DE2018719A1 - Tnazine derivatives - Google Patents

Description

Badische Anilin- & Soda-Fabrik AG 9Π1 B7 1 Q

Our sign Ο.Ζ, 26 733 Schs / AR 6700 Ludwigshafen, April 17th, 1970

Triazine derivatives

The present invention relates to valuable new iriazine derivatives with good fungicidal activity and fungicides containing these compounds.

It is known, the zinc salt of Äthylenbisdithiocarfcaminsäure (Zineb) or tetramethylthiuram disulfide (IMTD) as fungicides too use, but their effects are unsatisfactory.

It has been found that triazine derivatives of the formula

in which R .., R ₂ and R, each a Ν, Ιϊ-dichloramino or F _# H-dibromoamino group, R ₂ and R, furthermore each a methyl radical, a stearyl radical, a phenyl radical, the methoxy radical, chlorine or .the radical

A ··

-NC, where A and B each represent an ethyl or chloroethyl radical and A also means hydrogen, a good one have fungicidal effects *

This effect is particularly evident against the mushrooms, such as Aspergillus niger, and vegetable pattiogenic mushrooms from the Class of Phycomycetes. The fungicides are therefore particularly suitable for protecting liquid and solid materials such as glue, Wax and drilling oil emulsions, plastic dispersions or leather, against fungal attack and to protect vines against attack by the false powdery mildew fungus Piasmopara viticola.

The following applies when dividing up the new connections concerns;

As with melamine, direct chlorination in aqueous suspension according to.

R - NH ₂ + 2 Cl ₂ -> K - NCl ₂ + 2HCl

R = triazine residue 109845/1801 145/70 -2-

- 2 -. ■ O.Z. 26 733

considerable difficulties. The by-product - Hydrochloric acid inhibits the reaction. With increasing acid concentration, the reverse reaction becomes:

R- NHCl + HCl R - NH ₂ + Cl ₂

favored. Paneben becomes part of the amino-s-triazine through the resulting hydrochloric acid is converted into the hydrochloride, that is difficult to chlorinate. In addition, proceeds the implementation in acetate-buffered acetic acid solution for some substituted amino-s-triazines in a completely different way. This is how acetoguanamine is made. and chlorine and bromine, respectively, among them Conditions (K. Nencki, Chem, Ber. J), 232 (1976); A. Ostrogpvich, Bull.soc.Bukarest, t4, 49 (1905)) not 2-methyl-4,6-bisdichloramino-s-triazine, but according to

+ 2 HCl NH ₂ .HCl

2-! Erichloromethyl-4, ö-bis-amino-s-triazine hydrochloride.

Several processes are already known which deal with overcoming these difficulties in the chlorination of melamine. The production of hexachloromelamine can be carried out most advantageously (German Auslegeschrift 1 221 229) without the disadvantages listed above by reacting chlorine with melamine in the presence of water, if an aqueous suspension of melamine in the presence of an amount of a hexachloromelamine formed to solution 4es is sufficient Reacts water immiscible solvent with chlorine with stirring at temperatures below 60 ⁰ C, separates the hexachloromelamine after separating the aqueous phase from the solution by cooling or by evaporating the solvent and the mother liquor optionally returns to the chlorination stage.

Substituted N, N- bichloraiii.nu ~ s-triazines from substituted alino-s-triazines in aqueous solution with chlorine in the presence of a solution to the resulting

...... 109845/1902 _3_

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Mono- or bis-N / N-dichloramino-s-triazine sufficient amount a water-immiscible organic solvent.

The reactions can be carried out as in Melaein at elevated temperatures at about 60 ⁰ G when the rest of the triazine core remaining radicals, for example phenyl or stearyl, not co-react at this temperature. In the case of 2-methyl-4,6-bisamino-s-triazine, 2-chloro-4,6-bis-amino-s-triazine and 2-methoxy-4,6-bis-amino-s-triazine, it is advantageous to the chlorination should not be carried out above 30 to 40 ° C. In the case of 2,4-bischloro-6-amino-s-triazine as the starting material, it is necessary to carry out the reaction at 0 to 10 ° C. in order to exclude hydrolytic cleavage. The most favorable chlorination temperatures can easily be determined by means of a preliminary test; they are dependent on the resistance of the other residues on the triazine ring to chlorine as well as the pH of the solution and the solubility of the chlorinated amino-s-triazines in the organic solvent.

Chlorinated saturated and unsaturated solvents are suitable as solvents Hydrocarbons, especially chloroform, carbon tetrachloride, Di-, tri-, tetra- or pentachloroethane, trioder Tetrachlorethylene or mixtures thereof.

The solvents mentioned generally have an excellent, strongly temperature-dependent dissolving power for most mono- or bie-dichloramino-s-triazines, which is the advantage has that these solvents can be used simultaneously to recrystallize the desired products.

The advantage of the process lies in its easy accessibility very pure conversion products. As the starting connections used amino-s-triazines and the primary N-chloramino-s-triazines generally very difficult to use in water-immiscible solvents, the Ν, Ν-dichloramino-s-triazines on the other hand, are easily soluble, the course of the reaction can be followed precisely from the organic phase the mostly already very pure reaction product can be isolated.

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The chlorination can either be carried out by introducing chlorine or by continuous or discontinuous addition of a saturated solution of chlorine in the solvents mentioned. As a chlorinating agent, of course, can also be used with mother liquors saturated with chlorine can be used at low temperatures. The chlorine is here in at least equivalents Amounts, advantageously used in excess.

Analogous to the known processes for the preparation of chloromelamines, syntheses for the preparation of the bromine and iodine compounds are known.

The bromination of melamine was investigated both in organic solvents and in aqueous suspension. she leads to N-bromo derivatives with 2 to 6 bromine atoms (USA patents 2 184 888 and 2 472 361).

Another method is to obtain hexabromelamine by Action rom bromine on suspended in aqueous-alkaline solution Melamine and the addition of chlorine, alkali hypochlorite or hexachloromelamine to the reaction mixture (British patent specification 933 531).

As in the case of chlorination, the bromination of an amino-s-triazine according to

R- NH ₂ + 2 Br ₂ ■ R - HBr ₂ + 2HBr (R * Triazinreet)

the hydrohalic acid, which inhibits the reaction and with increasing SHure concentration favors the reverse reaction.

This difficulty can be overcome once «by knowing how stated above, in buckets Zweiphaeeaeyetem B.B. Carbon tetrachloride / water works or the hydrobromic acid formed during the reaction is removed from the equilibrium by means of bases, e.g. sodium hydrogen carbonate.

The Ν, Ν-Dlbromamino-s-triazines according to the invention are sum part in carbon tetrachloride, chloroform, methylene chloride, di-, tri-, tetra-, pentachloroethane etc. not to the same extent as the above

109845/1902 bad original -5-

. 2Q18719

wrote T $, N-rDiehloraaino-s-triazine soluble, Darua were the N-bromine compounds according to the invention. Broaieren the suspended ^ A ^ iino-s-triazine ait Broa _: in aqueous ^ elkaliacher, solution datrg ^ stejtlt. . _; ^ ^: - -.- · ■ - "■ ·

The broaing of the aaino-s-triazine suspended in 5 to 25 times the amount of water took place at 0 ° bJLs 50 ⁰ G ait ^ of the equivalent amount of broa or an excess of broa up to TOO ^ with the addition of the equivalent amount of sodium hydrogen carbonate. ■. _v .

Due to the generally lower heak activity of the Broas in relation to chlorine, a direct influence of the ligands R on the degree of brownness of the triangles can be ascertained.,. _t.-..-: .. ':, ..

Kretov and Iiavydow (Chia. Geterooikl.sded. 1965, Hr.6, p.934-938) describe the broadening of 4 * 6-Diaaino-s - tria ζ inen, which are in 2-position by electrophilic residues, such as CPj, CHFgi COGF, CHPCl, CF ₂ Cl, uad CiOl _2,. are substituted, and they only get, with difficulty, monobroaaaino-triazine and the only dibromaaino-s-triazine is 2-Ί ^l rifluoraθthyl-4-dibroaaaino-6-bΓoaaainp-s-tr4.azine in oily yield. ,; , ^,, .. - _; ■

It has been found that the Broaierung the Aaino _t-triazines by elektrophilf radicals such as Cl, is complicated and leads to Monobroaaainoe-triezi ". ■ ₄ .- _Vl _ _: ,. ,,. ,;, ^ ... ^,. ·. · ;;

Super-cool electron donors as ligands, such as alkyl, Aryl, Alkoxy, Alkylaaino, Dialkylaaino etc., because they have the basicity of the Kerjies and because the electron density ia nitrogen of the Increase aaimo group, the broaing of the aaino-a-triazines to dibroaaaino-8- »triazines.

The following new N, N-Dihalogenaaino-s-triaiin compounds will be mentioned in the individual cases

1) 2,4-Bis-iH, H-diohloraai »o) -6-ethyl-8-triazine

2) 2,4-BIs- (Jn, N-dichloraaino) -6-phenyl-8-triazine ^:

3) 2,4-BIe- (N, N-diohloraaino) -6-atearyl-e-triazine

4) 2,4-Bifl- | [N _f N-dichloroaiHo) -6-ethoxy-s-triazine

5) .2,4-BIe- (H, N-diohloraaino) -6-ohlor-e-triaain ....._ ■,

6) 2- (H, H-.Diohloriai »o) -4,6-bie-phenyl-a-triaiine ■ .._ ..,. , _r

10 9 8 4 5/1902 _BAD original

. - 6 - O.Z, 26 733

7) ^ {Nj-N-Mohloraml · ^.,. ,,., - ..

8) 2- (N _t iT

9) 2,4-Bisrv (N, N-dibroma ^

11) 2- (N, N-dibromoamineQ) -4-okl · ^: '>

12) 2- (N, N-dibromamino) »4 ^ Qhlor-6-diethylamine p-s-tTiaz; tp,

13) 2- (N, N ^ i) ibromamino) -4,6-bia (: methoxy) TS ^ triazine,,

14) 2,4 | 6-Tri8- (N, N-dibromamino) -s-triazine. -, -. ; _Γ,,

The parts given in the examples are parts by weight.

Example 1 _v . '/."V.'. ** ".". "."'.

1.25 parts of acetoguanamine are suspended in a mixture of 700 parts of carbon tetrachloride and 700 parts of water. . Into this mixture is introduced to 3O ⁰ g of chlorine gas at a rate of 1 liter / min * under stirring at 25 ° "After-10 to 20 minutes is the chlorinated acetoguanamine und.befindet in; the carbon tetrachloride phase. The · clear, aqueous phase, in. which the hydrogen chloride is dissolved * - is separated: and replaced by the same amount of fresh water and chlorine gas is introduced again. The process is repeated twice more so that a total of 37.5 parts (0.3 mol) of acetoguanamine are converted.

After, ending the. Implementation werden.die aqueous layers combined and extracted twice with IQO.Teile, carbon tetrachloride. All carbon tetrachloride phases are combined and concentrated in vacuo ^ (^ 14 mm. Hg). This gives 78 parts (corresponding to a yield of $ 9 $> of theory, based on the charged acetoguanamine) of 2,4-bis (N, N-dichloraminp) -6-methyl-Sftria "in (OAH ₃ PI ^ N ₅ ) in size yellow crystal needle. Das.Produkt has a melting point toh 73 ° at 74 ⁰ Q, a chlorine content (active) of 53.8 $> (theory: 54 _f 2 fi),

Example 2 ^

10 parts of benzoguanamine are suspended in 800 parts of carbon tetrachloride and 700 parts of water. Into this mixture is introduced under stirring at 35 ° C ⁰ 45 bia Chlorgaa with a Geaohwiadigkeit of 1 liter / min. After a few minutes, the two clear aqueous phase, in which the hydrogen chloride is dissolved, becomes "b-

. , _Vi 109845/1902 _BAD original ~ ⁷ "

■ - ■ "■ 'j; Approx

.- 7 - O.Z. 26th

As U "■

separated and replaced by "the same amount of fresh water and new benzoguanamine and again chlorinated. The process is repeated until a total of tie 50 parts of benzoguanamine have reacted. The carbon tetrachloride solution is separated off and at -25 ⁰ C cooled umd the auskrieta iridescent 2, 4-Bis- (N, N-dichloramino) -6-phenyl-e-triazine (Cg ₁ H ₅ Cl ₄ N ₅ ) is filtered off and dried, giving 49.6 parts of yellow crystals with a melting point of 135 ^° C

An additional 24.1 parts of crystals are recovered by removing the solvent. The total yield is 73.7 parts (= 84.9 % of theory) with buckets of chlorine content (active) clay 43 # (theory: 43.7 #). "* - '™ ^β * ^Äim ^ -

Example 3

30 parts of stereoguanamine are suspended in 1000 parts of carbon tetrachloride and 1000 parts of water. In this Hischumg, as described in Example 1 initiated with stirring at 25 ° to 35 ⁰ C Ohiorgas. After a few minutes the aqueous phase is renewed and again 30 parts of stereoguanamine are added and chlorinated. The process is repeated until a total of 150 parts of stereoguanamine have been converted. After the carbon tetrachloride solution has been separated off, the solvent is removed in vacuo. Urine contains 204 parts (= 99 £ of theory) 2,4-Bie- (N, N-dichloraaJjio) -6-h «ptadecyl-s-triaEin (C ₂₀ H ₅₅ Cl ^ H ₅ ) as crystalline substances with a melting point of 45 to 46 ⁰ C (chlorine (iktir) «ei. 56.4 Jt; calc. 56.2 t).

Example 4

As described in the preceding examples, 100 parts of 2-methoxy-4,6-bis-amino-s-triazine in a öemiech water * chlorinated 700 part carbon tetrachloride and 700 parts in small portions at 40 ° to 50 ⁰ C, wherein the hydrochloric acid aqueous phase is renewed five times. About half of the solvent is drawn off from the carbon tetrachloride solution. At -40 ° C., 190 parts (= 96 l> of theory) of 2,4-bis- (N, N-dichloramino) -6-methoxy-s-triazine (C ₄ H ₃ Cl ₄ ON ₅ ) fall in the form of a yellow crystalline product with a melting point of 86 ° to 87 ⁰ C (chlorine ^ aIt ₁ ; found: 51.0 · ^ calc. t 50.9 96).

109845/190 2 ^ ₀ ORIGINAL " ⁸ "

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Example 5

100 parts of 2-chloro-4,6-amino-s-triazine are added in small proportions as described in Example 1, is chlorinated in a mixture of 700 parts of carbon tetrachloride and 700 parts of water at 30 to 40 ⁰ G. Crystallize from the carbon tetrachloride solution, after previously removing about half of the solvent, at -30 ⁰ C 161 parts (82.7 $ of theory) 2,4-bis- (N, N-dichloramino) -6-chloro-s- triazine (0, H ₅ CIC) in the form of yellow crystals having a melting point of 119 ° to 120 ⁰ C of (chlorine Curr. Found .: 50.4 $> \ calc .: 50.1 $).

Example 6

49.6 parts of 2-amino-4,6-bis-phenyl-s-triazine are chlorinated in small portions into a mixture of 700 parts of carbon tetrachloride and 700 parts of water at 20 ° to 30 ⁰ C. From the carbon tetrachloride solution, after removing the solvent in vacuo, 60 parts (95 # of theory) 2- (N, N-Dlchloramino) -4,6-bis-phenyl-s-triazine (C ^, -H ^ ₀ CIgN.) obtained as a colorless crystalline product with a melting point of 136 ^° C. (chlorine act. found: 23.3 Pt calc .: 22.4 #).

Example 7

224 parts of freshly prepared 2,4-bis-chloro-6-amino-s-triazine are suspended in small portions in 1000 parts of carbon tetrachloride and 1000 parts of water and chlorinated at room temperature. Crystallize from the carbon tetrachloride solution by removing about 2/3 of the solvent at -20 ° to -30 ⁰ C 267 TTile (84.2 ji of theory) of 2- (N, N-Dichloramino) -4,6-biechlor-8- triazine (C ^ Cl ^ N.) as a yellow crystalline product with a melting point of 88 ° to 89 ⁰ C from (chlorine act. Found .: 30.8 $> \ calc .: 30.4 #).

Example 8

122 parts of 2-chloro- _7- ethylamino-6-amino-s-triazine are suspended in small portions in 700 parts of carbon tetrachloride and 700 parts of water and chlorinated at room temperature. From the carbon tetrachloride solution, after removing the solvent in vacuo, 161 parts (82.5 96 of theory) 2- (N, N-Diohloramino) -4-

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(N-chloro-ethylamino) -6-chloro-a-triazine (CKH ₅ Cl ₄ N ₅ ) as a yellow

crystalline product obtained a melting point of 63 ° to 65 ⁰ C old.

(Chlorine act. Found: 56.9 i ° \ calc. \ 38.5. #; Chlorine geθ. Found: 50.6 #; calc .: 51.3 #).

- Example 9

In a solution of 67.2 parts of sodium hydrogen carbonate in 500 parts of water, 25 parts of 2-methyl-4,6-diamino <-s-triazine are suspended · Under vigorous stirring at 0 ° to 5 ⁰ O I40 added parts of bromine, wherein strong carbon dioxide formation is observed. It will do stirred for 16 hours at 25 ⁰ C, the product bromide-washed and dried. 60 parts (68.2% of theory) of a red-yellow substance (0.H ₃ Br ₄ N ₅ ) with 71 »2 · ji are obtained. active bromine (theor. 71,4 ^), which ^{melts at 105 0} C with decomposition.

Example 10

7.05 parts of 2-methoxy-4,6-diamino-s-triazine are suspended in a solution of 16.8 parts of sodium hydrogen carbonate in 25% of water. Bei.20 ⁰ C. 35 parts of bromine were added. The mixture is stirred for a further 6 hours, and the solid product is filtered off with suction and dried. »Is obtained 15 parts (66.8 ^ of theory) of a yellow substance (C ₄ H ₃ Br ₄ N ₅ O) recrystallised from .Tetrachlorkohlenstoff 66.6 $> Brom active (theor. 69.9 9 ^) at the 117 ⁰ C melts.

Example 11

I »200 parts of water, 17.4 parts of 2-chloro-4-ethylamino-6-amino-s-triazine are suspended and 16.8 parts of sodium hydrogen carbonate are dissolved. 34 g (0.21 mol) of bromine are added slowly with stirring and, after the reaction has ended, the mixture is stirred for a further 14 hours. After working up the product, 33.2 parts (100 # of theory) of a red-yellow substance (C ₅ HgBr ₂ GlN ₅ ) with 46.5 ^ bromine active (theor. 48.2 #), which at 83 ° o ' melts.

^r ";■" ■■ "° Example 12

40.3 parts of 2-chloro-4-diethylamiiio-6-amino-s-triazine and 33.6 parts of sodium hydrogen are suspended in 500 parts of water - ^! carbonate dissolved. To do this, 70 parts are slowly set while stirring

109845/1902 -10-

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Bromine at O ⁰ O, stir for 1 hour at O ⁰ C and 13 hours at 2O ¹ V and dissolve 48 parts (67% of theory) of a red-yellow substance (C ₇ H ₁₀ Br _{2 ClN 5} ) from the product with methylene chloride, which crystallizes poorly.

Example 13 - ■ ■. , .. ■ -..-.

46.8 parts of 2,4-bis- (methoxy) -6-aminos-triazine are suspended in a solution of 50.4 parts of sodium hydrogen carbonate in 500 parts of water. 95 '9 parts of bromine are added between 0 ° and 5Q ⁰ C; it is stirred for 15 hours. The reaction product is drained off, washed free of bromide and dried.

80 parts (85 % of theory) of a yellow, crystalline substance (Ci-HgBr ₂ N. O ₂ ), which can be recrystallized from carbon tetrachloride, with 47.1 fo bromine active (theor. 51 $) and a melting point of 129 ⁰ C _.;

Example 14

12.6 parts of 2,4,6-tris-amino-s-triazine are suspended in a solution of 50.4 parts of sodium hydrogen carbonate in parts of water. For this purpose, ^{95.9 is added at 20 °} C. with vigorous stirring. Parts bromine, with strong formation of carbon dioxide being observed. After stirring for a further twelve hours, the product is filtered off with suction, washed free of bromide and dried in vacuo.

51 parts (85 $> of theory) of a red-yellow substance Ng) with 80 ϊ> bromine active (theor. 80 #), which are above

₅₅ g
13O ⁰ C melts with decomposition.

The agents according to the invention can be used as solutions, emulsions, Suspensions or dusts are used. The forms of application depend entirely on the intended use; You should ensure a fine distribution of the active substance in each case.

To produce directly sprayable solutions, hydrocarbons with boiling points higher than 150 ⁰ C, e.g. tetrahydronaphthalene or alkylated naphthalenes, or organic liquids with boiling points higher than 150 ⁰ C and one or more functional groups, e.g. the keto group, the subgroup, can be used

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ν r- vb ''. "■ ;. -

Ester group or the amide group, this group being a substituent on a hydrocarbon chain or a component a heterocyclic ring can be used as spray liquids. .

Aqueous application forms can be made from emulsion concentrates, fasting or wettable powders (wettable powders) by adding water be prepared. To produce emulsions, the substances can be used as such or dissolved in a solvent Wetting or dispersing agents, e.g. polyethylene oxidation products, can be homogenized in water or organic solvents. But it can also consist of active substance, emulsifying or Dispersant and possibly solvent-based concentrates are prepared that are suitable for dilution with water.

Dusts can be produced by mixing or grinding together of the active substances with a solid carrier, e.g. kieselguhr, talc, clay or fertilizer.

Example 15

The active ingredients are added to a nutrient solution that is optimally suited for the growth of the Aspergillus niger fungus in various amounts, graduated up to 10 parts per million parts of nutrient solution. In each case 20 ml of the nutrient solution treated in this way are inoculated in 100 ml Erlenmeyer flasks with 0.3 mg Aepergillue fungal spores. The flasks are heated for 120 hours at 36 ⁰ G and then the extent of fungal development, preferably on the Nährlösungsoberfläch "occurs evaluated.

Evaluation scheme: 0 = no fungal growth, graded up to 5 = uninhibited fungal growth (fungal cover on the surface of the nutrient solution closed).

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Aspergillus test

Active ingredient according to name Amount of active ingredient in the

Example no. Nutrient solution in parts

Active ingredient per million parts of nutrient solution

100 50 25 10

5 2,4-bis (N, N-dichloramino) -

6-chloro-s-triazine 0 0 0 2

4 2,4-BIs- (N, N-dichloramiao) -

6-methoxy-s-triazine 0 0 0 2

1 2,4-BIs- (N, N-dichloramino) -

. 6-methyl-B-triazine 0 0 0 2

2 2,4-BiS- (N, N-dichloramino) -6-phenyl-s-triazine 0 0 0 4

9 2,4-bis (N, N-dibromamino) -

6-methyl-s-triazine 0 0 0 0

10 2,4-BiS- (N, N-dibromamino) -

6-methoxy-s-triazine 0 00 0

11 2- (N, N-dibromamino) -4-ehlpr-

6-ethyl-ami »o-s-triazide 0 0 0 4

13 2- (N, N-dibromamino) -4,6-bis-

methoxy-s-triaziri 0 13 3

14 2,4,6-Tris- (N, N-dibromamino-

s-triazine 0 0 0 0

Comparison agent: TMTD 12 4 5 untreated (control) 5

Example 16

70 parts of the compound according to Example 1 are mixed with parts of N-methyl-ft-pyrrolidone and a solution is obtained which is suitable for Application in the form of the smallest drops is suitable.

Example 17

20 parts of the compound according to Example 2 are dissolved » % n of a mixture consisting of 80 parts of xylene, 10 parts of the adduct of 8 to 10 mol of ethylene oxide with 1 mol of oleic acid-N-monoethanolamide, 5 parts of the calcium salt of sodecylbenzenesulfonic acid and 5 parts of the adduct consists of 40 moles of ethylene oxide in 1 mole of castor oil. Pouring the solution into 100,000 parts of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.

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Example 18. .

20 parts of the compound according to Example 3 are in a mixture dissolved, the-from 40 parts of cyclohexanone, 30 parts of isobutanol,

20 parts of the addition product of 7 moles of ethylene oxide to 1 mole Isoootylphenol and 10 parts of the adduct of 40 moles of ethylene oxide and 1'MoI of castor oil consists. By pouring and fine Distributing the solution in 100,000 parts of water is obtained Aqueous dispersion which contains 0.02% by weight of the active ingredient.

Example 19

20 parts of the compound according to Example 4 are dissolved in a mixture consisting of 25 parts of cyclohexanol, 65 parts of a mineral oil fraction of boiling point 210 to 28O ⁰ C and 10 parts of the plant ^ - adduct of 40 mol of ethylene oxide to 1 mol of castor oil, Pouring obtained len water, an aqueous dispersion which contains 0.02 wt $ of the active _ingredient: and finely distributing the solution to 100 000 TEI..

Example 20.

20 parts of the active ingredient according to Example 5 are mixed with 3 parts of the sodium salt of diisobutylnpahthalin-QL-aulfonic acid, 17 Parts of the sodium salt of a ligninsulphonic acid from a SuIfit waste liquor and 60 parts of powdered silica gel mixed well and ground in a hammer mill. Finely distributing the mixture in 20,000 parts of water gives a Spray mixture containing 0.1% by weight of the active ingredient *

Example 21

3 parts of the compound according to Example 6 are intimately mixed with 97 parts of finely divided kaolin. One gets in this way a dust which contains 3 wt. # of the active ingredient.

Example 22

30 parts of the compound according to Example 7 are intimately mixed with a mixture of 92 parts of powdered silica gel and 8 parts of refined oil which has been sprayed onto the surface of this silica gel. In this way, a preparation of the active ingredient with good adhesion is obtained. . ·

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Claims (1)

, - 14 - O.Z. 26th Claims Triazine derivative of the formula in which R ₁ , R ₂ and R each denote an NjN-dichloramino or N, N-dibromoamino group, R ₂ and R * further each denote an alkyl group, a phenyl group, methoxyreet, chlorine or the group -l <g, where A and B each represent an ethyl or chloroethyl radical and A additionally denotes hydrogen. 2. 2,4-bis (N, N-dibromamino) -6-methyl-s-triazine. 5. 2,4,6-Tris- (N, N-dibroiuamino) -s-triazine. 4. Fungicide containing a triazine derivative as in claim marked. Aniline & Soda Factory in Baden 109845/1902