KR950006906B1 - Herbicidal S- (O-substituted-2,6-dichlorobenzohydroxymoyl) -N, N-diethylthio carbamate derivatives and preparation method thereof - Google Patents

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Description

Herbicidal S- (O-substituted-2,6-dichlorobenzohydroxymoyl) -N, N-diethylthio carbamate derivatives and preparation method thereof

The present invention provides a novel herbicidal S- (0-substituted-2,6-dichlorobenzohydroxymoyl) -N, N-diethylthiocarba represented by the general formula (I) following the introduction of oxime ether as a functional group. A mate derivative and its manufacturing method are provided.

Wherein R is C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₄ alkenyl or C ₃ -C ₄ alkynyl group or-(CH ₂ ) _n -CH (R ¹ ) -COOR ² , -CO-R ³ or -SO ₂ R ⁴ , or an acetonyl, methoxymethyl, methoxyethyl, cyanomethyl or dimethylaminoethyl group, where n is 0 or 1 and R ¹ is hydrogen, C ₁ -C ₃ alkyl or acetyl group, R ² is hydrogen or C ₁ -C ₃ alkyl group, R ³ is haloalkyl, aryl or substituted aryl group, R ⁴ is C ₁ -C ₆ alkyl, aryl or substituted And an aryl group, wherein the substituent of aryl in R ³ and R ⁴ is a methyl group or a halogen atom.

S-alkyl or S-benzyl carbamothionate derivatives have been actively studied since the 1960s and demonstrated herbicidal effect [“Chemistry of Pestilide”, KH Buchel, ED., John Wiley & Sons, New York, pp. .347-349], however, the compounds according to the present invention having introduced functional groups in the form of oxime ether as in the general formula (I) are compounds having a new structure in which no synthesis or herbicidal effect has been reported in the literature.

An object of the present invention is to provide a novel compound represented by the general formula (I), which exhibits a stronger herbicidal effect than conventional herbicides and exhibits particularly good herbicidal or plant growth inhibitory effects in germination pretreatment.

Hereinafter, the present invention will be described in detail.

The present invention relates to novel herbicidal S- (O-substituted-2,6-dichlorobenzohydroxymoyl) -N, N-diethylthio carbamate derivatives represented by the general formula (I).

The compound of general formula (I) is particularly useful as a pre-germination treatment herbicide, and is very preferable for weed removal in corn cultivation.

Of the substituents of the compound of formula (I), R all exhibits effective herbicidal activity in the above-defined ranges, but isopropyl, aryl, acetonyl, 2-methylcyanomethyl, N, N-diethylaminoethyl Preference is given to a benzoyl or methane sulfonyl group.

The compound represented by the general formula (I) as described above is synthesized through a reaction process as shown in Scheme A. Specifically, the compound is reacted with 2,6-dichlorobenzaldehyde and hydroxylamine hydrochloride to give 2,6- Dichlorobenzaldehyde was synthesized, and reacted in N-chlorosuccinimide (NCS) and N, N-dimethylformamide (DMF) to synthesize hydroxymoyl chloride derivative of the following general formula (III), followed by [Reference] Literature: J. Org. Chem., 302809 (1965)], which is obtained by reacting this with the N, N-diethylthiocarbamic acid diethylamine salt of the following general formula (IV). In the presence of a base, RX (where R is as defined above and X is a leaving element such as chlorine, bromine or iodine as a leaving group) is reacted to prepare the compound of the general formula (I).

As the solvent used at this time, N, N-dimethylformamide, dichloromethane, pyridine, water, acetone, etc. can be used, and as a base, sodium hydroxide, triethylamine, anhydrous potassium carbonate, sodium hydride, etc. can be used.

Scheme 1a

Representative compounds for the compound of formula (I) according to the present invention prepared as described above are shown in Table 1 below.

TABLE 1

In addition, in using the compound of this invention represented by the said General formula (I), it can be used as it is, or it can also be used in manufacturing forms, such as a hydrating agent, an emulsion, a granule, a liquid, or a powder.

Solid carriers or liquid carriers can be used to produce this type of preparation. Solid carriers include inorganic powder (kaolin, bentonite, montmorillonite, talc, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, apatite, synthetic hydrous silicon hydroxide), plant powder (soybean flour, flour, sawdust, tobacco powder) , Starch powder, crystalline cellulose), polymer materials (petroleum resin, vinyl chloride resin, ketone resin), alumina and beeswax can be used.

Liquid carriers include alcohols (methanol, ethanol, ethylene glycol, benzyl alcohol), aromatic hydrocarbons (toluene, benzene, xylene, methylnaphthalene), halogenated hydrocarbons (chloroform, carbon tetrachloride, chlorobenzene), ethers (dioxane, tetrahydrofuran ), Ketones (acetone, methyl ethyl keron, cyclonucleanone), esters (ethyl acetate, butyl acetate, ethylene glycol acetate), amides (dimethylformamide), nitriles (acetonitrile), ether alcohols (ethylene glycol, Ethyl ether), water, and the like.

Nonionic, anionic, cationic or amphoteric materials may be used as the surfactant used for emulsification or dispersion. Examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene kealkyl aryl ether, polyoxyethylene fatty acid ester, oxyethylene oxypropylene resin, polyoxyethylene alkyl phosphate, fatty acid salts, alkyl sulfates, alkyl sulfonates, alkyl aryl sulfo Nate, alkyl phosphate, polyoxyethylene alkyl sulfate, quaternary ammonium salt, etc.

However, the surfactant that can be used is not limited to these, and if necessary, glue, casein, starch, agar, polyvinyl alcohol, lignin sulfonic acid, etc. may be used as an adjuvant.

When preparing as a herbicide, the content of the material represented by the general formula (I) may be used in a weight ratio of about 1 to 95%, preferably 3 to 80% by weight.

The compound of the general formula (I) may be used together with other kinds of herbicides in order to improve the herbicidal effect, and in some cases, a synergy may be expected.

Moreover, the compound of general formula (I) can also be used as an insecticide, an nematicide, a fungicide, a plant regulator, or a fertilizer if needed.

Hereinafter, the present invention will be described in detail with reference to Examples.

Preparation Example 1: Preparation of 2,6-dichlorobenzohydroxymoyl chloride (III)

2,6-dichlorobenzaldehyde (II, 200 g, 1.14 mol) and 600 ml of ethyl alcohol were added to a 3 l flosk and heated and dissolved at about 60 ° C. Hydroxylamine hydrochloride (94 g, 1.35 moles) was added to 80 ml of distilled water, and a solution of sodium hydroxide (68 g, 1.7 moles) dissolved in 70 ml of distilled water was slowly added while maintaining the temperature of the reaction solution at 50-70 ° C.

After standing at room temperature for 18 hours, the mixture was diluted with 2 L of distilled water and separated by suction filtration. The solid was sufficiently washed with distilled water and dried to obtain 152 g of 2,6-dichlorobenz aldoxime (yield 70%, melting point 130 to 134 ° C).

Take 145 g of 2,6-dichlorobenz aldoxime and dissolve in 60 ml of N, N-dimethylformamide. 20 g of N-chlorosuccinimide was added while stirring at room temperature, and after 5 minutes, 25 ml of anhydrous hydrochloric acid gas was added. After 5 minutes, the reaction solution temperature was maintained at 30 ° C. and 20 g of N-chlorosuccinimide was added.

After standing for 1 hour, 20 g of N-chlorosuccinimide was added, and left at room temperature for 14 hours. The reaction solution was diluted with 2.5 L of ice water and extracted with ethyl ether (2 x 700 ml). The organic layer was collected, dried over anhydrous magnesium sulfate, and the solvent was extracted under reduced pressure to obtain 164 g of the target compound (III). (Yield 95.5%, Melting point 82-85 ° C)

Preparation Example 2 Preparation of S- (2,6-dichlorobenzohydroxymoyl) -N, N-diethylthiocarbamate (V)

Toluene was added to 2,6-dichlorobenzohydroxymoyl chloride (III, 163.8g, 0.73mol) and toluene containing N, N-diethylthiocarbamic acid diethylamine salt (0.73mol) while stirring with a mechanical stirrer. 680 ml of the solution was added dropwise keeping the temperature below 30 ° C.

After stirring for 18 hours at room temperature, 1 liter of distilled water was added thereto, followed by extraction with 500 ml of acetate ester. The organic layer was separated, washed with distilled water (3 × 500 ml), the solvent was extracted under reduced pressure, and the resulting solid was dried to obtain 139.8 g of the target compound (V).

Yield: 59.7%, m.p. : 142-147 ℃

¹ H NMR (chloroform-d ₃ ) δ 1.2 (t, 6H), 3.7 (q, 4H), 7.10-7.55 (m, 3H), 8.8 (s, 1H)

Example 1 Preparation of S- (O-Methyl-2,6-dichlorobenzohydroxymoyl) -N, N-diethylthiocarbamate (Compound 1)

S- (2,6-dichlorobenzohydroxymoyl) and NN-diethylthiocarbamate (2.0 g, 6.23 mmol) were dissolved in 25 ml of anhydrous N, N-dimethylformamide followed by 60% sodium hydride (0.28 g , 7 mmol) was added and left at room temperature for 1 hour with good stirring.

Methane iodide (0.89 g, 6.25 mol) was added and stirred at room temperature for 18 hours. The reaction solution was diluted with 100 ml of distilled water and extracted with 100 ml of acetate ester. The organic layer was separated, washed with distilled water (2 × 100 ml), dried over anhydrous magnesium sulfate, and the solvent was extracted under reduced pressure. The obtained crude product was separated and purified through tube chromatography (hexane: acetone = 9: 1) to obtain 1.45 g of the target compound.

Yield: 69.4%

¹ H NMR (chloroform-d ₃ ) δ 1.25 (t, 6H), 2.05 (s, 3H), 3.6 (q, 4H), 6.6-7.4 (m, 3H)

Example 2: Preparation of Compound 2

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 1, to synthesize a target compound.

Example 3: Preparation of Compound 3

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 1, to synthesize a target compound.

Example 4: Preparation of Compound 4

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 1, to synthesize a target compound.

Example 5 Preparation of Compound 5

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 1, to synthesize a target compound.

Example 6: Preparation of Compound 6

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 1, to synthesize a target compound.

Example 7: Preparation of Compound 7

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 1, to synthesize a target compound.

Example 8 Preparation of Compound 8

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 1, to synthesize a target compound.

Example 9 Preparation of Compound 9

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 1, to synthesize a target compound.

Example 10 Preparation of S-N, N-diethylcarbamoyl-α-mercapto-2,6-dichlorobenzylideneaminooxyacetic acid (Compound 10)

S- (2,6-dichlorobenzohydroxymoyl) -N, N-diethylthiocarbamate (3.0 g, 9, 35 mmol) was dissolved in 20 ml of distilled water with 0.8 g of sodium hydroxide, followed by chloroacetic acid (0.89 g, 9.42 mmol) was added.

After standing at room temperature for 5 days, the reaction solution was adjusted to pH 6.4 with 1N aqueous hydrochloric acid solution. 150 ml of ethyl acetate was extracted, the organic layer was washed with 150 ml of distilled water, dried over anhydrous magnesium sulfate, and the solvent was extracted under reduced pressure to obtain 0.94 g of the target compound.

Yield: 26.8%

¹ H NMR (chloroform-d ₃ ) δ 1.0-1.4 (t, 6H), 3.1-3.7 (m, 6H), 6.6-7.4 (m, 3H)

Example 11 Preparation of Compound 11

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 1, to synthesize a target compound.

Example 12 Preparation of Compound 12

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 1, to synthesize a target compound.

Example 13: Preparation of Compound 13

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 1, to synthesize a target compound.

Example 14 Preparation of Compound 14

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 1, to synthesize a target compound.

Example 15 Preparation of Compound 15

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 1, to synthesize a target compound.

Example 16: Preparation of Compound 16

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 1, to synthesize a target compound.

Example 17 Preparation of Compound 17

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 1, to synthesize a target compound.

Example 18 Preparation of Compound 18

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 1, to synthesize a target compound.

Example 19 Preparation of Compound 19

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 1, to synthesize a target compound.

Example 20 Preparation of S- (O-methoxymethyl-2,6-dichlorobenzohydroxymoyl) -N, N-diethylthiocarbamate (Compound 20)

S- (2,6-dichlorobenzohydroxymoyl) -N, N-diethylthiocarbamate (3.0 g, 9.35 mmol) was dissolved in 40 ml of anhydrous N, N-dimethylformamide, and chloromethylmethyl ether (0.76 g, 9.44 mmol) and anhydrous potassium carbonate (1.95 g) were added and stirred for 48 hours at room temperature.

The reaction solution was diluted with 150 ml of distilled water and extracted with 120 ml of ethyl acetate. The combined organic layers were washed with distilled water (2 × 100 ml), dried over anhydrous magnesium sulfate, and the solvent was extracted under reduced pressure to obtain 2.48 g of the target compound.

Yield: 73%

¹ H NMR (chloroform-d ₃ ) δ 1.25 (t, 6H), 3.25 (s, 3H), 3.6 (q, 4H), 4.65 (s, 2H), 6.-7.4 (m, 3H)

Example 21 Preparation of Compound 21

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 1, to synthesize a target compound.

Example 22 Preparation of Compound 22

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 1, to synthesize a target compound.

Example 23 Preparation of Compound 23

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 1, to synthesize a target compound.

Example 24 Preparation of Compound 24

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 20, to synthesize a target compound.

Example 25 Preparation of Compound 25

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 20, to synthesize a target compound.

Example 26 Preparation of S- (O-Chloroacetyl-2,6-dichlorobenzohydroxymoyl) -N, N-diethylthiocarbamate (Compound 26)]

S- (2,6-dichlorobenzohydroxymoyl) -N, N-diethylthiocarbamate (2.0 g, 6.23 mmol) and chloroacetone (0.6 g, 6.4 mmol) were dissolved in 25 ml of anhydrous dichloromethane, followed by pyridine ( 0.7 g, 8.85 mmol) was added and stirred at room temperature for about 3 hours. 100 ml of distilled water was added to the reaction mixture, followed by extraction with 100 ml of dichloromethane. The combined organic layers were washed with distilled water and saturated copper sulfate solution and the solvent was extracted under reduced pressure. The obtained crude product was separated and purified through tube chromatography (hexane: acetone = 9: 1) to obtain 0.75 g of the target compound.

Yield: 30.3%

¹ H NMR (chloroform-d ₃ ) δ 1.2 (t, 6H), 3.4 (q, 4H), 4.6 (s, 2H), 6.6-7.4 (m, 3H)

Example 27 Preparation of Compound 27

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 26, to synthesize a target compound.

Example 28 Preparation of Compound 28

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 26, to synthesize a target compound.

Example 29 Preparation of S- (O-Methanesulfonyl-2,6-dichlorobenzohydroxymoyl) -N, N-diethylthiocarbamate (Compound 29)

S- (2,6-dichlorobenzohydroxymoyl) -N and N-diethylthiocarbamate (2.0 g, 6.23 mmol) were dissolved in 20 ml of anhydrous pyridine, and then methanesulfonyl chloride (0.75 g, 6.5 mmol) was added thereto. Stir at room temperature for 18 hours. 150 ml of distilled water was added to the reaction solution, followed by extraction with 100 ml of dichloromethane. The organic layer was collected, washed with distilled water and saturated copper sulfate solution, and the solvent was extracted under reduced pressure to obtain Compound 29. The obtained crude product was separated and purified through tube chromatography (hexane: acetone = 9: 1) to obtain 0.63 g of the pure target compound.

Yield: 25.4%

¹ H NMR (chloroform-d ₃ ) δ 1.25 (t, 6H), 3.3-3.8 (m, 7H), 6.6-7.4 ((m, 3H)

Example 30 Preparation of Compound 30

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 29 to synthesize a target compound.

Example 31: Preparation of Compound 31]

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 29 to synthesize a target compound.

Example 32 Preparation of Compound 32

A compound corresponding to the substituent R was used and prepared in the same manner as in Example 29 to synthesize a target compound.

The results of the herbicidal activity evaluation test for the novel compounds of the general formula (I) according to the present invention and the above examples are illustrated in the following experimental examples.

Experimental Example

Sterilize the sandy loam mixed with the appropriate amount of fertilizer and place it in the test pot (foot condition: 348cm2, rice field condition: 115cm2). The number of pots used at this time was 2 pots of field conditions and 1 pot of paddy conditions per compound. Then, as field crops and weeds, tomatoes (L.esculentum), wheat (T.aestiuum), soybean (G.max), corn (Z.mays), Orchardgrass (D.glomerata), A.uridis, Seeds or underground seeds of R. japonicus, C. communis, A.indica, C. japonica, etc., in pots of field conditions and as paddy crops and weeds. (O.sativa), E.oryzieola, c.difforrmis, and A.keisak, each of the seeds are planted in pots of rice fields, and then crushed with finely soiled soil. Put it.

The test compound (field condition: 14 mg / pot, field condition: 4 mg / pot) of 4 kg / ha was dissolved using acetone as a solvent, and then the same amount was mixed with water to which a nonionic surfactant (Tween 20) was added. Spray 14 ml per pot for 4 ml per pot for non-conditioning.

Soil treatment before germination is treated on the 1st day after sowing, and lateral treatment after germination is prepared with drugs prepared on the 9th to 14th day after sowing. After treatment, grow them in a greenhouse for two to three weeks, and then examine their herbicidal effects by morphological and physiological evidence. In other words, 0% means no herbicidal effect, 10 ~ 30% slightly herbicidal effect, 40 ~ 60% moderate herbicidal effect, 70 ~ 90% severe herbicidal effect, and 100% means full herbicidal effect.

Table 2 shows the germination effect before germination obtained as a result of evaluating herbicidal activity by the above experiments on the representative compounds of the general formula (I) prepared according to the embodiment of the present invention.

TABLE 2

Claims (4)

S- (O-substituted -2,6-dichlorobenzohydroxymoyl) -N, N-diethylthio carbamate derivative represented by the following general formula (I). Wherein R is C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₄ alkenyl or C ₃ -C ₄ alkynyl or-(CH ₂ ) _n -CH (R ¹ ) -COOR ² , -CO-R ³ or -SO ₂ R ⁴ , or an acetonyl, methoxymethyl, methoxyethyl, cyanomethyl or dimethylaminoethyl group, where n is 0 or 1 and R ¹ is hydrogen, C ₁ -C ₃ alkyl or acetyl group, R ² is hydrogen or C ₁ -C ₃ alkyl, R ³ is haloalkyl, aryl or substituted aryl group, R ⁴ is C ₁ -C _v alkyl, aryl or substituted An aryl group, wherein the substituent of aryl in R ³ and R ⁴ is a methyl group or a halogen atom. The derivative according to claim 1, wherein R is isopropyl, aryl, acetonyl, 2-methylcyanomethyl, N, N-diethylaminoethyl, benzoyl or methanesulfonyl group. A herbicide using S- (O-substituted-2,6-dichlorobenzohydroxymoyl) -N, N-diethylthio carbamate derivative represented by the following general formula (I) as an active ingredient. Wherein R is as defined in claim 1 above. The preparation agent according to claim 3, wherein the herbicide is used for pre-germination treatment in corn cultivation.