CN1656894A - Diphenyl ether herbicide and its preparation method - Google Patents

Diphenyl ether herbicide and its preparation method Download PDF

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CN1656894A
CN1656894A CN 200410013568 CN200410013568A CN1656894A CN 1656894 A CN1656894 A CN 1656894A CN 200410013568 CN200410013568 CN 200410013568 CN 200410013568 A CN200410013568 A CN 200410013568A CN 1656894 A CN1656894 A CN 1656894A
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diphenyl ether
preparation
fluoro
solvent
ether herbicide
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孙志忠
侯艳君
高金胜
初文毅
闫鹏飞
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Heilongjiang University
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Heilongjiang University
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Abstract

A kind of diphenylether herbicides is prepared through reaction between 3,4-dichlorotrifluoro toluene, 4-fluoro-3-methylphenol and acid trap in solvent to obtain brown liquid, reaction on oxidizing agent and concentrated nitric and to obtain light yellows powder, acetylation reaction in solvent, adding L-ethyl lactate, and reaction under action of alkaline catalyst.

Description

Diphenyl ether herbicide and preparation method thereof
Technical field: the present invention relates to diphenyl ether herbicide and synthesis technique thereof, be specifically related to O-[2-fluoro-5-(2-chloro-α, α, α-trifluoro p-methoxyphenyl) benzoyl]-L-ethyl lactate weed killer herbicide and synthesis technique thereof.
Background technology: at present the kind of weed killer herbicide is a lot, but all there is consumption big (the per hectare consumption is up to 2~10 kilograms) in most of weed killer herbicides, and there is the shortcoming of unsafe factor in crops, and they have also caused bigger destruction to environment.In order to reach the purpose of highly effective and safe, people develop diphenyl ether compound in recent years, but the product synthesis technique complexity developed, yield is low, manufacturing cost is high, and its preparation method is difficult for realizing large-scale industrial production.
Summary of the invention: the present invention provides a kind of diphenyl ether herbicide and preparation method thereof in order to solve the shortcoming that the prior art consumption is big, cost is high, yield is low, and it has the advantage safe, efficient, that consumption is few.Diphenyl ether herbicide of the present invention is O-[2-fluoro-5-(2-chloro-α, α, a α-trifluoro p-methoxyphenyl) benzoyl]-L-ethyl lactate weed killer herbicide, its structural formula is
It is prepared by following step: a, condensation reaction: with 3,4-two chlorobenzotrifluorides, 4-fluoro-3-methylphenol and acid binding agent are (0.8~1.5) according to mol ratio: 1: 2 ratio joins in the solvent, the control reaction temperature was reacted 1~20 hour down at 140~180 ℃, decompression and solvent recovery then, the residue that obtains is a brown liquid, be 2-fluoro-5-(2-chloro-α, α, α-trifluoro p-methoxyphenyl) toluene (I); B, oxidation reaction: in the brown liquid that a step obtains, add oxidant and red fuming nitric acid (RFNA), wherein the mol ratio of brown liquid, red fuming nitric acid (RFNA) and oxidant is 1: 14: (0.02~0.05), the control reaction temperature was reacted 2~10 hours down at 165~175 ℃, then the decompression, suction filtration, the gained solid is carried out obtaining buff powder, i.e. 2-fluoro-5-(2-chloro-α after soda acid handles, α, α-trifluoro p-methoxyphenyl) benzoic acid (II); C; esterification: buff powder and acylating agent are joined in the solvent; the control reaction temperature was reacted 1~10 hour to the solvent refluxing temperature at 20 ℃; remove excessive acylating agent; add the L-ethyl lactate then; to the solvent refluxing temperature, reacted 2~15 hours at 0 ℃ in control reaction temperature under the effect of base catalyst; buff powder wherein; acylating agent; the mol ratio of L-ethyl lactate and base catalyst is 1: (1~2): 1.1: 1; decompression then; suction filtration; filtrate is washed; dry; distillation; obtain brown viscous liquid at last; be O-[2-fluoro-5-(2-chloro-α; α, α-trifluoro p-methoxyphenyl) benzoyl]-L-ethyl lactate (III).Its synthetic route is as follows:
Figure A20041001356800051
Weed killer herbicide of the present invention has safety, efficient, consumption is few, cost is low advantage, and its preparation method has that technology is simple, synthetic reaction is rapid, total recovery high (55.4%), low cost of manufacture, be convenient to the advantage of large-scale industrial production.
Embodiment one: the diphenyl ether herbicide of present embodiment is O-[2-fluoro-5-(2-chloro-α, α, a α-trifluoro p-methoxyphenyl) benzoyl]-L-ethyl lactate weed killer herbicide, its structural formula is
Figure A20041001356800052
It is prepared by following step: a, condensation reaction: with 3,4-two chlorobenzotrifluorides, 4-fluoro-3-methylphenol and acid binding agent are (0.8~1.5) according to mol ratio: 1: 2 ratio joins in the solvent, the control reaction temperature was reacted 1~20 hour down at 140~180 ℃, decompression and solvent recovery then, the residue that obtains is a brown liquid, i.e. 2-fluoro-5-(2-chloro-α, α, α-trifluoro p-methoxyphenyl) toluene (I); B, oxidation reaction: in the brown liquid that a step obtains, add oxidant and red fuming nitric acid (RFNA), wherein the mol ratio of brown liquid, red fuming nitric acid (RFNA) and oxidant is 1: 14: (0.02~0.05), the control reaction temperature was reacted 2~10 hours down at 165~175 ℃, then the decompression, suction filtration, the gained solid is carried out obtaining buff powder, i.e. 2-fluoro-5-(2-chloro-α after soda acid handles, α, α-trifluoro p-methoxyphenyl) benzoic acid (II); C; esterification: buff powder and acylating agent are joined in the solvent; the control reaction temperature was reacted 1~10 hour to the solvent refluxing temperature at 20 ℃; remove excessive acylating agent; add the L-ethyl lactate then; to the solvent refluxing temperature, reacted 2~15 hours at 0 ℃ in control reaction temperature under the effect of base catalyst; buff powder wherein; acylating agent; the mol ratio of L-ethyl lactate and base catalyst is 1: (1~2): 1.1: 1; decompression then; suction filtration; filtrate is washed; dry; distillation; obtain brown viscous liquid at last; be O-[2-fluoro-5-(2-chloro-α; α, α-trifluoro p-methoxyphenyl) benzoyl]-L-ethyl lactate (III).Described acid binding agent is a kind of or any several mixture in potash, sodium carbonate, sodium hydroxide and the potassium hydroxide; Solvent in a step is dimethyl sulfoxide (DMSO), N, a kind of or any several mixture in dinethylformamide, toluene, dimethylbenzene and the chlorobenzene; Oxidant is one or both the mixture in vanadium pentoxide and the manganese dioxide; Acylating agent is a kind of or any several mixture in thionyl chloride, phosphorus trichloride and the phosphorus oxychloride; Solvent in the b step is a kind of or any several mixture in toluene, benzene, dimethylbenzene, carrene, chloroform and the carbon tetrachloride; Base catalyst is triethylamine, pyridine, N, a kind of or any several mixture in accelerine, sodium carbonate and the sodium bicarbonate.
Embodiment two: the diphenyl ether herbicide of present embodiment is O-[2-fluoro-5-(2-chloro-α, α, a α-trifluoro p-methoxyphenyl) benzoyl]-L-ethyl lactate weed killer herbicide, its structural formula is
It is prepared by following step: a, condensation reaction: with 3,4-two chlorobenzotrifluorides, 4-fluoro-3-methylphenol and acid binding agent are that 1.1: 1: 2 ratio joins in the solvent according to mol ratio, the control reaction temperature was reacted 1~20 hour down at 140~180 ℃, decompression and solvent recovery then, residue is a brown liquid, be 2-fluoro-5-(2-chloro-α, α, α-trifluoro p-methoxyphenyl) toluene (I); B, oxidation reaction: in a, add oxidant and red fuming nitric acid (RFNA) in the brown liquid, wherein the mol ratio of brown liquid, red fuming nitric acid (RFNA) and oxidant is 1: 14: 0.03, the control reaction temperature was reacted 2~10 hours down at 165~175 ℃, then the decompression, suction filtration, the gained solid is carried out obtaining buff powder, i.e. 2-fluoro-5-(2-chloro-α after soda acid handles, α, α-trifluoro p-methoxyphenyl) benzoic acid (II); C; esterification: buff powder and acylating agent are joined in the solvent; the control reaction temperature was reacted 1~10 hour to the solvent refluxing temperature at 20 ℃; remove excessive acylating agent; add the L-ethyl lactate then; to the solvent refluxing temperature, reacted 2~15 hours at 0 ℃ in control reaction temperature under the effect of base catalyst; buff powder wherein; acylating agent; the mol ratio of L-ethyl lactate and base catalyst is 1: 1.5: 1.1: 1; decompression then; suction filtration; filtrate is washed; dry; distillation; obtain brown viscous liquid at last; be O-[2-fluoro-5-(2-chloro-α; α, α-trifluoro p-methoxyphenyl) benzoyl]-L-ethyl lactate (III).
Embodiment three: present embodiment is prepared by following step: a, condensation reaction: add 126g 4-fluoro-3-methylphenol, 236.5g 3 in the 400g dimethyl sulfoxide (DMSO), 4-two chlorobenzotrifluorides and 212g Anhydrous potassium carbonate, under 140~180 ℃ of temperature, reacted 1~20 hour, the recovered under reduced pressure dimethyl sulfoxide (DMSO), the gained residue disperses in water, obtains brown liquid 267.6g, be 2-fluoro-5-(2-chloro-α, α, α-trifluoro p-methoxyphenyl) toluene (I), yield is 88%; B, oxidation reaction: get 152g brown liquid, 4.6g vanadium pentoxide and 678.5g red fuming nitric acid (RFNA), under 165~175 ℃ of temperature, reacted 2~10 hours, steam about 30% red fuming nitric acid (RFNA), add big water gaging then, decompression, suction filtration, the gained solid is carried out after soda acid handles, obtain buff powder 111.9g, i.e. 2-fluoro-5-(2-chloro-α, α, α-trifluoro p-methoxyphenyl) benzoic acid (II), yield is 67%; C, esterification: in 300ml toluene, add the 83.5g buff powder, at room temperature drip the 44.3g thionyl chloride, react to the reflux temperature of toluene at 20 ℃ and to obtain acyl chlorides in 1~10 hour, remove excessive thionyl chloride and most of toluene then under reduced pressure, standby; Other adding 34.1g purity in 100ml toluene is 90% L-ethyl lactate and 25.3g triethylamine; under 0 ℃, be added drop-wise in the above-mentioned solution of acid chloride; the control temperature was reacted 2~15 hours to the solvent refluxing temperature at 0 ℃; cooling; decompression, suction filtration; filtrate is washed; use anhydrous magnesium sulfate drying; remove solvent with steam distillation then; obtain brown viscous liquid 102.2g at last, i.e. O-[2-fluoro-5-(2-chloro-α, α; α-trifluoro p-methoxyphenyl) benzoyl]-L-ethyl lactate (III), yield is 94%.Brown viscous liquid is defined as O-[2-fluoro-5-(2-chloro-α through infrared, nuclear-magnetism, Mass Spectrometer Method; α; α-trifluoro p-methoxyphenyl) benzoyl]-the L-ethyl lactate; carry out before the seedling and activity of weeding test behind the seedling to the composition of this chemical structural formula; wherein Ce Shi weeds are barnyard grass grass, Siberian cocklebur, lady's-grass, fennel fiber crops and duck grass etc., and the crop of test is soybean, wheat, peanut.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 growth period, carrying out the cauline leaf spraying by experimental scheme dosage with crawler type crop sprayer handles, processing is placed in the greenhouse and cultivates by the normal management method, routine observation examination material growth and development of plants situation, and in handling back 15 days, the range estimation medicament is to the growth inhibition situation of examination material plant, this inorganic agent is higher to the broad leaved weed activity, to the weed growth inhibiting rate more than 90%, safe to crop, consumption is little, and the per hectare consumption is no more than 20 grams.

Claims (10)

1, diphenyl ether herbicide is characterized in that it is O-[2-fluoro-5-(2-chloro-α, α, a α-trifluoro p-methoxyphenyl) benzoyl]-L-ethyl lactate weed killer herbicide, its structural formula is
Figure A2004100135680002C1
2, the preparation method of diphenyl ether herbicide, it is characterized in that it is prepared by following step: a, condensation reaction: with 3,4-two chlorobenzotrifluorides, 4-fluoro-3-methylphenol and acid binding agent are (0.8~1.5) according to mol ratio: 1: 2 ratio joins in the solvent, the control reaction temperature was reacted 1~20 hour down at 140~180 ℃, decompression and solvent recovery then, the residue that obtains is a brown liquid, i.e. 2-fluoro-5-(2-chloro-α, α, α-trifluoro p-methoxyphenyl) toluene; B, oxidation reaction: in the brown liquid that a step obtains, add oxidant and red fuming nitric acid (RFNA), wherein the mol ratio of brown liquid, red fuming nitric acid (RFNA) and oxidant is 1: 14: (0.02~0.05), the control reaction temperature was reacted 2~10 hours down at 165~175 ℃, then the decompression, suction filtration, the gained solid is carried out obtaining buff powder, i.e. 2-fluoro-5-(2-chloro-α after soda acid handles, α, α-trifluoro p-methoxyphenyl) benzoic acid; C; esterification: buff powder and acylating agent are joined in the solvent; the control reaction temperature was reacted 1~10 hour to the solvent refluxing temperature at 20 ℃; remove excessive acylating agent; add the L-ethyl lactate then; to the solvent refluxing temperature, reacted 2~15 hours at 0 ℃ in control reaction temperature under the effect of base catalyst; buff powder wherein; acylating agent; the mol ratio of L-ethyl lactate and base catalyst is 1: (1~2): 1.1: 1; decompression then; suction filtration; filtrate is washed; dry; distillation; obtain brown viscous liquid at last; be O-[2-fluoro-5-(2-chloro-α; α, α-trifluoro p-methoxyphenyl) benzoyl]-the L-ethyl lactate.
3, the preparation method of diphenyl ether herbicide according to claim 2 is characterized in that acid binding agent is a kind of or any several mixture in potash, sodium carbonate, sodium hydroxide and the potassium hydroxide.
4, the preparation method of diphenyl ether herbicide according to claim 2 is characterized in that the solvent in a step is dimethyl sulfoxide (DMSO), N, a kind of or any several mixture in dinethylformamide, toluene, dimethylbenzene and the chlorobenzene; Solvent in the b step is a kind of or any several mixture in toluene, benzene, dimethylbenzene, carrene, chloroform and the carbon tetrachloride.
5, the preparation method of diphenyl ether herbicide according to claim 2 is characterized in that oxidant is one or both the mixture in vanadium pentoxide and the manganese dioxide.
6, the preparation method of diphenyl ether herbicide according to claim 2 is characterized in that acylating agent is a kind of or any several mixture in thionyl chloride, phosphorus trichloride and the phosphorus oxychloride.
7, the preparation method of diphenyl ether herbicide according to claim 2 is characterized in that base catalyst is triethylamine, pyridine, N, a kind of or any several mixture in accelerine, sodium carbonate and the sodium bicarbonate.
8, the preparation method of diphenyl ether herbicide according to claim 2 is characterized in that 3 in a step, and 4-two chlorobenzotrifluorides, 4-fluoro-3-methylphenol and acid binding agent are 1.1: 1: 2 according to mol ratio.
9, the preparation method of diphenyl ether herbicide according to claim 2, the mol ratio that it is characterized in that brown liquid, red fuming nitric acid (RFNA) and oxidant in the b step is 1: 14: 0.03.
10, the preparation method of diphenyl ether herbicide according to claim 2 is characterized in that the mol ratio of buff powder, acylating agent, L-ethyl lactate and base catalyst in the c step is 1: 1.5: 1.1: 1.
CN 200410013568 2004-02-19 2004-02-19 Diphenyl ether herbicide and its preparation method Pending CN1656894A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101407462B (en) * 2007-10-09 2011-07-20 中国中化股份有限公司 Diphenyl ether compound and use thereof
CN101747202B (en) * 2008-12-11 2013-03-27 中国中化股份有限公司 2-chloro-benzoate compound and application thereof
CN103342630A (en) * 2013-07-30 2013-10-09 黑龙江大学 Method for synthesizing diaryl ether compounds

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101407462B (en) * 2007-10-09 2011-07-20 中国中化股份有限公司 Diphenyl ether compound and use thereof
CN101747202B (en) * 2008-12-11 2013-03-27 中国中化股份有限公司 2-chloro-benzoate compound and application thereof
CN103342630A (en) * 2013-07-30 2013-10-09 黑龙江大学 Method for synthesizing diaryl ether compounds
CN103342630B (en) * 2013-07-30 2015-01-21 黑龙江大学 Method for synthesizing diaryl ether compounds

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