CN103483199B - Preparation method of tetrafluoroterephthalate - Google Patents
Preparation method of tetrafluoroterephthalate Download PDFInfo
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- CN103483199B CN103483199B CN201310391519.2A CN201310391519A CN103483199B CN 103483199 B CN103483199 B CN 103483199B CN 201310391519 A CN201310391519 A CN 201310391519A CN 103483199 B CN103483199 B CN 103483199B
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- tetrafluoroterephthalate
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- 0 CC(C(C(C(*)C(CP)P)P)P)C#N Chemical compound CC(C(C(C(*)C(CP)P)P)P)C#N 0.000 description 3
- UUSODXRMARGLBX-UHFFFAOYSA-N NC1CC=CCC1 Chemical compound NC1CC=CCC1 UUSODXRMARGLBX-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/18—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group
- C07C67/22—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group from nitriles
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of tetrafluoroterephthalate, which comprises the following steps: reacting raw materials tetrafluoro-para-phthalonitrile and lower alcohol in a perfluor solvent at 0-60 DEG C by using trichloro-sym-triazine as a catalyst, and separating to obtain the tetrafluoroterephthalate. In the technique, the amount of the lower alcohol is only 5-10% more, the product high is yield, and the perfluor solvent is easy to recover and high in recovery rate. Compared with the existing preparation method, the preparation method disclosed by the invention has the characteristics of mild reaction conditions, high product yield, low production cost, fewer three wastes and the like, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of fine-chemical intermediate, particularly a kind of preparation method of pesticide intermediate tetrafluoroterephthalate.
Background technology
Tetrafluoroterephthalate is one of key intermediate of synthesis tetrafluoro terephthalyl alcohol, and tetrafluoro terephthalyl alcohol is the important source material of pyrethroid insecticides metofluthrin (metofluthrin), tefluthrin (tefluthrin) and the third Flumethrin (profluthrin) etc.
Metofluthrin is the High-efficiency mosquito eradication agent of Sumitomo company exploitation listing in 2005.This medicament volatility is high and insecticidal activity is distinguished, it is tens to tens times of medicament of evapotranspiring at present to the drug effect of various mosquito, battery type mosquito-repellent incense, vaporizer mosquito liquid, folding master mode and resin can be made to evapotranspire the products such as preparation, also can make the portable kill mosquito utensil in field.Tefluthrin is the pyrethroid insecticides of ICI company exploitation in 1986, mainly as soil insecticide, effectively can prevent and treat Coleoptera and the phosphorus wing order inhabited in soil and some Diptera pest, be applicable to the crop such as corn, beet.
The principal synthetic routes of existing tetrafluoroterephthalate is as follows:
1. tetrafluoro terephthalonitrile obtains tetrafluoroterephthalate through hydrolysis, chloride and esterification three-step reaction.This syntheti c route step is various, and the corrodibility of hydrolysis, chlorination reaction is large, and seriously polluted, need use acid binding agent during esterification, total recovery is low.
2. tetrafluoro terephthalonitrile obtains tetrafluoro terephthalic acid through hydrolysis, and then direct under catalysis and alcohol esterification obtains tetrafluoroterephthalate.This syntheti c route shortens a step than front method, but hydrolysis, esterification all need to use the stronger hydrochloric acid, sulfuric acid etc. of corrodibility be catalyzer, and large usage quantity, hydrolysis spent acid amount is large, and alcohol is much excessive, and yield and loss all comparatively seriously, are not suitable for suitability for industrialized production.
3. Chinese patent CN 1458137 reports that tetrachloro-p-phenylene's dimethyl chloride is fluoridized through Potassium monofluoride, esterification obtains tetrafluoroterephthalate.This preparation method's cost of material is low, but Potassium monofluoride fluoridation technical difficulty is high, needs to use phase-transfer catalyst and strong polar aprotic solvent etc., and serious three wastes, esterification has the hydrogen fluoride of severe corrosive to release, and has particular requirement to equipment.
Sum up above route, the main raw material of preparation tetrafluoroterephthalate is tetrafluoro terephthalonitrile or tetrachloro-p-phenylene's dimethyl chloride, these synthetic methods all need two steps or three-step reaction, there is cost high, serious three wastes, the shortcomings such as production security difference, thus find simple to operate, cost is low, the synthesis technique of security and the good tetrafluoroterephthalate of the feature of environmental protection has important practical significance.
Summary of the invention
In order to overcome the shortcomings such as tetrafluoroterephthalate complicated process of preparation in prior art, cost be high, seriously polluted, the invention provides a kind of novel method preparing tetrafluoroterephthalate.
It is raw material that the present invention proposes with tetrafluoro terephthalonitrile, prepares tetrafluoroterephthalate through direct catalytic esterification single step reaction.Synthetic route of the present invention is as follows:
Be that a classical functional group conversions reacts by nitrile and the direct step lactate synthesis ester of alcohol, there are following three principal features: 1) alcohol is greatly excessive, more than 5 times of consumption nitrile often, double as solvent; 2) with hydrochloric acid or sulfuric acid for catalyzer, and large usage quantity, general mol ratio is more than 20%; 3) temperature of reaction is higher, is generally 30 DEG C-100 DEG C.Although therefore this reaction is widely known by the people, there is obvious defect: greatly, material consumption energy consumption is large, and production efficiency is low for the yield of alcohol and waste; Catalyst levels is large, and corrodibility is large, and wastewater flow rate is large; Temperature of reaction is higher, and energy consumption is high.
The reaction defect of ester is converted into for nitrile, in conjunction with the feature that the alkalescence of tetrafluoro terephthalonitrile nitrogen is more weak, the condition such as catalyzer, solvent of applicant to reaction has carried out a large amount of experimental studies, discovery trichloro-triazine is combined with perfluoro solvent has outstanding advantage, specific in the direct esterification reaction of tetrafluoro terephthalonitrile, have catalyzer (for nitrile 0.01-0.05 doubly) and alcohol (more excessive than nitrile 10%) consumption little, reaction efficiency is high, the advantages such as temperature of reaction is low, and aftertreatment is simple.
The preparation method of the tetrafluoroterephthalate that the present invention proposes, it is characterized in that taking trichloro-triazine as catalyzer, tetrafluoro terephthalonitrile and lower alcohol react 3-12 hour in 0 DEG C-60 DEG C in perfluoro solvent, and separation and purification obtains tetrafluoroterephthalate.
Lower alcohol described in the application refers to that carbonatoms is the saturated unitary fatty alcohol of 1-4, and preferred alcohol is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol and sec-butyl alcohol.
In above-mentioned reaction, the preferred perfluoroolefine of described perfluoro solvent, research finds, carbon number perfluoroolefine boiling point is very little too low, reaction inconvenience, and loss is very large, and the too high perfluoroolefine boiling point of carbon number is higher, and cost recovery is high, therefore, the preferred C of perfluoro solvent
6-C
12perfluoroolefine, particularly preferably hexafluoropropylene trimer (perfluorinated nonene) and tetrafluoroethylene pentamer.
In above-mentioned reaction, the preferred 2.0-2.2:1.0 of mol ratio of lower alcohol and tetrafluoro terephthalonitrile; The preferred 1.5-4.0:1.0 of mol ratio of perfluoro solvent and tetrafluoro terephthalonitrile; The preferred 0.01-0.05:1.0 of mol ratio of trichloro-triazine and tetrafluoro terephthalonitrile.
The present invention take tetrafluoro terephthalonitrile as raw material, through obtaining tetrafluoroterephthalate with lower alcohol direct esterification under trichloro-triazine catalysis, and be solvent with perfluoroolefine, the advantages such as synthesis technique has reaction conditions gentleness, raw material is easy to get, with low cost, equipment requirements is low, production efficiency is high, the three wastes are few, security is good, have good industrial prospect.
Embodiment
Following instance chemical feedstocks used, solvent etc. are technical grade product, without being further purified.
embodiment 1 tetrafluoro terephthalonitrile prepares dimethyl tetrafluoroterephthalate
Tetrafluoro terephthalonitrile 20.0g (0.1mol), trichloro-triazine 200mg, 6.8g (0.21mol) methyl alcohol and 70mL perfluorinated nonene are in 60 DEG C of reaction 3h, remove perfluorinated nonene under reduced pressure, cooling, add 100mL water and stir 2h, suction filtration, is washed to pH ≈ 7, and drying obtains dimethyl tetrafluoroterephthalate 25.9g, yield 97.4%, content (high performance liquid chromatography and HPLC method) 98.3%.
embodiment 2 tetrafluoro terephthalonitrile prepares tetrafluoro diethyl terephthalate
Tetrafluoro terephthalonitrile 20.0g (0.1mol), trichloro-triazine 600mg, 10.1g (0.22mol) ethanol and 60mL tetrafluoroethylene pentamer are in 20 DEG C of reaction 6h, remove tetrafluoroethylene pentamer under reduced pressure, cooling, add 100mL water and stir 2h, suction filtration, is washed to pH ≈ 7, and drying obtains tetrafluoro diethyl terephthalate 28.8g, yield 98.0%, content (HPLC method) 97.6%.
embodiment 3 tetrafluoro terephthalonitrile prepares dimethyl tetrafluoroterephthalate
Tetrafluoro terephthalonitrile 20.0g (0.1mol), trichloro-triazine 800mg, 7.0g (0.22mol) methyl alcohol and 50mL perfluorinated nonene are in 40 DEG C of reaction 8h, remove perfluorinated nonene under reduced pressure, cooling, add 100mL water and stir 2h, suction filtration, is washed to pH ≈ 7, and drying obtains dimethyl tetrafluoroterephthalate 25.3g, yield 95.1%, content (HPLC method) 98.8%.
embodiment 4 tetrafluoro terephthalonitrile prepares tetrafluoro di-n-butyl terephthalate
Tetrafluoro terephthalonitrile 20.0g (0.1mol), trichloro-triazine 400mg, 15.5g (0.21mol) propyl carbinol and 80mL perfluorinated nonene are in 0 DEG C of reaction 10h, remove perfluorinated nonene under reduced pressure, cooling, add 100mL water and stir 2h, suction filtration, is washed to pH ≈ 7, and drying obtains tetrafluoro di-n-butyl terephthalate 33.8g, yield 96.6%, content (HPLC method) 98.2%.
comparative example 1 tetrafluoro terephthalonitrile prepares dimethyl tetrafluoroterephthalate
Tetrafluoro terephthalonitrile 20.0g (0.1mol), vitriol oil 2.0g and 80mL methanol eddy reaction 16h, remove methyl alcohol under reduced pressure, cooling, add 200mL water and stir 2h, suction filtration, is washed to pH ≈ 7, and drying obtains dimethyl tetrafluoroterephthalate 23.6g, yield 88.7%, content (HPLC method) 97.8%.
comparative example 2 tetrafluoro terephthalonitrile prepares tetrafluoro terephthalic acid diisopropyl ester
Tetrafluoro terephthalonitrile 20.0g (0.1mol), methylsulfonic acid 1.2g, 13.2g (0.22mol) Virahol and 60mL perfluorinated nonene are in 50 DEG C of reaction 6h, remove perfluorinated nonene under reduced pressure, cooling, add 200mL water and stir 2h, suction filtration, is washed to pH ≈ 7, and drying obtains tetrafluoro terephthalic acid diisopropyl ester 25.8g, yield 80.1%, content (HPLC method) 96.5%.
comparative example 3 tetrafluoro terephthalonitrile prepares tetrafluoro diethyl terephthalate
Tetrafluoro terephthalonitrile 20.0g (0.1mol), trichloro-triazine 800mg and 80mL alcohol reflux reaction 12h, remove ethanol under reduced pressure, cooling, add 200mL water and stir 2h, suction filtration, is washed to pH ≈ 7, and drying obtains tetrafluoro diethyl terephthalate 24.6g, yield 83.7%, content (HPLC method) 95.8%.
The technician of the industry should be appreciated that, the present invention is not restricted to the described embodiments, describe in above-described embodiment and specification sheets just in order to principle of the present invention is described.Without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, and these all fall in the scope of protection of present invention.
Claims (3)
1. the preparation method of a tetrafluoroterephthalate, it is characterized in that: take trichloro-triazine as catalyzer, tetrafluoro terephthalonitrile and lower alcohol react 3-12 hour in 0 DEG C-60 DEG C in perfluoro solvent, remove perfluoro solvent under reduced pressure, cooling, add water stirring, suction filtration, be washed to pH ≈ 7, drying obtains tetrafluoroterephthalate, wherein said lower alcohol is the saturated unitary fatty alcohol containing 1 to 4 carbon atom, and described perfluoro solvent is perfluorinated nonene or tetrafluoroethylene pentamer.
2. the preparation method of tetrafluoroterephthalate as claimed in claim 1, is characterized in that: described lower alcohol is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol and sec-butyl alcohol.
3. the preparation method of tetrafluoroterephthalate as claimed in claim 1, it is characterized in that: the mol ratio of lower alcohol and tetrafluoro terephthalonitrile is 2.0-2.2:1.0, the mol ratio of perfluoro solvent and tetrafluoro terephthalonitrile is 1.5-4.0:1.0, and the mol ratio of trichloro-triazine and tetrafluoro terephthalonitrile is 0.01-0.05:1.0.
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| CN111909035B (en) * | 2020-08-18 | 2024-01-16 | 周敏 | Preparation method of tetrafluoroterephthalic acid for reducing waste emission |
| CN114835558A (en) * | 2022-04-22 | 2022-08-02 | 苏州亚科科技股份有限公司 | Preparation process of 2,3,5, 6-tetrafluoro terephthalyl alcohol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1575260A (en) * | 1977-04-29 | 1980-09-17 | Lummus Co | Production of esters from nitrile |
| CN102432470A (en) * | 2010-09-29 | 2012-05-02 | 蒙健 | Novel production process of chlorthal |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1575260A (en) * | 1977-04-29 | 1980-09-17 | Lummus Co | Production of esters from nitrile |
| CN102432470A (en) * | 2010-09-29 | 2012-05-02 | 蒙健 | Novel production process of chlorthal |
Non-Patent Citations (3)
| Title |
|---|
| 三聚氯氰在催化有机合成中的应用;温飞等;《精细石油化工》;20071130;第24卷(第6期);第71－75页 * |
| 汪朝阳等.全氟溶剂.《绿色化学通用教程》.2007,第36页. * |
| 田兆军等.2-氟-6-甲氧基苯甲酸的合成.《氟化工》.2011,第18卷(第6期),第4-5页. * |
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Address after: 324000 Quzhou province high tech Industrial Park, Huayang Road, No. 36, Zhejiang Patentee after: Zhejiang Hisun pharmaceutical Limited by Share Ltd Address before: 324004 Zhejiang province Quzhou Huayang Road, hi tech Industrial Park, No. 36 Patentee before: ZHEJIANG CHEMSYN PHARM. CO., LTD. |