CN1411719A - Heteroepoxyacetamide-2-(1,3-benzothiazole-2-base oxygen)-N-(4-fluorophenyl)-N-(1-methyl ethyl) acetamide weedicide and its preparation - Google Patents
Heteroepoxyacetamide-2-(1,3-benzothiazole-2-base oxygen)-N-(4-fluorophenyl)-N-(1-methyl ethyl) acetamide weedicide and its preparation Download PDFInfo
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- CN1411719A CN1411719A CN 01128279 CN01128279A CN1411719A CN 1411719 A CN1411719 A CN 1411719A CN 01128279 CN01128279 CN 01128279 CN 01128279 A CN01128279 A CN 01128279A CN 1411719 A CN1411719 A CN 1411719A
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- acetamide
- fluorophenyl
- benzothiazole
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Abstract
The present invention relates to a kind of heterocyclic oxyacetamide-2-(1,3-benzothiazole-2-oxy)-N-(4- fluorophenyL)-N-(1-methyl ethyl) acetamide weedicide and its preparation method. Its preparation method has three steps: A. making chloroacetylation reaction to produce chloroacetamide; B. making esterification reaction to produce ester; and C. making condensation reaction. Said weedicide can inhibit growth of weeds, and its plant safety is high.
Description
Technical field: the present invention relates to weed killer herbicide of a kind of amide-type and preparation method thereof.
Background technology: the weed killer herbicide kind is a lot of at present, but it is big all to exist consumption mostly, and general per hectare consumption reaches the shortcoming that plant is existed unsafe factor up to the 2-10 kilogram.In order to reach safe and efficient purpose, people develop the acetamide oxide compounds in the amide-type in recent years, but mainly concentrate on the exploitation of heterocyclic moiety; And the product synthesis technique complexity of developing, length not only consuming time, and also yield is low, so its manufacturing cost height makes its preparation method be difficult for realizing large-scale industrial production.。
Summary of the invention: the phenyl ring that The present invention be directed to the acetamide oxide in the amide-type partly improves, develop that a kind of heterocycle acetamide oxide---2-(1,3-benzothiazole-2-base oxygen)-and N-(4-fluorophenyl)-N-(1-Methylethyl) acetamide herbicide, its preparation method is provided simultaneously; Make it can reach purpose safe and efficient, that consumption is little, and make its preparation method can be simple, the yield height be convenient to large-scale industrial production.Acetamide oxide weed killer herbicide among the present invention is the compound structure general formula with oxyacetamide: ROCH (R
1) CON (R
2) (R
3) in the phenyl ring of unsubstituted change into the fluorine-containing substituted benzene ring in 4-position, thereby the synthetic chemistry structural formula is:
Weed killer herbicide, the preparation method of weed killer herbicide of the present invention is that in the following order three steps realize; The first step is a chlorine acetylation, adopt acylating agent, acid binding agent, amine, solvent reaction to generate chloro-acetamide, the mol ratio of each reactant is, amine: acylating agent: acid binding agent=1.0: 1.0～2.0: 1.0～2.0, solvent is an amount of, reaction temperature be-5 ℃ to the solvent refluxing temperature, the time is 1-15 hour; Second step was esterification, and chloro-acetamide and anhydrous sodium acetate, solvent action are generated ester, and the mol ratio of each reactant is, chloro-acetamide: anhydrous sodium acetate=1.0: 1.0～2.0, solvent is an amount of, reaction temperature be 0 ℃ to the solvent refluxing temperature, the time is 1-10 hour; The 3rd step was condensation reaction, be with esterification products and chloro benzo thiazole in the following hydrolysis limit condensation of highly basic condition, the mol ratio of each reactant is carboxylate: the chloro benzo thiazole: alkali=1.0: 1.0～1.5: 1.5～10, reaction temperature is 0 ℃-100 ℃, and the time is 2-5 hour.Its synthesis route is:
The wherein combination of selecting chloracetyl chloride or monoxone and phosphorus oxychloride for use of the acylating agent in the first step chlorine acetylation.Mol ratio when monoxone and phosphorus oxychloride combination is phosphorus oxychloride: monoxone=1: 3.0.Acid binding agent selects for use pyridine, triethylamine, two for any one or a few the combination in methylaniline, sodium carbonate, the sodium bicarbonate.Solvent is selected any one or a few the combination in acetone, carrene, chloroform, carbon tetrachloride, benzene, the toluene for use.Second solvent of step in the esterification selected any one or a few the combination in hydro carbons, ethers, benzene, the toluene for use.Highly basic in the 3rd step condensation reaction is selected any one in sodium hydroxide or the potassium hydroxide for use, and their concentration is 15-60%.Carry out before the seedling and activity of weeding test behind the seedling to the composition of this chemical structural formula, the weeds of test are monocotyledon weed: barnyard grass, lady's-grass, green foxtail; Broadleaf weed: Cassia tora, youth-and-old-age, piemarker; The crop of test is corn, soybean, rape.At sectional area is 100cm
2The ceramic whiteware basin in sowing germinate target examination assortment consistent, cover the thick table soil of 0.5cm, behind the suppression trickle, management method is cultivated routinely, treat respectively to try the material plant and grow to required growthdevelopmental stage, carry out the cauline leaf spraying by experimental scheme dosage with crawler type crop sprayer and handle.Soil treatment is in spraying sowing in preceding 12 hours, suppression trickle before the seedling.Processing is placed in the greenhouse and cultivates by the normal management method, routine observation examination material plant production developmental state, and in handling back 15 days, the range estimation medicament suppresses situation to the production of examination material plant, and this weed killer herbicide seedling pre-treatment monocotyledon weed activity is higher, to the weed growth inhibiting rate more than 90%, seedling post processing effect is lower than the seedling pre-treatment, safe to crop, consumption is little, and the per hectare consumption is no more than 1.0kg.The preparation method of this weed killer herbicide is simple, and synthetic reaction is rapid, and yield is up to 98.9%.And low cost of manufacture, be convenient to realize large-scale industrial production.
Embodiment one: present embodiment is the compound structure general formula with oxyacetamide: ROCH (R
1) CON (R
2) (R
3) in the phenyl ring of unsubstituted change into the fluorine-containing substituted benzene ring in 4-position, thereby synthetic chloroacetamide---2-(1,3-benzothiazole-2-base oxygen)-N-(4-fluorophenyl)-N-(1-Methylethyl) acetamide herbicide, its chemical structural formula is:
Embodiment two: present embodiment is that in the following order three steps are implemented:
Synthesizing of first step 2-chloro-N-(1-Methylethyl)-N-(4-fluorophenyl) acetamide (I): in the 50ml chloroform, add N-(1-Methylethyl)-4-fluoroaniline 18.6g, drip chloracetyl chloride 13.6g then, reaction is 1-15 hour under-5～115 ℃ of conditions, in reactant, add 10ml water again, then reactant liquor is poured in the water of 100ml and stirred, separate organic layer, use the chloroform extraction water layer, merge organic layer, organic layer is washed to faintly acid, decompression distillation 5mmHg collects 140-143 ℃ of cut and gets yellow transparent liquid 21.8g, and yield is 95.0%.
Synthesizing of second step 2-acetoxyl group-N-(1-Methylethyl)-N-(4-fluorophenyl) acetamide (II): get (I) 21.0g, anhydrous sodium acetate 9.0g, toluene 38ml, above three kinds of article are mixed the back to react 1-10 hour under 0-110 ℃ of condition, cooled and filtered, with toluene 10ml washing leaching cake, filtrate steaming is desolventized, get yellow liquid 22.9g, yield is 99.3%.
The 3rd step 2-(1,3-benzothiazole-2-base oxygen)-and N-(4-fluorophenyl)-N-(1-Methylethyl) acetamide (III) synthetic: in the sodium hydroxide 30ml of 20-40% concentration solution, adding 2-chloro benzothiazole 14.1g and (II) 22.0g under the 0-100 ℃ of condition, reacted 2-5 hour, add water after the cooling, regulating pH value with hydrochloric acid is faintly acid, filters washing, drying gets white crystal 27.3g.The yield of present embodiment is 98.8%, mp.99-100 ℃, and M
+=344,
1HNMR:CDCl
3: 1.087 (6H, d), 4.706 (2H, s), 5.010 (1H, t), 7.167 (1H, d), 7.187 (1H, d), 7.207 (1H, d), 7.265 (1H, d), 7.284 (1H, t), 7.335 (1H, t), 7.608 (1H, d), 7.628 (1H, d).IR：V
C＝0.1671cm
-1。
Claims (9)
1, heterocycle acetamide oxide---2-(1,3-benzothiazole-2-base oxygen)-N-(4-fluorophenyl)-N-(1-Methylethyl) acetamide herbicide, it is the compound structure general formula with oxyacetamide: ROCH (R
1) CON (R
2) (R
3) in the phenyl ring of unsubstituted change into the fluorine-containing substituted benzene ring in 4-position, it is characterized in that the chemical structural formula of synthetic compound is:
2, heterocycle acetamide oxide---2-(1,3-benzothiazole-2-base oxygen)-and the preparation method of N-(4-fluorophenyl)-N-(1-Methylethyl) acetamide herbicide, the preparation method who it is characterized in that weed killer herbicide of the present invention is that in the following order three steps realize; The first step is a chlorine acetylation, adopt acylating agent, acid binding agent, amine, solvent reaction to generate chloro-acetamide, the mol ratio of each reactant is, amine: acylating agent: acid binding agent=1.0: 1.0～2.0: 1.0～2.0, solvent is an amount of, reaction temperature be-5 ℃ to the solvent refluxing temperature, the time is 1-15 hour; Second step was esterification, and chloro-acetamide and anhydrous sodium acetate, solvent action are generated ester, and the mol ratio of reactant is, chloro-acetamide: anhydrous sodium acetate=1.0: 1.0～2.0, solvent is an amount of, reaction temperature be 0 ℃ to the solvent refluxing temperature, the time is 1-10 hour; The 3rd step was condensation reaction, be with esterification products and chloro benzo thiazole in the following hydrolysis limit condensation of highly basic condition, the mol ratio of reactant is carboxylate: the chloro benzo thiazole: alkali=1.0: 1.0～1.5: 1.5～10, reaction temperature is 0 ℃-100 ℃, and the time is 2-5 hour; Its synthesis route is:
3, heterocycle acetamide oxide according to claim 2---2-(1; 3-benzothiazole-2-base oxygen)-and the preparation method of N-(4-fluorophenyl)-N-(1-Methylethyl) acetamide herbicide, it is characterized in that the acylating agent in the first step chlorine acetylation is a chloracetyl chloride.
4, according to claim 2,3 described heterocycle acetamide oxide---2-(1; 3-benzothiazole-2-base oxygen)-preparation method of N-(4-fluorophenyl)-N-(1-Methylethyl) acetamide herbicide; it is characterized in that acylating agent is the combination of monoxone and phosphorus oxychloride; the two mol ratio is phosphorus oxychloride: monoxone=1: 3.0.
5, according to claim 2,3 described heterocycle acetamide oxide---2-(1,3-benzothiazole-2-base oxygen)-and the preparation method of N-(4-fluorophenyl)-N-(1-Methylethyl) acetamide herbicide, it is characterized in that acid binding agent selects for use pyridine, triethylamine, two for any one or a few the combination in methylaniline, sodium carbonate, the sodium bicarbonate.
6, according to claim 2,3 described heterocycle acetamide oxide---2-(1,3-benzothiazole-2-base oxygen)-and the preparation method of N-(4-fluorophenyl)-N-(1-Methylethyl) acetamide herbicide, it is characterized in that solvent selects any one or a few the combination in acetone, carrene, chloroform, carbon tetrachloride, benzene, the toluene for use.
7, heterocycle acetamide oxide according to claim 2---2-(1,3-benzothiazole-2-base oxygen)-and the preparation method of N-(4-fluorophenyl)-N-(1-Methylethyl) acetamide herbicide, it is characterized in that solvent in the second step esterification selects any one or a few the combination in hydro carbons, ethers, benzene, the toluene for use.
8, heterocycle acetamide oxide according to claim 2---2-(1,3-benzothiazole-2-base oxygen)-preparation method of N-(4-fluorophenyl)-N-(1-Methylethyl) acetamide herbicide, it is characterized in that the highly basic in the 3rd step condensation reaction is hydrochlorinate sodium, its concentration is 15-60%.
9, according to claim 2,8 described heterocycle acetamide oxides---2-(1,3-benzothiazole-2-base oxygen)-N-(4-fluorophenyl)-N-(1-Methylethyl) acetamide herbicide, it is characterized in that highly basic is potassium hydroxide, its concentration is 15-60%.
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| CN 01128279 CN1411719A (en) | 2001-10-11 | 2001-10-11 | Heteroepoxyacetamide-2-(1,3-benzothiazole-2-base oxygen)-N-(4-fluorophenyl)-N-(1-methyl ethyl) acetamide weedicide and its preparation |
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| CN 01128279 CN1411719A (en) | 2001-10-11 | 2001-10-11 | Heteroepoxyacetamide-2-(1,3-benzothiazole-2-base oxygen)-N-(4-fluorophenyl)-N-(1-methyl ethyl) acetamide weedicide and its preparation |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817803A (en) * | 2010-04-29 | 2010-09-01 | 贵州大学 | Beta-amino acid esters having optical activity and containing benzothiazole groups and synthetic method and application thereof |
| CN103664675A (en) * | 2013-11-27 | 2014-03-26 | 浙江省诸暨合力化学对外贸易有限公司 | Method for preparing 2-chloro-N-(4-fluorophenyl)-N-isopropylacetamide |
| CN107721948A (en) * | 2017-11-16 | 2018-02-23 | 江苏绿叶农化有限公司 | A kind of preparation method of flufenacet |
-
2001
- 2001-10-11 CN CN 01128279 patent/CN1411719A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817803A (en) * | 2010-04-29 | 2010-09-01 | 贵州大学 | Beta-amino acid esters having optical activity and containing benzothiazole groups and synthetic method and application thereof |
| CN101817803B (en) * | 2010-04-29 | 2011-09-28 | 贵州大学 | Beta-amino acid esters having optical activity and containing benzothiazole groups and synthetic method and application thereof |
| CN103664675A (en) * | 2013-11-27 | 2014-03-26 | 浙江省诸暨合力化学对外贸易有限公司 | Method for preparing 2-chloro-N-(4-fluorophenyl)-N-isopropylacetamide |
| CN103664675B (en) * | 2013-11-27 | 2016-05-18 | 浙江省诸暨合力化学对外贸易有限公司 | The preparation method of a kind of chloro-N-of 2-(4-fluorophenyl)-N-isopropyl acetamide |
| CN107721948A (en) * | 2017-11-16 | 2018-02-23 | 江苏绿叶农化有限公司 | A kind of preparation method of flufenacet |
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