DE1445055B - 2-halo-4,6-diamino-s-triazine. Ana: J.R. Qeigy AQ, Basel (Switzerland) - Google Patents

Description

L 44OUOO

The invention relates to new Z-halogen- ^ o-diaminos-triazine derivatives as well as the use of these compounds for weed control.

It has been found that l-halo- ^ o-diaminos-triazine derivatives the general form! I.

Ha

with a reactive functional derivative of a carboxylic acid of the general formula VI

HOOC-Ri

(VI)

N N

K /

CO-R,

R,

where Hai is a chlorine or bromine atom. Ri the methyl. Ethyl or isopropyl radical, R ₁ and R -. \ The ethyl, allyl or - methoxypropyl radical and Ri means a hydrogen atom or the ethyl radical, have excellent herbicidal activity.

A cyanuric acid trihalide can be used to prepare the new triazine derivatives defined above. such as cyanuric chloride or cyanuric bromide. in any order one after the other with 1 mole of one Acylamide alkali salt of the general formula II and. in the presence of an acid-binding agent, with 1 mole of an amine of the general formula III

H-N

, CO - R ₁

R,

Η —Ν

(ID

(III)

until

have the above meanings.

where Ri g g

implement.

A variant of this process is that of known compounds of the general Formula IV

N N

- Hal

(IV)

in which Hal. Ru and Ri have the meanings given above have, goes out, and this with 1 mol of an alkali salt of an acylamide of the general Formula II is reacted in an inert organic solvent.

You can also prepare compounds of the general formula I by adding a compound of the general formula V

R.,

Shark

N N

nh

(V)

in which Hal. R> to Ri have the above meanings.

wherein Ri has the meaning given above. in particular with an excess of an anhydride of such an acid, by heating in one inert, preferably between 100 and 150 C boiling organic solvent acylated. To the To achieve good yields, the reaction conditions and the reaction time are preferred between 1 and 5 hours to be chosen so that monoacylation without simultaneous too extensive hydrolysis of the nuclear halogen by the Acylation liberated acid occurs in the starting materials.

According to a variant of this process, compounds of the general formula I can also be obtained if you want the monoacylation of the compound of general formula V by reaction with a low molecular weight aliphatic ketene, especially with carbomethylene in the presence of a Catalyst, such as small amounts of a mineral acid, accomplished.

The compounds of general formula I are particularly suitable as active ingredients for combating of weeds for both selective suppression and eradication of weeds among crops as well as for the total destruction and prevention of undesired vegetation. Under Weeds are also undesirable, e.g. B. understood previously grown crops. the The compounds defined above are also suitable as active ingredients for exercising other inhibitory effects Influences on plant growth, in particular defoliation, acceleration of ripening through premature drying out, e.g. B. potato plants, also reduction of the fruit set, extension the harvest period and shelf life. The new compounds of general formula I. can for weed control in the form of solutions. Emulsions. Suspensions or dusts come into use. The forms of application depend entirely on the intended use. All the application forms have to ensure that the active ingredient can be finely distributed. Especially with the total killing of vegetation, with premature drying out as well as defoliation, the effect can be caused by the use of inherently phytotoxic carriers, such as B. high-boiling mineral oil fractions are strengthened; on the other hand, there is selectivity the growth inhibition when using carrier substances which are indifferent to plants, e.g. B. in selective weed control, in general more clearly to their advantage.

In particular, higher-boiling organic liquids are used to produce solutions, like mineral oil fractions. Coal tar oils and also vegetable and animal oils are considered. Around To facilitate the dissolution of the active ingredients in these liquids, small amounts can optionally be used organic liquids with better dissolving power and mostly lower boiling points, d. H. Solvent. such as alcohols, e.g. B. ethanol or isopropanol. Ketones, ζ. B. acetone. Butanone or Cyclohexanone, diacetone alcohol, cyclic hydrocarbons, ζ. B. benzene. Toluene or xylene, chloro-

rated hydrocarbons, ζ. B. tetrachloroethane or Ethylene chloride or mixtures of the above substances are added.

The aqueous application forms are primarily emulsions and dispersions. The substances are preferably used as such or in one of the abovementioned solvents Emulsifiers or dispersants homogenized in water. Of cationic emulsifiers or dispersants quaternary ammonium compounds are mentioned as examples, and anion-active as examples Emulsifier soap, soft soap, alkali salts of aliphatic long-chain sulfuric acid monoesters, of aliphatic-aromatic sulfonic acids or of long-chain alkoxyacetic acids and as nonionic emulsifiers, polyethylene glycol ethers of fatty alcohols or alkylphenols and Polycondensation products of ethylene oxide. On the other hand, you can also use an active ingredient, emulsifier or dispersant and optionally solvent existing liquid or paste-like concentrates which are suitable for dilution with water.

Dust and grit can first be mixed or ground together Active substance can be produced with a solid carrier. The following can be considered: talc, Diatomaceous earth, kaolin. Bentonite, calcium carbonate, tricalcium phosphate, sand, but also wood flour, Cork flour and other materials of vegetable origin. On the other hand, the substances can also be absorbed onto the carrier materials by means of a volatile solvent. By adding Wetting agents, e.g. B. the above emulsifiers, and protective colloids, e.g. B. sulphite waste liquor, Powdered preparations and pastes can be suspended in water and used as wettable powders be made.

The various application forms can be used in the usual way by adding substances, which the distribution and the ability to penetrate the soil depending on the depth of the roots to be combated Improve or reduce weeds, be adapted more closely to the purposes of use. as well their biological effect can be broadened by adding substances with bactericidal or fungicidal properties Properties, e.g. B. to achieve general soil sterilization or in selective weed control to protect the cultivated plants from other harmful organisms. Fabrics that too affect plant growth, such as. B. 3-Amino-1,2,4-triazole. to speed up the Onset of action or, such. B. salts of u, a-dichloropropionic acid, may be desirable to broaden the herbicidal spectrum of activity. The combination with fertilizers may mean a saving in labor and can do the Increase the resilience of the cultivated plants to be protected.

Examples of typical application forms are given below. Parts mean in it Parts by weight.

example 1

K) parts of active ingredient. e.g. 2-chloro-4-ethylamino-6- (N-acetylethylamino) -1, 3,5-triazine (Mp. 104 to 105 "C) and 90 parts of talc, are in a ball mill, grind to the greatest fineness with a pin mill or another suitable mill. The resulting mixture serves as a dusting agent.

Example 2 5

20 parts of active ingredient, e.g. B. 2-Bromo-4-ethylamino-6- (N-acetyläthy! Amino) -1.3,5-triazine (Mp. 113 to 115 C), are in a mixture of 48 parts of diacetone alcohol, 16 parts of xylene and 16 parts ίο an anhydrous, high molecular weight condensation product of ethylene oxide with higher fatty acids _ solved. This concentrate can be mixed with water to form emulsions of any desired concentration be diluted.

Example 3

50 to 80 parts of active ingredient, e.g. B. 2-chloro-4-ethylamino-6- (N-acetylethylamino) -1, 3,5-triazine (M.p. 104 to 105C) with 2 to 5 parts of a wetting agent, e.g. B. a sulfuric acid ester, e.g. B. sulphite waste liquor, and 14 to 44 parts of an inert, solid support material, such as. B. kaolin, bentonite, chalk or kieselguhr, mixed and then finely ground in a suitable mill. The received wettable powder can be mixed with water and gives very stable suspensions.

Example 4

10 parts of active ingredient, for example 2-chloro-4-ethylamino-6- (N-propionylethylamino) -i, 3,5-triazine (melting point 89 to 91 ' ¹ C) are in 60 to 80 parts of a high-boiling organic liquid such as z. B. coal tar oil, diesel oil or spindle oil, which 30 to 10 parts of xylene are added, dissolved.

B e i s ρ i e 1 5

5 to 10 parts of 2-bromo-4-ethylamino-6- (N-acetyl-

ethylamino) -l, 3,5-triazine (melting point 113 to 115 "C) are mixed with 95 to 90 parts of calcium carbonate (= ground Limestone) mixed and ground. The product can be used as a grit.

Example 6

95 parts of a granular carrier material, e.g. B.

Sand, or carbonate of lime, is mixed with 1 to 5 parts of water. Isopropanol or polyethylene glycol moistened and then with 5 parts of 2-chloro-4-ethylamino-6- (N-acetylethylamino) -1.3,5-triazine mixed (m.p. 104 to 105 C).

The above or a more active ingredient mixture, e.g. B. from 10 parts of active ingredient and 90 parts of calcium carbonate can also be a multiple amount, e.g. B. 100 to 900 parts of an optionally water-soluble Artificial fertilizers, such as. B. ammonium sulfate or urea, are added.

Example 7

50 parts of active ingredient, e.g. B. 2-Chloro-4-allylamino-6- (N-acetylallylamino) -1, 3,5-triazine (Mp. 74 to 77C) are introduced into 45 parts of xylene and 5 parts of a mixture of polyethylene oxide condensation products and sulphite liquor added. Man contains a concentrate for the preparation of emulsions, which emulsifies in water in any ratio

fts can be.

The amounts of active ingredient required for selective weed control depend on the sensitivity the weeds, the hardiness

UOO

the crops, the time of application, the climatic conditions and soil conditions between about 0.25 and 10 kg per hectare, while for the complete prevention of vegetation generally 5 to 20 kg per hectare are to be used. In special cases the above application rates are also exceeded.

Example 8

Seed trays are filled with soil and each tray is filled with seeds from one of the following 'plants sown: mustard, sugar beet, spinach and cucumber. Immediately after sowing, the surface area of the peel per square meter is increased 1 g of 2-chloro-4-äthylamino-6- (N-acetyI-äthylamino) -l, 3,5-triazine in 100 ml of water sprayed on, which corresponds to 10 kg of active substance per hectare. The seedlings were 3 weeks after sowing of all four plant species completely dead.

Example 9

An existing population of kullur plants will grow some time after the seed plants have emerged or after setting the seedlings per square meter with 300 ml of an aqueous preparation of 0.1 g 2 - chloro - 4 - ethylamino - 6 - (N - acetylethylamino) -1,3,5-triazine sprayed, which corresponds to a concentration of 1 kg of active ingredient per hectare. To For 48 days it was found that turnip cabbage, leek, corn and vetch remained undamaged. Wheat, barley and rapeseed are only very slightly damaged, while beans, clover, carrots and spinach are completely dead was.

In addition to this extremely selective effect on cultivated plants, this active substance showed also has an excellent effect against the seed weeds (Mercuriaiis-, Veronica and Umbelüferenarten etc.). whose growth has been completely suppressed.

Analogously to the preceding examples, for. B. the following compounds as active ingredients apply:

2-chloro-4 - (; '- methoxypropylamino) -6- [N-acetyl- (y-methoxypropylamino)] - 1,3,5-triazine,
M.p. 61 to 64 "C;

2-chloro-4-diethylamino-6- (N-acetylethylamino) -1.3,5-triazine. Kp.o. (xxi »125" C.

Example 10

The seeds of the test plants were sown in a freshly prepared bed. Immediately after sowing became the substances

2-chloro-4,6-bis-ethylamino-s-triazine (according to

Swiss patent 342 784)
II 2-chloro-4-isopropylarnino-6-ethylamino-s-triazine (according to Swiss patent 342 784)

III 2 - methyl mercapto - 4,6 - bis - isopropylamino - triazine (according to Swiss patent 337 019)

IV 2-chloro-4-äthyIamino-6- (N-acetyIäthylamino) -s-triazine (according to the present invention)

V 2-Bromo-4-ethylamino-6- (N-acetylethylamino) -

s-triazine (according to the present invention)
VI 2 - chlorine - 4 - diethylamino - 6 - (N - acetyläthylamino) -s-triazine (according to the present invention)

VII 2-chloro-4 - (; - methoxypropylamino) -6- [N-acetyl - (; ■ - methoxypropylamino)] - s - triazine (according to the present invention)
VIII 2-chloro-4-alIylamino-6- (N-acetylethylamino) -

s-triazine (according to the present invention)
IX 2-chloro-4-allylamino-6- (N-acetylal! Ylamino) -s-triazine (according to the present invention)

in a concentration of 1.2 or 5 kg of active substance sprayed on the surface of the soil per hectare. The behavior of the rising plants was observed for 30 days and assessed according to the following scale:

no damage = 0

slight damage = +

severe damage = + +

Failure in <· ■ '"= number

Results A) Concentration 1 kg of active substance per hectare

connection Corn wheat barley Rapeseed mustard celery onion cauliflower Turnip cabbage weed I. 0 10 + + 80 + 10 + + 100 + 90 II 0 90 20th 90 100 100 + 100 80 100 III 0 20th -Ι -Ι 0 + 0 50 0 85 IV 0 0 Ο Ο 0 0 0 0 0 75 V 0 0 0 0 0 0 + + + 85

Corn B) concentration 2 barley cg active ingredient per hectare mustard alfalfa cauliflower weed connection 0 wheat 30th Rapeseed 10 100 100 100 I. 0 80 100 90 100 100 100 100 II 0 100 0 100 0 90 90 85 III 0 0 0 80 0 -f 90 V 0 0 0 0 + + 0 80 VI 0 +

7 8

C) Concentration 5 kg of active substance per hectare

connection Corn barley Flax alfalfa Red clover mustard weed I. 0 80 100 100 100 100 100 II 0 100 100 100 100 100 100 III 0 40 100 90 100 + 95 VII 0 0 0 0 0 0 100 VIII 0 0 0 0 0 0 90 IX 0 + - 0 0 0 0 70

Weed effect

The weed population consisted of the following [5 Weeds together: Matricaria chamomilla. Raphanus raphanistrum, Capsella Bursapastoris, Stellaria media, Chenopodium album, Amaranthus lividus, Polygonum persicaria and Plantago media.

The results show that the active compounds IV to IX according to the invention are similarly good herbicides Like the known compounds I to III, they have an effect on the weed population. The active ingredients IV to IX, however, are far more tolerable by plants in the case of various cultivated plants than the known active ingredients I to III.

Example 11

The seeds of the test plants were sown in a freshly prepared bed. Immediately after sowing were "the substances

I 2-chloro-4,6-bis-ethylamino-s-triazine (according to Swiss patent 342 784)

II l-chloro ^ -isipropylarnino-o-ethylamino-s-tnazine (according to Swiss patent 342 784)

III 2- methylmercapto ^ o-bis-isopropylaminos - triazine (according to Swiss patent 342 784)

X 2-chloro-4-ethylamino-6- (N-propionyl-N-ethylamino) -s-triazine (according to the present invention)

Sprayed onto the soil surface at a concentration of 5 kg of active substance per hectare. Behaviour of the emerging plants was observed for 30 days and according to the following scale judged:

no damage = 0
severe damage = + +
slight damage = +
Failure in% = number

Results

connection Muis wheat Flax Soybean Rapeseed weed I. 0 100 100 100 100 100 II 0 100 100 100 100 100 III 0 100 100 100 ■ 100 90 X 0 + 0 0 0 90

The weed population consisted of the following weeds: Mercurialis. a veronica and a species of umbellifer, Chenopodium. Galium. Capsella, Papaver and Sherardia.

The result shows that the active ingredient X according to the invention has a similarly good herbicidal action has on the weed population like the known compounds I to III. However, the active ingredient X has in the case of various cultivated plants, a significantly greater plant tolerance than the known ones Active ingredients I to III.

Example 12

Seed trays were filled with soil, with various Plants are sown and then the surface of the earth with the substances

XI 2-chloro-4-ethylamino-6- (N-isobutyrylethylamino) -s-triazine (according to the present invention), melting point 97 to 100.degree
I 2-chloro-4,6-bis-ethylamino-s-triazine (according to

Swiss patent 342 784)
II sprayed 2-chloro-4-ethylamino-6-isopropylamino-s-triazine (according to Swiss patent 342 784) at a concentration of 5 kg of active ingredient per hectare. After 3 weeks, the condition of the test plants was assessed on the following scale:

10 =

Normal state
9 to 1 = growth inhibition
Extent)
Dead plant

Results

(depending on

0 =

oats Effect after 3 weeks mustard connection 9 1 XI 0 0 I. 0 0 II Ryegrass 10 ■ 0 0

The result shows that the active ingredient XI according to the invention acts more selectively than the known ones Compounds 1 and II. By having the same effect on the weeds mustard the plants oats and Raygrass practically not damaged.

909 541/88

Claims (2)

1 44O UOO Claims: 1. New 2-halo-4,6-diamino-s-triazines of the general formula I. Shark R, NN, CO-R ₁ (D where Hai is a chlorine or bromine atom, Ri den Methyl, ethyl or isopropyl radical, Rj and R: i the ethyl, allyl or methoxypropyl radical and Ri is a hydrogen atom or the ethyl radical means. 2. Use of 2-halo-4,6-diaminos-triazine derivatives of the general formula I. Shark ^R 3 CO-R ₁ IN where Hai is a chlorine or bromine atom, Ri is the methyl, ethyl or isopropyl radical, Rz and R =! denotes the ethyl, allyl or j-methoxypropyl radical and Ri is a hydrogen atom or the ethyl radical, for weed control.