KR830002046B1 - Herbicide composition - Google Patents

Abstract

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Description

Herbicide composition

The present invention relates to a herbicidal composition containing a 2-substituted 4-aryl-5-riazolecarboxylic acid or a derivative thereof of the following general formula effective as an emollient.

In the above general formula

n is 0 or 1,

X is selected from the group consisting of halogen, alkoxy, phenoxy and halophenoxy,

Y and Z are each independently selected from the group consisting of hydrogen, halogen, trifluoro methyl, nitro and lower alkyl,

When n is 1, R 'is hydrogen, alkyl of up to 6 carbon atoms or agriculturally acceptable cation and when n is 0, R' is chlorine.

As used herein, "lower alkyl" or "lower alkoxy" includes alkyl or alkoxy groups of up to 5 carbon atoms.

"Alkyl" includes branched, unbranched and cyclic alkyl groups.

"Halogen" includes blots, chlorine, fluorine and oxo.

"Halofenoxy" means phenoxy substituted with one or two halogen moieties.

"Agriculturally acceptable cation" means a cation commonly used to form salts or free acids. Such cations include, but are not limited to, alkali metals, alkaline earth metals, substituted amines and ammonia cations. The present invention relates to novel 2-substituted-4-aryl-5-thiazolecarboxylinic acid and derivatives thereof as well as to use as a method and composition for reducing the damage of herbicides. In other words, the present invention is characterized by treating rice cultivation or rice seed with an effective amount of 2-substituted-4-aryl-5-thiazole carboxylic acid and its derivatives, and thus 2-chloro-2, 6'-diethyl- A novel composition and method for reducing the damage of direct sowing rice due to N- (butoxymethyl) acet anilide (hereafter chlorochlorom).

Butachloro is very useful for removing weeds in growing crops, especially transplanted rice. The use of butachloros directly on rice in various proportions necessary to remove weeds or inhibit growth causes damage to rice growth. Therefore, butachloro cannot be used to remove weeds in the presence of directly sown rice. Mitigators composed of compounds can treat rice seeds, rice cultivation areas or the rice itself so as to advantageously reduce the damage caused by the application of herbicides without apparently reducing herbicidal effects on weeds.

The damage of rice caused by the application of butachlor according to the present invention is carried out by the effective amount of the emollient consisting of the 2-substituted-4-aryl-5-thiazole carboxylic acid having a general formula or a derivative thereof to the sowing or rice cultivation of rice. By application, weed removal can be reduced without being reduced.

Effective emollients according to the present invention are as follows, but not limited thereto. Ethyl-2-chloro-4-phenyl-5-thiazole carboxylate: ethyl 2-chloro-4-m-trifluoromethylphenyl-5-thiazole carboxylate: ethyl 2-chloro-4-P-fluorophenyl -5-thiazole carboxylate: ethyl 2-chloro-4-P-chlorophenyl-5-thiazole carboxylate: ethyl 2-chloro-4-0-chlorophenyl-5-thiazole carboxylate: ethyl 2-chloro 4-m-tolyl-5-thiazole carboxylate: ethyl 2-chloro-4-P-nitrophenyl-5-thiazole carboxylate: ethyl 2-ethoxy-4-phenyl-5-thiazole-carboxylate : Ethyl 2-ethoxy-4-m-trifluoromethylphenyl-5-thiazole carboxylate: ethyl 2- (2 ', 4'-dichlorophenoxy) -4-m-trifluoromethylphenyl-5-thia Solcarboxylate: 2-chloro4-phenyl-5-thiazolecarboxylic acid: 2-chloro-4-m-trifluoro-methylphenyl-5-thiazolecarboxylic acid: 2-chloro-4-phenyl-5-thiazole carbo Nyl chloride: 2-chloro-4-P-chlorophenyl-5-thiazole acid: 2-chloro-4-P -Chlorophenyl-5-thiazolecarbonyl chloride: methyl 2-chloro-4-phenyl-5-thiazole carboxylate: methyl 2-chloro-4-P-chlorophenyl-5-thiazole carboxylate: n-propyl 2-Chloro-4-phenyl-5-thiazole-carboxylate: isopropyl 2-chloro-4-phenyl-5-thiazole-carboxylate: n-propyl 2-chloro-4-P-chlorophenyl-5 -Thiazole-carboxylate: sodium salt of 2-chloro-4-phenyl-5-thiazole carboxylic acid: sodium salt of 2-chloro-4-P-chlorophenyl-5-thiazole carboxylic acid: 2-chloro-4- Isopropylamine salt of phenyl-5-thiazolecarboxylic acid: Triethanol amine salt of 2-chloro-4-phenyl-5-thiazolecarboxylic acid.

Preferred are emollients in which X is halogen, in particular chlorine.

More preferred is when n is 1 and R 'is lower alkyl, especially ethyl.

In general, the 2-substituted-4-aryl-5-thiazole carboxylic acid of the general formula can be prepared by two methods.

When X is a halogen, in particular chlorine, as a preferred compound, the preparation used is carried out according to the following scheme.

According to the above scheme, β-amino-cinnamate prepared by the method described in Lukes et al, Collection Czechoslow, Chem. Commun., Vol. 25, page 607, 1960 is reacted with chlorocarbonylsulphenyl chloride and Heat to about 100 ° C. The resulting mixture is crystallized with petroleum ether and then reacted with an excess of phosphorus oxychloride at reflux to convert into a suitable 4-acetyl-2-chloro-5-thiazole carboxylate which is suitable for 4-acetyl-2,3-dihydro. 2-oxo-5-thiazole carboxylate is produced. Excess phosphorus oxychloride is removed under reduced pressure and the residue is poured into ice water. Extraction with ether gives the desired product.

To further illustrate the present invention, the following examples are described.

Example 1

Preparation of ethyl 2-chloro-4-phenyl-5-thiazole carboxylate

A solution of 11.6 g (0.112 mol) of chlorocarbonyl sulfen chloride in 10 ml of chlorobenzene in a solution of 20.0 g (0.105 mol) of ethylβ-amino-cinnamate dissolved in 40 ml of chlorobenzene while cooling on ice Add. The reaction mixture is heated at 110 ° C. for 2 hours, then cooled and treated with petroleum ether. The precipitate was heated with hot benzene, cooled and filtered to give 1.44 g (55%) of ethyl 2, 3-dihydro-2-oxo-4-phenyl-5-thiazole carboxylate as yellow needles. A mixture of 3.0 g (0.012 mol) of ethyl 2, 3-dihydro-2-oxo-4-phenyl-5-thiazole carboxylate and 14 ml of phosphorus oxy chloride is refluxed for 24 hours and cooled. The reaction mixture is poured into ice water. Solid precipitate is extracted with ether. The ether solution is dried and concentrated under reduced pressure. The residue was recrystallized from hexane to obtain 2.2 g (68%) of 2-chloro-4-phenyl-5-thiazole carboxylate having a melting point of 56 to 57 ° C.

Elemental Analysis: C ₁₂ H ₁₀ ClNO ₂ S

Calculated: C, 53.83; H, 3.76; N, 5.23; Cl, 13.24; S, 11.98

Found: C, 53.86; H, 3.78; N, 5.21; Cl, 13.14; S, 11.98.

Example 2

Preparation of ethyl 2-chloro-4-m-rifluorotomethyl-phenyl-5-thiazole carboxylate

In a solution of 14.4 g (0.119 mol) of ClCOSCl dissolved in 100 ml of chlorobenzene, 28.5 g (0.110 mol) of ethyl β-amino-m-trifluoromethyl cinnamate in 20 ml of chlorobenzene was 20 to 25 ° C. Add from The reaction mixture is stirred at 80 ° C. for 1 hour, cooled, and treated with 100 ml of petroleum ether (30 to 75 ° C.). The precipitates were collected to give 16.7 g of a yellow needle with a melting point of 167 to 170 ° C. and then recrystallized from benzene to give 13.5 g (39%) of ethyl 2,3-dihydro-2-oxo-4 with a yellow needle having a melting point of 168 to 171 ° C. Obtain-(m-trifluoromethylphenyl) -5-thiazole carboxylate. A mixture of 8.0 g (0.0253 moles) of ethyl 2, 3-dihydro-2-oxo-4- (m-trifluoromethylphenyl-5-thiazole carboxylate and 30 ml of POCl ₃ is heated under reflux for 60 hours. Excess POCl ₃ is removed under reduced pressure and the black residue is treated with 100 ml of water The aqueous mixture is extracted twice with 100 ml of ether The combined ether extracts are dried over magnesium sulfate and concentrated under reduced pressure to give 9.6 g of black. After obtaining the color oil, it was chromatographed on 180 g of silica gel, and after removing the initial fraction, the fraction eluted with 600 ml of hexane-ether (4: 1V / V) was left to stand containing 5.7 g (67%) of oil. Solidification according to Melting point 26.5 to 27 ° C

Elemental Analysis: C ₁₃ H ₉ ClF ₆ NO ₂ S

Calculated: C, 46.50; H, 2. 70; N, 4.17; Cl, 10.56

Found: C, 46.61; H, 2.71; N, 4.19; Cl, 10.70

Another method for preparing the 2-halo-4-aryl-5-thiazole carboxylate of the present invention-substituted benzoyl acerate is reacted with sulfuryl chloride to produce 2-chloro benzoyl acetate, which is reacted with thiourea in ethanol under reflux. Reaction to convert to 2-amino-4-aryl-5-thiazolecarboxylate. Ethanol is removed under reduced pressure and the residue is neutralized with sodium bicarbonate to give 2-amino-4-aryl-5-thiazolecarboxylic acid ester. The solution of the ester in a suitable acid is diazotized with sodium nitrite at -5 to 30 < 0 > C. The resulting diazonium salt solution is poured into the corresponding copper halide or potassium iodide solution. At the end of the gas release, the reaction mixture is extracted with ether. After the ether extract is dried and concentrated, the residue is purified by kugelrohr distillation or chromatography under reduced pressure.

The following reaction schemes and examples are set forth for the purpose of clarity.

Example 3

Preparation of ethyl 2-chloro-4- (P-fluorophenyl) -5-thiazole carboxylate

A mixture of 10.5 g (0.05 mole) ethyl P-fluorobenzoyl acetate, 6.7 g (0.05 mole) sulfuryl chloride and 30 ml chloroform is refluxed for 18 hours and cooled. The chloroform solution is washed with water, dried (MgSO ₄ ) and concentrated under reduced pressure. The residue was distilled to give 10.8 g (88%) of ethyl-2-chloro- (P-fluoro) -benzoyl acetate. 10.8 g (0.0441 mol) of ethyl 2-chloro- (P-fluoro)- A mixture of benzoyl acetate, 3.36 g (0.0441 moles) thiourea, 20 mL water and 10 mL ethanol is refluxed for 3 hours. Ethanol is removed under reduced pressure. The residue is made basic with saturated sodium bicarbonate. The solid is filtered, washed with water and recrystallized with ethanol to give 8.9 g (76%) of ethyl 2-amino-4- (P-fluorophenyl-5-liazole carboxylate) of a white prism having a melting point of 205 to 208 ° C. To 4.0 g (0.0150 mole) of ethyl 2-amino-4- (P-fluorophenyl) -5-riazole carboxylate are added 30 ml of concentrated hydrochloric acid and 30 ml of glacial acetic acid. The carboxylate is slowly dissolved in the chloroform solution The reaction mixture is cooled in an ice bath to 0-5 ° C. To the mixture is added 4.0 g (0.058 moles) of sodium nitrite with vigorous stirring. Stir for 5 minutes at 5 to 10 ° C. and pour a solution of 1.48 g (0.0150 mol) of copper chloride in 20 mL of concentrated hydrochloric acid After the release of the gas, the reaction mixture is diluted with water The chloroform layer is separated and the top layer is chloroform Extract the combined chloroform solution into water. And washed sequentially with saturated sodium bicarbonate, dried over magnesium sulfate, and concentrated under reduced pressure, and the residue was recrystallized from ethanol to give 3.3 g (77%) of ethyl 2-chloro-4- () with an orange needle having a melting point of 113 to 114 ° C. P-fluorophenyl) -5-thiazole carboxylate is obtained.

Elemental Analysis: C ₁₂ H ₉ ClF NO ₂ S

Calculated: C, 50.44; H, 3. 17; N, 4.90

Found: C, 50.42; H, 3.18; N, 4.90

Example 4

Preparation of ethyl 2-chloro-4-p-chlorophenyl-5-thiazole carboxylate

To a mixture of 121.87 g (0.936 mol) of ethyl aceto acetate, 314 ml of benzene and 626 ml of water, which is stirred vigorously under cooling (5 ° C.), 41.25 ml of 33% sodium hydroxide is added. 177.0 g (1.01 mole) of P-chloro benzoyl chloride and 188.8 mL of 33% sodium hydroxide are simultaneously added over 2 hours using two dropping funnels to the mixture. The reaction mixture becomes a paste. The reaction mixture is heated at 35 ° C. for 1 hour, cooled and filtered to obtain 170.0 g of sodium salt of ethyl 2-benzoyl acetoacetate. A portion (150 g) of this salt is added to a mixture of 39.0 g (0.729 moles) of ammonium chloride and 78 mL of ammonium hydroxide dissolved in 780 ml of water. The mixture is stirred at 40-50 ° C. for 3 hours and cooled in an ice bath. The precipitate is filtered to give 115.5 g of a yellow solid which is distilled with cogel to give 76.0 g (38% based on ethyl aceto acetate) of impure ethyl P-chlorobenzoyl acetate. A mixture of 40.0 g (0.175 moles) of impure ethyl P-chlorobenzoyl acetate, 24.2 g (0.18 moles) of sulfuryl chloride and some chloroform was refluxed for 6 hours, cooled and concentrated to give 49.0 g of impure ethyl 2-chloro- Obtain P-chlorobenzoyl acetate. A mixture of 46.0 g (0.174 moles) of impure ethyl 2-chloro-P-chlorobenzoyl acetate 13.25 g (0.174 moles) thiourea and 174 mL of ethanol is refluxed for 2 hours and cooled. The precipitate is filtered off and neutralized with saturated sodium bicarbonate. The insoluble material is filtered to give 37.0 g (80%) of ethyl 2-amino-4-P-chlorophenyl-5-riazole carboxylate at a melting point of 108 to 200 ° C. To the mixture are added 4.0 g (0.0434 moles) of sodium nitrite in 20 minutes with stirring at -5 to 0 <0> C. The reaction mixture is stirred at −5 to 0 ° C. for 10 minutes and poured into a mixture of 4.0 g (0.04 mol) of copper chloride, 20 mL of concentrated hydrochloric acid, and 20 mL of water. The reaction mixture is stirred at room temperature for 30 minutes after gas evolution ends. The precipitate was filtered to obtain 10.5 g of solid, which was distilled by Kugel (melting at 145 ° C., 0.05 mm Hg) to obtain 6.0 g of 120 ° C. in solids of 113 ° C. 4.4 g (37%) of ethyl-2-chloro-4-P-chlorophenyl-5-thiazole carboxylate are obtained.

Elemental Analysis: C ₁₂ H ₉ Cl ₂ NO ₂ S

Calculated: C, 47.70; H, 3.00; N, 4.64

Found: C, 47.71; H, 2.97; N, 4.55

Example 5

Preparation of ethyl 2-chloro-4- (O-chlorophenyl) -5-thiazole carboxylate

80.0 g (0.457 moles) of O-chlorobenzoyl chloride in a cooled (5 ° C.) mixture of 55.0 g (0.428 moles) of ethyl acetoacetate, 70 ml of benzene, 18.3. Ml of 33% sodium hydroxide and 141 ml of water, and 76 ml of 33% sodium hydroxide are added simultaneously with vigorous stirring within 1 hour as described in Example 4. The aqueous solution of the sodium salt of ethyl O-chloro benzoylacetoacetate is stirred for 1 hour with 22.5 g (0.424 moles) of ammonium chloride. The aqueous solution is saturated with 25.0 g sodium chloride. Some precipitate formed at this time is filtered. Analysis of this material indicated mainly sodium salt of ethyl O-chloro benzoyl acetoacetate. Sodium salt and aqueous filtrate are combined and acidified with dilute hydrochloric acid. The separated oil is extracted with ether. The ether solution is dried (MgSO ₄ ) and concentrated under reduced pressure. The residue is distilled with cogel to give 30.0 g of oil containing mainly ethyl O-chlorobenzoyl acetoacetate. This material was stirred with a mixture of 7.2 g ammonium chloride, 14 mL ammonium hydroxide and 150 mL water, and treated as described in Example 4, 16.6 g 15% of impure ethyl O-chlorobenzoyl having a purity of about 92%. Acetate is obtained. A mixture of 15.0 g (0.065 mole) ethyl O-chlorobenzoyl acetate 9.5 g (0.070 mole) sulfuryl chloride and 20 ml chloroform was refluxed for 6 hours and concentrated to give 17.3 g of impure ethyl 2-chloro-0-chlorobenzoyl Acetate is obtained. Melting point of a mixture of 17.0 g (0.065 mole) ethyl 2-chloro-O-chlorobenzoyl acetate, 4.94 g (0.065 mole) thiourea and 65 mL ethanol was refluxed for 2 hours and treated as described in Example 4 Obtain 15.0 g of solid at 114 to 136 ° C and recrystallize it twice with ethanol to yield 5.8 g (31%) of ethyl 2-amino-4- (O-chlorophenyl) -5-thiazole carboxyl having a melting point of 162 to 164 ° C. Get rate. A portion (1.0 g) of this material was recrystallized from toluene to obtain 0.75 g of pure ethyl 2-amino-4- (O-chlorophenyl) -5-thiazole-carboxylate having a melting point of 165 to 166 ° C. A solution of 4.2 g (0.015 mol) of ethyl 2-amino-4- (O-chlorophenyl) -5-thiazole carboxylate in 59 mL of 85% phosphoric acid and 15 mL nitrile acid are described in Example 4. Diazotize with 1.12 g (0.016 moles) of sodium nitrite as shown. The diazonium salt solution is poured into 7.5 mL concentrated hydrochloric acid and 1.50 g (0.015 mol) of copper chloride solution in 7.5 mL water. The reaction mixture is treated as described in Example 4 to give 4.0 g of oil which is distilled with kugel (at 150 ° C., 0.3 mm) to give 2.0 g of oil. This material is purified to give 0.66 g (15%) of ethyl 2-chloro-4- (O-chlorophenyl) -5-thiazole carboxylate as a colorless liquid.

Elemental Analysis: C ₁₂ H ₉ Cl ₂ NO ₂ S

Calculated: C, 47.69; H, 3.00; N, 4.63; Cl, 23.43

Found: C, 47.61; H, 3.02; N, 4.62; Cl, 23.45

Example 6

Preparation of ethyl 2-chloro-4- (m-toyl) -5-thiazole carboxylate

221.5 g (1.430 mole) m-toluoylchloride in a cooled (5 ° C.) mixture of 137.5 g (1.05 mole) ethyl aceto acetate, 174 ml benzene, 325 ml mole and 45.8 ml 33% sodium hydroxide, and 190 ml of 33% sodium hydroxide are added simultaneously as described in Example 4. An aqueous solution of the sodium salt of ethyl m-toluoyl-acetate was stirred overnight with 56.3 g of ammonia chloride, treated as described in Example 4, distilled with cugel (95-98 ° C., 0.05 mmHg), and then 38.0 g ( 17%) of impure ethyl m-toluoyl acetate is obtained. A mixture of 20.6 g (0.1 mole) of impure ethyl m-toluoyl acetate, 13.6 g (0.105 mole) of sulfuryl chloride and 30 ml of chloroform was refluxed for 6 hours and 25.0 g of ethyl 2- as described in Example 4 Chloro-m-toluoyl acetate is obtained and used directly as described below. Recrystallized from 22.58 g (0.1 mol) of ethyl 2-chloro-m-toluoyl acetate, 7.6 g (0.1 mol) of thiourea and 100 ml of ethanol to 11.6 g (44%) of ethyl 2 with a melting point of 185 to 187 ° C. Obtain amino-4- (m-tolyl) -5-thiazole carboxylate. The mother liquor is concentrated to give 4.5 g (17%) of ethyl 2-amino-4- (m-tolyl) -5-thiazole carboxylate, which is less pure, having a melting point of 183 to 184 ° C. To a cooled (-5 ° C.) mixture of 10.5 g (0.04 mol) of ethyl 2-amino-4- (m-tolyl) -5-thiazolecarboxylate and 80 ml of 75% phosphoric acid was added 40 ml of 70% nitric acid. Add. To the mixture is added 3.0 g (0.0434 moles) of sodium nitrite with vigorous stirring in 20 minutes. The reaction mixture is stirred for 10 minutes and poured into a mixture of 4.0 g (0.04 mol) of copper chloride, 20 mL of concentrated hydrochloric acid, and 20 mL of water. After the end of the gas discharge, the reaction mixture was extracted with ether, dried (MgSO ₄ ) and concentrated under reduced pressure to obtain 10 g of oil, which was distilled with kugel (from 135 to 140 ° C. and 0.05 mm) to give 6.5 g of oil and ethanol. Crystallization was carried out to give 3.9 g (34%) of the desired product as a white solid with a melting point of 41 to 42 캜.

Elemental Analysis: C ₁₃ H ₁₂ ClNO ₂ S

Calculated: C, 55.42; H, 4. 29; N, 4.97; Cl, 12.58

Found: C, 55.38; H, 4.33; N, 4.99; Cl, 12.53

Example 7

Preparation of ethyl 2-chloro-4- (P-nitrophenyl) -5-thiazole carboxylate

Ethyl 2-chloro-P obtained from ethyl P-nitrobenzoyl acetate and sulfuryl chloride according to the method described in Balog et al. Studio. Univ.Bebes.Boylai., Vol. 1, No. 2, Page 155 (1960). -Nitro benzoyl acetate was converted to ethyl 2-amino-4-Pnitrophenyl-5-thiazole carboxylate by treatment with thiourea by the method of the above document 10.0 g in 100 mL concentrated hydrochloric acid and 100 mL glacial acetic acid ( To a cooled (154C) solution of 0.0334 mol) ethyl 2-amino-4- (P-nitrophenyl) -5-thiazole carboxylate is added 7.0 g (0.101 mol) of sodium nitrite within 15 minutes. Stir for 10 minutes and pour a solution of 3.78 g (0.038 moles) of copper chloride in 60 mL of concentrated hydrochloric acid Slowly developing gas is accelerated when 50 mL of water is added to the reaction mixture.

The reaction mixture gradually becomes yellow due to precipitation of white solids. The precipitate is extracted with chloroform. The chloroform solution is dried (MgSO ₄ ) and concentrated under reduced pressure. The residue is boiled with hot methanol and filtered. The solid is recrystallized from acetone-chloroform to give 2.4 g of the desired product having a melting point of 146 to 148 ° C.

Elemental Analysis: C ₁₂ H ₈ ClN ₂ O ₄ S

Calculated: C, 46.09; H, 2. 90; N, 8.95; Cl, 11.34

Found: C, 46.08; H, 2.92; N, 8.95; Cl, 11.23

Homologs in which X is lower alkoxy, phenoxy or halo phenoxy are prepared by treating the corresponding 2-chloro compound with sodium alkoxide or potassium phenoxide. Sodium alkoxides such as sodium ethoxide are prepared from sodium and anhydrous ethanol. The reaction mixture containing sodium alkoxide and a suitable 2-chloro compound is stirred for a long time and poured into dilute hydrochloric acid. The organic layer is extracted with ether. The ether solution was dried and concentrated and the residue was distilled with cogel under reduced pressure (2mm) to ethyl 2-ethoxy-4-phenyl-5-thiazole carboxylate or ethyl 2-ethoxy-4- (m-trifluoro Romethylphenyl) -5-thiazolecarboxylate is obtained.

Example 8

Preparation of ethyl 2-ethoxy-4-phenyl-5-thiazole carboxylate

To a solution of 1.8 g (0.078 g atoms) of sodium and 25 mL of anhydrous ethanol (dehydrated with Mg (OEt) ₂ ), prepared NaOC ₂ H ₅ , 4.0 g (0.0149 mol) of the product of Example 1 were added. The reaction mixture is stirred at room temperature under N ₂ for 20 hours and poured into 6N hydrochloric acid cooled with 50 ml of ice. The mixture is extracted twice with 50 ml of ether. The ether extract is dried (MgSO ₄ ) and concentrated under reduced pressure. The residue was distilled on a 2 mm (140 to 170 ° C.) kugel to give 3.55 g (86%) of the desired product, a white solid with a melting point of 32 to 34.

Melting Point: 32 ~ 34 ℃

Elemental Analysis: C ₁₄ H ₁₅ NO ₃ S

Calculated: C, 60.63; H, 5. 45; N, 5.05

Found: C, 60.62; H, 5. 46; N, 5.06

Example 9

Preparation of ethyl 2-ethoxy-4- (m-trifluoromethylphenyl) -5-thiazole carboxylate

1.0 g (0.00298 mol) of the product of Example 2 is added to a NaOC ₂ H ₅ solution prepared with 0.5 g (0.217 g atoms) of sodium and 25 ml of absolute ethanol. The solution is stirred for 16 hours at room temperature and 50 ml of 6N hydrochloric acid is poured out. The mixture is extracted twice with 50 ml of ether. The combined ether solutions are washed with saturated sodium bicarbonate, dried (MgSO ₄ ) and concentrated under reduced pressure. The residue is chromatographed on 20 g of silica gel using ether-petroleum ether (1: 5V / V) as eluent. The first 300 mL eluate was concentrated under reduced pressure and the residue was distilled on the cogel at 2 mm (temperature 140-170 ° C.) to yield 0.65 g (63%) of the desired product as a white solid with a melting point of 69-72 ° C.

Melting Point: 69-72 ° C

Elemental Analysis: C ₁₅ H ₁₄ F ₃ NO ₃ S

Calculated: C, 52.17; H, 4.09; N, 4.06

Found: C, 52.12; H, 4.08; N, 4.09

Example 10

Preparation of ethyl 2- (2 ', 4'-dichlorophenoxy-4- (m-trifluoromethylphenyl) -5-thiazolecarboxylate

3.68 g (0.0110 moles) of ethyl 2-chloro-4-m-rifluoromethylphenyl-5-thiazole carboxylate, 1.96 g (0.0120 moles) of 2,4-dichlorophenol, 1.66 g (0.012 moles) of Potassium carbonate and 50 ml of acetone are refluxed for 22 hours. Acetone is removed under reduced pressure. The residue is treated with 50 ml of water and extracted with 100 ml of ether. The ether solution is weighed with 50 ml of sodium bicarbonate, 30 ml of 10% sodium hydroxide and 50 ml of water, then dried (MgSO ₄ ) and concentrated under reduced pressure. The residue was recrystallized twice with hexane to obtain 4.1 g (81%) of the desired product as a white needle having a melting point of 72 to 73 ° C.

Elemental Analysis: C ₁₉ H ₁₂ F ₃ Cl ₂ NO ₂ S

Calculated: C, 49.36; H, 2.62; N, 3.03; Cl, 15.34

Found: C, 49.32; H, 2.62; N, 3.04; Cl, 15.40

Various esters can be prepared by reaction of the corresponding acid chloride with a suitable alcohol. Acidates are prepared by reacting the free acid with thionylchloride. Salts can be prepared by reacting the free acid with a suitable base.

Example 11

Preparation of 2-chloro-4-phenyl-5-thiazole carboxylate

A mixture of 53.4 g (0.2 moles) of ethyl 2-chloro-4-phenyl-5-thiazole carboxylate, 8.0 g (0.2 moles) of sodium hydroxide 200 m and 400 ml of tetrahydrofuran was stirred for 16 hours and ether Extract with The organic layer is discarded. The aqueous layer is acidified and the precipitate is collected and air dried to give 43.2 g (90%) of the desired product with a melting point of 170 to 171 ° C.

Elemental Analysis: C ₁₀ H ₆ ClNO ₂ S

Calculated: C, 50.11; H, 2.52; N, 5.84

Found: C, 50.06; H, 2.55; N, 5.84

Example 12

Preparation of 2-chloro-4-phenyl-5-thiazole carbonylchloride

A mixture of 40.6 g (0.17 mole) of 2-chloro-4-phenyl-5-thiazolecarboxylate and 100 ml of thionyl chloride was heated in a steam bath for 6 hours and concentrated under reduced pressure to give a white solid with a melting point of 53 to 55 ° C. Obtain 38.0 g of acid chloride.

Elemental Analysis: C ₁₀ H ₅ Cl ₂ NOS

Calculated: C, 46.53; H, 1.95; N, 5.43

Found: C, 46.45; H, 1.99; N, 5.41

Example 13

Preparation of Methyl 2-chloro-4-phenyl-5-thiazole carboxylate

5.16 g (0.02 mol) of the compound of Example 12 and 40 mL of methanol are refluxed for 1 hour and concentrated under reduced pressure. The residue solid is stirred with ether. The ether solution is washed with saturated sodium bicarbonate (MgSO ₄ ) and concentrated under reduced pressure to give 3.10 g (61%) of the desired product as a white solid with a melting point of 55 to 57 ° C.

Elemental Analysis: C ₁₁ H ₈ ClNO ₂ S

Calculated: C, 52.07; H, 3. 17; N, 5.52

Found: C, 52.02; H, 3. 21; N, 5.50

Example 14

Preparation of n-propyl-2-chloro-4-phenyl-5-thiazole carboxylate

A mixture of 5.16 g (0.02 mol) of Example 12 compound and 40 mL of n-propanol is refluxed for 7 hours and concentrated under reduced pressure. The residue, waxy material (6.09 g), is stirred with ether and filtered to obtain 1.0 g of a solid having a melting point of 155 to 156 占 폚. The ether solution is washed with saturated sodium bicarbonate, dried (MgSO ₄ ) and concentrated under reduced pressure to give 3.5 g of waxy material which is heated with hexane and filtered. The hexane filtrate is concentrated under reduced pressure to give 2.1 g of oil which is dissolved in ether. The ether solution is washed with 10% sodium hydroxide solution and dried (MgSO ₄ ) and filtered under reduced pressure to obtain 1.8 g of oil which is distilled with cogel to give 1.4 g of the desired product as colorless oil, n _D ²⁵ = 1.5868.

Elemental Analysis: C ₁₃ H ₁₂ ClNO ₂ S

Calculated: C, 55.41; H, 4. 29; N, 4.97

Found: C, 55.35; H, 4. 30; N, 4.95

According to a new aspect of the present invention, 2-substituted-4-aryl-5-thiazole carboxylates and derivatives thereof are effective for reducing herbicide damage to rice. The amount of emollient used in the compositions and methods of the present invention may vary depending on the method of application, application rate, environmental factors, as well as other factors known in the art. The amount used in each case is the amount that is used to mitigate the crop's damage due to the mitigation effective amount, ie herbicide.

Emollients can be mixed with herbicides and applied to rice cultivation areas or directly to rice seeds. Application in the "cultivation area" means application to plant growth media such as soil, seeds, germinated seedlings, roots, stems, leaves, flowers, fruits or other plant parts.

The following examples are performed to demonstrate the effect of 2-substituted-4-yl-5-thiazolecarboxylates and derivatives thereof. These examples are merely shown to illustrate new aspects of the invention and are not intended to be limited to this range.

Example 15

Fill the container with good surface soil and fill it to a depth of approximately 1.27 cm from the top of the container. For testing, predetermined rice seeds are placed on top of the soil. Measure enough soil to almost fill the container and place it in the second container. The measured amount of emollient dispersed or dissolved in a suitable carrier is treated in the soil in the second container. The measured amount of butachloro dispersed or dissolved in a suitable carrier is sprayed onto the soil already treated with the emollient. Thoroughly mix the soil containing emollients and herbicides. This mixing is sometimes done by incorporating herbicides and emollients into the soil. By mixing or incorporating the laxative and herbicides are uniformly dispersed in the soil. Cover the seeds with soil containing emollients and herbicides and flatten the pan. Place the pan on a sand bench in the greenhouse and irrigation as needed. The plants are observed after approximately 21 days and the results are recorded as inhibition rates of each seed. In each test a pan of plants containing no herbicides and emollients is made for control. In addition, to verify the herbicidal effect of the laxative alone in each test, the plant's pan is made from soil covering the seed without the herbicide and only the measured amount of laxative is incorporated into the soil covering the seed. The herbicidal effect of herbicides in each series of tests is observed in the pans of plants treated with the same amount of herbicide only. The "relaxing effect" adds the herbicidal effect when applied alone as a herbicide to the herbicidal application alone (but in any case, their total does not exceed 100) and incorporates herbicides and laxatives into the soil as described above. Measured by subtracting the herbicidal effect obtained.

Table I summarizes the results obtained by testing the compounds of the invention according to the method of Example 15.

TABLE I

Example 16

Fill the clay pot with quality topsoil. A measured amount of emollient dispersed or dissolved in a suitable carrier is sprayed onto the soil surface. A measured amount of butachlor herbicide dissolved in a solvent is sprayed onto the soil surface. Pre-soaked rice is irrigated with water in advance and sown in pots where the water surface is lowered below the soil surface for one week. Pots are irrigated to at least the soil surface during the test period. Observe plants after approximately 21 days and record the results as inhibition rate of rice. As in Example 15, each test pot contains soil treated with butachlor only. In each test, the pot contains soil treated only with emollients. Pots are also made from untreated herbicides and emollients. Mitigating effect is measured according to Example 15.

Table II summarizes the results obtained by testing the compounds of the invention according to the method of Example 16.

TABLE II

Example 17

5.08 cm of high quality subsoil is filled into 7.62 cm deep plastic pots. A predetermined number of blood seeds are sown on the soil surface. A measured amount of emollient dispersed or dissolved in a suitable carrier is sprayed onto the soil surface. A measured amount of butachlor herbicide dissolved in a solvent is sprayed onto the soil surface. Pre-soaked rice is irrigated with water in advance and sown in pots leveled below the soil surface for a week to allow blood to germinate. Pots are irrigated to the soil surface during the test period. Observe plants after approximately 21 days and record the results as percentage inhibition of rice. In each test, a pot containing soil treated with butachlor only is prepared. Pots containing soil treated only with emollients in each test are also prepared. Also prepare pots containing untreated soil. Table III shows the test results carried out according to the method of Example 17.

TABLE III

Example 18

5.08 cm of high quality subsoil is filled into 7.62 cm deep plastic pots. Sprinkle a predetermined number of blood seeds on the soil surface. A measured amount of emollient dispersed or dissolved in a suitable carrier is sprayed onto the soil surface. A measured amount of butachlor herbicide dissolved in a solvent is sprayed onto the soil surface. Pre-soaked rice is irrigated with water in advance and sown in pots leveled below the soil surface for one week. Pots are irrigated to the soil surface during the test period. Observe plants after approximately 21 days and record the results as percentage inhibition of rice. In each test, a pot containing soil treated with butachlor only is prepared. Pots containing soil treated only with emollients in each test are prepared. Also prepare pots containing untreated soil. Table IV shows the test results performed according to the method of Example 18.

Example 19

5.08 cm of high quality subsoil is filled into 7.62 cm deep plastic pots. Predetermined number of weed seeds and paddy seeds

Table IV

Spray the ruler to the soil surface. Butachlor and ethyl 2-chloro-4-phenyl-5-thiazole carboxylate are applied to the soil surface layer as a mixed mixture by shaking the treated soil surface layer in a plastic bag. The surface layer is placed in a full seed pot. Observe plants after approximately 21 days and record the results as inhibition rate. In each test, pots containing soil treated with bracchlorman are prepared. Pots containing soil treated only with emollients in each test are prepared. Table V shows the test results performed according to the method of Example 19.

TABLE V

The above example holds that the thiazole carboxylates of the present invention are effective in reducing damage caused by herbicides in crops, in particular sorghum and rice. The laxative may be applied to arable land in the form of a herbicidally effective amount of butachlor herbicide and a laxative, or the arable land may be treated with an effective amount of herbicide and then treated with the laxative and vice versa. The ratio of herbicide and emollient depends on the type of crop to be protected, the type of weed to be removed and the type of herbicide to be used, but usually the ratio of herbicide to emollient is 1:25 to 25: 1 by weight, preferably 1: 5 to 5: Used as 1).

Herbicides, emollients or mixtures thereof may be applied alone to arable land or together with liquid or solid auxiliaries relevant in the art. A mixture containing usually suitable herbicides and emollients is prepared by mixing the herbicides and emollients together with adjuvants including diluents, weight agents, carriers and modifiers. It is obtained as granules, pellets, hydrates, powders, solutions, and aquatic preparations in the form of emulsions or emulsions. The mixture may thus contain adjuvants such as finely divided solid particles, organic solvents, water, hydrating agents, dispersants or emulsions or suitable mixtures thereof.

Finely divided solid carriers and extenders effective when applying herbicides, emollients or mixtures thereof to arable land include talc, clay, pumice, silica, diatomite, quartz, table top, sulfur, cork powder, wood powder, walnut powder, chalk , Light dust and charcoal. Typical liquid diluents include stradded solvents, acetone, alcohols, glycols, ethyl acetate and benzene. Such compositions, particularly solutions and wetting agents, contain one or more surfactants as modifiers in an amount sufficient to readily disperse a given composition in water or oil.

"Surfactant" refers to the inclusion of a hydrating, dispersing, suspending and emulsifying agent. Such surfactants are well known. (Reference: US Patent Nos. 2,547,724, 3 and 4)

Generally, the composition of the present invention contains 5 to 95 parts herbicide and emollient, 1 to 50 parts surfactant and 4 to 94 parts solvent. (All parts by weight are based on the total weight of the composition).

Application of herbicides, emollients or mixtures thereof in liquid or solid granular form is carried out in conventional manner using spargers, acid branches, booms and hand sprayers, atomizers and granulators. The composition may also be applied from an airplane in the form of an acid or spray. If desired, the application of the compositions of the invention to plants can also be carried out by incorporating the compositions into soil or other media.

Claims (1)

A herbicide composition characterized by containing a herbicidally effective amount of butachlor and a moderately effective amount of a compound of another general formula in a weight ratio of 1:25 to 25: 1.

In the above general formula n is 0 or 1, X is selected from the group consisting of halogen, lower alkoxy, phenoxy and halophenoxy, Y and Z are independently selected from the group consisting of hydrogen, halogen, trifluoromethyl, nitro and lower alkyl, When n is 1, R 'is hydrogen, lower alkyl, or an agriculturally acceptable cation, and when n is 0, R' is a chlorine atom.