried out in a greenhouse under the same conditions as described in the previous example, with the difference that the herbicides were applied from the ground after the crop plants and weeds appeared, the narrow-leaved crops (Graminace_en) having two or three leaves and the broad-leaved crops (dicotyledons) had three to five leaves (treatment after surface emergence).

Cotton plants were not tested in this experiment, and neither Papaver rhoeas nor Amaranthus retroflexus of the weeds were taken into account.

45 days after the treatment, the phytotoxicity to the useful plants and the weeds was observed and expressed as a percentage analogous to the evaluations in the previous examples.

The results are summarized in Table V below.

Example 14

A greenhouse experiment similar to that described in Example 12 was carried out with a treatment before the appearance of the plants on the surface, but using 8.2 and 0.5 kg / ha, the products tested being partly different and among the useful plants the soybeans were omitted and the weeds Polygonum persicaria were also examined.

40 days after the treatment, the phytotoxicity of the various compounds towards the useful plants and the weeds was determined according to the evaluation scale according to Example 11. The results are summarized in Table 6 below.

Example 15

A field test was carried out on sandy / muddy soil, with the crops being sown in one direction in adjacent rows and the weeds being sown perpendicular to the rows of crops.

The herbicides, formulated as indicated in Example 6, were sprayed in aqueous suspension after the crops were sown and before the crops and weeds appeared on the surface (pre-emergence treatment).

The results were noted 40 days after the treatment, during which a total of 200 mm of rain fell.

A scale from the European Weed Research Society (E.W.R.S.) with the following rating numbers was used to indicate the phytotoxicity towards the useful plants:

1 = 0% phytotoxicity

2 = 2.5% "

3 = 5% "

4 = 10% "

5 = 15% "

6 = 25% "

7 = 35% "

8 = 62.5% "

9 = 100% "

To determine the effect of the compounds tested on the weeds present on the fields treated with the various herbicides, the percentage reduction in weeds was determined in relation to an untreated control field.

The results are summarized in Table VII below.

Claims (15)

1. Compound of the general formula wherein R [deep 1] is a methyl or ethyl group; R [deep 2] is a methyl group; R [deep 3] is hydrogen or an alkyl radical having 1 to 4 carbon atoms; R [deep 4] is an alkyl radical having 1 to 4 carbon atoms; X chlorine, the group wherein R [deep 5] is hydrogen or an alkyl group having 1 to 4 carbon atoms and R [deep 6] is an alkyl group having 1 to 4 carbon atoms, or the group S - R [deep 7], wherein R [deep 7] is an alkyl group having Is 1 to 4 carbon atoms. 2. Process for the preparation of a compound of the general formula where R [deep 1] is a methyl or ethyl group, R [deep 2] is a methyl group, R [deep 3] hydrogen or an alkyl radical with 1 to 4 carbon atoms, R [deep 4] is an alkyl radical with 1 to 4 carbon atoms, X chlorine, the group wherein R [deep 5] is hydrogen or an alkyl group having 1 to 4 carbon atoms and R [deep 6] is an alkyl group having 1 to 4 carbon atoms, or the group S - R [deep 7], wherein R [deep 7] is an alkyl group having 1 to 4 carbon atoms, mean, characterized in that cyanuric chloride with a 2-hydroxy-2-alkylnitrile in the presence of an acid acceptor (B) to form 2,4-dichloro-6- (2-cyano-2-alkoxy) -s-triazine and a salt according to the following reaction equation and then the 2,4-dichloro-6- (2-cyano-2-alkoxy) -s-triazine in the presence of an acid acceptor (B) with an aliphatic amine to form a 2-chloro-4-alkylamino-6- (2 -cyano-2-alkoxy) -s-triazines and a salt according to the following reaction equation: 3. The method according to claim 2, characterized in that the 2-chloro-4-amino-6- (2-cyano-2-alkoxy) -s-triazine is then mixed with an aliphatic amine in the presence of an acid acceptor to form a 2, 4-bis-alkyl-amino-6- (2-cyano-2-alkoxy) -s-triazines and a salt according to the following reaction equation: 4. The method according to claim 2, characterized in that the 2-chloro-4-alkylamino-6- (2-cyano-2-alkoxy) -s-triazine then with an alkyl mercaptan in the presence of an acid acceptor (B) to form one 2-alkylthio-4-alkylamino-6- (2-cyano-2-alkoxy) -s-triazines and a salt according to the following reaction equation: 5. The method according to claim 2, characterized in that the reaction (1) in a mixture of water and acetone or water and methyl ethyl ketone at a temperature between -7 and + 7 ° C in the presence of a strong base at a pH between 9 and 11 and the reaction (2) carried out in a conventional manner at a temperature between -7 and + 7 ° C. 6. The method according to claim 3, characterized in that the reaction (1) in a mixture of water and acetone or water and methyl ethyl ketone at a temperature between -7 and + 7 ° C in the presence of a strong base and at a pH value between 9 and 11 and the reactions (2) and (3) in a conventional manner and otherwise reaction (2) at a temperature between -7 and + 7 ° C and reaction (3) at a temperature between 30 and 100 ° C . 7. The method according to claim 4, characterized in that the reaction (1) in a mixture of water and acetone or water and methyl ethyl ketone at a temperature between -7 and + 7 ° C in the presence of a strong base and at a pH value between 9 and 11 and the reactions (2) and (4) in a conventional manner and otherwise reaction (2) at a temperature between -7 and + 7 ° C and reaction (4) at a temperature between 30 and 100 ° C . 8. The method according to claim 2, characterized in that the reactions are carried out in one stage. 9. Means for the selective destruction of weeds in crops and / or complete weed eradication and / or growth regulation of plants and / or destruction of algae and aquatic plants, consisting of a compound according to claim 1, optionally mixed with other weedkillers and / or surface-active agents , Suspending agents, emulsifiers and inert carrier materials in the form of a powder, a paste, a solution or a granulate. 10. Agent according to claim 9, containing 2-ethylamino-4-iso-propylamino-6- (2-cyano-2-propoxy) -s-triazine, 2-ethyl-amino-4-sec-butylamino-6- (2 -cyano-2-propoxy) -s-triazine or 2-ethylamino-4-tert-butylamino-6- (2-cyano-2-propoxy) -s-triazine as an active substance. 11. A method for treating plants by spraying an agent according to any one of claims 9 to 12 onto the soil. 12. The method according to claim 11, characterized in that the spraying takes place before sowing. 13. The method according to claim 11, characterized in that the spraying takes place before the appearance of the plants. 14. The method according to claim 11, characterized in that the spraying takes place after the appearance of the plants. 15. The method according to claim 11, characterized in that a product according to any one of claims 9 to 12 for the selective destruction of the weeds is sprayed in an amount that allows 0.1 to 10 kg of active substance according to claim 1 to reach one hectare of land and for complete weed killing in an amount that allows 1 to 40 kg of active substance according to claim 1 to reach one hectare, sprayed.