JPS5919533B2 - N-(benzenesulfonyl)carbamate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to N-(benzenesulfonyl)carbamates and their uses.

Although many herbicides are readily toxic to many weed pests, their effects on important cultivated plants are also non-selective or not sufficiently selective. Therefore, many herbicides cause damage not only to the weeds to be controlled, but also to some extent to desirable cultivated plants. This is also true of many herbicidal compounds that have been commercially successful and are available as commercial products. These herbicides include triazines, urea derivatives, halogenated acetanilides, carbamates,
Examples include thiocarbanates. Some examples of these compounds are described in U.S. Pat. No. 2,913,327;
No. 037853, No. 3175897, No. 3185
No. 720, No. 3198786 and No. 35823
It is described in No. 14. The damaging side effects of various herbicides on cultivated crops are particularly inconvenient and undesirable.

Even when applied to the soil at recommended doses to control broadleaf weeds and grasses, they can sometimes cause severe dysfunction or growth arrest in crop plants. Abnormal growth of crop plants in this way leads to reduced crop yields. Therefore, research has continued into herbicides with good selectivity.

Various attempts have been described to overcome this problem.

For example, U.S. Pat.
No. 64768 describes the treatment of crop seeds with certain "hormonal" antagonists before sowing. These prior art methods involve not only herbicides but also
Protective agents are also sufficiently specific for certain cultivated plant species or in their antagonistic properties. Prior art antagonists have not been significantly effective. The aforementioned patents provide detailed illustrations of seed treatments using different classes of compounds which do not suggest the present invention. US Pat. No. 3,799,760 and US Pat. No. 3,933,894 and East German Patent No. DL7498
No. 2 describes some of the N-benzenesulfonyl carbamate compounds described therein.

Also, Berichte, Volume 37, No. 6
On page 99, certain compounds are specifically described. However, none of these prior art studies show that the compounds are thiocarbamate herbicides, particularly S-n-propyl N,
Its usefulness as a herbicide antidote to N-di-n-propylthiocarbamate is not expected or readily analogous. Also, from any of these prior art,
N-benzenesulfonylcarbanates and active thiocarbanate herbicides, especially S-n-propyl N,N
- Improved herbicidal compositions using di-n-propylthiocarbamates are not anticipated or readily analogous. This invention provides novel N-(substituted benzenesulfonyl)
Carbamates, when applied in a variety of ways and used with herbicides, especially thiocarbamate herbicides,
It consists of an active herbicide antidote that is useful for protecting crops from damage and reducing crop damage.

Cultivated crop plants are protected from damage caused by thiocarbamate herbicides and this damage is prevented by applying carbamate herbicides in various ways, each alone or in admixture or combination with other compounds. , has been found to decrease.

Furthermore, as another effect, the tolerance of plants to these herbicides can be substantially increased by adding N-(substituted benzenesulfonyl) carbamate detoxifying compounds to the soil. Certain of the compounds shown here are considered novel compounds and have the general formula: (wherein X is a hydrogen atom, a bromine atom, a chlorine atom, a methoxy group, a trifluoromethyl group, or a methyl group; n!'';t
An integer from 1 to 3 (however, when X is a bromine atom, trifluoromethyl group, or methoxy group, n
is l; and R is a haloalkyl group having 1 to 6 carbon atoms, of which halo is l to 6 chlorine, bromine or fluorine atoms, or 3
or anokynyl group having 4 carbon atoms, halopropenyl, alkynyl group having 3 to 6 carbon atoms, dialkylamino group having 2 to 8 carbon atoms in total, 3 to 6 carbon atoms in total Cyanoalkylthioalkyl groups having carbon atoms, phosphotumethyl groups, trifluoroacetamidomethyl groups, phenyl groups substituted with lower alkyl (said lower alkyl groups each have 1 to 4 carbon atoms), 4-chlorophenylthio Methyl group, alkoxyalkyl group having 2 to 6 carbon atoms, alkylthioalkyl group having 2 to 6 carbon atoms, 2 to 6
a cyanoalkyl group having 3 to 7 carbon atoms, an alkoxycarbonylalkyl group having 3 to 7 carbon atoms, 2
a formamide alkyl group having 6 carbon atoms;
4 to 7 carbon atoms. alkoxycarbonylalkenyl group having 3 to 6 carbon atoms, 1,3-dioxacyclohexane-5,5-methylmethylene group, phenyl group, chlorophenyl group, benzyl group, 4-chlorobenzyl group Group, (4-
methoxybenzyl group, 3-pyridylmethyl group, phenoxyethyl group, 3-phenylpropyne-2-2nyl group, methylthioacetimino group, acetonimino group, or benzaldoimino group).

Further, in the above general formula, when X is a trifluoromethyl group and n is l, R is an alkyl group,
It is a haloalkyl group, a propenyl group or an alkynyl group.

) In the above description, the following embodiments contemplate various groups of substituents.

The haloalkyl group in R is a linear or branched alkyl group having 1 to 6 carbon atoms, and "halo"
consisting of chlorine, bromine or fluorine atoms included in the phrase, the halo substituents being from 1 to 6 and being mono-, di-, tri-, tetra- or hexa-substituted. Examples of alkyl moieties included in preferred embodiments include methyl, ethyl, n-propyl, isopropyl,
Mention may be made of n-butyl, secondary butyl, isobutyl or tertiary butyl. Alkynyl groups in R preferably include those having 3 to 6 carbon atoms and having at least one acetylenic bond, ie a triple bond, examples of which include propargyl (propynyl), 2-
Examples include butynyl, 3-butynyl, 191-dimethyl-3-butynyl, and the like. As an alternative mode of action, the compounds according to the invention can interfere with the normal herbicidal action of the thiocarbamate herbicide and another herbicide, rendering it selective. It has been observed that the presence of the antidote described herein, in its absence, reduces the phytotoxicity of various thiocarbamate herbicides used for weed control to various crops. Whatever the mode of action, the corresponding good and desirable effect is that the herbicidal effect of thiocarbamate herbicides is continuous, whereas the associated herbicidal effect on the desired crop species is The goal is to reduce The advantages and usefulness of this are discussed below. Therefore, J herbicide antidote. l and ``
Phrases such as "antidote effective amount" are intended to describe an effect that is counter to the normal damaging herbicidal response that a herbicide might exhibit.

Whether it is called a herbicide, interfering agent, protectant, antagonist, etc. will depend on its precise mode of action. Although the mode of action varies, the desired effect is that of the method of treating the soil or furrow in which seeds, crops are sown. So far, no satisfactory system has been developed for this purpose. The compounds of the invention of the general formula above are prepared by different methods depending on the starting materials.

One common method of preparing N-(benzenesulfonyl)alkynyl carbamates is to react the appropriate alkynol with benzenesulfonyl isocyanate.

More specifically, the reaction is carried out using catalytic amounts of triethylamine and dibutyltin dilaurate in the presence of a solvent such as benzene or chloroform. In some cases a catalyst is not necessary. After the reaction is complete, the product is recovered by filtration or evaporation of the solvent. If necessary, the product is recrystallized from a suitable solvent. A common method for preparing N-benzenesulfonylalkyl carbamates is to prepare N-benzenesulfonylalkyl carbamates in the presence of a catalyst such as potassium carbonate.
The solution is to react the appropriate benzenesulfonamide with an alkyl chloroformate.

Solvents are commonly used to accelerate the reaction and aid in work-up of the product. After deep extraction and drying, the product is further purified by trituration with hexane or recrystallization from a suitable solvent. In most cases,
The structure was confirmed by infrared absorption spectroscopy, nuclear magnetic resonance spectroscopy or mass spectroscopy. The compounds of this invention and their production methods will be explained in more detail with reference to the following examples.

A list of compounds obtained by the methods described herein is shown below the examples of production methods. Compound numbers are attached to the compounds and used for identification elsewhere in this specification. Example 1 Preparation of 2-butyn-1-yl p-toluenesulfonyl carbamate 2-butyn-1-ol 1.75f1 (0.
4.99 (0.025 mol) of p-toluenesulfonyl isocyanate was added to a solution of chloroform 25a (0.025 mol) and chloroform 25a.
mol) was added gradually.

An exothermic reaction took place and the resulting product was removed by evaporation of the solvent. This gave 6.49 of the title compound with a melting point of 85-90°C. Example 2 - Preparation of bromopropyl p-toluenesulfonyl carbamate In a manner similar to that given in Example 1, 3.4 mL of 2-bromo-1-propanol in 25 ml of chloroform was prepared.
f1 (0.025 mol) and 4.9 g (0.025 mol) of p-toluenesulfonyl isocyanate were reacted.

After similar post-treatment to remove the solvent, n=1.537
The title compound of No. 5 was obtained in a yield of 8.4 g D°.

Example: Preparation of hexafluoroisopropyl p-toluenesulfonyl carbamate.

In a similar manner as described in Example 1, 4.29 ml of Sym-hexafluoroisopropanol and 4.29 ml of p-toluenesulfonyl isocyanate in 25 ml of chloroform were prepared.
9 g (0.025 mol) were reacted with the addition of 2 drops of triethylamine as a catalyst.

After similar post-treatment to remove the solvent, the melting point was 69-75.
8.9 °C of the title compound was obtained. Example N - Preparation of (p-chlorobenzenesulfonyl)propargyl carbamate Propargyl alcohol containing 1 drop of triethylamine and 1 drop of dibutyltin dilaurate.
．． 79 (0.03 mol) and benzene 20wL1, p-chlorobenzenesulfonylisocyanate 6.
A solution of 5f1 and benzene 25Tf11 was added.

The reaction was exothermic and the temperature was allowed to rise to 30°C. The mixture was stirred at room temperature for several hours and the precipitated solid was filtered off, washed with a little hexane and dried. 8.0 g (98% of calculated value) of the title compound with a melting point of 106 DEG -108 DEG C. were obtained. This purity has a melting point of 120.
The temperature was 5-121°C. This structure was confirmed by infrared absorption spectra, nuclear magnetic resonance spectra, and mass spectra. Example N - Preparation of (p-chlorobenzenesulfonyl)ethyl carbamate p-chlorobenzenesulfonamide 6.19 (0.032 mol), potassium carbonate 1
0.89 (0.078 mol) and ethyl chloroformate 3
．． 79 (0.034 mol) was stirred in acetone 40d and refluxed for 2 hours.

The mixture thickened while heating, so add 3 parts of acetone.
It was diluted by adding 0 ml freshly. Add 1 part of the cooled distillate to 1 part of water.
The mixture was poured into 50ml and passed through Celite. While cooling, the solution was made acidic with hydrochloric acid, the pH was adjusted to about 2, and the product was extracted with benzene. The extract was washed with water and dried over anhydrous magnesium sulfate. Removal of the solvent gave the title compound, mp 89-90°C, yield 5.59 (calcd. 6
5%). This structure was confirmed by IR. Example N - Preparation of (p-methoxybenzenesulfonyl)ethyl carbamate.

p-methoxybenzenesulfonamide 5.09 (0.0
32 mol), potassium carbonate 10.89 (0.078 mol) and ethyl chloroformate 3.79 (0.034 mol)
was refluxed in acetone 40d for 2.5 hours.

The product is worked up analogously to the examples and has a melting point of 110-
Yield 3.99 (47% of calculated value) of the title compound at 116°C
Obtained with. The compounds shown in the table below were obtained by the method described above.

The herbicides indicated in the table and elsewhere are used where they effectively control undesirable plant growth.

The ranges as used herein will yield representative results within the recommended amounts indicated by the supplier. Therefore, weed control in each case is commercially acceptable within the desired or recommended amount. It is clear that the classes of herbicides described and exemplified herein are characterized as effective herbicides exhibiting such activity.

The degree of herbicidal activity also varies depending on the particular compound and the particular combination of compounds in this class. Similarly, the degree of activity will also vary to some extent depending on the species of plant to which the particular herbicidal compound or combination is applied. Therefore, specific herbicidal compounds or combinations can be readily selected to control undesirable plant species. According to this invention, prevention of damage to desired crop species is achieved in the presence of specific compounds or combinations. Good plant species that can be protected by this method are not intended to be limited to the particular crops used in the examples. The herbicidal compounds used in the application of this invention are the general class of active thiocarbamate herbicides.

That is, it is a compound in the class of herbicidally active compounds that are effective against a wide range of plant species, without distinction between desirable and undesirable plant species. The method of controlling plant growth consists of applying a herbicidally effective amount of a herbicidal compound as described herein to the area, ie, plant habitat, where control is desired. The composition presented in this invention comprises an antidote as described above and a preferred active herbicidal compound selected from the class of thiocarbamate herbicides, with representative examples of said thiocarbamate herbicides being For example, (circle S-ethyldipropylthiocarbamate, S-ethyldiisobutylthiocarbamate, S-propyldi-n-propylthiocarbamate, S
-Ethylcyclohexylethylthiocarbamate, S-
Ethyl hexahythro 1H-azepine-1-carbothioate, 2,3,3-trichloroaryl N,N-diisopropylthiocarbamate, S-isopropyl-1-
(5-ethyl-2-methylpiperidine)carbothioate and the like. They may be used alone or in various combinations or with other classes of herbicide compounds, e.g.
2-chloro-4-ethylamino-6-isopropylamino-S-triazine, 2-chloro-4,6-bis(ethylamino)-3-triazine, 2-(4-chloro-6-
Ethylamine-S-triazin-2-monylamino)-2
It can also be used together with triazines such as -methylpropionitrile or 2-chloro-4-cyclopropylamino-6-isopropylamino-S-triazine. An embodiment within the scope of this invention is a two-component or bulk herbicide system in which the first component is one or more thiocarbamate herbicides and the second component is a detoxifying compound. It consists of things.
Thus, the detoxifying compound is selective in that it reduces phytotoxic effects on desirable or preferred crops, but exhibits phytotoxicity on undesired or unwanted plant growth. It is understood that it is used in an amount effective to achieve the desired effect. Therefore, soils treated with such systems are highly useful and desirable, and even crops that would be damaged when herbicides are used alone cannot be transplanted into such treated soils. It will be possible. Therefore, soils treated with the herbicides and antidotes described herein are good, desirable, and useful. Herbicide as used herein refers to a compound that inhibits or limits plant growth or plant growth.

Such suppressing or limiting effects include all conditions that deviate from natural development, such as withering, growth retardation, defoliation, dehydration, inhibition of growth due to overgrowth, burrowing, accelerated thinning, and the like. The term "plant" refers to a growing plant, including germinated seeds, seedlings and roots as well as aerial parts. Evaluation Instrument Flat boxes used for growing crops and weed species were filled with loamy sandy soil.

A raw material solution consisting of a herbicide and each antidote compound was produced as follows. A) Add 1560 ~ of the herbicide S-n-propyl N,N-di-n-propylthiocarbamate (VERNAM6E) to 250 ml of water.
diluted to

Applying 5 ml of this solution to a flat corresponds to 6 tb/A per flat (based on its surface area). B) Antidote Each antidote compound 78 was dissolved in 20 TILI of acetone containing 1% Tween [Tween 2 O 8 (polyoxyethylene sorbitan monolaurate)].

This 5T! 1 t mixed before planting (play plant)
Incorporated method (PPI) equals 5 tb/A per flat.

The herbicide and antidote were applied to the soil together as tank mix using the pre-plant mixing method.

To produce mixed tank mixes, VERNA
M857nl was mixed and then incorporated into the soil from the flat while being charged in a rotary mixer. The following weeds and crops were individually sown in treated soil in flats:
Watergrass (EchinOch)
FOx
(Satariaviridis) and soybean (Glycinemax) flats were placed on benches in a greenhouse maintained at 70-90 eF (approximately 20-30°C).

The soil was watered to improve plant growth. Damage ratings were performed 2 and 4 weeks after application. Each flat treated with herbicide alone served as the basis for determining the degree of damage reduction made by the herbicide antidote. The table below shows the results expressed in percentage of crop protection by the measures described above.

The protection rate was determined by comparison with flat boxes not treated with the antidote compounds of this invention. Seed Treatment Test Small flat boxes were filled with FeltOn loamy sandy soil.

At this point the herbicide was mixed with the soil and applied. The soil from each flat was placed in a 5-gallon cement mixer where the herbicide was applied using a predetermined amount of a stock solution containing approximately 75% active ingredient 7801!9 in 12571 L1 of water while mixing the soil. . 5 d of the raw material solution was administered to the soil using a constant volume pipette. Stock solution 5a, when applied to the soil in the flat, will contain an amount equivalent to 6 pounds of herbicide per acre. After mixing the herbicide, the soil was returned to the flat box. The seeds are thus sown in flat boxes of soil treated with herbicides and of untreated soil.

One pint (approximately 0.47 t) of soil sample was pre-removed from each flat and placed next to each flat for later use to cover the seeds. The soil was leveled and furrows 6 0.5 inches (approximately 1.3 C7 rL) deep were made for sowing the seeds. Treated and untreated seeds were sown alternately in each furrow. In each trial, soybean seeds were sown in each row.
The rows were spaced approximately 1.5 inches apart from each other. The seeds were treated with a raw material solution prepared by dissolving 250 ml of antidote compound in 2.5 ml of acetone, and when 0.5 ml of this raw solution was used to treat 10 V of soybean seeds, 0.5%w be equal to each other. Antidote compounds can also be used as liquid slurries and powders or powders. In some cases (round acetone can be used to dissolve powdered or solid compounds so that they can be applied more effectively to the seeds), after sowing in a flat, a pint of soil sample previously set aside before sowing. It was covered with soil.

The flat box was placed on a bench in a greenhouse where the temperature was maintained at 70-79'F. The flat boxes were watered as needed to improve plant growth. Inhibition rate evaluation was performed 4 weeks after treatment. In each test,
Herbicides were applied alone and in combination with seed protectants.

Seed protection agents were also used alone to investigate their phytotoxicity. Untreated adjacent rows were utilized to observe good lateral movement of the antidote compound through the soil. The degree of effect was investigated by comparison with control. S-
In a seed treatment test using the herbicide n-propyl N,N-di-n-propylthiocarbamate, compound No. 17 showed 50% protection against treated soybean seeds. That is, damage to soybean seedlings grown from seeds treated with Compound No. 17 compared to untreated seeds grown in soil containing the thiocarbamate herbicide.
It has decreased by at least 50%. Evaluation Instruments and Methods Flat boxes used for growing crops and weed species were filled with loamy sandy soil.

Various methods of administration may be used, for example, 1) the herbicide and antidote may be mixed separately before planting, or 2) the herbicide and antidote may be administered together in a tank mix. Application method of mixing and then sowing seeds in soil treated with herbicidally effective compositions of thiocarbamate herbicides and antidotes; and treatment of crop seeds with an antidote compound before sowing into the herbicide-treated soil. Raw material solutions of other typical thiocarbamate herbicides and antidote compounds were prepared as follows.

Herbicide C) S-ethyldi-n-propylthiocarbamate
260 mg of EPTC-EPTAMO6E was dissolved in 200 g of water.

When applying 4IL1 of this to the soil from the seeding flat,
equals 1 tb/A when applying 80 gallons of water per acre, and 3 mj is 0.75
Corresponds to 1b/A.

D) S-isopropyl 1-(5-ethyl-2-methylpiperidine)carbothioate (R-12001) 390
~ was dissolved in 200 ml of acetone containing 1% Tween (Tween2O8).

Also, 975m9 was dissolved in 250mI3 of acetone.
If 5 ml of this solution is applied to the seeding flat, it corresponds to 2 tb/A when mixed before planting, and the 6WLI corresponds to 6 tb/A. E) 520 η of S-ethyldiisobutylthiocarbamate (SUTAN86E) or s-ethylcyclohexylethylthiocarbamate (RONEE skewer D6E) was dissolved in 200 d of water. If 4m1 is applied to the soil from the sowing box, water per acre is 80
When applying a gallon (approximately 303 tons), this corresponds to 2 tb/A.

6tb/A or 12tb/A & Maru 1300
If ~ or 26~ is dissolved in 250TI11 of water, 6
m1 corresponds to each desired amount.

F) 2,3,3-trichloroaryl N,N-diisopropylthiocarbamate (AVADEXB?DZJ4
E) 1219 mf dissolved in 300 a of distilled water gives 6
Tnt corresponds to 3tb/A.

1S-Ethylhexamine 1H-azepine-1-carbothioate (4) RDRA black D8E) 857 ~ in water 2
50T! When dissolved in Ll, its 5WL1 yields 4 tb/L when applied to pre-mixed soil from a seeding flat.
A, and its 2.5 mt corresponds to 2 tb/A.

Antidote For each antidote compound, 1% of active ingredient 250η
2.5 ml of acetone containing Tween20-Tween2O8 (polyoxyethylene sorbitan monolaurate)
When dissolved in , a solution of 0.5WLI corresponds to 0.5% w/w for 10y of seeds.

For 0.25% seed treatment, add 0.25ml of acetone 0.
．． When diluted with 25d, the solution 0.5a will be equal to 0.25% i per 10r of seeds.

This solution is used in various amounts for seed treatment measures,
For example, for a 0.10% dilution, 0.1 ml was diluted with 0.4 ml of acetone. 1) For each antidote compound used in the "in-furrow" administration method, 95 to 95 active ingredients are dissolved in 15 d of acetone containing Tween 208, and 1.5 ml is applied to the seeds and soil in half the trench of the flat box. This corresponds to 5 tb/A.

When 1.0tb/A is desired (circle 0.3a to 1.0tb/A)
Dilute 2a with acetone.

J) “Tank mixes” For each antidote compound used in the pre-plant mixing test, when 39~ of the active ingredient is dissolved in 10 ml of acetone containing 1% Tween 208, when 5 d is applied to soil in a flat box, 5 tb. Corresponds to /A.

The above raw material solution was used for in-sulcus administration of the antidote.

As a preparatory step, one pint (approximately 0.47 t.
) soil samples were taken and used to cover the seed soil after being treated with the raw solution. The soil was leveled before sowing. The herbicide raw material solution has an active ingredient content of 1 tb/
A and Z4 were mixed in equal proportions and in the soil of a flat box for sowing before planting so that they were in a predetermined proportion.

Seed Preparation Number ζ A row of grooves 0.25 inches deep was cut in each treated box in the longitudinal direction.

After sowing, the flat was divided into two halves using a wooden barrier and one of the halves of the flat was sprayed with 1.5a of raw material solution directly onto the exposed seeds and soil. The untreated section of the flat was used for herbicide evaluation and allowed the antidote to be observed to migrate laterally through the soil. Seeds were covered with previously removed untreated soil samples. For tank mixes applied as pre-implant admixtures, the following solutions and procedures were used:

Mix 5 ml of herbicide raw solution A or C with the antidote compound raw solution J5WLl and apply it to the soil in each flat box so that the herbicide and antidote are 1 tb/A and 5 tb/A, respectively. I prepared it. For pre-plant (seeding) mixing, the mixed stock solution is poured into the soil while being loaded into a 5 gallon rotary mixer.
Other raw material solutions can also be used in predetermined proportions by tank mix means. For seed treatment, 10 r of seeds are placed in a suitable container and shaken with 0.5 d of antidote raw material solution H or other aforementioned raw material solutions, and the seed treatment is 0.5% to 0.25% vl. /W. O. l25%Wh or 0.
It was set to be equal to 1% w^.

Shaking was continued until the seeds were evenly coated. The antidote compound can also be applied as a liquid slurry and as a powder or powder treatment. The treated seeds were sown in soil in which a herbicide stock solution was loaded into the soil at a rate corresponding to 1 tb/A of active ingredient prior to planting. All flats were placed on benches in a greenhouse maintained at 70-900F (approximately 20-30C). Water was sprinkled on the soil to improve plant growth. Damage evaluation was performed 2 and 4 weeks after administration. Each box treated with herbicide alone served as a control to determine the percent damage reduction caused by the herbicide antidote.
These results are shown in Table 1. In side-by-side trials with a variety of weed species and crops, compared to check or control flats, did weed control remain and at the same time crop species be protected? or damage) was reduced.

The control box did not contain any antidote compound. The table below further shows these results. The compounds and compositions of this invention are used as effective herbicidal compositions comprising antidotes and thiocarbamate herbicides as described above.

The herbicidal composition was tested as described above. Preferred herbicidal compositions include a thiocarbamate herbicide and a detoxifyingly effective amount of the general formula: ? 0 (wherein, X is a hydrogen atom,
A methyl group, a methoxy group, a chlorine atom or a bromine atom, and R is an alkyl group having 1 to 4 carbon atoms or a haloalkyl group having 2 to 6 carbon atoms (here, halo is a chlorine atom having 1 to 6 atoms). , a bromine atom or a fluorine atom),
Alkenyl group having 3 to 6 carbon atoms, chloroalkenyl group having 3 to 6 carbon atoms, dialkylamino group having 2 to 6 carbon atoms containing alkynyl group having 3 to 6 carbon atoms, trifluoroacetamidomethyl group, 4 -chlorophenylthiomethyl group, fuconyl group, 3-phenylpropynyl-2-yl, 3-pyridylmethyl group or phosphotmethyl group).

Composition G for protecting cultivated crop plants according to this invention
It consists of an antidote and an active herbicidal compound as described above.

This composition of herbicide and antidote is prepared by mixing the active herbicide and antidote together with a suitable carrier and/or other distribution agent, optionally with the addition of a spreading agent or solvent. And it can be manufactured by a conventional method by pulverizing. The detoxifying compounds and compositions of this invention may be used in any convenient manner.

Solvents or inert carriers are not required in low volume spray methods where neat technical materials can be used as sprays. That is, the composition comprising the detoxifying compound and the thiocarbamate herbicide can be formulated into an emulsified concentrate, liquid, wettable powder, dust, granule, or any other convenient form. In its preferred form, a non-phytotoxic amount of the herbicide detoxifying compound is mixed with the intended herbicide and incorporated into the soil before or after sowing. However, it is also understood that detoxifying compounds can be incorporated into the soil after the herbicide has been incorporated into the soil. The crop seeds themselves can be treated with a non-phytotoxic amount of a detoxifying compound and then sown into soil previously treated with a herbicide, or they can be sown into untreated soil, It can also be treated with herbicides afterwards. Addition of this detoxifying compound does not affect the herbicidal activity of the herbicide. Another method of application is illustrated in the example above. The amount of detoxifying compound present is approximately 0.0% of the detoxifying compound described herein based on parts by weight of herbicide.
001 to about 30 parts by weight.

The exact amount of detoxifying compound will be determined in an economical proportion to the amount that can be used most effectively. Non-phytotoxic, but effective amounts of detoxifying compounds may be used in the herbicidal compositions and methods described above. After treatment with the antidote and herbicide according to the invention, a soil is obtained that is new in composition.

The soil is improved in its ability to grow crops and suppress weeds. Additionally, the soil treated with herbicides and antidotes has particular utility for sowing and growing crop seeds that would otherwise be damaged by herbicides. While herbicides have the utility of suppressing undesirable plant growth,
This detoxifying compound reduces the damage caused by the herbicide to the crop species, and the soil treated with the herbicide and detoxifying compound is treated with the herbicide in the presence of the otherwise damaging herbicide. By the way, it provides an improved medium for growing crops. Thiocarbamates can also be applied to the soil when using the detoxifying compounds and improved herbicide systems of this invention.

The herbicide can also be applied to the soil by pre-sowing (pre-planting) incorporation. In accordance with this invention, the herbicide can also be pre-applied to sow the crop seeds - then the antidote can be administered as a pre-emergent surface application. Although this herbicide, seeding, and antidote sequence of application is unusual, it is completely effective in reducing damage to plant crops that would otherwise be damaged by the thiocarbamates. It is.
Evaluation Testing on Legumes It has been found that the various detoxifying compounds described herein are capable of reducing damage to the class of crops known as legumes.

Here, "legume" means a plant that has a symbiotic relationship with nitrogen-fixing organisms. For example, soybeans, various quail beans (Phaese
Olus vulgaris (L.), peanut,
Examples include Alpha Al JA and Clover 1st class. S-ethyldi-n-propylthiocarbamate (EPTAyD) (EPTC), a representative thiocarbamate herbicide
The following test was conducted to investigate the effect of using the above-mentioned compound in reducing damage to leguminous plants.

A variety of edible beans and peas were tested. The antidote is 1 or 2 tb/A (approximately 0.45 or 0.9k
g/A) before sowing, and 6 tb/A (approximately 2.
It was applied in a tank mix with EPTC mixed before seeding at a ratio of 4kfI/A). Raw material solution antidote: 39 grams of each antidote compound was dissolved in 25 d of acetone and used.

The 2.5a is 1tbA (0.4
5kg/A). Herbicide: EPTAM8l5
6O7llf was dissolved in 250 mt of water and used.

The 5d was mixed with 61bA (2.4kg/A
). The tested crops were white kidney beans (Nav
ybean-NB), Kidneybean
n1KB), PintObean-PB: PhaeseOlusvul
garisL. ) and pea (Pisl)
sati-VuOOLL. ).

The weed used in the test was Watergrass
s-WG) and FOXtail-
FT). The compound number is 2 per acre.
lb (0.9 kg) completely protected kidney bean leaves.

Compound No. 28 Compound 2 pounds per 6 acres (0
．． 9kg) protected 50 kidney beans. 2 pounds (0.9 kg) per acre of compound number 28
When used, pea damage was reduced by 375%.

[Brief explanation of the drawing]

The figures are infrared absorption spectra, nuclear magnetic resonance spectra, or mass spectra of the compounds according to the present invention. Figure 3 shows the nuclear magnetic spectrum of Compound No. 9, and Figure 4 shows the infrared spectrum of Compound No. 14.
The infrared spectrum of "Compound No. 15", FIG. 5 is the infrared spectrum of "Compound No. 22", and FIG. 6 is the infrared spectrum of "Compound No. 22".
7 shows the infrared spectrum of "Compound No. 25," FIG. 8 shows the red body spectrum of "Compound No. 30," and FIG. 9 shows the infrared spectrum of "Compound No. 31." 10A is the infrared spectrum of "Compound No. 44", FIG. 10B is the nuclear magnetic spectrum of "Compound No. 44", and FIG. 11A is the nuclear magnetic spectrum of "Compound No. 44".
The infrared spectrum of "Compound No. 45" in Figure 11B is the infrared spectrum of "Compound No. 40" in Figure 12, the infrared spectrum of "Compound No. 40"
The infrared spectrum of compound number 46, Figure 13A, is
The infrared spectrum of the same "Compound No. 47", Fig. 13B is the mass svector of the same "Compound No. 47", Fig. 14 is the infrared spectrum of the same "Compound No. 48", Fig. 15A
is the infrared spectrum of “Compound No. 49”, and FIG. 15B is the nuclear magnetic spectrum of “Compound No. 49”.
Figure 6 shows the infrared spectrum of “Compound No. 53”, the first
Figure 7 shows the infrared spectrum of “Compound No. 86”, the first
Figure 8 shows the infrared spectrum of “Compound No. 90”, the first
Figure 9A is the infrared spectrum of the same "compound number 100",
FIG. 19B shows a mass spectrum diagram of the same "Compound No. 100".

Claims (1)

[Claims] 1. General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X is a hydrogen atom, a bromine atom, a chlorine atom, a methoxy group, a trifluoromethyl group, or a methyl group; n is An integer from 1 to 3 (where X is a bromine atom,
When it is a trifluoromethyl group or a methoxy group, n
R is an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 2 to 6 carbon atoms (where halo is 1 to 6 chlorine, bromine or fluorine); , an alkenyl group having 3 or 4 carbon atoms, a halopropenyl group, an alkynyl group having 3 to 6 carbon atoms, a dialkylamino group having a total of 2 to 8 carbon atoms, a total of 3 to 6 carbon atoms cyanoalkylthioalkyl radicals having carbon atoms of Methyl group, alkoxyalkyl group having 2 to 6 carbon atoms, alkylthioalkyl group having 2 to 6 carbon atoms, cyanoalkyl group having 2 to 6 carbon atoms, alkoxy group having 3 to 7 carbon atoms carbonylalkyl group, formamidoalkyl group having 2 to 6 carbon atoms, alkoxycarbonylalkenyl group having 4 to 7 carbon atoms, alkylcarbonylalkyl group having 3 to 6 carbon atoms, 1,3-di Oxacyclohexane-5,5-methylmethylene group, phenyl group, chlorophenyl group, benzyl group, 4-chlorobenzyl group, 4-methoxybenzyl group, 3-pyridylmethyl group, phenoxyethyl group, 3-phenylpropyn-2-yl group , methylthioacetimino group, acetimino group and benzalimino group. However, when X is a trifluoromethyl group and n is 1, R is an alkyl group, a haloalkyl group, a propenyl group, or an alkyl group. ), the indicated compound. 2
The compound according to item 1 above, wherein X is a chlorine atom and R is an alkyl group. 3. The compound according to item 2 above, wherein R is ethyl. 4. The compound according to item 1 above, wherein X is a methyl group and R is an alkynyl group. 5. A compound according to clause 4, wherein 5R is 2-butyl. 6. The compound according to item 1 above, wherein X is a chlorine atom and R is an alkyl group. 7. The compound according to item 6 above, wherein R is 2-propynyl. 8. The compound according to item 6 above, wherein R is 3-butynyl. 9. The compound according to item 6 above, wherein R is 1,1-dimethyl-3-butynyl. 10. The compound according to item 7 above, wherein R is 2-butynyl. 11. The compound according to item 1 above, wherein X is a bromine atom and R is an alkynyl group. 12. The compound according to item 11 above, wherein 12R is 2-propynyl. 12. The compound according to item 11 above, wherein 13 R is 2-butynyl. 14. The compound according to item 1 above, wherein X is a hydrogen atom and R is a haloalkyl group. 15. The compound according to item 14, wherein 15R is 2,2,2-trifluoroethyl. 15. The compound according to item 14 above, wherein 16 R is 2-chloroethyl. 15. The compound according to item 14, wherein 17R is 2,2-dichloroethyl. 18 General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X is a hydrogen atom, bromine atom, chlorine atom, methoxy group, trifluoromethyl group, or methyl group; n is an integer from 1 to 3 Yes, (however, X is a bromine atom,
When it is a trifluoromethyl group or a methoxy group, n
R is an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 2 to 6 carbon atoms (where halo is 1 to 6 chlorine, bromine or fluorine); , an alkenyl group having 3 or 4 carbon atoms, a halopropenyl group, an alkynyl group having 3 to 6 carbon atoms, a dialkylamino group having a total of 2 to 8 carbon atoms, a total of 3 to 6 carbon atoms sialkylthioalkyl, phosphonomethyl, trifluoroacetamidomethyl, phenyl substituted with lower alkyl, each lower alkyl having 1 to 4 carbon atoms, 4-chlorophenylthio Methyl group, alkoxyalkyl group having 2 to 6 carbon atoms, alkylthioalkyl group having 2 to 6 carbon atoms, cyanoalkyl group having 2 to 6 carbon atoms, 3
Alkoxycarbonylalkyl group having 7 to 7 carbon atoms, formamidoalkyl group having 2 to 6 carbon atoms, alkoxycarbonylalkenyl group having 4 to 7 carbon atoms, alkyl group having 3 to 6 carbon atoms carbonyl alkyl group, 1,3-dioxacyclohexane-5,5-methylmethylene group, phenyl group,
Chlorophenyl group, benzyl group, 4-chlorobenzyl group, 4-methoxybenzyl group, 3-pyridylmethyl group, phenoxyethyl group, 3-phenylpropyn-2-yl group, methylthioamotoimide group, acetimino group and benzalimino group, selected from the group consisting of. However, when X is a trifluoromethyl group and n is 1, R is an alkyl group, a haloalkyl group, a propenyl group, or an alkynyl group. ) is applied to crops as a thiocarbamate herbicide, which is non-toxic to plants and effective for detoxification, and is applied to the soil where crops are sown and grown. How to reduce damage. 19. The method according to item 18, wherein X is a chlorine atom and R is an alkyl group. 20. The method according to item 19, wherein 20 R is ethyl. 21. The method according to item 18, wherein X is a methyl group and R is an alkynyl group. 22. The method according to item 21 above, wherein 22R is 2-butynyl. 22. The method according to item 21, wherein 23 R is 3-butynyl. 24. The method according to item 18, wherein X is a chlorine atom and R is an alkynyl group. 25. The method according to item 24, wherein 25R is 2-propynyl. 25. The method according to item 24, wherein 26R is 3-butynyl. 27. The method according to item 24, wherein R is 1,1-dimethyl-3-butynyl. 25. The method according to item 24, wherein 28R is 2-butynyl. 29. The method according to item 18, wherein X is a bromine atom and R is an alkynyl group. 30. The method of item 29 above, wherein R is 2-propynyl. 31. The method according to paragraph 29, wherein 31 R is 2-butynyl. 32. The method according to item 18, wherein X is a hydrogen atom and R is a haloalkyl group. 33. The method according to item 32, wherein 33 R is 2,2,2-trifluoroethyl.