CN1068106A - The new method synthetic herbicide of monoetherization oxyfluorfen - Google Patents
The new method synthetic herbicide of monoetherization oxyfluorfen Download PDFInfo
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- CN1068106A CN1068106A CN 91107429 CN91107429A CN1068106A CN 1068106 A CN1068106 A CN 1068106A CN 91107429 CN91107429 CN 91107429 CN 91107429 A CN91107429 A CN 91107429A CN 1068106 A CN1068106 A CN 1068106A
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Abstract
The present invention has introduced the industrial route of the new method synthetic herbicide of a kind of monoetherization oxyfluorfen.This route is with 3, and 4-two chlorobenzotrifluorides and Resorcinol are raw material, makes product through condensation, ethylization, nitrated three-step reaction.It has advantages such as technology is easy, recovery rate is high, production cost is low than existing other operational paths.
Description
The present invention has introduced a kind of synthetic method of fluorine-containing diphenyl ether herbicide.
The weedicide that oxyfluorfen is before the bud by U.S. rom Haars Co., Ltd exploitation, uses behind the bud is mainly used in the rice field and prevents and kill off multiple broad-leaved class, Cyperaceae, annual grassy weeds gramineous.Its common name is oxyfluozfen, and commodity are called Goal, chemistry 2-chloro-1-(3-oxyethyl group by name-4-nitro) phenoxy group-4-(trifluoromethyl) benzene, its chemical structural formula is as follows:
The more synthetic route of relevant oxyfluorfen report has dual-ether method, (U.S.4,093,446 U.S.4,358,308 both at home and abroad; U.S.4,419,122; U.S.4,419,123; U.S.4,419,124) but the 2-chloro-4-trifloro methyl phenol sylvite that this method generated still can't utilize, so 3, the unit consumption height of 4-two chlorobenzotrifluorides, production cost is also high.The oxyfluorfen industrial product route that present U.S. rom Haars Co., Ltd is adopted is monoether hydroxyl protection method (U.S.4,093,446; U.S.4,358,308; U.S.4,419,122; U.S.4,419,123; U.S.4,419,124), but also there is the shortcoming that step is oversize, total recovery is too low in this method.In addition, though after also having back etherification method (bamboo Song Zhefu, weedicide research overview P448 Ger2,619,489) and back etherificate nitrofication process (openly specially permit 49-70,937; Report such as Ger 2,007,737), but all difficult suitability for industrialized production that realizes of these methods.
For overcoming above-mentioned shortcoming, the present invention introduces the operational path of the new method synthesizing oxyfluorfen of a kind of monoetherization.This route with 3,4-two chlorobenzotrifluorides and Resorcinol be raw material, in potassium hydroxide aqueous solution, generate intermediate 2-chloro-α α α-trifluoro p-methylphenyl-3-hydroxyl phenylate (abbreviation monoether) with the dimethyl sulfoxide (DMSO) catalyzing and condensing, the monoether of gained is in alkali metal hydroxide aqueous solution, after the ethyl sulfate ethyl changes into 2-chloro-α α α-trifluoro p-methylphenyl-3-oxyethyl group phenylate (be called for short oxyethyl group monoether), nitrated and obtain oxyfluorfen with nitrating agent again.Its reaction formula is as follows:
In the above-mentioned reaction formula the first step reaction with 3,4-two chlorobenzotrifluorides and Resorcinol be raw material, intermediate 2-chloro-α α α-trifluoro p-methylphenyl-3-hydroxyl phenylate (abbreviation monoether) is produced in reaction in dimethyl sulfoxide (DMSO) and potassium hydroxide aqueous solution, and its yield is about 70%.
In the reaction of second step, monoether ethylizes through ethyl sulfate, in alkali metal hydroxide aqueous solution and produces 2-chloro-α α α-trifluoro p-methylphenyl-3-oxyethyl group phenylate (being called for short the oxyethyl group monoether), wherein also available monobromethane of ethyl sulfate or monochloroethane replace, and this step reaction yield can reach more than 95%.
Employed alkali metal hydroxide aqueous solution can be sodium hydroxide, potassium hydroxide or other alkali metal hydroxide aqueous solution when monoether became metal-salt, was best with aqueous sodium hydroxide solution wherein.Its concentration can be between 1%～saturated solution.Be the best with 5%～15% especially wherein.
The mol ratio of monoether and alkali metal hydroxide and ethyl sulfate can be between 1: 1: 0.5～1: 3: 3, and is best with 1: 1.5: 1.4～1: 1.8: 1.9.Simultaneously, the dropping time of ethyl sulfate should be controlled between 1～3 hour when ethylizing.
In the building-up process of oxyethyl group monoether, can suitably add some organic solvents, as benzene, ethylene dichloride, chloroform, tetracol phenixin, toluene etc.
The nitrating agent that uses when oxyethyl group monoether monoether is nitrated is generally the nitration mixture of nitric acid and sulfuric acid, acetic acid or aceticanhydride, and wherein the nitration mixture with nitric acid and aceticanhydride is best.Employed concentration of nitric acid can be at 30～98%(nitrosonitric acid) between, serve as better wherein with 50～80%.
The mol ratio of oxyethyl group monoether and nitric acid, aceticanhydride can be between 1: 1: 1～1: 8: 10, and is best with 1: 2: 3～1: 4: 8.Its nitrated temperature should be chosen between-10～+ 25 ℃, and is the best with-5～+ 5 ℃.The nitrated time was generally 1～8 hour, with 2～4 hours for well.
The reaction of this step is with oxyethyl group protection hydroxyl, and nitrated as carrying out in the presence of the solvent with aceticanhydride, yield can reach more than 70%.And acetic acid can be recycled.
The present invention adopts new monoether to be combined to route, than U.S. rom Haars Co., Ltd employed now monoether hydroxyl protection method industrialized route totally shortened for two steps.As in 3,4-two chlorobenzotrifluorides come, three step synthetic total recoverys can reach more than 45%, so improved yield widely, reduced production cost.
Adopt the content of route products obtained therefrom of the present invention to reach 〉=70%, not less than the product of other operational path gained.
Example 1
In 250 milliliters of there-necked flasks, put into Resorcinol 33 grams (0.3 mol), potassium hydroxide 37 gram (0.66 mol), 24.7 milliliters in water, 40 milliliters of dimethyl sulfoxide (DMSO), stir and be warming up to 160 ℃.Be cooled to 100 ℃, add 3,4-two chlorobenzotrifluorides 33.6 grams (0.15 mol), continue to be warming up to 160 ℃ and kept 5 hours.Cooling adds entry, and is adjusted to acidity with concentrated hydrochloric acid.With 50 milliliters of benzene extractions, the benzene layer is washed to neutrality with sodium carbonate solution, gets benzole soln 81.9 grams of monoether, and content is 37%, pure yield 70%.
Example 2
In 250 milliliters of there-necked flasks, drop into monoether 17.38 grams (0.05 mol), 10% aqueous sodium hydroxide solution, 33 grams (in sodium hydroxide 0.08 mol), be heated to 70 ℃, drip ethyl sulfate 11.40 grams (0.07 mol), 70 ℃ of insulations 2 hours.Cooling is poured out in separating funnel, extracts with ethylene dichloride.The ethylene dichloride layer washes with water to neutrality, boils off ethylene dichloride, gets deep yellow solid oxyethyl group monoether 18 grams, and 30～35 ℃ of fusing points, content are 90.08%, yield 98%.
Example 3
In 250 milliliters of there-necked flasks, throw monoether 17.38 gram (0.05 mol), 10% potassium hydroxide aqueous solution, 55 grams, 45 milliliters of benzene, be heated to 70 ℃, be incubated 1 hour, drip ethyl sulfate 11.39 grams (0.07 mol), be incubated 1 hour.Cooling is poured out in separating funnel, divides three extractions with 30 milliliters of benzene.The benzene layer washes with water to neutrality, boils off benzene, gets deep yellow solid oxyethyl group monoether 17.2 grams, and content is 90.11%, yield 98%.
Example 4
In 250 milliliters of there-necked flasks, drop into monoether 17.38 grams (0.05 mol), 45 milliliters of benzene, 10% aqueous sodium hydroxide solution, 33 grams (in sodium hydroxide 0.08 mol), be heated to 70 ℃, dripping bromine ethane 8.06 grams (0.07 mol) were 70 ℃ of insulations 2 hours.Cooling is poured out in separating funnel, divides three extractions with 10 milliliters of benzene.The benzene layer washes with water to neutrality, boils off benzene, cools off to such an extent that deep yellow solid oxyethyl group monoether 17 restrains content 89.96%, yield 96.75%.
Example 5
In 100 milliliters of there-necked flasks, drop into 14.7 gram oxyethyl group monoethers (content 90%, 0.042 mol), the vitriol oil 27.6 gram stirring and dissolving.Be cooled to-3 ℃, drip nitrosonitric acid 27.6 grams (0.06 mol), be warming up to 10 ℃ then, stirred 2 hours, pour in the beaker of 100 ml waters and ice cube, separate out clean sugar like product, with 50 milliliters of ethylene dichloride dissolution extraction, the ethylene dichloride layer washes with water to neutrality, get brown semi-solid 15.04 grams, content 50.58%, pure yield 50.10%.
Example 6
In 250 milliliters of there-necked flasks, drop into 33.2 gram oxyethyl group monoether (content 90%, 0.094 mol) and 133 milliliters of aceticanhydrides.Drip 2000 gram 66% nitric acid (0.283 mol) at 0 ℃, stirred 2 hours at 0 ℃ then,, filter filtrate and add water, add 50 milliliters of ethylene dichloride extractions with the neutralization of solid carbonic acid potassium.Acetic acid is reclaimed in the water layer distillation.The ethylene dichloride layer washes with water to neutrality.Boil off solvent and get 34.0 gram oxyfluorfens, placement is brown solid, content 70.15%, 60～70 ℃ of fusing points, pure yield 70.19%.
Claims (12)
1, a kind of with 3,4-trichlorobenzotrifluoride and Resorcinol be the method for feedstock production oxyfluorfen, it is characterized in that by 3,4-two chlorobenzotrifluorides and Resorcinol condensation generate intermediate 2-chloro-α α α-trifluoro p-methylphenyl-3-hydroxyl phenylate (abbreviation monoether), after the ethyl-based formulation ethyl changes into 2-chloro-α α α-trifluoro p-methylphenyl-3-oxyethyl group phenylate (be called for short oxyethyl group monoether), nitrated and make with nitrating agent again.
2, by the described preparation method of claim 1, it is characterized in that the condensation of monoether is carried out in the aqueous solution of dimethyl sulfoxide (DMSO) and potassium hydroxide.
3, by the described preparation method of claim 1, it is characterized in that employed ethyl-based formulation can be ethyl sulfate, monobromethane or monochloroethane, wherein is better with the ethyl sulfate.
4, ethylizing by claim 1,3 described monoethers, is solvent with the alkali metal hydroxide aqueous solution when it is characterized in that ethylizing, and wherein is better with the aqueous sodium hydroxide solution.
5, by the described alkali metal hydroxide aqueous solution of claim 4, its concentration can serve as better with 5%～15% between 1%～saturated solution.
6, ethylize by claim 1,3,4 described monoethers, it is characterized in that the mol ratio of intermediate monoether, alkali metal hydroxide and ethyl-based formulation can be between 1: 1: 0.5～1: 3: 3, and be best with 1: 1.5: 1.4～1: 1.8: 1.9.
7, by the described ethyl-based formulation of claim 3, its dropping time should be controlled between 1～3 hour.
8, press the nitrated of the described oxyethyl group monoether of claim 1, it is characterized in that employed nitrating agent is the nitration mixture of nitric acid and sulfuric acid, acetic acid or aceticanhydride, wherein the nitration mixture with nitric acid and aceticanhydride is best.
9, by the described nitric acid of claim 8, its concentration is preferably between 50～80%.
10, by claim 1,8 described oxyethyl group monoether and nitrating agents, wherein the mol ratio of oxyethyl group monoether and nitric acid, aceticanhydride can be between 1: 1: 1～1: 8: 10, and is best with 1: 2: 3～1: 4: 8.
11, by claim 1,8 described nitrated, its nitrated temperature should be between-5～+ 5 ℃.
12, by claim 1,8 described nitrated, its nitrated time at 2～4 hours for well.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 91107429 CN1068106A (en) | 1991-06-21 | 1991-06-21 | The new method synthetic herbicide of monoetherization oxyfluorfen |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 91107429 CN1068106A (en) | 1991-06-21 | 1991-06-21 | The new method synthetic herbicide of monoetherization oxyfluorfen |
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| CN1068106A true CN1068106A (en) | 1993-01-20 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372594A (en) * | 2010-08-21 | 2012-03-14 | 李坚 | Application of reaction in preparing oxyfluorfen and in other organic synthesis |
| CN103539643A (en) * | 2012-07-16 | 2014-01-29 | 江苏英力科技发展有限公司 | Method for preparing 2-ethoxy-6-chloro-toluene |
| CN103787890A (en) * | 2014-02-28 | 2014-05-14 | 江苏省激素研究所股份有限公司 | Synthetic method of acifluorfen |
| CN103980127A (en) * | 2014-04-03 | 2014-08-13 | 山东滨农科技有限公司 | Preparation method for oxyfluorfen |
| CN113683511A (en) * | 2021-08-31 | 2021-11-23 | 广东立威化工有限公司 | Synthesis method of 2-chloro-4-trifluoromethylphenyl-4 '-nitro-3' -ethoxy phenyl ether |
-
1991
- 1991-06-21 CN CN 91107429 patent/CN1068106A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372594A (en) * | 2010-08-21 | 2012-03-14 | 李坚 | Application of reaction in preparing oxyfluorfen and in other organic synthesis |
| CN102372594B (en) * | 2010-08-21 | 2016-02-24 | 武汉工程大学 | The application in oxyfluorfen and other organic synthesis is being prepared in a kind of reaction |
| CN103539643A (en) * | 2012-07-16 | 2014-01-29 | 江苏英力科技发展有限公司 | Method for preparing 2-ethoxy-6-chloro-toluene |
| CN103539643B (en) * | 2012-07-16 | 2015-07-29 | 江苏英力科技发展有限公司 | A kind of method preparing the chloro-toluene of 2-oxyethyl group-6- |
| CN103787890A (en) * | 2014-02-28 | 2014-05-14 | 江苏省激素研究所股份有限公司 | Synthetic method of acifluorfen |
| CN103980127A (en) * | 2014-04-03 | 2014-08-13 | 山东滨农科技有限公司 | Preparation method for oxyfluorfen |
| CN113683511A (en) * | 2021-08-31 | 2021-11-23 | 广东立威化工有限公司 | Synthesis method of 2-chloro-4-trifluoromethylphenyl-4 '-nitro-3' -ethoxy phenyl ether |
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