FR2477837A1 - HERBICIDE COMPOSITION BASED ON 4-AMINO-3-METHYL-6-PHENYL-1,2,4-TRIAZINE-5- (4H) ONE THIOCARBAMATE DERIVATIVE AND THE APPLICATION OF THIS COMPOSITION TO THE DESTRUCTION OF UNDESIRABLE PLANTS - Google Patents

Abstract

THIS COMPOSITION CONTAINS AS ACTIVE INGREDIENTS: -A THIOCARBAMATE DERIVATIVE OF GENERAL FORMULA (CF DRAWING IN BOPI) IN WHICH ONE OF THE X OR Y REPRESENTS A HYDROGEN ATOM AND THE OTHER IS A CHLORINE ATOM AND -4-AMINO -3-METHYL-6-PHENYL-1,2,4-TRIAZINE-5- (4 H) -ONE OF GENERAL FORMULA (CF DRAWING IN BOPI)

Description

The present invention relates to a herbicidal composition and

  the application of this composition to the destruction

undesirable plants.

  In recent years, many herbicides have been developed, the application of which has led to

  manpower in the agricultural sector. Name-

  many problems regarding efficiency and job security

  certain herbicide products nevertheless make it desirable

  the arrival of new improved herbicides. Wave-

  particularly with insistence on herbicides which, while effective in low weed numbers, do not exert any harmful effects on the weeds.

  crops and do not pollute the environment.

  The object of the invention is to satisfy these requirements. Thus, it firstly relates to a herbicidal composition which contains as active ingredient a combination of a thiocarbamate derivative of general formula iy C8H

X CH 2SC-N <I

  C2H5 in which one of X or Y is hydrogen and the other is

  a chlorine atom and a 4-amino-3-methyl-6-phenyl-1,2,4-

triazine-5 (4H) one of formula o

Q N-NH2 II

CH

  The compounds of formula I are known to be effective herbicides for certain annual grasses such as Echinochloa spp., Diitar, Setaria spp. and Poa

  annua spp. and Cerus sp. annual and useful for the ds-

  herbage crops such as rice, corn, soy

and the beetroot.

  The compounds of formula II are also known herbicides for destroying various broad-leaved annual plants such as Polygonum spp., Chenopodium album, Amaranthus albus and Stellaria media, treated during their growing season, with such efficiency that cause virtually no damage in some cultures

  and especially in beet crops.

  Each of the compounds of formulas I and II, however, is not always effective as a completely selective herbicide, if used in small amounts or at low concentration, for the control of weeds growing in beet fields. Thus

  the compounds of formula I exhibit excellent activity

  herbicide against grasses by application prior to removal from the soil, without affecting beet harvests, but are insufficient to completely destroy broadleaf and grassy plants

  soil, if they are used in low or low

  tration. On the other hand, the compound of formula II exhibits excellent herbicidal activity against broad-leaved plants, by application to the plants when taken out of the soil, with a high degree of selectivity and practically does not exert any activity. effects on beet crops, but it is not effective, if applied before emergence from the soil, against broadleaf plants or grasses. Herbicide activity is eliminated if it rains soon after application, and is insufficient for broadleaf plants already

in the adult stage.

  The combination, according to the invention, of the compounds of formulas I and II makes it possible to destroy large-leaved plants before their release from the soil, and after their release from the soil, grasses and broadleaf plants with

  adult stage, which was previously impossible by

  plication of the compounds taken separately. The composition according to the invention therefore has a significant herbicidal activity with respect to a whole range of undesirable plants, including annual grasses and broad-leaved plants, throughout their growth period, by application before or after their growth. out of the soil, in small quantities or at low concentration. In addition, the composition according to the invention is resistant to rain and therefore has a durable herbicidal activity. We can

  think that high stability under different conditions

  tions, the high activity particularly with regard to

  adult broadleaf plants and the im-

  The composition of the invention is due to the ease with which the compound of formula II can be absorbed into the body of plants using the compound of formula I. The invention is in fact based on the discovery according to the invention. which combination of the compounds of formulas I and II,

  not only compensates for the deficiencies of each

  above mentioned elementary compositions, but also produces an unexpectedly high synergistic effect, so that the composition according to the invention can destroy both grasses and broadleaf plants growing in beet fields, and that its activity herbicide

  remains high over the entire period of growth of

  herbs, by application before and after their release from the soil. It has also been found that the composition according to the invention is effectively applicable only to

  beets, but also spinach, barley, corn, but.

  In another aspect, the invention relates to a method

  inhibiting weed growth in crops

  beet, spinach, barley, corn and corn kernels, which consists in applying to the planted surface, before or after the crop is removed from the soil, a composition containing as active ingredients a compound of formula I and a compound of formula II in an amount sufficient to

  inhibit weed growth, but insufficient

  health to damage the crops. In the application before leaving the soil, the composition may be applied, preferably by spraying to soils in which the plants to be harvested have been sown. In post-soil application, the composition is usually applied to the stems and leaves of the plants, preferably by spraying. As examples of compounds of formula I,

  used in the composition according to the invention, the compounds

  following compounds Compound A S- (p-chlorobenzyl) -N, N-diethylthiocarbamate

C Q CH2SC-N <, '

  - 2H Compound X S- (o-chlorobenzyl) -N, N-diethylthiocarbamate c v

O CH2SC N

  The synergistic effect of the herbicidal composition according to the invention is particularly significant for certain specific ratios of the compound I and the compound II, but this ratio can vary quite significantly. In general, it is indicated to use between 0.05 and 10 parts by weight, and preferably between 0.125 and 4 parts by weight, and

  preferably between 0.25 and 2 parts by weight of the com-

  pos6 of formula II (hereinafter referred to as compound C) for one part by weight of the compound of formula I. The herbicidal composition according to the invention may be subject to preparations containing from 0.5 to 80% by weight of active ingredients such as powders or wettable grains, emulsions, powders, grains,

  suspensions flowing easily or the like.

  In the preparation of the herbicidal composition according to the invention, the active ingredients are mixed with a diluent or a carrier. Mention may be made, as diluent or solid support, of talc, bentonite, clay, kaolin, diatomaceous earth, white carbon (colloidal silica filler), vermiculite, lime, sand, calcium carbonate, dolomite, magnesia powder, fuller's earth, ammonium sulphate and urea. As diluent or liquid carrier, there may be mentioned alcohols, dioxane, actone, cyclohexane,

  methylnaphthalene, dimethylformamide and acetonitrile.

  Surfactant products that can be added to

  compositions according to the invention as emulsifiers

  cation, dispersion or suspension may be of the type

  cationic, anionic or nonionic. Cationic products

  include, for example, ammonium compounds

  quaternary such as cetyltrimethylammonium bromide.

  As anionic products, mention may be made of the soaps, the salts of aliphatic monoesters of sulfuric acid, such as sodium lauryl sulphate and the salts of sulphonated aromatic compounds, such as dodecyl benzene sulphonate, sodium, calcium or ammonium lignosulphonate, and

  butylnaphthalene sulfonate. Products of the non-

  ionic products include, for example,

  densification of ethylene oxide with fatty alcohols such as olefinic alcohol and cetyl alcohol or with alkylphenols such as octylphenol, nonylphenol and octylcresol, partial esters derived from long chain fatty acids and hexitol anhydrides such as sorbitol monolaurate and the condensation products of these partial esters with ethylene oxide such as polyoxyethylene sorbitan monolaurate. It is also possible to add to the herbicidal compositions according to the invention various conventional additives such as carboxymethylcellulose and

the same as locust beans.

  The useful dose of active ingredients of the composition according to the invention depends on the atmospheric conditions, the state of the soil, the form of the composition, the season of application, the method of application, the type of harvest to be protected, the type and stage of growth of the herbs to be destroyed; it is usually between

  0.5 and 30 kg, preferably between 2 and 12 kg and especially

  between 5 and 8 kg per hectare in soil treatment

  or foliage treatment. The composition is usually

  it is preferably applied at a concentration of 500 to 30,000 ppm, preferably 2,000 to 20,000 ppm and especially 5,000 to 10,000 ppm of active ingredients. In the case of application of the herbicide composition by spray from an aircraft, the concentration of active ingredients

  is between 10,000 and 75,000 ppm. For example, we

  verise between 0.5 and 1.5 kg of active ingredients at a rate

from 20 to 50 liters per hectare.

  The herbicidal composition of the invention is applied in undiluted or diluted form to the water, to the soil or to the stems and leaves of the plants as above mentioned. It is also possible to add other herbicides to this composition in order to increase its activity substantially.

herbicide.

  The present invention will be better understood elsewhere and

  its advantages will be apparent from the description and

  examples that follow, illustrating it without, however,

  limit. This is how we can vary the pro-

  portions of the ingredients as well as the types of media.

  Unless otherwise indicated, the parts, percentages and ratios

ports are given by weight.

  a) Emulsifiable Concentrate Dissolves between 5 and 80%, preferably between 10 and 70% and more preferably from 15 to 30% of active ingredients, the ratio of the compounds of formulas I and II being 1: 0.05 - 10, in 5 to 90% and preferably 30 to 60%

  a liquid carrier to which is added from 1 to 40% and

  5 to 20% of an emulsifying agent.

  b) Wettable powder 5 to 80% and preferably 50% of active ingredients are milled and mixed well, the ratio of the compounds of formulas I and II being 1: 0.05-10, 1 to 20% and preferably 5 to 10% of a surfactant product and 5 to

  and preferably 40 to 70% of a solid support.

  c) Dusts 90-99.5% and preferably 9599% of a solid carrier is preferably milled and mixed with 0.5 to 10% and preferably 1 to 5% of active ingredients, the ratio of

  Formula I and II being 1: 0.05-10.

d) Granules

  It grinds and blends well at 60 - 99.5% and

  90-98% of a solid support 0.5 - 40% and pre-

  2 - 10% of active ingredients, the ratio of the compounds of formulas I and II being 1: 0.05-10; we

  knead with water, granulate and dry.

  Example 1 - Wettable powder A wettable powder is prepared by homogeneously mixing and grinding 30 parts of compound A, 20 parts of compound C, 2 parts of sodium alkylbenzene sulfonate, 3 parts of polyvinyl alcohol, 20 parts of carbon. White

  and 25 parts of finely pulverized clay.

  Example 2 - Wettable powder A wettable powder is prepared by homogeneously mixing and grinding 40 parts of compound B, 20 parts of compound C, 2 parts of sodium alkylbenzenesulphonate, 3 parts of polyvinyl alcohol, 20 parts of carbon.

  white and 15 parts of diatomaceous earth-

  Example 3 - Wettable powder A wettable powder is prepared by homogeneously mixing and grinding 30 parts of compound A, 10 parts of compound C, 2 parts of sodium alkylbenzenesulphonate, 3 parts of polyvinyl alcohol, 20 parts of carbon.

  white and 35 parts of finely pulverized clay.

  Example 4 - Wettable powder A wettable powder is prepared by homogeneously mixing and grinding 40 parts of compound B, 10 parts of compound C, 2 parts of sodium alkylbenzenesulphonate, 3 parts of polyvinyl alcohol, 20 parts of carbon.

  white and 25 parts of finely pulverized clay.

  Example 5 - Wettable powder A wettable powder is prepared by homogeneously mixing and grinding 30 parts of compound A, 30 parts of compound C, 2 parts of sodium alkylbenzenesulphonate, 3 parts of polyvinyl alcohol, 20 parts of carbon.

  white and 15 parts of diatomaceous earth.

  Example 6 - Wettable powder A wettable powder is prepared by homogeneously mixing and grinding 50 parts of compound A, 2.5 parts of compound C, 3 parts of polyoxyethylenealkylarylether,

  3 parts of calcium lignosulfonate, 30 parts of

  white bone and 11.5 parts of finely pulverized clay.

  Example 6 - Wettable powder A wettable powder is prepared by homogeneously mixing and grinding 5 parts of compound B, 50 parts of compound C, 2 parts of sodium alkylbenzenesulphonate, 3 parts of calcium lignosulfonate, 10 parts of earth.

  of diatoms and 30 parts of finely pulverized clay.

  Example 7 - Wettable powder A wettable powder is prepared by homogeneously mixing and grinding 5 parts of compound B with 50 parts of compound C, 2 parts of sodium alkylbenzenesulphonate, 3 parts of calcium lignosulfonate, 10 parts of earth.

  of diatoms and 30 parts of finely pulverized clay.

  Example 8 - Emulsion An emulsion is prepared by homogeneously mixing 10 parts of compound A, 20 parts of compound C, 6 parts

  of polyoxyethylenealkylarylether, 4 parts of alkylaryl

  sodium fonate and 60 parts of dimethylformamide.

  EXAMPLE 9 Emulsion An emulsion is prepared by homogeneously mixing parts of compound B, 5 parts of compound C and 4 parts.

  of sodium alkylarylsulfonate, 6 parts of polyoxyethylene

  alkylarylether and 55 parts of dimethylsulfoxide.

  EXAMPLE 10 Granules Granules are prepared by homogeneously mixing and grinding 5 parts of the compound A, 5 parts of the compound C, 2 parts of polyvinyl alcohol, 15 parts of diatomaceous earth and 73 parts of clay, by mixing. the mixture ground with addition of water, granulating the mixture and drying the granules. Example II - Granules Granules are prepared by dissolving 10 parts of compound

  A and 0.5 part of compound C in 3 parts dimethylformate

  mammae and spraying 86.5 parts of diatomaceous earth

  in the form of granules with the solution obtained.

  EXAMPLE 12 Granules Granules are prepared by homogeneous mixing and grinding of one part of compound B, 10 parts of compound C, 1 part of sodium alkylbenzenesulphonate, 5 parts of white carbon, 50 parts of bentonite and 30 parts of talc. , by kneading

  this mixture, in the granulaut and drying the granules.

  EXAMPLE 13 Powder A powder is prepared by homogeneous mixing and grinding of 3 parts of compound B, 1 part of compound C, 0.5 part of

  white carbon and 95.5 parts of clay.

  Example 14 - Ponder A powder is prepared by homogenous mixing and grinding of 8 parts of compound A, 0.5 part of compound C, 15 parts of diatomaceous earth, 50 parts of clay and 26.5 parts

of talc.

  EXAMPLE 15 Powder A mixture of 0.5 parts of compound B, 5 parts of compound C and 2 parts is prepared by homogeneous mixing and bryoageo.

  of white carbon and 94.5 parts of clay.

  The tests described below were carried out to remove the excellent herbicidal activity of the composition according to the invention. Each test makes it possible to realize that the use of each elemental compound gives insufficient herbicidal activity, but that the combined use of these compounds according to the invention leads to a herbicidal activity greater than the sum of that of each of the compounds.

  components on a whole range of plants.

Example 16 -

  This example illustrates the herbicide activities on any

  a variety of undesirable plants as well as phyto-

  beet-toxin toxicity of the compositions according to the invention by treating the plants before they leave the soil. Each time, thirty (30) seeds of each of the following plants: beet (Beta vulgaris),

  barnyard (Echinochloa crusgalli), Kentucky bluegrass

  Nuns (Poa annua), ladybird (Polygonum lapathifolium) and crow's feet (Chenopodium album var., centrorubrum Makino) were planted in culture soil contained in 2,000 cm2 polyethylene containers. After covering the soil seeds, each of the wettable powders prepared in Examples 1 and 3 in diluted form with water to give the concentrations of the products

  presented in Table 1, are uniformly

  on the ground at a rate of 500 liters per hectare. 25 days after spraying the fresh weight of the test plants is measured, from which growth inhibition (%) is calculated as follows. Plant fresh weight Growth inhibition (%) = (1) treated area) Fresh weight of plant grown in untreated space x 100. .....

  The results are collated in Table 1. For comparison purposes, similar tests were performed in which each of the compounds used in the compounds were used.

  above positions are applied separately in the

  conditions above; the results are also

appeared in Table 1.

TABLE 1

  HERBICIDE ACTIVITY AND PHYTOTOXICITY TO BEETS

BY TREATMENT BEFORE EXIT FROM THE GROUND

  Compound e Growth Inhibition Rate (X)

of application ...... ...

  (kg / ha) Beetroot Turf Grass Persicaire Crow's foot meadow

A 3 0 89 86 23 19

B 3 0 81 83 25 20

C 2 O 23 63 100 100

  C __ _ _ _ _ _ _ _ _ _ _ _ i _ _ _ _ _ _ _ _ _ _ i i __ _ __ _ [__i _____ [_ i [_ [1 __ [[ii

1 0 6 20 80 79

A 3

+ 0O 100 100 100 100

C 2

A 3

+ 0O 100 100 100 100

C 1

B + O 100 100 100 100

C 2

B 3

+ 0 100 100 100 100

C 1

r \) - "J, -." D4 CD) E J4 - "4

Example 17

  This example illustrates herbicide activities on different

  pests and phytotoxicity to beverages

  Raves composition according to the invention by treatment plants after leaving the soil. Two thousand cm2 of polyethylene containers, filled with culture soil, are grown in beets (stage 1 to 2 leaves).

  barnyard grass (stage 2 to 2.5 leaves), pasture

  meadow (1.5 to 2 leaf stage), lady's meadow (stage

  1 to 2 leaves) and crow's feet (1.5 to 2 leaf stage).

  Each of the wettable powders prepared is diluted according to

  examples 2 and 4 with water to obtain the concentra-

  In Table 2, the stems and leaves of the plants are sprayed at a rate of 500 liters per hectare. 20 days after spraying, the fresh weight of the test plants is measured and the inhibition is calculated.

  of growth (%) according to formula III.

  The results are collected Table 2.

  ACTIVITY? ICIDE AND PhIYTOTOXICTT TIS-A.VIS DOS BETTE RAVES BY

  TPAITEMNT ON THE TIES AND FEUILL; D: CC @ UR 'GROWTH

  Inhibition rate of croosa-ne (%) Application compound (kg I ha) On Beetroot Eurasian Blue-legger Goose leg brace back close

A 4 O 78 70 13 10

  B o 75 70 1.6 2 o 59 1 o. % 9 32 40 A o0 1O0 00 93 100 A

+ 0 96 100 86 93

c

+ 0 * 1 00 100 100

C 2

B 4

+ 0 99 100 85 96

C i J-Pl: - Ca -4 '"4

Example 18 -

  This example illustrates the herbicidal activities on yellow foxtail (Setaria viridis Beauv.) And amaranth (amaranthus albus) composition according to the invention by treatment before and after output of the soil plants. Seeds

  species examined are placed on the surface of the

  polyethylene bags containing 2,000 cm2 of soil and covered with 0.5 cm of soil. Each of the wettable powders prepared according to Examples 5 and 4 is diluted with water to obtain the concentrations of active compounds given in Table 3; the soil is sprayed in the pre-emergence tests and the stems and leaves in the trials of the plants grown at a rate of 500 liters per hectare. 20 days after spraying, the fresh weight of the plant examined is calculated from the formula IIIIt growth inhibition (%)

  the results are collected in Table 3.

TABLE 3

  HERBICIDE ACTIVITY BY TREATMENT DIFFERENT

STAGES OF GROWTH

  Apprenticeship rate S. V. A.a S.vSv. A.a.

Compound plication .....

  (kg / ha) Pre - emergence 0.5_i F 1-1.5 F 1.5 2 F 2.5, 3 F 2.5, 3 F 3.5 4, 5 FA 4 98 53 86 50 42 il 10 O0

B 4 100 58 88 52 47 20 13 7

C 4 4 O O 92 O 79 O 42

1 9 O O 88 o 51 o 14

A 4

+ 100 100 100 100 93 97 60 89

C 4

A 4

+ 100 96 100 100 89 92 58 84

C 1

B 4

+ 100 100 100 100 96 99 66 92

c 4

B 4

+ 100 100 98 100 92 96 60 91

  C i Not treated 0 0 0 0 0 0 0 0 S.v. Setaria viridis Beauv .; 0.5o-1 F: stage 0.5, - 1 sheet A.a. Amaranthus albus ro -, 4. -j4, co Co4 \ Jn -

Claims (7)

  1. A herbicidal composition characterized in that it comprises as active ingredients - a thiocarbamate derivative of general formula 1 | C2H5 I 2 I X CH2SC-N < 2H5   in which one of the X or Y represents an atom of hy-   drogen and the other is a chlorine atom and   4-amino-3-methyl-6-phenyl-1,2,4-triazine-5- (4H) - one of general formula O C) N N_NH2 CH3   2. The herbicidal composition according to claim 1 characterized   in that the compound of formula I is S- (p-chloro) benzyl) -N, N-diethylthiolcarbamate.   3. Herbicidal composition according to claim 1 characterized   in that the compound of formula I is S- (o-chloro) benzyl) -N, N-diethylthiolcarbamate.   4. A herbicidal composition according to any one of the   1 to 3 characterized in that it contains between   0.5 and 80% by weight of active ingredients.   5. A herbicidal composition according to any one of the   Claims 1 to 4, characterized in that the ratio of the compound of formula I to the compound of formula II is between 1: 0.05 and 1: 10 in weight.   6. Herbicidal composition according to claim 5 characterized   in that the ratio is between 1: 0.125 and 1: 4 by weight.   7. Inhibition of plant growth inhibition   desirable in that it consists in applying to the plants or the soil in which these   plants a herbicidally effective amount of   herbicide position according to any of the reveoEdi.i cations 1 to 6.   Process according to claim 7, characterized by the fact that the composition is based on the amounts of 0.05 to 30 l of ingredients per hectaxeo   9 Proces ed selo la reenlcea'o 8 etri en 8, .. c.   the application rate is 2 and 12 g of the actiús actiús by the apeo