DE1219726B - Selective herbicide - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

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AOIn

German class: 451-19 / 02

1,219,726 G 28306IV a / 451 November 4, 1959 June 23, 1966

The present invention relates to selective herbicides containing new triazine derivatives as herbicidal active ingredients.

From the German Auslegeschrift 1011 904 are already herbicidally effective 4,6-diamino-2-triazine derivatives became known that on the nitrogen atoms of the two amino groups by alkyl or alkenyl radicals are substituted and those in the 2-position are a chlorine atom or an alkoxy or alkyl mercapto group wear.

These known s-triazine derivatives are primarily general herbicides for total kill any plant growth and leave only a few useful plants (e.g. maize) practically unaffected. Selective effects can only be achieved with these active ingredients if certain ones are meticulously adhered to Dosages in certain associations of useful plants and unwanted plants can be achieved, but this selectivity is not very specific; i.e., these active ingredients do not leave generally certain plant species (except maize) undamaged in practical doses.

4,6-Diamino-s-triazines substituted in the 2-position in a manner analogous to the above, which are attached to one of the both amino groups carry an alkoxyalkyl radical and on the other amino group by alkyl or alkenyl radicals are mono- or disubstituted, have not yet been described.

It has now been found that new s-triazine compounds of the formula

I.

Selective herbicide

NN
Ri-NH-L J-NH-R ₂

in which X is chlorine or the methoxy or methyl mercapto radical, Ri is an alkyl or alkenyl radical at most 5 carbon atoms and R2 is an alkoxyalkyl radical With a total of at most 6 carbon atoms means a good selective herbicidal Have an effect. The herbicidal compositions which contain these new active ingredients can be used as a pre- or Post-emergence agents are used, especially in the cultivation of cereals, linaceae such as flax and flax, legumes such as alfalfa, beans, peas and clover varieties and potatoes without these Crop plants are damaged.

Applicant:

J. .R. Geigy A. G., Basel (Switzerland)

Representative:

Dr. F. Zumstein, Dipl.-Chem. Dr. rer. nat. E. Assmann

and Dipl.-Chem. Dr. R. Koenigsberger,

Patent Attorneys, Munich 2, Bräuhausstr. 4th Named as inventor: Dr. Enrico Knüsle, Riehen; Dr. Hans Gysin, Basel (Switzerland) Claimed priority: Switzerland of 5 November 1958 (65 811.65 814)

Examples of active ingredients are:

1. 2-chloro-4-ethylamino-6 -> '- methoxy-propylaminos-triazine, M.p. 157 to 158 ° C;

2. 2-chloro-4-ethylamino-6 -> '- isopropoxy-propylamino-s-triazine, M.p. 144 to 146 ° C;

3. 2-chloro-4-ethylamino-6 - ^ - methoxy-äthylaminos-triazine, mp 166-167 ⁰ C;.

4. 2-chloro-4-isoproρylamino-6-y-methoxy-proρylamino-s-triazine, m.p. 112 to 114 ⁰ C.

5. 2-chloro-4-isopropylamino-6-y-isopropoxypropylamino-s-triazine, mp 99 to 100 ⁰ C.

6. 2-chloro-4-isopropylamino-6- / j-methoxy-ethylamino-s-triazine, M.p. 94 to 96 ° C;

7. 2-chloro-4-isopropylamino-6-y-ethoxy-propylamino-s-triazine, Bp 0.001 151 to 158 ° C;

8. 2-chloro-4-n-propylamino-6-y-methoxy-propylamino-s-triazine, M.p. 174 to 175 ° C;

9. 2-chloro-4-allylamino-6-y-methoxy-propylaminos-triazine, M.p. 169 to 171 ° C;

10. 2-methoxy-4-ethylamino-6-y-methoxy-propylamino-s-triazine, M.p. 81 to 83 ° C;

11. 2-methoxy-4-ethylamino-6-ß-methoxy-ethylamino-s-triazine, mp 80 to 8I ⁰ C.

12. 2-methoxy-4-ethylamino-6- (3-ethoxy-ethylaminos-triazine, Bp 0.008 155-157 ° C;

13. 2-methoxy-4-isopropylamino-6-y-methoxypropylamino-s-triazine, mp 82-83 ⁰ C.

14. ^ -Methoxy ^ -isoamylamino-o-y-methoxypropylamino-s-triazine, B.p. oo6 167 ° C;

609 580/384

15. 2-Methoxy-4-allylammo-6-y-metlioxy-propylamino-s-triazine, M.p. 83 to 87 ° C;

16. 2-Methyhttercapto-4-ethylamino-6-y-methoxypropylamino-s-triazine, M.p. 82 to 84 ° C;

17. 2-methylmercapto-4-ethylammo-6- / S-methoxyethylamino-s-triazine, M.p. 70 to 75 ° C;

18. 2-methylmercapto-4-ethylamino-6-y-ethoxypropylamino-s-triazine, Bp 0.002 168 to 171 ° C;

19. 2-methylmercapto-4-ethylamino-6 | 8 äthoxyäthylamino-s-trkzin, Kp.o, 4170-175 ⁰ C;

20. 2-methylmercapto-4-n-propylamino-6-y-methoxy-propylamino-s-triazine, M.p. 63 to 71 ° C;

21. 2-methylmercapto-4-isopropylamino-6-y-methoxy-propylamino-s-triazine, M.p. 68 to 70 ° C;

22. 2-methylmercapto-4-isopropylamino-6 - /? - ethoxyethylamino-s-triazine, M.p. 70 to 75 ° C;

23. 2-methylmercapto-4-isopropylamino-6- ^ methoxy-ethylamino-s-triazine, M.p. 106-107 ° C;

24. 2-methylmercapto-4-isopropylamino-6-y-ethoxypropylamino-s-triazine, Bp 185 to 195 ° C;

25. 2-methylmercapto-4-isoamylamino-6-y-methoxypropylamino-s-triazine, Bp 0.004 175 to 183 ° C;

26. 2-methylmercapto-4-allylamino-6-y-methoxypropylamino-s-triazine, Bp 0.007155 to 165 ° C.

The new active ingredients can be used by methods known per se, mostly in the presence of indifferent ones Solvent, by reacting cyanuric chloride with the corresponding alkyl or alkenyl amines and the corresponding alkoxyalkylamines in the presence of acid-binding agents and, if X does not Chlorine is still with an alkali metal methylate or an alkali metal methyl mercaptide in any Sequence to be established. One can of course also use known cyanuric chloride derivatives in which a chlorine atom of the cyanarchic chloride molecule has already been replaced by an alkylamine or alkenylamine is replaced and optionally a second chlorine atom by the methoxy or methyl mercapto radical, and these intermediates with an alkoxyalkylamine in the presence convert hydrochloric acid binding agents. Molar excesses of the can also be used as acid-binding agents appropriate amine can be used.

The compounds mentioned above and other compounds of the general ones defined at the beginning Formula I are particularly suitable as selective active ingredients for weed control agents, i.e. for selective ones Suppression and eradication of weeds under crops, especially in cereals, Linaceae, legumes and potato plantings. Among weeds are here too undesirable, e.g. B. understood previously grown crops.

The selective herbicides according to the invention can be in the form of solutions, emulsions, suspensions or dusts are provided, the application forms depend entirely on the Uses. All the application forms must have a fine distributability of the active substance guarantee. The selectivity of growth inhibition comes with the use of generally more clearly to their advantage in relation to carrier substances which are indifferent to plants.

Vegetable and animal oils in particular are suitable for the preparation of solutions. In order to facilitate the dissolution of the active ingredients in these liquids, if necessary small amounts of organic liquids with better dissolving power and mostly lower boiling points, d. H. Solvents such as alcohols e.g. B. ethanol or isopropanol, ketones, e.g. B. acetone, Butanone or cyclohexanone, diacetone alcohol, cyclic hydrocarbons, e.g. B. benzene, toluene or Xylene, chlorinated hydrocarbons, e.g. B. tetrachloroethane or ethylene chloride, or mixtures of the the above substances are added.

The aqueous work-up forms are primarily emulsions and dispersions. The substances are preferably communicated as such or in one of the abovementioned solvents Emulsifiers or dispersants homogenized in water. Of cationic emulsifying or Examples of dispersants are quaternary ammonium compounds, and examples that are anion-active 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, it can also be used as an active ingredient, emulsifier or dispersant and, if appropriate, solvent existing liquid or paste-like concentrates are made that are suitable for dilution with Suitable for 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, Powdery preparations and pastes can be suspended in water and used as sprays be made.

The various application forms can be used in the usual way by adding substances, which the distribution and the ability to penetrate into the soil depending on the root depth of the one 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. Other substances, which affect plant growth can also be added, such as. B. 3-Ammo-1,2,4-triazole to accelerate the onset of action, or other selectively herbicidal substances z. B. from the urea and carbamate series, as well as inorganic substances.

The combination with fertilizers means where appropriate a labor saving and can increase the resilience of the cultivated plants to be protected increase.

The required amounts of active ingredient vary with selective weed control depending on the

Sensitivity of weeds, the resistance of the cultivated plants, the time of application, the climatic conditions and soil conditions between about 0.25 and 10 kg per hectare. In special cases, the above application rates can also be exceeded.

Example 1 (pre-emergence) ■

Seed trays are filled with soil and sown with 20 seeds each of the test plants oats (cereals) and mustard (weeds) (sowing depth 1 cm). Immediately after sowing, the known comparison compound 2-methylmercapto-4,6-bis-isopropylamino-s-triazine I and the active ingredients according to the invention corresponding to the numbers in the list of active ingredients on columns 2 and 3 are added in concentrations of 0.2 g / m ² ( = 2 kg / ha) in the form of 2% suspensions applied to the surface of the relevant seed tray by means of an automatic spray device.

After 21 days, the tabular evaluation was carried out according to the decimal scale:

10 = normal condition (no damage), 0 = plant completely dead, 1 to 9 = intermediate stages.

30th

35

40

45 area of the parcels was 0.15 g / m ² (= 1.5 kg / ha). Comparative plots of the field with the known herbicidal active ingredients 2-chloro-4,6-bis- (ethylamino) -s-triazine (I) and 2-methylmercapto-4,6-bis (isopropylamino) were tested in the same way and with the same concentration. -s-triazine (II) treated.

3 months after the treatment, the evaluation of the results showed the following tabulated Image;

Scale used:

0 = no damage,
4 = total loss,
1 to 3 = intermediate stages.

In the last column, the weed effect is shown as a percentage of that determined on the blind test plots Weed effect (0% = weed effect in the blind test) stated. As weeds they were Weeds of various species that grow rampant in wheat fields are usually represented.

substance oats mustard I. 0 0 3 8th 0 5 10 1 6th 7.5 0 7th 8th 0.5 11 7.5 0 12th 10 2.5 14th 10 0 21 10 0 24 * 8th 0 25 * 10 2.5

Means application concentration 0.05 g / m ² .

The comparison substance I also shows the effect profile 0 0 at this concentration.

All tested according to the above method, ten according to the invention Active ingredients are clearly superior to the known compound I in terms of selectivity in oats, in that they do not damage oats or only slightly, but the weed mustard practically completely destroy.

Example 2 (post-emergence)

Winter wheat of the »Probus« variety was sown in the usual way on a trial field in late autumn, and in the following spring, after they had reached a height of 20 to 25 cm, the weed plots of this test field with dispersions of the following, the numbers of List of active ingredients treated on columns 2 and 3 corresponding active ingredients according to the invention, so that the final concentration of each active ingredient on the

substance Winter wheat Weed effect 15th 0 90% 18th 0 95% 19th 0 85% 20th 0 950 / ,, 21 0.5 97% 22nd 0 950/0 23 0.25 970 / " 24 0.5 90% 26th 0 90%, I. 4th 950/0 II 2 900 / "

After the treatment with the active compounds according to the invention, the wheat showed no or practically no no damage with a weed efficiency between 85 and 97%, while the comparison substance II on wheat 'caused clearly visible damage and the comparison substance I caused the wheat crops completely destroyed.

Example 3

Seed trays with a surface area of about 25 × 35 cm and a depth of 7 cm were filled with humus sand and then sown with flax (Linum usitatissimum), white mustard (Sinapis alba) and spergula (Spergula arvensis). Immediately after sowing, the various seed trays were filled with dispersions of the active ingredients according to the invention (substance number corresponds to the numbering in the active ingredient table on columns 2 and 3) and the known comparative substance 2-methylmercapto-4,6-bis- (isopropylamino) -s-triazine (I) sprayed so that the active ingredient concentration was in each case 0.1 g / m ² seed pan area.

The results obtained after 18 days are shown in a table on a scale of ten:

10 = normal condition (no damage),
0 = plants completely dead,
1 to 9 = intermediate stages.

substance Flax mustard Spörgel 1 8.5 2 0.5 4th 7.5 0 0 13th 8th 0.5 0.5 16 6th 0.5 0 20th 7.5 4.5 0 21 10 1.5 0 I. 0.5 1 0

While the weeds mustard and spörgel were destroyed or very severely damaged by all substances with this dosage of 0.1 g / m ² , the compounds according to the invention caused no or only slight damage to flax. In contrast, the known comparative substance I practically completely destroys linseed in the same low dose.

Example 4

Flax (Linum usitatissimum) is sown in a test field with humus, sandy loam soil. After sowing, individual plots of this field are mixed with dispersions of active ingredients according to the invention and the comparative substances 2-methylmercapto-4,6-bis- (isopropylamino) -s-triazine (I) and 2-methylmercapto-4-ethylamino-6-isopropylamino -s- triazine (II) treated so that the concentration of active ingredient was 0.5 g / m ² surface in each case. The substance numbers of the active ingredients according to the invention used correspond to the numbering in the list of active ingredients on columns 2 and 3. The effect found after 30 days is shown in a table. The "Flax" column lists the crop failure in percent of an untreated test plot (100% = total failure) and the "Weed effect" column lists the destruction of the weed population (also in percent) that had the following weeds: Matricaria chamomilla (chamomile ) dominant, Raphanus raphanistrum (Heiierich), Capsella bursa pastoris (shepherd's purse), Stellaria media (chickweed), Chenopodium album (goose foot), Amarantus lividus, Polygonum persicaria and Plantago media (plantain).

substance Effect on flax Weed effect 9 0% 100% 10 0% 100% 11 0% 100% (slight damage) 21 0% 100% I. 100% 95% II 100% 100%

Example 5

Bush beans (Leguminose) and chamomile (Matricaria sp.) And Hederich (Raphanus raph.) As weed plants are sown as test plants in freshly prepared seed beds. The known herbicides 2-chloro-4äthylamino-6-isopropylamino-s-triazine (I) and 2-methoxy-4,6-bis-isopropylamino-s-triazine (II) as well as the 2- Methylmercapto-4-isopropylamino-6 - (γ -methoxy-propylarnino) -s-triazine (III) in concentrations of 0.5 g / m ² each sprayed onto the corresponding beds as suspensions, and the state of growth of the plants is continuously monitored and assessed after 55 days on the following scale (pre-emergence):

5 = normal growth,
0 = plants dead,
1 to 4 = intermediate stages.

The result is shown in a table:

substance Broad bean chamomile wild radish I. 1 1 1 II 1.5 1 1 III 5 1 . 1

The active ingredient III according to the invention acts selectively in that it contains French beans as opposed to compounds -I and II does not damage, kills the weeds chamomile and hederich to the same extent.

If one uses alfalfa (Medicago

sativa) and Serradella clover (Ornithopus sativus) and, as weeds, chamomile and chickweed (Stellaria medica) in seed beds and the post-emergence method is used, in which the beds with the plants are in the 4- to 6-leaf stage about 1 month after sowing uniformly with emulsions or suspensions of the known active ingredient 2-chloro-4-ethylamino-6-isopropylamino-s-triazine I and the material according to the invention 2-chloro-4-ethylamino-6- (γ-methoxypropylamino) -s-triazine IV in such Splashed quantities such that the concentration is 0.5 g / m ² , according to the above evaluation scale, the following picture is obtained after 70 days:

In contrast to I, the material IV according to the invention also has a complete effect on the legumes extremely selective.

Example 6

Two potato varieties were planted in a test field with humus, sandy loam soil (»Lori« and »Voran«). Immediately after the tubers were laid, they were piled up with earth, whereby the tubers were covered about 10 cm high. The main weeds were: Chenopodium album (goosefoot), Polygonum persicaria (peach knotweed), Polygonum convolvulus (bindweed knotweed), Amaranthus sp. (Amaranth), Capsella bursa pastoris (Shepherd's purse), Plantago lanceolata (ribwort), Stellaria media (chickweed).

As a test substance, the 2-methylmercapto-4-isopropylamino-6- γ- methoxypropylamino-s-triazine according to the invention in the form of an aqueous di-

substance alfalfa Serradella clover chamomile Chickweed I.
IV 1.2
5 1.2
-5 1
1.5 1
1

spersion applied with a logarithmic sprayer at an initial concentration of 0.5 g / m ² and a final dilution of one twenty-fifth of the initial concentration. At the time of this treatment, no shoots of the potatoes could be seen, while the weeds were almost exclusively in the germination stage. This high application rate of 0.5 g / m ² caused no damage to the potatoes, while 70% of the weeds were destroyed at concentrations of 0.1 g / m ^2.

Claims (1)

Claim: Selective herbicide, characterized by a content of new triazine derivatives 10 the general formula
X NN. I. Ri- NH-L J-NH-R ₂ in which X is chlorine or the methoxy or methyl mercapto radical, Ri is an alkyl or alkenyl radical with a maximum of 5 carbon atoms and R2 denotes an alkoxyalkyl radical with a total of at most 6 carbon atoms. Documents considered: German Auslegeschrift No. 1 011 904. When the application was announced, two priority documents were displayed