CN106831361B - A kind of method that dihalo trifluoroethane prepares trifluoro vinyl virtue ether compound - Google Patents
A kind of method that dihalo trifluoroethane prepares trifluoro vinyl virtue ether compound Download PDFInfo
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- CN106831361B CN106831361B CN201510888230.0A CN201510888230A CN106831361B CN 106831361 B CN106831361 B CN 106831361B CN 201510888230 A CN201510888230 A CN 201510888230A CN 106831361 B CN106831361 B CN 106831361B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/24—Preparation of ethers by reactions not forming ether-oxygen bonds by elimination of halogens, e.g. elimination of HCl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/30—Hetero atoms other than halogen
- C07D333/32—Oxygen atoms
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Abstract
The present invention relates to a kind of methods for synthesizing trifluoro vinyl virtue ether compound, belong to the field of chemical synthesis.The present invention synthesizes trifluoro vinyl virtue ether compound using dihalo trifluoroethane as starting material with phenolic compound under the proper conditions.Synthetic method provided by the invention is compared with the traditional method, and has many advantages, such as that reaction condition is mild, easy to operate, yield is moderate, and because of its simple process, low in cost, pollution is small, is expected to realize industrialized production.
Description
Technical field
The present invention relates to a kind of synthetic methods of trifluoro vinyl virtue ether compound, belong to the field of chemical synthesis.
Background technique
It is general fluoropolymer-containing excellent in addition to having by the polymer of Material synthesis of trifluoro vinyl arylene ether compound
Outside performance, due to containing ehter bond flexible, and the dissolubility and meltbility for assigning it common fluoro-containing macromolecule material not having
(glass transition temperature is between 80~120 DEG C), solves the problems, such as common fluoro-containing macromolecule material poor processability, is used in combination
Interlayer insulating materials, the proton exchange membrane of fuel cell, the dielectric of wave guide, optical instrument coating, antigen on spacecraft
Coating and high-temperature lubricant of sub- oxygen etc..However, the synthetic method of trifluoro vinyl arylene ether compound exists instead at present
Answer condition harsh, complex procedures are tediously long, higher cost, it is difficult to the defects of realizing large-scale production.
In Organic fluoride industrial production, tetrafluoroethene is the important source material for producing fluororesin, fluorubber.Tetrafluoroethene generally passes through
Monochlorodifluoromethane cracking preparation, can also generate by-product-trifluoro second of 0.1%-0.2% or so simultaneously in cracking process
Alkene (Trifluoroethylene, abbreviation TrFE or HFC-1123).Trifluoro-ethylene and bromine addition can prepare dibromo trifluoroethane.
As can preparing trifluoro vinyl virtue ether compound as raw material for existing using the exhaust gas dibromo trifluoroethane that tetrafluoroethene generates
Production cost can be significantly reduced by having for manufacturing enterprise, realize large-scale production.
Summary of the invention
The present invention selects under the proper conditions using dihalo trifluoroethane and phenolic compound as starting material, using series connection
Method one-pot synthesis trifluoro vinyl virtue ether compound.This method is with universality is wide, reaction condition is mild, yield is moderate, work
The features such as skill is simple, low in cost, easy to operate.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of method that dihalo trifluoroethane prepares trifluoro vinyl virtue ether compound, includes the following steps:
(1) phenolic compound Ar-OH, alkali and solvent are added in reactor, heating reaction；
(2) dihalo trifluoroethane is added dropwise into gained systemStep is added after completion of dropwise addition into system
Suddenly the aqueous solution of alkali described in (1) obtains three to extract, dry, remove solvent, column chromatography or recrystallization after reaction
Fluoride-based virtue ether compound；
Wherein, Ar is selected from aromatic ring, heterocycle, condensed ring etc., and wherein aromatic hydrocarbons is monosubstituted or polysubstituted, substituent group H, aryl,
The substituent groups such as alkyl；
X1、X2Each independently represent Cl, Br, I.
In synthetic method of the present invention, the phenolic compound, dihalo trifluoroethane are those skilled in the art
What member was grasped can be achieved common compounds of the invention.Wherein, comprehensively considered based on the condition of production, phenol generalization of the present invention
Close the preferred phenol of object, 4- bromophenol, betanaphthol, thiophene -3- alcohol；The preferred dibromo trifluoroethane of the dihalo trifluoroethane, 1-
The chloro- iodo- 1,1,2- trifluoroethane of 2-.
The synthetic route of the preparation of above-mentioned trifluoro vinyl virtue ether compound is as follows:
In synthetic method of the present invention, in step (1), the alkali selection highly basic or weak base, in the present invention
It is preferred that the weak base such as the highly basic such as potassium hydroxide, sodium hydride, potassium tert-butoxide or sodium carbonate, triethylamine, potassium carbonate.
In synthetic method of the present invention, total dosage of alkali used is equivalent to 0.1~10 equivalent of phenolic compound, excellent
Select 2~3 equivalents, further preferred 2.5 equivalent；Wherein, in step (1), the dosage of alkali used is equivalent to phenolic compound
1.3~1.8 equivalents, preferably 1.5 equivalents；In step (2), what the dosage of alkali used was equivalent to phenolic compound 0.8~1.2 works as
Amount, preferably 1.0 equivalents.
In synthetic method of the present invention, in step (1), the solvent can be polarity or nonpolarity；It is preferred that DMSO, first
Benzene.
In synthetic method of the present invention, in step (1), mole of the phenolic compound and dihalo trifluoroethane
Feed ratio is 1:0.1~1:5, preferably 1:1.
Synthetic method of the present invention can be achieved in large temperature range, as reacted step (1) in can -20~
Occurring within the scope of 200 DEG C, reaction can occur within the scope of -20~100 DEG C in step (2), certainly under the conditions of temperature is lower,
Reaction time can accordingly extend or yield is lower.The ideal response condition of the method for the invention is determined through many experiments are as follows:
In step (1), reaction temperature is 90~110 DEG C；Reaction time is 5~7h；In step (2), before dihalo trifluoroethane is added dropwise
System temperature is controlled at 50~70 DEG C, preferably 60 DEG C, and temperature to reaction is maintained to terminate.
As a preferred embodiment of the present invention, the method for the trifluoro vinyl virtue ether compound, including walk as follows
It is rapid:
(1) phenolic compound Ar-OH, alkali and solvent are added in reactor, 90~110 DEG C are heated 5~6 hours；
(2) system temperature is reduced to 50~70 DEG C, and dihalo trifluoroethane is added dropwiseAdd step (1)
Described in alkali aqueous solution, to extract, dry, remove solvent after reaction, column chromatography or recrystallization, i.e. acquisition trifluoro-ethylene
Base virtue ether compound.
Compared with prior art, the present invention reaction condition it is simpler it is mild, yield is moderate, simple process, it is easy to operate,
It is at low cost, environmental pollution is small, be expected to realize industrialization large-scale production.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
The synthesis of 1 trifluoro vinyl phenylate (3a) of embodiment
A kind of method that dihalo trifluoroethane prepares trifluoro vinyl virtue ether compound, includes the following steps:
(1) phenol 9.4g, potassium hydroxide 8.4g, solvent polarity solvent DMSO 200mL are added in reactor, 100
DEG C reaction 6 hours；
(2) system is cooled to 60 DEG C, dibromo trifluoroethane 24.1g is added dropwise, property addition quality is dense again for completion of dropwise addition
40% potassium hydroxide aqueous solution 17ml is spent, extracts after reaction, is dry, removing DMSO, being purified to obtain nothing with column chromatography method
Color liquid trifluoro vinyl phenylate (3a) (13g), yield 76%.
The synthesis of the bromo- 4- of 2 1- of embodiment (trifluoro vinyl oxygroup) benzene (3b)
It is prepared using method same as Example 1, difference is:
1), phenol is replaced with to phenolic compound 4- bromophenol 17.2g；
2) dibromo trifluoroethane, is replaced with into the iodo- 1,1,2- trifluoroethane 24.4g of the chloro- 2- of 1-；
After reaction, the bromo- 4- of 1- (trifluoro vinyl oxygroup) benzene (3b), yield 72% are obtained.
The synthesis of 3 2- of embodiment (1,2,2- trifluoro vinyl oxygroup) naphthalene (3c)
It is prepared using method same as Example 1, difference is:
1), phenol is replaced with to phenolic compound betanaphthol (14.4g)；
After reaction, 2- (1,2,2- trifluoro vinyl oxygroup) naphthalene (3c), yield 75% are obtained.
The synthesis of 4 2- of embodiment (1,2,2- trifluoro vinyl oxygroup) thiophene (3d)
It is prepared using method same as Example 1, difference is:
1), phenol is replaced with to phenolic compound thiophene -3- alcohol (10g),
After reaction, 2- (1,2,2- trifluoro vinyl oxygroup) thiophene (3d), yield 56% are obtained.
The synthesis of 5 trifluoro vinyl phenylate (3a) of embodiment
It is prepared using method same as Example 1, difference is:
1) potassium hydroxide, is replaced with into weak base potassium carbonate；
Reaction terminates to obtain trifluoro vinyl phenylate (3a), yield 70%.
The synthesis of 6 trifluoro vinyl phenylate (3a) of embodiment
It is prepared using method same as Example 1, difference is:
1) potassium hydroxide dosage, is reduced to 0.84g；
Reaction terminates to obtain trifluoro vinyl phenylate (3a), yield 6%.
The synthesis of 7 trifluoro vinyl phenylate (3a) of embodiment
It is prepared using method same as Example 1, difference is:
1) potassium hydroxide dosage, is increased into 84g；
Reaction terminates to obtain trifluoro vinyl phenylate (3a), yield 76%.
The synthesis of 8 trifluoro vinyl phenylate (3a) of embodiment
It is prepared using method same as Example 1, difference is:
1) polar solvent DMSO, is replaced with into nonpolar solvent toluene；
Reaction terminates to obtain trifluoro vinyl phenylate (3a), yield 74%.
The synthesis of 9 trifluoro vinyl phenylate (3a) of embodiment
It is prepared using method same as Example 1, difference is:
1) reaction temperature in step 1), is down to -20 DEG C；
Reaction terminates to obtain trifluoro vinyl phenylate (3a), yield 5%.
The synthesis of 10 trifluoro vinyl phenylate (3a) of embodiment
It is prepared using method same as Example 1, difference is:
1) reaction temperature in step 1), is increased to 200 DEG C；
Reaction terminates to obtain trifluoro vinyl phenylate (3a), yield 32%.
The synthesis of 11 trifluoro vinyl phenylate (3a) of embodiment
It is prepared using method same as Example 1, difference is:
1) reaction temperature in step 2), is reduced to -20 DEG C；
Reaction terminates to obtain trifluoro vinyl phenylate (3a), yield 13%.
The synthesis of 12 trifluoro vinyl phenylate (3a) of embodiment
It is prepared using method same as Example 1, difference is:
1), increasing reaction temperature in step 2) is 100 DEG C；
Reaction terminates to obtain trifluoro vinyl phenylate (3a), yield 63%.
The synthesis of 13 trifluoro vinyl phenylate (3a) of embodiment
It is prepared using method same as Example 1, difference is:
1) dibromo trifluoroethane dosage, is reduced to 0.24g；
Reaction terminates, and obtaining trifluoro vinyl phenylate (3a) is mark amount.
The synthesis of 14 trifluoro vinyl phenylate (3a) of embodiment
It is prepared using method same as Example 1, difference is:
1), dibromo trifluoroethane dosage is increased as 120g；
Reaction terminates, and obtaining trifluoro vinyl phenylate (3a) yield is 76%.
The synthesis of 15 trifluoro vinyl phenylate (3a) of embodiment
It is prepared using method same as Example 1, difference is:
1), the step 1) reaction time is shorten to 0.1 hour；
Reaction terminates, and obtaining trifluoro vinyl phenylate (3a) is mark amount.
The synthesis of 16 trifluoro vinyl phenylate (3a) of embodiment
It is prepared using method same as Example 1, difference is:
1), the step 1) reaction time is increased to 96 hours；
Reaction terminates, and obtaining trifluoro vinyl phenylate (3a) yield is 67%.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (7)
1. a kind of method that dihalo trifluoroethane prepares trifluoro vinyl virtue ether compound, which is characterized in that including as follows
Step:
(1) phenolic compound Ar-OH, alkali and solvent are added in reactor, heating reaction；
(2) dihalo trifluoroethane is added dropwise into gained systemStep is added after completion of dropwise addition into system
(1) aqueous solution of alkali described in, to extract, dry, remove solvent, column chromatography or recrystallization, i.e. acquisition trifluoro after reaction
Vinyl aromatic (co) ether compound；
Wherein, Ar is selected from aromatic ring, heterocycle, condensed ring, and wherein aromatic hydrocarbons is monosubstituted or polysubstituted, and substituent group H, aryl, alkyl take
Dai Ji；
X1、X2Each independently represent Cl, Br, I.
2. the method according to claim 1, wherein the phenolic compound is selected from phenol, 4- bromophenol, β-naphthalene
Phenol, thiophene -3- alcohol.
3. the method according to claim 1, wherein the dihalo trifluoroethane be selected from dibromo trifluoroethane,
The iodo- 1,1,2- trifluoroethane of the chloro- 2- of 1-.
4. method according to claim 1 to 3, which is characterized in that in step (1), the dosage of alkali used is equivalent to
The 1.3-1.8 equivalent of phenolic compound；In step (2), the 0.8-1.2 that the dosage of alkali used is equivalent to phenolic compound works as
Amount.
5. method according to claim 1 or 2, which is characterized in that in step (1), the solvent is selected from DMSO or toluene.
6. method according to claim 1 or 2, which is characterized in that in step (1), reaction temperature is 90~110 DEG C；Instead
It is 5~7h between seasonable；
In step (2), system temperature is controlled at 50~70 DEG C before being added dropwise and maintains to reaction to terminate by dihalo trifluoroethane.
7. the method according to claim 1, wherein including the following steps:
(1) phenolic compound Ar-OH, alkali and solvent are added in reactor, 90~110 DEG C are heated 5~6 hours；
(2) system temperature is reduced to 50~70 DEG C, and dihalo trifluoroethane is added dropwiseAdd institute in step (1)
The aqueous solution for stating alkali, to extract, dry, remove solvent, column chromatography or recrystallization, i.e. acquisition trifluoro vinyl virtue after reaction
Ether compound.
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| CN103865066A (en) * | 2014-03-06 | 2014-06-18 | 中国科学院上海有机化学研究所 | Low-dielectric-constant polymer containing hexafluoro-cyclobutyl ether and organic siloxane as well as preparation and application of low-dielectric-constant polymer |
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| CN103865066A (en) * | 2014-03-06 | 2014-06-18 | 中国科学院上海有机化学研究所 | Low-dielectric-constant polymer containing hexafluoro-cyclobutyl ether and organic siloxane as well as preparation and application of low-dielectric-constant polymer |
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