CN105503582A - Continuous production method for trifluoro monochloro chrysanthemic acid - Google Patents
Continuous production method for trifluoro monochloro chrysanthemic acid Download PDFInfo
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- CN105503582A CN105503582A CN201410491735.9A CN201410491735A CN105503582A CN 105503582 A CN105503582 A CN 105503582A CN 201410491735 A CN201410491735 A CN 201410491735A CN 105503582 A CN105503582 A CN 105503582A
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Abstract
The invention discloses a continuous production method for trifluoro monochloro chrysanthemic acid. The method includes the steps of (1) performing an addition reaction to prepare 3,3-dimethyl-4,6,6-trichloro-7,7,7-trifluoro heptylic acid ester with 3,3-dimethyl-4-pentenoic acid methyl ester and trifluorotrichloroethane as initial raw materials; (2) performing a cyclization reaction with sodium tert-butoxide to generate cis(trans)-3-(2,2-dichloro-3,3,3-trifluoropropyl)-2,2-dimethyl cyclocarboxylate; and (3) performing a saponification reaction to prepare 3-(2-chloro-3,3,3-trifluoro-propylene-1-yl)-2,2-dimethylcyclopropane carboxylic acid, namely, the trifluoro monochloro chrysanthemic acid. In the invention, continuous control is employed in the production method, so that the method is simple in process, is high in equipment utilization, is high in yield and stable in quality of products, is low in production cost and has a wide application prospect.
Description
Technical field
The present invention relates to a kind of preparation method of compound, be specifically related to the continuous production method of trifluoro one chlorine chrysanthemumic acid.
Background technology
Trifluoro one chlorine chrysanthemumic acid has another name called time acid, chemical name is 3-(chloro-3,3, the 3-tri-fluoro-propylene-1-bases of 2-)-2,2-dimethyl cyclopropane carboxylic acid is the important intermediate of the pyrethroids such as cyhalothrin, bifenthrin, seven fluorobenzene chrysanthemum esters, seven fluorine s.
Structural formula is as follows:
Domestic current production method is with 3,3-dimethyl-4-pentenoic acid methyl ester and Freon 113 for starting raw material, through addition, cyclisation, saponification, acidification reaction, then through extraction, freezing, refining, dry and obtain trifluoro one chlorine chrysanthemumic acid.Domestic prior art all adopts interval synthesis technique, addition reaction adopts cuprous chloride, Monoethanolamine MEA BASF is catalyzer, addition reaction produces catalyzer tar, need through layering, distillation, washing, the multiple working procedures such as distillation obtain affixture, addition, cyclization causes system moisture content to increase because interrupter method synthesizes, speed of response is slow, by product increases, product yield and quality obviously decline, reclaim starting material cannot use, saponification is reacted in methanol system, the saponification reaction time is long, crude product trifluoro one chlorine chrysanthemumic acid yields poorly, Methanol Recovery loss is large, adopt batch production method, production cycle is long, yield poorly, unstable product quality, energy consumption is large, raw material consumption is high, production cost is high, be unfavorable for large-scale production.
Summary of the invention
The present invention overcomes the many production unfavorable factors of batch production method; provide the production method that a kind of trifluoro one chlorine chrysanthemumic acid is better; by continuous production method Simplified flowsheet step; shorten life cycle of the product; reduce facility investment, reduce production cost, improve trifluoro one chlorine chrysanthemumic acid quality product and output; providing one more rationally easy, is the method being more conducive to the large-scale production of trifluoro one chlorine chrysanthemumic acid.
Realizing technical scheme of the present invention is:
A kind of trifluoro one chlorine chrysanthemumic acid continuous production method, obtains chloro-7,7, the 7-trifluoro heptanoates of 3,3-dimethyl-4,6,6-tri-with 3,3-dimethyl-4-pentenoic acid methyl ester and Freon 113 for starting raw material is produced through addition reaction; Produce obtained along trans-3-(chloro-3,3, the 3-trifluoro propyls of 2,2-bis-)-2,2-diformazan basic ring carboxylicesterss through cyclization with potassium tert.-butoxide again; Last and potassium hydroxide produces obtained 3-(chloro-3,3, the 3-tri-fluoro-propylene-1-bases of 2-)-2,2-dimethyl cyclopropane carboxylic acids, i.e. trifluoro one chlorine chrysanthemumic acid through saponification reaction.
Described addition reaction medium is the trimethyl carbinol, and addition reaction catalyst is benzoyl peroxide, and described reaction exists
Material of being back to back in pipeline reactor reacts.After completion of the reaction, material obtains chloro-7,7, the 7-trifluoro heptanoates of 3,3-dimethyl-4,6,6-tri-after rectifying tower is continuously separated.
In described addition reaction, the molar ratio of 3,3-dimethyl-4-pentenoic acid methyl ester, Freon 113, catalyzer benzoyl peroxide is 1:1.35:0.05, and addition reaction pressure is 0.35MPa.
Described cyclization medium is DMF, and temperature of reaction is-15 DEG C.After completion of the reaction, material is separated through continuous rectification and obtains along trans-3-(chloro-3,3, the 3-trifluoro propyls of 2,2-bis-)-2,2-diformazan basic ring carboxylicesterss.
In described cyclization, the mol ratio of chloro-7,7, the 7-trifluoro heptanoates of 3,3-dimethyl-4,6,6-tri-and potassium tert.-butoxide is 1:1.18.
Described saponification reaction catalyzer is Tetrabutyl amonium bromide.Reaction terminates rear material through hcl acidifying, solvent extraction, refines, dries to obtain 3-(chloro-3,3, the 3-tri-fluoro-propylene-1-bases of 2-)-2,2-dimethyl cyclopropane carboxylic acids, i.e. trifluoro one chlorine chrysanthemumic acid.Along trans-3-(chloro-3,3, the 3-trifluoro propyls of 2,2-bis-)-2,2-diformazan basic ring carboxylicesterss in described saponification reaction: potassium hydroxide: catalyzer (Tetrabutyl amonium bromide) mol ratio is 1:2.8:0.02.
Compared with prior art, its remarkable advantage is in the present invention:
1, addition reaction of the present invention adopts BPO initiator to be single catalyst, reduces production cost.
2, adopt BPO initiator be catalyzer without the need to being separated, need the technological process of productions such as layering, washing, precipitation, Simplified flowsheet step when to avoid with cuprous chloride and Monoethanolamine MEA BASF complex compound be catalyzer.
3, cyclization is owing to adopting continuous loop reaction, and changing rhythmic reaction is continuously feeding continuous discharge, and shorten the cyclization cycle, equipment investment significantly reduces.
4, cyclization adopts continuously feeding, seals and do not contact with air in process, and reduce and cause producing side reaction because batch production operating process material absorbs moisture content, quality product yield all improves a lot.
5, saponification adopts duct type reaction, successive reaction, and continuously acidizing is refined, and shorten activity time, saponification equipment investment significantly reduces.
6, saponification is without methanol as solvent, and employing Tetrabutyl amonium bromide is catalyzer, improves reactive behavior, and greatly shorten the saponification reaction time, output is doubled and redoubled, and reduces Methanol Recovery operation simultaneously, avoids methanol loss.
7, trifluoro one chlorine chrysanthemumic acid adopts continuous production method, has simplified production craft step, has shortened life cycle of the product, decreased production unit, and reduce by product and produce, unit consumption of product has had and significantly declines, and improves product production and quality,
Comprehensive benefit is remarkable.
Embodiment
Continuous prodution trifluoro one chlorine chrysanthemumic acid method, the method, comprises the following steps for starting raw material with 3,3-dimethyl-4-pentenoic acid methyl ester and Freon 113:
A) respectively from tank field by 3,3-dimethyl-4-pentenoic acid methyl ester, Freon 113, the trimethyl carbinol, BPO (benzoyl peroxide) is metered into static mixer with mass flowmeter, again by pipeline reactor reacting by heating, control reactant system pressure at 0 ~ 0.35MPa, temperature reacts completely at 60 ~ 120 DEG C.Then adopt rectifying tower continuous rectification to be separated, obtain affixture.Reaction formula is:
B) respectively from tank field by chloro-for 4,6,6-tri-7, fluoro-3, the 3-dimethyl-g acid esters of 7,7-tri-and sodium tert-butoxide, DMF mass flowmeter measure and under-15 DEG C of conditions, carry out cyclization by loop reactor in proportion, reactant is continuous in rectifying separation again, obtains cyclisation thing.Reaction formula is:
C) by 3-(2,2-bis-chloro-3,3,3-trifluoro propyl)-2,2-diformazan basic ring carboxylicesters (cyclisation thing) and liquid caustic soda, carry out saponification reaction in the presence of a catalyst, and reactant is obtained trifluoro one chlorine chrysanthemumic acid after continuously acidizing, extraction, freezing and crystallizing, press filtration, oven dry.Reaction formula is:
In above synthetic method, 3,3-dimethyl-4-pentenoic acid methyl ester: Freon 113: BPO=1:1.5:0.015 (mol ratio); Affixture: potassium tert.-butoxide=1:1.18 (mol ratio); Cyclisation thing: sodium hydroxide: in catalyzer=1:2.8:0.02 (mol ratio) the present invention, content is mass percent.In this specification sheets, all raw materials are commercially available technical grade.
Below in conjunction with specific embodiment, the present invention is described in further detail
Embodiment 1
The synthetic method of trifluoro one chlorine chrysanthemumic acid comprises the following steps:
A) continuous production method of 4,6,6-tri-chloro-7,7,7-tri-fluoro-3,3-dimethyl-g acid esters (affixture):
Respectively 3,3-dimethyl-4-pentenoic acid methyl ester, Freon 113, catalyst B PO, the trimethyl carbinol are pressed 1:1.5:0.015:2 (molar ratio) from tank area, first control to be metered into static mixer by respective pipeline with mass flowmeter, mix.With product pump, addition raw mixture material is pumped into heating and thermal insulation reaction in pipeline reactor again, control reaction pressure≤0.35MPa, temperature of reaction≤115 DEG C, 3,3-dimethyl-4-pentenoic acid methyl ester content≤0.2% in on-line period analytical reaction material, determines the reactant pipeline reactor residence time, after on-line period detection is qualified, continuous discharge is to tundish, then rectifying is continuously separated F113, the trimethyl carbinol, obtains heavy constituent addition reaction product at the bottom of tower continuously.Adduct content >=97.5%, pale yellow oily liquid body, yield >=99%, boiling point 134 ~ 136 DEG C/6mmHg (literature value 132 ~ 137 DEG C/6mmHg).
B) along the continuous production method of trans-3-(chloro-3,3, the 3-trifluoro propyls of 2,2-bis-)-2,2-diformazan basic ring carboxylicesters (cyclisation thing):
Measure addition reaction from tank field with mass flowmeter respectively, sodium tert-butoxide, DMF presses 1:1.15:2.5 (mol ratio), loop reactor is entered respectively by after 0 ~ 15 DEG C of heat exchanger cooling, continuously feeding is carried out in reaction, regulate optimum reflux ratio value, on-line checkingi, cyclized by treatment thing content≤0.2% of self-actuated sampler sampling analysis reaction mass, by in cyclization material continuous discharge to pre-thermal buffer, after preheating, rectifying is continuously separated the trimethyl carbinol, DMF, continuous discharge at the bottom of tower obtains yellow oily heavies liquid along trans-3-(2, 2-bis-chloro-3, 3, 3-trifluoro propyl)-2, 2-diformazan basic ring carboxylicesters (cyclization thing), yield >=97%, along inverse ratio >=90%.
The continuous production method of trifluoro one chlorine chrysanthemumic acid:
C) respectively from tank field by cyclization thing, potassium hydroxide, catalyzer (Tetrabutyl amonium bromide) is by 1:2.8:0.02 (mol ratio), mixed by static mixer with under meter, mixed solution adds in pipeline reactor and is heated to 85 ~ 105 DEG C of reactions by continuous product pump, the cyclized by treatment thing < 0.1% of on-line checkingi analytical reaction material, cyclization thing is fully saponified, reaction solution is to tundish, again by static mixer continuously with hcl acidifying to pH=3, continuous extraction, be separated, crystallization, dry, pack to obtain trifluoro one chlorine chrysanthemumic acid fine work, content >=99% (liquid spectrometry), gas spectrum content >=99.8%mp:111.4 ~ 112.0 DEG C (reference value mp110.2 ~ 111.5 DEG C).
Reference examples
Batch production trifluoro one chlorine chrysanthemumic acid method:
A) addition reaction preparation:
Add 3,3-dimethyl-4-pentenoic acid methyl ester, Refrigerant R 113, Monoethanolamine MEA BASF, cuprous chloride, the trimethyl carbinol in 2000ml stainless steel pressure still, be stirred and heated to 120 DEG C, react 8 hours, sampling analysis is qualified, cooling, layering, distillation, washing, redistillation removes moisture content, obtains addition reaction.
B) preparation of cyclization thing:
400 grams of trimethyl carbinols, 150 grams of DMF, 65 grams of sodium tert-butoxides are added in 1000ml reaction flask, stir freezing under in--10 DEG C, drip addition reaction 150 grams, drip off the qualified end reaction of sampling analysis in a hour, vacuum distillation recovered solvent (applying mechanically after removing moisture content), then wash distillation and obtain cyclization thing 135 grams.
C) preparation of trifluoro one chlorine chrysanthemumic acid
100 grams of cyclization things are added in 1000ml reaction flask, 100 grams of methyl alcohol, reflux adds 260 grams of liquid caustic soda in batches, reflux 24 hours, react complete, methyl alcohol is reclaimed in underpressure distillation, and add water hcl acidifying PH=3, suction filtration obtains trifluoro one chlorine chrysanthemumic acid crude product, then obtains fine work trifluoro one chlorine chrysanthemumic acid with refining methanol.
Claims (10)
1. a trifluoro one chlorine chrysanthemumic acid continuous production method, is characterized in that: with 3,3-dimethyl-4-pentenoic acid methyl ester and Freon 113 for starting raw material obtains chloro-7,7, the 7-trifluoro heptanoates of 3,3-dimethyl-4,6,6-tri-through addition reaction; Obtain along trans-3-(chloro-3,3, the 3-trifluoro propyls of 2,2-bis-)-2,2-diformazan basic ring carboxylicesterss with sodium tert-butoxide through cyclization again; Last saponification reaction obtains 3-(chloro-3,3, the 3-tri-fluoro-propylene-1-bases of 2-)-2,2-dimethyl cyclopropane carboxylic acids, i.e. trifluoro one chlorine chrysanthemumic acid.
2. trifluoro one chlorine chrysanthemumic acid continuous production method according to claim 1, it is characterized in that: described addition reaction medium is the trimethyl carbinol, addition reaction catalyst is benzoyl peroxide, and described successive reaction is carried out continuously in pipeline reactor.
3. trifluoro one chlorine chrysanthemumic acid continuous production method according to claim 1, is characterized in that: after described addition reaction, and material rectifying is continuously separated and obtains chloro-7,7, the 7-trifluoro heptanoates of 3,3-dimethyl-4,6,6-tri-.
4. trifluoro one chlorine chrysanthemumic acid continuous production method according to claim 1, it is characterized in that: in described addition reaction, the molar ratio of 3,3-dimethyl-4-pentenoic acid methyl ester, Freon 113, catalyzer (benzoyl peroxide) is 1:1.35:0.01 ~ 0.05, and reaction pressure is 0.35MPa.
5. trifluoro one chlorine chrysanthemumic acid continuous production method according to claim 1, is characterized in that: described cyclization medium is potassium tert.-butoxide, and temperature of reaction is-15 DEG C.
6. trifluoro one chlorine chrysanthemumic acid continuous production method according to claim 1, is characterized in that: after described cyclization, and material continuous rectification is separated and obtains along trans-3-(chloro-3,3, the 3-trifluoro propyls of 2,2-bis-)-2,2-diformazan basic ring carboxylicesterss.
7. trifluoro one chlorine chrysanthemumic acid continuous production method according to claim 1, is characterized in that: in described cyclization, the mol ratio of chloro-7,7, the 7-trifluoro heptanoates of 3,3-dimethyl-4,6,6-tri-and potassium tert.-butoxide is 1:1.18.
8. trifluoro one chlorine chrysanthemumic acid continuous production method according to claim 1, is characterized in that: described saponification reaction catalyzer is Tetrabutyl amonium bromide.
9. trifluoro one chlorine chrysanthemumic acid continuous production method according to claim 1, it is characterized in that: described saponification reaction terminates rear material through hcl acidifying, solvent extraction, refine, dry to obtain 3-(2-chloro-3,3,3-tri-fluoro-propylene-1-base)-2,2-dimethyl cyclopropane carboxylic acids, i.e. trifluoro one chlorine chrysanthemumic acid.
10. trifluoro one chlorine chrysanthemumic acid continuous production method according to claim 8, it is characterized in that: along trans-3-(2,2-bis-chloro-3,3 in described saponification reaction, 3-trifluoro propyl)-2,2-diformazan basic ring carboxylicesterss, potassium hydroxide, Tetrabutyl amonium bromide mol ratio be 1:2.8:0.02.
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Cited By (5)
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| CN106928051A (en) * | 2015-12-31 | 2017-07-07 | 江苏优士化学有限公司 | A kind of synthetic method of cis lanbda-cyhalothric acid |
| CN111116363A (en) * | 2019-12-27 | 2020-05-08 | 山东潍坊润丰化工股份有限公司 | Preparation method of carboxylic ester compound |
| CN112028772A (en) * | 2020-09-23 | 2020-12-04 | 江苏春江润田农化有限公司 | Preparation method of 4,6, 6-trichloro-7, 7, 7-trifluoro-3, 3-dimethyl methyl heptanoate |
| CN112661601A (en) * | 2020-12-31 | 2021-04-16 | 南京伟鑫生物医药有限公司 | Continuous production equipment for trifluoro monochloro chrysanthemic acid |
| CN115611706A (en) * | 2022-10-10 | 2023-01-17 | 安徽海顺化工有限公司 | Waste gas treatment process for producing trichloro-cyanic acid |
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Cited By (8)
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| CN106928051A (en) * | 2015-12-31 | 2017-07-07 | 江苏优士化学有限公司 | A kind of synthetic method of cis lanbda-cyhalothric acid |
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| CN112028772B (en) * | 2020-09-23 | 2021-09-28 | 江苏春江润田农化有限公司 | Preparation method of 4,6, 6-trichloro-7, 7, 7-trifluoro-3, 3-dimethyl methyl heptanoate |
| CN112661601A (en) * | 2020-12-31 | 2021-04-16 | 南京伟鑫生物医药有限公司 | Continuous production equipment for trifluoro monochloro chrysanthemic acid |
| CN115611706A (en) * | 2022-10-10 | 2023-01-17 | 安徽海顺化工有限公司 | Waste gas treatment process for producing trichloro-cyanic acid |
| CN115611706B (en) * | 2022-10-10 | 2023-10-27 | 安徽海顺化工有限公司 | Waste gas treatment process for producing trifluoro chlorocyanic acid |
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