JPS60149504A - Synergistic herbicide composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Protecting crops from weeds and other vegetation that inhibit crop growth has always been a frequent 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.

Because this combination represents a potency or level of activity that exceeds what we would expect the compounds to have based on knowledge of their individual potencies, this result is often synergistic. It is called action l.

The invention is based on the discovery that the combined use of certain thiol carbamates and dimethylurea, whose herbicidal potency individually is known, produces 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. Pat. No. 3,185,720 [Chiles et al.
Ti1lea et al, +) May 25, 1965
No. 3,198,786 [Tilles et al.
et at, +) August 3, 1965] and 2,
No. 913,327 [Tilles et al.
, ) November 17, 11959].

N'-(3-chloro-4-methylphenyl)-N,N-
Dimethylurea is commonly known as chlortoluron.
toluron), which is sold in Europe under the trade name Dicuran by Chino (Switzerland).

There are now two components: (a) a thiol carbamate of the formula where X is hydrogen, chlorine or bromine, Hl and R2
are independently selected from the group consisting of C8-C6 alkyl and C3-C7 cycloalkyl); (b) an effective herbicide amount of a dimethylurea compound of the following formula; It has now been discovered that a composition comprising a mixture of the following has a synergistic effect in controlling undesirable vegetation.

The term l alkyl 1 is used herein to represent straight chain and branched chain groups. Examples of alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, etc.
Butyl, isobutyl, etc. All carbon atom ranges are inclusive of their upper and lower limits.

Examples of useful thiol carbamates are shown below: 1, 8-benzyl dipropyl thiol carbamate 2, 8-benzyl ethyl i, 2-di 1-y-lubrovir thiol carbamate 3, 8-(2- chlorobenzyl) -N,N-diethyl thiol carbamate 4.8-(4-chlorobenzyl) -N,N-diethyl thiol carbamate These and other thiol carbamates which fall within the scope of the present invention are as described above. U.S. Pat. Nos. 2.913.327, 3,185,720 and 3.198,786,
Further, U.S. Pat. No. 3,144.

No. 475, No. 21992,091 and 3.207.77
It can be manufactured by the method described in No. 5.

A preferred thiol carbamate for future use is S-benzyl dipropyl thiol carbamate.

Preferred dimethylureas for use in the compositions of the invention are N'-(3-chloro-4-methylphenyl)-N,N
-dimethylurea.

Here, the terms I synergy' and 'synergistic l' mean that the combination of herbicides exhibits the potency that would reasonably be expected of the combination based on the respective potencies at which each herbicide was applied independently. When expressing a potency higher than the potency, it is used to convey the observed V vermilion.

The term "herbicide W" is used here to indicate a compound that controls or alters plant growth. is used to indicate the amount of such a compound or combination of such compounds that can be used.

Effects that control or alter include all effects that deviate from natural development, such as withering, retarding, leaf burn, dwarf growth, and the like. The term ``plant'' is used to include all post-emergent vegetation ranging from stinging to established vegetation.

In the compositions of the present invention, the weight ratio of thiol carbamate to chlortoluron for synergistic herbicidal response is from about 0.01:1 to about 20:1, preferably about 0.01:1 to about 20:1.
1:1 to about 10=1, optimally 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 compositions of the invention:
0.011 to 56 Kf per hectare (0.01 to 50 Bonds per knee) of active ingredient, preferably 1
0.11 to 28 per hectare (0.1 to 28 per hectare)
It is most efficiently used at an active ingredient ratio of 1 to 25 bonds).

This composition is particularly effective in controlling Gallium aline (Galium ap, arine).

EXAMPLE 1 An experiment was investigated in a greenhouse in which the combination of chlortoluron (compound 1 of Table 1) and one of the S-benzyl thiol carbamates produced a synergistic response. These S-benzyl thiol carbamates are prepared as follows: Compound 2: S-benzyl dipropyl thiol carbamate & compound a: s-benzyl ethyl-1+ 2-'
) Methylpropyl thiol carbamate crystal 3 An aluminum pan measuring 18 x 12 x 5 cm was filled with loamy clay and six grooves were dug across the middle of each flat. A supplement of five dicotyledonous plant species was sown in a ditch and allowed to bloom in the soil. Plant types are classified by the following: Sugar beet (SR-TM) [Bet, a vulgaris]
(L,) ) [Tefmono) fumitory (FUM) [Fumaria offlci
nalis (L, l) Yaemugura (B D SW) Shirokaran (MD) [Cinnabis alpensis (5 inapia arve
nsis (L,):] Nakaba Kishigishi (CD) [Rumex crispu
s + (L, ):) Six monocot species of persimmon were sown in the same manner as the dicotyledonous plants: BKGR (BKGR) Avena fatua (WO) Avena fatua (L,
) ) Aretinochahiki (PBRO) Bromus sterilis (Bromus 5terili)
s(L,)) Lolium parenne (BAIG) Lolium parenne (PRGR)
(L,)] Bunko wheat (WHFL) Triticum aestium [Triticum aes]
tivum (L,) :] 'f on the same day as the day when the husks were sown.
The chemical solutions were formulated as follows: All other compounds, except Nidiclon or Chlortoluron, were of technical grade and supplied as 50% emulsifying concentrates. The technical grade compound was bathed using a 1 part acetone to water ratio. A chemical solution was applied to the soil using an edge-shaped spray table for application as a pre-emergence treatment.

This table calculates the spray volume to 750 tons per hectare (
80 gallons per knee car). Each compound was used alone in the following ratios: Compound 1 (dicran) - 1.0 and 2 per hectare
．． 0 Kf.

2 and 3 - 0.5, 1.0 per hectare
.

2.0 and 4. Ox? .

All ratios applied were Compound 1 (Dicran) plus Compound 2 or Compound 3.

Next, the flatbed was placed in a shaded greenhouse and sprayed with water to keep it moist overnight. The temperature was kept in the range of 15-27°C. The flatbed was kept moist throughout each experiment.

Two to three weeks after treatment, the crown of each seedling was visually evaluated for control of growth by all sources of uplift damage. Untreated flatbed seedlings are used as a standard, and 0% damage or growth control corresponds to growth in standard flatbeds. 100%
Growth control corresponds to complete withering.

Herbicide interaction responses were determined by Limpel.
) formula [Limpel (Limpel * L, E +
et at, , ) 1962 1 Weed Control by I ime
thyl -tetrachlororoterephth
alate Alone and CertainCo
mbinations, )'Proc, NEW
CC), gi Volume 6 48-53M) KfZl”r#f
Lllll! L*: (where E = Expected awn response value X = Observed value or % of growth control when the herbicide is used alone (0) Y = Second herbicide used alone The observed value of growth control when the observed value is greater than the calculated value, or the response is the one that results in the somai effect, and the value that results in the somai effect arises from the independent chemical treatment. It can be understood that this is the value shown when the interaction response is larger than the sum of the responses.Antagonistic responses are the opposite case.

Results Looking at the above data, Compound 1 (Dicran), when used in combination with either Compound 2 or 3, shows a synergistic herbicide response in both monocot and dicotyledonous Citrus. We can conclude that we can obtain .

The S-benzyl thiol carbamate mentioned here is
Also, for this S-benzyl thiol carbame, wo, w
K It:i Chlorsulfuron, 2-chloro-N
-(:(4-Methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-benzenesulfonamide, known as )
By combining with other types of herbicides such as those sold in , it is possible to evaluate in the same manner as in Example 1 described above. Other compounds that can be evaluated in combination with the S-pendylthiol carbamate mentioned here are 2
-Chloro-4-(ethylamino)-6-(inpropylamino)-8-triazine, sold under the trade name Aatrex by Tever Geiki Co., Ltd., and also sold under the trade name Aatrex by Monsanto Chem Co., Ltd.
ical Company, St. Louis, Missouri, under the trade name Lasso. Also, 2-[:(4-
Chloro-6-(ethylamino>-S-triazine-2-
yl)aminoco-2-methylpropionitrile, sold under the trademark Bladex by Shell Co., Hughston, Texas, and others having the same general structure may also be evaluated. can.

S-benzyl thiol carbamate is also available in 1983
U.S. Patent Application No. 486,73 filed on April 20, 2013
It can be evaluated in combination with phenoxydiphenoxypentanoic acid ester and bhiuridyl phenoxypentane ester as described in No. 0 and No. 486.750.

Special compounds among these are ethyl 4-(4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy]-3-hydroxypentanoate, 4-[4
-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxif-3-hydroxypentanoate methyl, and 4-(4-(3-chloro-5-trifluoromethyl-2-phenoxy)phenoxif-3 -ethyl hydroxypentanoate.

S-benzyl thiol carbamate compounds are also used in phenoxyphenoxypropion versions and their esters, as described in German Patent No. 2,531,643, and also in British Patent No. 1,599,121-1. can be evaluated in combination with pyridylphenoxypropione m and their esters, as described and required in .

The S-benzyl thiol carbamate compounds described herein are also available from Rohm & No.
nd Haas Company), spring 7%
US, Pennsylvania, Ni↓l [title Go + J (Goal
), 2-chloro-1-(3-ethoxy-4-nitrophenoxy)-4-() IJ fluoromethyl)pensene and sold under the trade name Blazer 28 by Hirom & Haas.
) and sold by Rho-Boulin Chemical Company (Rho
ne-PoulencChemical Compa
5-[2-chloro-4-()lifluoromethyl), sold under the trademark Tackle Z A S , Monmouth, N.Y., or under the trademark Tackle Z AS When combined with a phenoxyphenyl structure herbicide treated with sodium phenoxy-2-nitrobenzoate,
They can be evaluated for their activity as synergistic herbicides.

Other herbicides that can be tested for synergistic herbicide activity in combination with the S-benzyl thiol carbamates described herein are acetanilide-00 herbicides, manufactured by Monsanto Co. Mon5an
2-chloro-2',6'-diethyl-N-(
Methoxymethyl) acetanilide, Tevar Kaikyi Co., Ltd.
Ministry of Agriculture, Greensboro
, North Carolina, under the trademark name 1 Yual (Du
2-chloro-2-N-(2-
It is a compound represented by ethyl-6-methylphenyl LN-(2-meth)oxy-1-methylethyl)acetamide. (a)% (trade name Manae) (trade name, among others, by Monsanto Company, St. Louis, Missouri) (Ma
chete) and others of the same general structure.

1^j1 Other herbicides that are expected to provide synergistic herbicide action in combination with the S-benzyl thiol carbamates mentioned here are known by the common name asul.
an ) and a carbamate such as methylsulfanilyl-carbamate, sold under the trade name Asilan. Other suitable carbamates include those available from Gulf Corp., Chicago;
Belushi of Illinois 5. A/Department (Ve181eol
Division) under the trade name Calpain (Car).
byne), 4-chloro-2-butynyl-N-chlorocarbanilate and PPG Industries, Pittsburgh (
isopropyl m-chlorocarbanilate, sold under the trade name Furloe by John F., Pittsburgh, Pennsylvania.

Other compounds include Elanco (Blanc).

Products Company), ElkLilly Company (D Branch, Greenfield, Indiana) under the trade name Treflan.
α, α sold at.

Stauffer Chemical Comp.
any), Westport
Trademark name Betasan (Be
N-(2-mercaptoethyl)pensene sulfonamide, commonly known as cicamba (
dicamba) and Persicol Chemical Co. (Velalc).
3, sold under the trade name Banvel by olChemical Company.
6-dichloro-〇-anisic acid.

Additionally, other herbicides whose activity as a herbicide can be evaluated in combination with S-benzyl thiol carbamate include RO-NEET, sold by Stourer Chemical Co. under the trade name RO-NEET. There, S
-Ethyl N-ethylthiocyclohexane carbamate, manufactured by Stowsoar Chemical Company under the trade name Nibutam (EPT)
S-ethyl dipropyl, sold by
Thiol carbamate, sold under the trade name 5utan by Stouffer Chemical Company, S-ethyl diisobutyl thiol carbamate, sold under the trade name Avadex by Monsanto Company, St. Louis, Missouri. 5-(2,
3-dichloroallyl)-diisopropyl thiol carbamate, sold under the trade name Vernam by Stauffer Chemical Co., Westboat, Konenacut; 5-((4-
Chlorophenyl)methyl)-ethyl carbanothioate. Additionally, a defibrillator compound mentioned herein that may be evaluated to provide a synergistic effect in combination with the fc S-benzyl thiol carbamate is the compound manufactured by Shell Chemical Co., Hughston, Texas under the trade name Atrazine. 2-Chloro-4-(ethylamino)-6-(isopropylamine>-S-triazine, sold by Shell Chemical Co., Hughston, Texas, under the trade name Bladex)
2-[[[4-chloro-6-(ethylamino)-S-triazin-2-yl]amine]-2-
Methylpropionitrile, sold by Civer-Geigy, Inc., Green Spolo, North Carolina;
It is a common triazine including 2,4-bis(isopropylamine)-6-(methylthio)-8-triazine.

The same and other triazine compounds are manufactured by Civer-Geigy under the trade name Cabrol 80 Double x-(ca, pr
2゜4-bis(isopropylamine)-6-(methylthio)-s-triazine, sold under the trade name Milogard 80W) and 2-chloro, sold under the trade name Milogard 80W by Civer-Geigy. -4,6-bis(inpropylamine)-8-triazine and others.

The synergistic response of the combined use of S-benzyl dipropyl thiol carnocumate with one of the following herbicides was tested in a series of experiments: isopropylphenyl) W,W-dimethylurea compound N1523-(3,4-dichlorophenyl)-1
-Methoxy-1-methylurea compound 11NLL6: 1.3-dimethyl-3-(2-benzothiazolyl)urea compound 9NLL7: N-(3-chloro-4-methoxyphenyl)-N,N-' )) Chylurea compound N[L8:1-n
-butyl-3-(3,4-dichlorophenyl)-1-#
-lurea compound N[L9: 2-t-butylamino-4-ethylamino-6-methylthio-8-triazine compound N[LI
O: S-2,3,3-trichloroallyl diisopropyl thiol carbamate trialllate cH3 \ Compound Na1l: α, α, α-trifluoro2,6
-Sinitro N,N-Sifurovir-p-)luidine trifluralin compounds Nos. 4 to 11 are all commercially available and known in the art.

The test was conducted as follows: A 19 x 8 x 6 aluminum pan was filled with loamy sand and six trenches were dug across each flat bed. I sowed this noble with the following plant pole: Fool's Fist Parsley (FOPA)
) (fool's parsley) Aethusa Cynap
ium) Sparrow Sparrow (BKGR) a. Hekyu,,su,Myios Royzu (Alopecur)
us myosuroid (11B) Oat (W
G) Avena fatua, Sugar beet (SBTM), Beta vulgaris, Brassica napus (RAJN), Brassica napus, Poverty brome (PBRO), Broms steri Squirrel (Bromus 5terili)
s) Fumitorii (FUM) (fumitory) Tsuma. Fumaria off
icinalia) Catchweed Bedstraw
(BDWS>(catchweed bedstraw
) Gallium aparin
e) Barley (n A) Hordeum vulgar
e) Rat wheat (ARG) Lolium multiflorum (Lolium multiflorum)
florum) Scented Mayride (MARE)
) (Scented mayweed) Matricaria recutita
ecutita) Poppy (POP) Papaver spp.
) Fusayoshi (REFiD) Pbalaris ar
undinaceB6) Sparrowberry (ABG) Boa annua (Poa annua) Mustard (
MD) Sinapis arvensis
sis) Common wheat (WHFL) Triticum aes
tivum) Veronlca hed (ILSW) Veronlca hed
erifolia) One portion of all the branches of the above plants were used in each of eight separate tests. The solutions of chemicals sprayed on the same day as the sowing were prepared as follows: compounds were used as formulations or technical grades (see data table). Technical grade compounds were brought into solution using a 1:1 ratio of acetone to water. The formulation was dissolved only in water.

A solution of the chemical was sprinkled onto the red surface for pre-emergent application using a straight spray table.

This table calculates the spray volume to 235 tons per hectare (
25 gallons per knee car). Each compound was used alone in the following application ratios.

Compounds m 1 0.25, 0.50, 1.00 and 2.00 Compounds Fish 4 0.25.0.50, 1.00 and 2.00 Compounds Ha 5 0.50, 1.00,
2.00 and 3.00 Compound N16 0.50, 1.0
0, 2.00 and 3.00 compounds? &L7 1.00,
2.00, 3.00 and 4.00 compounds N+L8 1.
oo, ZOo, 3.00 and 4.00 Compound 1
m9 0.50, 1.00. 2.00 and 3.00 Compounds NL&10 0.125, 0.25, 0.50 and 1
．． 00 Compound Na1l O,0625,0,125,0
, 25 and 0.50 compounds Nll were used at all possible application ratios in separate tests with each of compounds N14 to N[Lll. Each test was arranged as a 5 x 5 factorial arrangement (including 0 use ratios) and was designed as a complete 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 was kept in the range of 15-27°C. 'The flat bed was kept moist throughout each experiment.

After 6 days and 15-20 days after treatment, one batch of each seedling was visually evaluated for growth control due to all sources of injury. Untreated flat bed seedlings were used as a standard. 0%
injury or growth control corresponds to growth in a standard flat bed. Controlling the growth of 100 inches is equivalent to complete withering.

Herbicide interaction responses were evaluated using the Rimbell equation as previously described.

The response or interaction relationship (6) from treatment with the combined herbicides is assumed to be synergistic (S) once the observed value is greater than the expected value. It is understood that a synergistic response should be one in which 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 groups show the averaged data and results of each experiment. It can be concluded that when compound NIL1 is used in combination with any of compounds 4-11, a synergistic herbicidal response can be obtained.

The compositions of the invention, when applied to undesirable plants for pre-emergence or post-emergence treatment, exhibit synergistic herbicidal activity in controlling the growth of these vegetation. Generally, the composition is in the form of a formulation containing, in addition to the active composition, inert and sometimes active ingredients or a diluent carrier. Such ingredients or carriers are water, organic solvents, surfactants, oils, hook-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 impregnated with synergistic compounds and comprising a viscous carrier plus one or more narrow surfactants. The surfactant helps the powder disperse into the liquid medium to provide a stable, barkable dispersion. A wide variety of narrow surfactants, such as long-chain fatty alcohols, alkali metal salts of oxidized fatty alcohols, salts of sulfonic acids, esters of long-chain fatty acids, free omega-substituted polyethylene glycols with relatively long alcohol groups; A polyhydric alcohol can be used.

Also, when the synergistic composition is applied in the form of a solution dissolved in a suitable bath, - can be obtained. It is a petroleum fraction with a boiling point range of oil, xylene, and kerosene, and an aromatic petroleum fraction with a high content of methylated naphthalene.

The formulation of choice is an emulsifying formulation consisting of an oily solution of herbicide with an emulsifier. Prior to use, the concentrate is diluted with water to form an oily emulsion. Emulsifiers are generally anionic and nonionic surfactants. Other additives such as spreading and sticking agents may be included in the emulsifiable IIkm product.

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.

Agent: Patent attorney Hideaki Kurihara Procedural amendment (spontaneous) February 21, 1985 Manabu Shiga, Commissioner of the Japan Patent Office1, Indication of the case Patent application No. 1982-2551702, Name of the invention: Herbicide composition that produces synergistic action 3. Relationship with the case of the person making the amendment Patent applicant address: United States of America, Connecticut 06881
Westport (no street address) Name: Sean Miles Twoper 4, Representative of Stouffer Chemical Company, Agent 〒105 The detailed description of the invention column in the specification is amended as follows.

(1) Page 60 of the specification, “Table 4 (Continued)”, 5th from the left
4 Oka “Sparrow”, bottom row 12r8J is “5”
I am corrected.

(2) Page 67 of the same book [Table 8 J, 4th column from the left, "Sugar beet", 6th line from the bottom = "S" is corrected to "3".

(3) Page 69 of the same book, "Table 9", second yuzu from the right, "oat", line 11 from the top: "S" is corrected to "5" by 11.

that's all

Claims (1)

[Claims] (1), (a) Thiol carbamate of formula R (in the formula,
X is water volume, chlorine or bromine, Bl and V are C3 to C
6-alkyl and C, to C, cycloalkyl) as a herbicide, and (b) the effectiveness as a herbicide of the dimethylurea compound of the formula 'eL'. A synergistic herbicide composition comprising a mixture of (a) and (bl) in a ratio of about 0.01:1 to about 20:1. 1), (a) benzyl cifirovir thiol carbamate, and (b) is N'-(3-chloro-
4-Methylphenyl)-N,N-')iflurea. (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 d, which is N-dimethylurea. (4), (a) is 5-(2-chlorobenzyl)-N,
N-diethyl thiol carbamate, and (b) is N'-(,3-chloro-4-methylphenyl)-N,N
- dimethyl urea, set I according to claim 1
It thing. (5), (a) Thiol carbamate of the following formula (wherein, X
is hydrogen, chlorine or bromine, R1 and R2 are C0 to C
(b) N-(4-isopropylphenyl) N/. an effective amount of N'-dimethylurea as a herbicide;
) to (b) weight ratio of about 0. A synergistic herbicidal composition comprising a 1 to about 20:1 mixture of O and O. (6), (a) Thiol carbamate of the following formula (wherein X is hydrogen, chlorine or bromine, and R1 and R2 are C1
~ C6 alkyl and C3-c7 cucroalkyl)) and (b) 3 (3,4-dichlorophenyl)-1-methoxy-1- Mef#K”
its (!: t, a synergistic herbicide composition comprising a mixture of (a) to (b) noi ii in a ratio of about 0.01:1 to about 20:1. (7), (a ) Thiol carbamate of the following formula (wherein X is hydrogen, chlorine or bromine and R1 and R2 are C1
~C6 alkyl and cs~C, cycloalkyl) and a herbicidally effective amount of (bit, a-dimethyl-
3-(2-benzothiazolyl)urea (a) versus (b)
) OJ[t A synergistic herbicide composition comprising a mixture of OJ[t in a ratio of about o, ot:iz to about 20:1. (8), (a) Thiol carbamate of the following formula (wherein,
X is hydrogen, chlorine or bromine, R1 and R2uC, ~
(b) N-(3-chloro-
(4-methoxyphenyl) N I N 7 methylurea in a ratio of (a) to (b) from about 0.01:1 to about 2.
A synergistic herbicide composition comprising a 0:1 mixture. (9), (a) Thiol carbamate of the following formula (wherein,
X is hydrogen, chlorine or bromine, and R1 and R2 are C1-
and (b) in-butyl-3-
(3,4-dichlorophenyl)-1-methylurea,
The in ratio of (a) to (b) is about 0.01:1 to about 20:
A synergistic herbicide composition comprising a mixture of IK. (10), (a) Thiol carbamate of the following formula (wherein Xt'i is hydrogen, chlorine or bromine) R1 and R2
(b) 2t-butylamino-4-ethylamino-6-methylthio; -8-triazine and (a) R=j (weight ratio of bl about 0.01:1
A synergistic herbicide composition comprising a mixture of from about 20 to about 1. (11), (a) Thiol carbamate of the following formula (wherein X is hydrogen, chlorine or bromine, and RI and R2 are C
(b) S-2,3. 3-trichloroallyl-diisopropyl thiol carbamate in a weight ratio of (a) to (b) of 0.01:1.
A synergistic herbicide composition comprising a mixture of from about 20 to about 1. (12), (a) Thiol carbamate of the following formula (wherein X is hydrogen, chlorine or bromine, R1 and R1 are C
1-C6 alkyl and C1-C,cycloalkyl); and (b) α,α,α-trifluoro-2,6-sinitro-N , N-dipropyl=p-
) luidine, (a) to (b) weight ratio o, oi:
A synergistic herbicide composition comprising a mixture of about 20:1. (13), the weight ratio of (a) to (b) is approximately 0.1:1&
Claims 1.2, 3, and 4 where approximately 10=1
゜5.6, 7.8.10.11 or 12 compositions described. (14) The weight ratio of (a) to (b) is about 0.1:1 to about 5=1. , 10.11 or 12JJl. (15), (a) Thiol carbamate of the following formula (wherein X is hydrogen, chlorine or bromine, and R1 and BR are C
8-C6 alkyl and Cs-C7 cycloalkyl); and (b) a herbicidally effective amount of a dimethylurea compound of formula m. A method for controlling vegetation, comprising applying a herbicide composition comprising a mixture to undesirable vegetation as a pre-emergence treatment or a post-emergence treatment. (16), Claims in which (a) is S-benzyl dipropyl thiol carbamate, and (b) is N'-(3-chloro-4-methylphenyl)-N,N-dimethylurea. The composition according to item 15. (17), (a) is S-benzyl ether 1.2-
Dimethylpropyl thiolcarrenomate,
(b) is N'-(3-chloro-4-methylphenyl)-
The composition according to claim 15, which is N,N-dimethylurea. (1B), (a) is 5-(2-chloro-benzyl)-
N. N-diethyl thiolcarno (mate, Cb)
)KaN'-(3-chloro-4-methylphenyl-) The composition according to item 15. (19), (a) Thiolcarno(mate(
In the formula, X is hydrogen, chlorine or bromine, and 11 and R2 are C1-C. and (b) N-(4-isopropylphenyl)-N'. Effective amount of N'-dimethylurea as a herbicide and vs(a
) and (b) in a weight ratio of from 0.01:1 to about 20:1, applied to undesirable vegetation as a pre-emergence or post-emergence treatment. A method of controlling said vegetation. (20), (a) Thiolcarno(mate(
In the formula, X is hydrogen, chlorine or a compound, and 11 and R2t
, L Ct-C6 alkyl and Cs-C, cycloalkyl) as herbicides; and (b) 3-(3,4-dichlorophenyl). -1-methoxy-1-methylurea (&
) to (b) in a weight ratio of about o, oi2 to about 20:1, applied to undesirable vegetation as a pre-emergence or post-emergence treatment. A method of controlling said vegetation. (21), (a) Thiol-carbamate of the following formula (
In the formula, X is hydrogen, chlorine or bromine, Hl and R"t
iC, ~C6 alkyl and C3~C7 cycloalkyl) as a herbicide, and (bH,3-dimethyl-3
-(2-benzothiazolyl)urea, (a) versus (bl
by applying a synergistic herbicide composition comprising a mixture in a weight ratio of from about 0.01:1 to about 20:1 to the undesirable vegetation as a pre-emergence or post-emergence treatment. How to control vegetation. (22), (a) Thiol carbamate of the formula (wherein X is hydrogen, chlorine or bromine, R' and R"l"
(b) N-(a-chloro-
4-Me)xyphenyl)-N,N-dimethylurea,
Weight ratio of (a) to (b) from 0.01:1 to about 20=
1. A method for controlling undesirable vegetation by applying a synergistic herbicide composition comprising a mixture of 1 and 2 as a pre-emergent or post-emergent treatment to said vegetation. (23), (a) Thiol carbamate of the following formula (wherein X is hydrogen, chlorine or bromine, and R1 and R2 are C
(b) in-butyl-3-
(3,4-dichlorophenyl)-1-methylurea,
The weight ratio of (IL) to (bl) is 0.01: mm to about 20
A method of controlling undesirable vegetation by applying a synergistic herbicide composition comprising a mixture of 1. (24), (a) Thiol carbamate of the following formula (wherein, X is hydrogen, chlorine or bromine, R1 and R2 are C
(b) 2-t-butylamino-4-ethylamino-6-methylthio; -8-triazine and a synergistic herbicide composition comprising a mixture of (a) to (b) in a weight ratio of from 0.01:1 to about 20:1 to undesirable vegetation before emergence. A method of controlling said vegetation by applying it as a treatment or post-sibling treatment. (25), (IL) Thiol carbamate of formula v (
a herbicidally effective amount of b) s-2e3. 3-trichloroallyl-diisopropyl thiol carbamate in a weight ratio of (a) to (b) of 0.01:1.
A method of controlling unwanted vegetation by applying a synergistic herbicide composition comprising a mixture of from about 20:1 to about 20:1 to said vegetation as a pre-treatment or post-emergence treatment. . (26), (C3 thiol carbamate (wherein, X is hydrogen, chlorine or bromine, R1 and R2 are C8
~C6 alkyl and Cs~C,cycloalkyl); and (b) α,α,α-trifluoro-2,6-dinitro-N. . N-dipropyl-p-
Toluidine, (a) vs. (b) Tsutakura ratio 0.01:
A method of controlling undesirable vegetation by applying a synergistic herbicide composition comprising a 1 to about 20:1 mixture as a pre- or post-emergent treatment to said vegetation. (27), the weight ratio of (a) to (b) is fJO, 1:1
Claim 15.1 (i
, 17, 18° 19. 20, 21, 22. 23, 24.
25 or 26. (2B), Claims 15.16 and 17, wherein the M ratio of (a) to (b) is about o, i:i to about 5:1.
．． 1B. The method described in 19.20.21.22.23, 24.25 or 26. (29>, (a) Thiol carbamate of the following formula, where X is hydrogen, chlorine or bromine, and R1 and R2 are C
(b) an effective amount as a herbicide of a dimethylureated compound of the following formula; an effective amount and ((+) an inert diluent carrier and a mixture of (a) to (b) in a weight ratio of from 1:1 to about 20:1) to achieve a synergistic effect. (30), (a) is S-benzyl dipropyl thiol carbamate, and (b) is N'-(3-chloro-4-methylphenyl), N*N y Mef.
The composition according to claim 29, which is a urine accumulation! 1
Of course. (31), (&) is S-benzyl ethyl 1,2-
Dimethylpropyl thiol carbamate, (b
) is N'-(3-chloro-4-methylphenyl)-N
, Claim No. 29fJ consisting of N-dimethylurea
4. The composition according to item 4. (32), (a) is 5-(2-rioo-benzyl)
-N. N-diethyl thiol carbamate, and (b) is N'-(3-chloro-4-methylphenyl)-N,N
-dimethylurea. The composition according to claim 29JJ. (33), (a) Thiol carbamate of the following formula (wherein, X is hydrogen, base or bromine, R1 and R2 are C
(b) N-(4-isopropylphenyl)-N'. an effective amount of N'-dimethylurea as a herbicide; and (c)
A synergistic herbicidal composition comprising a mixture of (a) to (b) in a weight ratio of from 0.01:1 to about 20:1 with an inert diluent carrier. (34), (a) Thiol carbamate of the following formula (wherein, X is aqueous, chlorine or bromine, 11 and R2 are C
independently selected from the group consisting of I-C6 alkyl and C5-C7 cucroalkyl); A synergistic compound comprising a mixture of 1-methylurea and an inert diluent carrier in a weight ratio of (a) to (b) from 0.01:1 to about 20:1. (35), (IL) a thiol carbamate of formula r (
where X is hydrogen, chlorine, or bromine, and 11 and R2 are independently selected from the group consisting of C, % C, Cl, and C5 to C, cycloalkyl. (b) 1,3-dimethyl-3-(2-benzothiazolyl)urea; and (c) an inert diluent carrier in a weight ratio of (a) to (b) of 0.01:1. A synergistic herbicide composition comprising a mixture of from about 20 to about 1. (36), (a) Thiol carbamate of formula 11 (
wherein X is hydrogen, chlorine or bromine, and 11 and R2 are independently selected from the group consisting of C1-C, alkyl and C5-C, cycloalkyl. (b) N-(3-chloro-4-methoxyphenyl) N
# A synergistic compound comprising a mixture of (a) to (b) (0.01:1 to about 20:1 by weight) N-dimethylurea and (c) an inert diluent carrier. (37), (a) Thiol carbamate of the following formula (wherein X is hydrogen, chlorine or bromine,
1~C67 le # /l/ and fcI! ' = c7 cycloalkyl)); and (b) 1-n-butyl-3-(3,4-dichlorophenyl)-1-mef. (c) an inert diluent carrier in a ratio of M (1) to (b) of about 0.01:1 to about 20:1, resulting in a synergistic effect. Herbicide composition. (38), (a) Thiol carbamate of the following formula (wherein X is hydrogen, chlorine or bromine, and R1 and R2 are C1
- C6 alkyl and C1-C7 cycloalkyl) in an herbicidally effective amount; (b) 2-t-butylamino-4-ethylamino-6-;
A synergistic mixture comprising methylthio-8-triazine and (e) an inert diluent carrier in a weight ratio of (a) to (b) from 0.01:1 to about 20:1. A herbicide composition that provides. (39), (a) Thiol carbamate of the formula (wherein X is hydrogen, chlorine or bromine, and R' and R2 are C
1-C6 alkyl and C6-c7 cycloalkyl); A synergistic mixture of a thiol carbamate and (c) an inert diluent carrier in a weight ratio of (a) to (b) from 0.01:1 to about 20=1. Herbicide composition. (40), (a) Thiol carbamate of the following formula (wherein X is hydrogen, chlorine or bromine, Bl and R'I are independently from the group consisting of C1-C6 alkyl and C5-C?cycloalkyl) (b) α,α,α-trifluoro-2,6-sinitro-N,N-dipropyl-1)-)luidine; and (c) an inert herbicide. A synergistic herbicidal composition comprising a mixture of (a) to (b) in a ratio of from about 20:1 to about 20:1. (41), (&) to (b) x amount ratio is approximately 0.1:1
! Is it? Claim No. 29,3 which is J10:1
0.31.32゜33.34,35,36.37.38
．． The composition according to item 39 or 40. (42), (a) vs. (b) noil (iii ratio is about 0
．． Claim 29 ranging from 1:172 to about 5:1
．． 30, 31, 32° 33.34, 35.36, 37,
38. The composition according to item 39 or 40. (43), (a) Thiol carbamate of the following formula (wherein, X is hydrogen, chlorine or bromine, and R2 and R2 are
(b) thiol carbamates, phenoxyphenyl derivatives, triazines, acetanilides, carbamates, and substituted carbamates; A synergistic herbicidal composition comprising a herbicidally effective amount of a selected from the group consisting of penscensulfo/amides.