CN104803883A - Synthesis method of cyhalofop-butyl - Google Patents
Synthesis method of cyhalofop-butyl Download PDFInfo
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- CN104803883A CN104803883A CN201510137411.XA CN201510137411A CN104803883A CN 104803883 A CN104803883 A CN 104803883A CN 201510137411 A CN201510137411 A CN 201510137411A CN 104803883 A CN104803883 A CN 104803883A
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Abstract
The invention discloses a synthesis method of cyhalofop-butyl. The method comprises steps as follows: butyl L-lactate and paratoluensulfonyl chloride are taken as raw materials and have a condensation reaction I in an organic solvent, a condensation product I is produced, the condensation product I and hydroquinone have an etherification reaction under the alkaline condition, an etherification product is produced and has a salt forming reaction in an organic solvent under the alkaline condition, a etherate salt is produced, the etherate salt and 3,4-difluorobenzonitrile have a condensation reaction II, and the cyhalofop-butyl is produced. The method has the advantages as follows: clean production is realized, the solvents during reactions can be recycled, no waste acid is produced during production, produced HCI can be absorbed by water and then sold as hydrochloric acid, produced KF can also be sold, so that three-wastes can be reduced, the cost can be reduced, and the benefit can be increased.
Description
Technical field
The present invention relates to a kind of synthetic method of cyhalofop-butyl.
Background technology
Cyhalofop-butyl belongs to aryloxyphenoxypropionic class weedicide, effective object is paddy rice (transplants and live), to paddy rice etc., there is excellent selectivity, selectivity is based on different accretion rates, in paddy rice body, cyhalofop-butyl by two acid-state degraded rapidly to acetyl-CoA carboxylase non-activity, thus can have the security of height to paddy rice.Be mainly used in preventing and kill off important gramineous weeds.Cyhalofop-butyl is efficient to Semen Euphorbiae, have certain preventive effect to low age barnyard grass, also can prevent and kill off, lady's-grass, Paspalum distichum, Herba Setariae Viridis, Herba Eleusines Indicae, amur foxtail etc.Because it degrades rapidly in soil and in typical paddy field water either, therefore to succession crop safety.
Paddy rice is as the staple food crop of China, and the weedicide for it also has wide market, therefore, needs a kind of simple synthetic method efficiently to synthesize this safe weedicide cyhalofop-butyl.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of synthetic method of simple cyhalofop-butyl efficiently.
The technical solution used in the present invention is: a kind of synthetic method of cyhalofop-butyl, condenses I is generated for raw material carries out condensation reaction I in organic solvent with Pfansteihl butyl ester and Tosyl chloride, condenses I and Resorcinol carry out etherification reaction in the basic conditions and generate etherification product, etherification product in organic solvent, carry out salt-forming reaction under alkaline condition and generate etherate salt, etherate salt and 3,4-difluorobenzonilyile carry out condensation reaction II and generate cyhalofop-butyl.
Chemical equation is as follows:
Organic solvent described in condensation reaction I is toluene, and solvent load is 2 times of Tosyl chloride quality, and the temperature of condensation reaction I is 110-120 DEG C, and return time is 2-3h, and condensation reaction I obtains the toluene solution of condenses I after terminating.
Alkali described in etherification reaction is liquid caustic soda, and consumption is 1.6 times of condenses I quality, and the temperature of etherification reaction is 50-60 DEG C, and the reaction times is 8-9h, after etherification reaction terminates, adds water washing, and the organic layer underpressure distillation obtained removes desolventizing, the etherification product obtained.
Organic solvent described in salt-forming reaction is DMF, and solvent load is 2 times of etherification product quality, and described alkali is solid potassium hydroxide, and consumption is 1.6 times of etherification product quality, and the temperature of salt-forming reaction is 100-110 DEG C, obtains etherate salt after reflux dewatering.
The temperature of reaction of condensation reaction II is 100-110 DEG C, and the reaction times is 15-16h, and after condensation reaction II terminates, lower the temperature except after desalting, remove organic solvent under reduced pressure, residue from ethanol recrystallization obtains cyhalofop-butyl.
Advantage of the present invention is: cleaner production, the solvent recoverable in reaction process.Production process does not produce spent acid, and the HCl of generation can sell as outside hydrochloric acid with after water absorption, and the KF of generation also can sell in addition, thus the minimizing three wastes reduce costs, and improve income.
Embodiment
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, and this embodiment, only for explaining the present invention, does not form the restriction to protection scope of the present invention.
Embodiment 1
A kind of synthetic method of cyhalofop-butyl comprises the following steps:
(1) condensation reaction I
Add in condensation I still together with toluene by the Pfansteihl butyl ester measured, Tosyl chloride, jacket steam is warmed up to 110 DEG C of back flow reaction 2h, and the HCl that reaction produces picks out outdoor absorption and makes hydrochloric acid.After reaction terminates, be down to room temperature by chuck water coolant, obtain the toluene solution of condenses, proceed to next step operation.
(2) etherification reaction
Upper step gained material is proceeded in etherification kettle, add load weighted Resorcinol to be again uniformly mixed, drip the liquid caustic soda measured and react, dropwise rear steam jacket and be warmed up to 50 DEG C, insulation reaction 8h, after sampling analysis is qualified, chuck is cooled to room temperature, adds water washing, the waste water of washing send wastewater treatment, organic layer at 85 DEG C, be decompressed to after first normal pressure-0.092MPa distillation deviate from toluene apply mechanically, the etherate obtained proceeds to next step.
(3) salify, condensation reaction II
By etherate, solid potassium hydroxide, DMF drops in condensation II still and stirs, be warming up to 100 DEG C subsequently, be decompressed to-0.092MPa after first normal pressure and carry out dehydration reaction, after dehydration terminates, add 3, 4-difluorobenzonilyile, after keeping 100 DEG C to react 15h, after sampling analysis is qualified, be down to room temperature, there is crystallization, filter out outside KF and sell, filtrate is warming up to 100 DEG C, decompression-0.092MPa deviates from DMF and applies mechanically, precipitation terminates the cooling of rear chuck and drops to room temperature, add ethyl alcohol recrystallization again, crystallization under room temperature is cooled to by chuck, send after filtration in rake type drier, automatically packed finished product is packaged to be after drying at 60 DEG C, filtration obtains mother liquor and send ethanol distillation still, air distillation recovery ethanol at 80 DEG C, distillation residue send fixed-end forces after collecting.
Claims (5)
1. the synthetic method of a cyhalofop-butyl, it is characterized in that: generate condenses I with Pfansteihl butyl ester and Tosyl chloride for raw material carries out condensation reaction I in organic solvent, condenses I and Resorcinol carry out etherification reaction in the basic conditions and generate etherification product, etherification product in organic solvent, carry out salt-forming reaction under alkaline condition and generate etherate salt, etherate salt and 3,4-difluorobenzonilyile carry out condensation reaction II and generate cyhalofop-butyl.
2. the synthetic method of a kind of cyhalofop-butyl according to claim 1, it is characterized in that, organic solvent described in condensation reaction I is toluene, solvent load is 2 times of Tosyl chloride quality, the temperature of condensation reaction I is 110-120 DEG C, return time is 2-3h, and condensation reaction I obtains the toluene solution of condenses I after terminating.
3. the synthetic method of a kind of cyhalofop-butyl according to claim 1, it is characterized in that, alkali described in etherification reaction is liquid caustic soda, consumption is 1.6 times of condenses I quality, and the temperature of etherification reaction is 50-60 DEG C, and the reaction times is 8-9h, after etherification reaction terminates, add water washing, the organic layer underpressure distillation obtained removes desolventizing, the etherification product obtained.
4. the synthetic method of a kind of cyhalofop-butyl according to claim 1, it is characterized in that, organic solvent described in salt-forming reaction is DMF, solvent load is 2 times of etherification product quality, described alkali is solid potassium hydroxide, consumption is 1.6 times of etherification product quality, and the temperature of salt-forming reaction is 100-110 DEG C, obtains etherate salt after reflux dewatering.
5. the synthetic method of a kind of cyhalofop-butyl according to claim 1, it is characterized in that, the temperature of reaction of condensation reaction II is 100-110 DEG C, reaction times is 15-16h, after condensation reaction II terminates, lower the temperature except after desalting, remove organic solvent under reduced pressure, residue from ethanol recrystallization obtains cyhalofop-butyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510137411.XA CN104803883A (en) | 2015-03-27 | 2015-03-27 | Synthesis method of cyhalofop-butyl |
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| CN201510137411.XA CN104803883A (en) | 2015-03-27 | 2015-03-27 | Synthesis method of cyhalofop-butyl |
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| CN201510137411.XA Pending CN104803883A (en) | 2015-03-27 | 2015-03-27 | Synthesis method of cyhalofop-butyl |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105601538A (en) * | 2016-02-02 | 2016-05-25 | 江苏丰山集团股份有限公司 | Preparation method of cyhalofop-butyl |
| CN107253912A (en) * | 2017-05-02 | 2017-10-17 | 江苏永凯化学有限公司 | The synthetic method of cyhalofop-butyl |
| CN109053443A (en) * | 2018-08-06 | 2018-12-21 | 杭州华东医药集团浙江华义制药有限公司 | The bromo- 3- aldehyde radical-phenoxy group of 4-(4-)-benzonitrile synthetic method |
-
2015
- 2015-03-27 CN CN201510137411.XA patent/CN104803883A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105601538A (en) * | 2016-02-02 | 2016-05-25 | 江苏丰山集团股份有限公司 | Preparation method of cyhalofop-butyl |
| CN105601538B (en) * | 2016-02-02 | 2018-01-23 | 江苏丰山集团股份有限公司 | A kind of preparation method of cyhalofop-butyl |
| CN107253912A (en) * | 2017-05-02 | 2017-10-17 | 江苏永凯化学有限公司 | The synthetic method of cyhalofop-butyl |
| CN107253912B (en) * | 2017-05-02 | 2020-07-31 | 江苏永凯化学有限公司 | Synthetic method of cyhalofop-butyl |
| CN109053443A (en) * | 2018-08-06 | 2018-12-21 | 杭州华东医药集团浙江华义制药有限公司 | The bromo- 3- aldehyde radical-phenoxy group of 4-(4-)-benzonitrile synthetic method |
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Application publication date: 20150729 |