JPH0416441B2 - - Google Patents

Description

[Detailed description of the invention]

Protecting crops from weeds and other vegetation that inhibit crop growth is a recurring problem in agriculture. To overcome this problem, researchers in the field of synthetic chemistry have produced a wide range of chemicals and chemical compositions that are effective in controlling such undesirable growth. Many types of chemical herbicides have been published and many are in commercial use. In some cases, active herbicides have been found to be more effective when used in combination than when used alone. This result is often referred to as a "synergistic effect" because the combination represents a potency or level of activity that exceeds what one would expect the compounds to have based on knowledge of their individual potencies. ” is called. The present invention relates to the use of herbicides whose potency as herbicides is known.
It is based on the discovery that certain thiol carbamates and certain dimethylureas can be used in combination to provide a synergistic effect. It is known in the art that the two compounds making up the combination that is the subject of the present invention independently exhibit an effect on plant growth. Thiol carbamates are used as herbicides in U.S. Patent No.
No. 3185720 [Tilles et al., 1965, 5]
March 25th] No. 3198786 [Tilles et al.
August 3, 1965] and No. 2913327 [Tilles et al., November 17, 1959]. N'-(3-chloro-4-methylphenyl)
-N,N-dimethylurea, whose common name is chlor toluron, is sold in Europe under the trade name Dicuran by Civer-Geigy GmbH (Switzerland). There are now two components: (a) a thiol carbamate of the formula ^{( b} ₎ a _dimethylurea compound of the formula It has now been discovered that a composition comprising a herbicidally effective amount of a herbicide provides a synergistic effect in controlling undesirable vegetation. The term "alkyl" is used herein to represent straight chain and branched chain groups. Examples of alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and the like. All carbon atom ranges are inclusive of their upper and lower limits. Examples of thiol carbamates useful in this invention include: 1 S-benzyl dipropyl thiol carbamate 2 S-benzyl ethyl 1,2-dimethylpropyl thiol carbamate These and other species falling within the scope of this invention The thiol carbamates of
Nos. 2913327, 3185720 and 3198786, as well as US Pat. A preferred thiol carbamate for use in the present invention is S-benzyl dipropyl thiol carbamate. A preferred dimethylurea for use in the compositions of the invention is N'-(3-chloro-4-methylphenyl)-N,N-dimethylurea. Here, the terms "synergism" and "synergistic effect" mean that the combination of herbicides has a potency that is greater than or equal to the potency that would reasonably be expected for the combination based on the potency of each herbicide applied independently. used to convey observed results when expressing the titer of The term "herbicide" is used herein to refer to compounds that control or alter the growth of plants. The term "herbicidally effective amount" is used to indicate the amount of such compounds or combinations of such compounds that are capable of producing a controlling or altering effect. Controlling or altering effects include all effects that deviate from natural development, such as withering, retarding, leaf burn, dwarf growth, etc. The term "plant" is used to include all emerging vegetation ranging from seedlings to established vegetation. In the compositions of the present invention, the weight ratio of thiol carbamate to chlortoluron whose herbicidal response is synergistic is from about 0.01:1 to about 20:1, preferably from about 0.1:1 to about 10:1. , optimally from about 0.1:1 to about 5:1. The ratio applied will vary depending on the weed to be controlled and the degree of control desired. Generally, in the composition of the present invention, 0.011 to 56 kg/ha
(0.01 to 50 pounds per acre) of active ingredients,
Preferably, active ingredient ratios of 0.11 to 28 kg per hectare (0.1 to 25 pounds per acre) are most efficiently used. This composition is particularly suitable for
It is effective in controlling Gallium aparine. Example 1 Experiments were conducted in a greenhouse to obtain a synergistic response when using chlortoluron (compound 1 of Table 1) in combination with one of the two S-benzyl thiol carbamates. These S-
The benzyl thiol carbamate is as follows: Compound 2: S-benzyl dipropyl thiol carbamate Compound 3: S-benzyl ethyl-1,2-dimethylpropyl thiol carbamate Aluminum pans measuring 18 x 12 x 5 cm were filled with loamy sand and six trenches were dug across the entire width of each pan. Seeds of five biphyllous plant species were sown in a furrow and covered with soil. The plant types are: Sugar beet (SB-TM) Beta vulgaris (L.) Tefmono fumitory (FUM) Fumaria oficinalis
officinalis (L.)〕 Yaemugura (BDSW)〔Galium aparine
(L.)] White mustard (MD) [Sinapis arvensis
(L.)] Nagabaxigin (CD) [Rumex crispus
(L.) Seeds of six monocotyledonous species were sown in the same manner as the dicotyledonous plants: Alopecurus (BKGR) Alopecurus
myosuroides Huds. Oat (WO) Avena fatua (L.) Bromus steilis (L.) Bromus steilis (BAIG) Hordeum vulgare
(L.) Igri〕 PRGR Lolium perenne (L.) White wheat (WHFL) Triticum eistium
aestivum (L.)] Chemical solutions sprayed on the same day as sowing were prepared as follows: All other compounds except ziclone or chlortoluron were used with technical grades and % emulsifying concentrate. Acetone to water ratio 1:
The solution of No. 1 was used to make an industrial grade compound into a solution.
The chemical solution was spread onto the soil surface using a linear spray table for application as a pre-emergence treatment. This table was calibrated using a spray volume of 750 per hectare (80 gallons per acre). Each compound is
Used alone in the following ratios: Compound 1 (dicran) - 1.0 per hectare and
2.0Kg, Compounds 2 and 3 - 0.5, 1.0, 2.0 per hectare
and 4.0Kg. All ratios applied are for compound 1 (dicran)
Compound 2 or Compound 3 was added to the solution. Next, the flatbed was placed in a shaded greenhouse and sprayed with water overnight to keep it moist. The temperature ranged from 15 to 27°C.
The flatbed was kept moist throughout each experiment. Two to three weeks after treatment, each seedling was visually evaluated for control of growth by all sources of injury. Untreated flatbed seedlings are used as a standard, and 0% injury or growth control corresponds to growth in standard flatbeds. 100% growth control corresponds to complete withering. The herbicide interaction response is determined by the Limpel equation [Limpel, LE, et al.
al.) 1962 “Weed Control by
Weed Control by Dimethyl- Tetrachloroterephthalate Alone and In Certain Combinations
tetrachloroterephthalate Alone and Certain
Combinations.) “Proceeding N.E.C. (Proc.NEWCC),
Vol. 16, pp. 48-53): E = X + Y - XY / 100, where E = expected response value %(0) The value may be understood to be the value indicated when the interaction response is greater than the sum of the responses resulting from independent chemical treatments.Antagonistic responses may be the opposite.

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[Table] Results Looking at the above data, when compound 1 (dicrane) is used in combination with either compound 2 or 3, the effect on both monocotyledonous and dicotyledonous plant species is
It can be concluded that various synergistic herbicidal responses can be obtained. The S-benzyl thiol carbamate described herein is alternatively referred to as S-benzyl thiol carbamate, commonly referred to as chlorsulfuron, 2-
Chloro-N-[(4-methoxy-6-methyl-1,
known as 3,5-triazin-2-yl)aminocarbonyl]-benzenesulfonamide;
In combination with other herbicides, such as those sold under the trademark Glean by DuPont, Wilmington, Del., evaluations can be made in the same manner as in Example 1 above. Another compound that can be evaluated in combination with the S-benzylthiol carbamate described here is 2-chloro-4-(ethylamino)-6-(isopropylamino)-S-triazine, available from CiberKygy under the trade name Aatrex
It is commonly referred to as triandine, sold under the trademark Lasso by the Mosanto Chemical Company, St. Louis, Missouri.
Also, 2-[(4-chloro-6-(ethylamino)-S
-triazin-2-yl)amino]-2-methylpropionitrile, Ciel, Hyuston;
Trade name Bladex from Texas
Compounds such as those sold in 2007 and others with the same general structure can also be evaluated. S-benzyl thiol carbamate is also
U.S. Patent Application No. filed April 20, 1983
It can be evaluated in combination with phenoxyphenoxypentanoate and pyridyl phenoxypentanoate as described in No. 486730 and No. 486750. A special compound among these is 4-[4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy]-
Ethyl 3-hydroxypentanoate, 4-[4-(3
-methyl chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy]-3-hydroxypentanoate, and 4-[4-(3-chloro-5-trifluoromethyl-2-phenoxy)phenoxy]-3- It is ethyl hydroxypentanoate. S-benzyl thiol carbamate compounds are also used in phenoxyphenoxypropionic acids and their esters, as described in German Patent No. 2531643, and also in British Patent No. 1599121.
pyridylphenoxypropionic acids and their esters, as described and claimed in this issue. The S-benzyl thiol carbamate compound described herein is also 2-chloro-thiol, sold under the trademark Goal by Rohm and Haas Company, Spring House, Pennsylvania. 1-
(3-ethoxy-4-nitrophenoxy)-4-
(trifluoromethyl)benzene and sold by Rohm and Haas under the trade name Blazer2S and sold by Rohm and Haas under the trade name Blazer2S.
Rhone−Poulenc Chemical
5-[2-Chloro-4-(trifluoromethyl), sold under the trade name Tackle2AS by the Company, Monmouth, New Jersey, Inc.
When combined with a herbicide of the phenoxyphenyl structure represented by sodium phenoxy]-2-nitrobenzoate, it can be evaluated for activity as a synergistic herbicide. It should be noted that other herbicides that can be tested for synergistic herbicide activity in combination with the S-benzyl thiol carbamate described here are herbicides of the acetanilide structure, manufactured by Monsanto Company. ), St. Louis, Missouri, under the trademark Lasso, 2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide,
Sold under the trade name Dual by Civer-Geigy, Inc., Department of Agriculture, Greensboro, North Carolina, 2
-Chloro-2-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide.
Other examples include N-(butoxymethyl)-2-chloro-2',6'-diethylacetanilide, sold under the trademark Machete by Monsanto Company, St. Louis, Missouri; There are other general structures. Another herbicide that is expected to have a synergistic effect as a herbicide in combination with the S-benzyl thiol carbamate mentioned here is the generic name asulan, which is sold under the trade name Asilan. carbamates such as methylsulfanilyl carbamate.
Other suitable carbamates include 4-chloro-2-butynyl-N-, sold under the trademark Carbyne by the Velsicol Division of Gulf Corp., Chicago, Ill. Chlorocarbanilate and isopropyl m-chlorocarbanilate sold under the trademark Furloe by PPG Industries, Pittsburgh, Pennsylvania. Other compounds include α, which is sold under the trade name Treflan by Elanco Products Company, a branch of Eli Lilly Company, Greenfield, Indiana; ，
α,α-trifluoro-2,6-dinitro-N,
Stauffer Chemical Co., Ltd. (N-dipropyl-p-toluidine and O,O-diisopropylphosphorodithioate-S-ester)
N-(2-
mercaptoethyl)benzenesulfonamide;
3,6-
dichloro-0-anisic acid. Further, as another herbicide whose activity as a herbicide can be evaluated in combination with the S-benzyl thiol carbamate of the present invention, there is a herbicide manufactured by Stourer Chemical Co., Ltd. under the trade name RO-NEET (RO-NEAT).
NEET) S-Ethyl N-
Ethylthiocyclohexane carbamate, trade name Eptam (EPTAM) by Stouffer Chemical Company
S-ethyl dipropyl thiol carbamate, sold by Stauffer Chemical Company under the trade name Sutan;
Ethyl diisobutyl thiol carbamate,
S-(2,3-dichloroallyl)-diisopropyl thiol carbamate sold under the trade name Avadex by Monsanto Company, St. Louis, Missouri; sold under the trade name Vernum by Stauffer Chemical Co., Waist Pouch, Connecticut; S- sold at (Vernam)
Propyl dipropyl thiol carbamate and S-[(4-chlorophenyl)methyl]-diethyl carbanothioate, sold under the trade name Saturn by Kagome Kagaku Co., Tokyo, Japan. Additionally, herbicide compounds that may be evaluated to provide a synergistic effect in combination with the S-benzyl thiol carbamate described herein include Siel Chemical Co., Hyuston, Texas;
2-chloro-4-(ethylamino)-6, sold under the trade name Atrazine by
-(isopropylamino)-S-triazine, sold under the trade name Bladex by Schiel Chemical Co., Hughston, Texas;
2-[(4-chloro-6-(ethylamino)-S-triazin-2-yl]amino]-2-methylpropionitrile, sold by Civer-Geigy, Greensboro, North Carolina, 2,4-bis(isopropylamino)-6-
It is a general triazine including (methylthio)-S-triazine. Other triazine compounds include 2,4-bis(isopropylamino)-6-(methylthio)-, which is sold by Civer-Geigy under the trade name Caprol 80W.
s-triazine and 2-chloro-4,6-bis(isopropylamino)-s-triazine, sold by Civer-Geigy under the trade name Milogard 80W, and others. Synergism in weed control with the use of chlortoluron and S-benzyl thiol carbamate. Tested in an experiment: Compound No. 4: N-(4-isopropylphenyl)-
N′,N′-dimethylurea isoproturon Compound No. 5: 3-(3,4-dichlorophenyl)-
1-methoxy-1 methylurea linuron Compound No. 6: 1,3-dimethyl-3-(2-benzothiazolyl)urea methabenzthiazuron Compound No. 7: N-(3-chloro-4-methoxyphenyl)-N,N-dimethylurea methoxyuron Compound No. 8: 1-n-butyl-3-(3,4-dichlorophenyl)-1-methylurea neburon Compound No. 9: 2-t-butylamino-4-ethylamino-6-methylthio-s-triazine terbutryn Compound No. 10: S-2,3,3-trichloroallyl diisopropyl thiol carbamate triallate Compound No. 11: α,α,α-trifluoro-2,6
-dinitro-N,N-dipropyl-p-triidine trifluralin Compounds No. 4-11 are all commercially available and known in the art. The test was carried out as follows: aluminum pans measuring 19 x 8 x 6 cm were filled with loamy sand and six trenches were dug across each pan. In this furrow I sowed the following plant species: fool's parsley.
(FOPA) Aethusa sinapium (FOPA)
Cynapium) BKGR Alopecurus myosuroides Oat (WG) Avena fatua Sugar beet (SBTM) Beta vulgaris Brassica napus (RAJN) Brassica napus・Brome (poverty brome)
(PBRO) Bromus sterilis fumitory (FUM) Fumaria oficinalis
officinalis) catchweed bedstraw (BDWS) Gallium aparine (BA) Hordeum vulgare (ARG) Lolium multiflorum (ARG)
multiflorum) Scented Mayweed (Scented
mayweed) (MARE) Matricaria mekyuchita (Matricaria mekyuchita)
recutita) Poppy (POP) Papabelle SP. (Papaver spp.) Kusayoshi (REED) Phalaris arundinacea (Phalaris
arundinaceae) Poa annua (ABG) Mustard (MD) Sinapis arvensis White wheat (WHFL) Triticum
aestivum) Veronica hedelifolia (ILSW)
Hederifolia) All or part of the above plant species were used in each of eight separate tests. Solutions of chemicals sprayed on the same day as sowing were prepared as follows: Compounds were used as formulations or technical grades (see data table). Acetone to water ratio 1:
The solution of No. 1 was used to make an industrial grade compound into a solution.
The formulation was dissolved in water only. A solution of the chemical was sprinkled onto the upper surface for application as a germ treatment using a straight spray table. This table calculates the spray volume to 235 (1
25 gallons per acre). Each compound was used alone in the following application ratios. Kg per hectare Compound No. 1 0.25, 0.50, 1.00 and 2.00 Compound No. 4 0.25, 0.50, 1.00 and 2.00 Compound No. 5 0.50, 1.00, 2.00 and 3.00 Compound No. 6 0.50, 1.00, 2.00 and 3.00 Compound No. 7 1.00, 2.00, 3.00 and 4.00 Compound No. 8 1.00, 2.00, 3.00 and 4.00 Compound No. 9 0.50, 1.00, 2.00 and 3.00 Compound No. 10 0.125, 0.25, 0.50 and 1.00 Compound No. 11 0.0625, 0.125 , 0.25 and 0.50 Compound No. 1 was used at all possible application ratios in separate tests with each of Compounds No. 4 through No. 11. Each test was arranged as a 5 x 5 factorial arrangement (including 0 use ratios) and was designed as a fully randomized block design with two replicates. After spraying the flatbed, it was placed in a shaded greenhouse and sprayed with water overnight to keep it moist. The temperature ranged from 15 to 27°C. The flatbed was kept moist throughout each experiment. After 6 to 15-20 days post-treatment, each seedling was visually evaluated for control of growth by all sources of injury. Untreated flat bed seedlings were used as a standard. 0% injury or growth control corresponds to growth on a standard flatbed. 100% growth control corresponds to complete withering. Herbicide interaction responses were evaluated using the Limpel equation as previously described. The response or interaction relationship (R) from treatment with the combined herbicides is assumed to be synergistic (S) when the observed value is greater than the expected value. It is understood that a synergistic response should be one where the interaction response is greater than the sum of the responses from the individual chemical treatments. Responses that result in antagonism are the opposite case. It is additive (AD) when the observed value and the expected value are equal. The following eight tables show the averaged data and results for each experiment. It can be concluded that when compound No. 1 is used in combination with any of compounds No. 4 to 11, various synergistic herbicidal responses can be obtained.

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The compositions of the present invention, when applied to undesirable plants for pre-emergence or post-emergence treatment, exhibit synergistic herbicidal activity in controlling the growth of these vegetations. Generally, the compositions are in the form of formulations that contain in addition to the active composition an inert or sometimes active ingredient or a diluent carrier. Such ingredients or carriers are water, organic solvents, surfactants, oils, water-in-oil emulsions, wetting agents, dispersing agents, and emulsifying agents. Generally, synergistic formulations are in the form of wettable powders, solutions or emulsifiable concentrates. Wettable powders are finely divided compositions comprising a viscous carrier impregnated with synergistic compounds plus one or more surfactants.
The surfactant helps the powder disperse into the liquid medium to form a stable sprayable dispersion. A wide variety of surfactants, such as long-chain fatty alcohols, alkali metal salts of sulfated fatty alcohols, salts of sulfonic acids, esters of long-chain fatty acids, and relatively long-chain free omega-substituted polyethylene glycols with alcohol groups. Polyhydric alcohols can be used. The synergistic composition can also be applied to the foliage in the form of a solution in a suitable solvent. Commonly used solvents for synergistic formulations are kerosene, fuel oil, xylene, petroleum fractions with a boiling range above kerosene, aromatic petroleum fractions rich in methylated naphthalenes. The formulation of choice is an emulsifiable concentrate consisting of an oily solution of herbicide with an emulsifier. Prior to use, this concentrate is diluted with water to form an emulsion of suspended oil droplets. Emulsifiers are generally anionic and nonionic surfactants. Other additives such as spreading and sticking agents may be included in the emulsifiable concentrate. The previously mentioned formulations may be applied to the vegetation in a conventional manner, either before or after the emergence of the vegetation to be controlled. The vegetation may be at any post-emergent stage ranging from seedlings to fully grown plants. The application may be accomplished with conventional equipment such as ground spreaders or aerial spreaders. Many other application techniques will be apparent to those skilled in the agrochemical industry.

Claims (1)

[Claims] 1 (a) Thiol carbamate of the following formula: (In the formula, R ¹ is an alkyl group selected from C ₃ H ₇ or C ₂ H ₅ groups, and R ² is an alkyl group selected from C ₃ H ₇ or [Formula] group. However, R ¹ is a C ₃ When H is ₇ groups, R ² is
When it is a C ₃ H ₇ group and R ¹ is a C ₂ H ₅ group, R ² is a [Formula] group. ) and (b) a dimethylurea compound of the following formula: A synergistic herbicidal composition comprising a mixture of (a) and (b) in a herbicidally effective amount in a weight ratio of 0.01:1 to 20:1. 2 (a) is S-benzyl-dipropyl-thiol carbamate, and (b) is N'-(3-chloro-4-
The composition according to claim 1, which is (methylphenyl)-N,N-dimethylurea. 3 (a) is S-benzyl-ethyl-1,2-dimethylpropyl-thiol carbamate, and (b) is
N′-(3-chloro-4-methylphenyl)-N,
The composition according to claim 1, which is N-dimethylurea.