CN102942458A - Preparation method of vinyl ether compound - Google Patents
Preparation method of vinyl ether compound Download PDFInfo
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- CN102942458A CN102942458A CN2012105045404A CN201210504540A CN102942458A CN 102942458 A CN102942458 A CN 102942458A CN 2012105045404 A CN2012105045404 A CN 2012105045404A CN 201210504540 A CN201210504540 A CN 201210504540A CN 102942458 A CN102942458 A CN 102942458A
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Abstract
The invention discloses a preparation method of a vinyl ether compound. The vinyl ether compound is benzyloxy vinyl ether or triethyleneglycol divinyl ether. The preparation method is characterized by comprising the following steps: 1, preparing a catalyst [Ir(COD)Cl]2, wherein the catalyst [Ir(COD)Cl]2 is prepared by dissolving iridous chloride and 1,5-cyclooctadiene in water and alcohol and performing reflux reaction under waterless and oxygen-free conditions; 2, dissolving the catalyst [Ir(COD)Cl]2 and raw materials such as alcohol, vinyl acetate and sodium carbonate, and performing reflux reaction under a waterless and oxygen-free atmosphere; and 3, after the reaction is finished, washing with water, performing reduced pressure distillation, and performing column chromatography to obtain the product. The preparation method effectively solves the problems of high catalyst cost, high reaction temperature, complicated operation, high solvent toxicity and the like in the prior art, thereby providing a green preparation method of a vinyl ether compound, which has the advantages of high yield and simple operation steps.
Description
One, technical field
The invention belongs to the synthetic field of organic compound, be specifically related to a kind of preparation method of vinyl ethers compound.
Two, background technology
Vinyl ethers monomer can be used as reactive thinner and is used for the systems such as Resins, epoxy, acrylic resin and unsaturated polyester, in fields such as electronic material, printing ink, printing, coating wide application space is arranged.Domesticly start late on the one hand at this, so far monomer production is unrealized industrialization also, and the commercially available prod all is external import packing, and the vinyl ethers series product tool of developing rapidly China has very important significance.
Because vinyl ethers compound preparation method's singularity, from the thirties, the method for vinyl ethers compound preparation has been applied for patent protected mostly, wherein is no lack of the major companies such as BASF, Du Pont, Standard Oil Company, General Electric.China is about to face the challenge that entry into the World Trade Organization brings, almost be blank in this field of vinyl ether compound, want to produce the industrialization product of oneself, and try hard to catch up, exploitation has own Patent right vinyl ether series product and just seems more urgent and important.
Triethylene glycol divinyl ether (Triethyleneglycol Divinyl Ether, DVE-3) is a kind of novel functional monomer, and molecular formula is C
10H
18O
4The triethylene glycol divinyl ether is a kind of chemical intermediate, can be used as linking agent, also can be used as the radiation protection system reaction monomers, and this material can directly be used in computer master making (CTP) production process.
The method for preparing at present vinyl ethers compound mainly contains following five kinds: 1, acetylene method (Favorskii-Shostakovskii method); 2, dehydrohalogenation method; 3, acetals, 4, vinylchlorid and alkoxide reaction method, 5, pure exchange process.
Acetylene method is a kind of traditional technique, is namely under high pressure made by alcohol and acetylene gas direct reaction, and general formula is as follows:
This reaction obtains product once going on foot, and problem never is resolved but the explosion hazard of the equipment of high pressure-temperature, acetylene gas, yield be low etc.;
Dehydrohalogenation method is the method with the acetylene method synchronized development, reaction expression as:
The reaction conditions of this method is gentle than acetylene method, but the raw material mix of reaction is had requirement, and this is because vinyl ether compound can not prepare with the synthetic method of general ethers, thereby synthetic target product also is subject to certain limitation.And the catalysis of this reaction needed mercury salt, toxicity is larger;
Acetals, take acetaldehyde and alcohol as the acetals of raw material dealcoholysis behind acetal, raw material cheaply is easy to get, reaction temperature and, but yield is lower, by product is more.
Vinylchlorid and alkoxide reaction method, the early stage method of Reppe is under pressure, and the pure reactant salt of vinylchlorid and various alcohols also can be used as the method for the extraordinary vinyl ether of current manufacturing, and reaction expression is as follows:
Cheap vinylchlorid and use mean that by the pure reactant salt that sodium hydroxide or sodium form it is feasible utilizing low reaction activity or expensive alcohols to react.Use polarizable medium (DMF, DMSO) step of also may spouting to promote such reaction.But this reaction response condition is harsh, and is unfavorable for industrialization.
What research was more at present is pure exchange process; take alcohol as raw material; under the catalysis of [Ir (COD) Cl] 2 and alkali; in the atmosphere of nitrogen protection; the vinyl of vinyl-acetic ester is transferred on the alcohol; the method productive rate is higher, but catalyzer is more expensive, and exists and to need the problems such as pyroreaction, trivial operations, solvent toxicity are larger.
Document (Yoshio Okimoto.Development of a Highly Efficient Catalytic Method forSynthesis ofVinyl Ether.J.Am.Chem.Soc.2002,124,1590-1591) use pure exchange process, take alcohol as raw material, at [Ir (COD) Cl]
2Under the catalysis of sodium acetate, the vinyl of vinyl-acetic ester is transferred on the alcohol, but easily suction of sodium acetate, weathering and flammable, dangerous property, in addition catalyzer [Ir (COD) Cl] in the document
2Preparation need high temperature reflux, trivial operations, and use toluene as solvent, toxicity is larger, does not meet the aim of Green Chemistry.
Three, summary of the invention
The object of the present invention is to provide the preparation method of a kind of green, productive rate height, the simple vinyl ethers compound of operation steps.
Realize that the object of the invention technical solution is: a kind of preparation method of vinyl ethers compound, described vinyl ethers compound is benzyloxy vinyl ether or triethylene glycol divinyl ether, and the method for preparing described vinyl ethers compound may further comprise the steps:
The first step, the preparation of catalyzer specifically may further comprise the steps:
1) with iridous chloride, 1, the 5-cyclooctadiene is added in the reaction unit, then adds entry and pure mixture in reaction unit, and stirring obtains reaction solution;
2) vacuumize after the reaction unit sealing, inflated with nitrogen, reaction solution reflux in the atmosphere of nitrogen is reacted;
3) after reaction finishes, make reaction solution be cooled to room temperature and filtration, filter residue is dry with the methanol wash final vacuum, and the gained solid is also with methanol wash and vacuum-drying after the filtrate decompression distillation, and the product of twice drying is required catalyzer, merges stand-by;
Second step, catalyzer, raw alcohol, vinyl acetate, yellow soda ash that the first step is prepared are added to reactor, then add organic solvent in reactor, and stirring obtains reaction mixture, and described raw alcohol is triethylene glycol or phenylcarbinol;
The 3rd step vacuumized after the reactor sealing, inflated with nitrogen, and reaction mixture reflux in the atmosphere of nitrogen is reacted;
The 4th step after reaction finishes, made reaction mixture be cooled to room temperature, added ethyl acetate in the reaction mixture and water extracts, and separated organic phase a;
The 5th step, the 4th step separated add saturated sodium chloride solution among the organic phase a obtain and extract, then separate organic phase b;
The 6th step, with after the organic phase b underpressure distillation by silica gel column chromatography and take sherwood oil and ethyl acetate as elutriant separates, obtain target product triethylene glycol divinyl ether.
The preparation method of vinyl ethers compound of the present invention, the first step 1) described in the mol ratio of iridous chloride and 1,5-cyclooctadiene be 1: 2～1: 6; The first step 1) described in alcohol be Virahol, ethanol or propyl carbinol, and described water and alcohol volume ratio be 1: 1～3: 1; The first step 2) described in reflux to carry out temperature of reaction be 80～130 ℃, the time is 10～14h; Described in the second step in the raw alcohol mol ratio of hydroxyl and vinyl acetate be 1: 1～1: 2, the mol ratio of hydroxyl and catalyzer is 1: 0.006～1: 0.05 in the raw alcohol, the mol ratio of hydroxyl and yellow soda ash is 1: 0.01～1: 0.2 in the raw alcohol; Organic solvent described in the second step is toluene, benzene, p-Xylol or does not add organic solvent; The reflux temperature is 80～120 ℃ described in the 3rd step, and the time is 6～18h.
The present invention compared with prior art, its remarkable advantage is: 1, domestic synthetic report about vinyl ethers compound is less, the invention provides a kind of novel method for preparing vinyl ethers compound; 2, the present invention utilizes enclosed system to be used as reactor synthetic catalyst [Ir (COD) Cl]
2, need not high temperature, easy and simple to handle, and productive rate is higher, used organic solvent is the mixture of nontoxic second alcohol and water, has realized the aim of Green Chemistry; 3, than the method for external synthesizing ethylene pyridyl ethers compound, the present invention has adopted solvent-free scheme to replace poisonous toluene solvant, and productive rate is more or less the same; The alkali that the present invention uses is yellow soda ash, cheaply easily gets, and is more stable, and better effects if.
Four description of drawings
Fig. 1 is the preparation method's of vinyl ethers compound of the present invention catalyzer [Ir (COD) Cl]
2Preparation flow figure.
Fig. 2 is the preparation method's of vinyl ethers compound of the present invention process flow sheet.
Fig. 3 is the preparation method's of the vinyl ethers compound of the present invention nuclear-magnetism phenogram of target product triethylene glycol divinyl ether.
Five embodiments
Below in conjunction with accompanying drawing the present invention is described in further detail.
A kind of preparation method of vinyl ethers compound, described vinyl ethers compound is benzyloxy vinyl ether or triethylene glycol divinyl ether, in conjunction with Fig. 1, Fig. 2, the method for preparing described vinyl ethers compound may further comprise the steps:
The first step, the preparation of catalyzer specifically may further comprise the steps:
1) with iridous chloride, 1, the 5-cyclooctadiene is added in the reaction unit, then adds entry and pure mixture in reaction unit, and stirring obtains reaction solution;
2) vacuumize after the reaction unit sealing, inflated with nitrogen, reaction solution reflux in the atmosphere of nitrogen is reacted;
3) after reaction finishes, make reaction solution be cooled to room temperature and filtration, filter residue is dry with the methanol wash final vacuum, and the gained solid is also with methanol wash and vacuum-drying after the filtrate decompression distillation, and the product of twice drying is required catalyzer, merges stand-by;
Second step, catalyzer, raw alcohol, vinyl acetate, yellow soda ash that the first step is prepared are added to reactor, then add organic solvent in reactor, and stirring obtains reaction mixture, and described raw alcohol is triethylene glycol or phenylcarbinol;
The 3rd step vacuumized after the reactor sealing, inflated with nitrogen, and reaction mixture reflux in the atmosphere of nitrogen is reacted;
The 4th step after reaction finishes, made reaction mixture be cooled to room temperature, added ethyl acetate in the reaction mixture and water extracts, and separated organic phase a;
The 5th step, the 4th step separated add saturated sodium chloride solution among the organic phase a obtain and extract, then separate organic phase b;
The 6th step, with after the organic phase b underpressure distillation by silica gel column chromatography and take sherwood oil and ethyl acetate as elutriant separates, obtain target product triethylene glycol divinyl ether.
The preparation method of vinyl ethers compound of the present invention, the first step 1) described in the mol ratio of iridous chloride and 1,5-cyclooctadiene be 1: 2～1: 6; The first step 1) described in alcohol be Virahol, ethanol or propyl carbinol, and described water and alcohol volume ratio be 1: 1～3: 1; The first step 2) described in reflux to carry out temperature of reaction be 80～130 ℃, the time is 10～14h; Described in the second step in the raw alcohol mol ratio of hydroxyl and vinyl acetate be 1: 1～1: 2, the mol ratio of hydroxyl and catalyzer is 1: 0.006～1: 0.05 in the raw alcohol, the mol ratio of hydroxyl and yellow soda ash is 1: 0.01～1: 0.2 in the raw alcohol; Organic solvent described in the second step is toluene, benzene, p-Xylol or does not add organic solvent; The reflux temperature is 80～120 ℃ described in the 3rd step, and the time is 6～18h.
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1: take the benzyloxy vinyl ether as example, chemical equation is as follows:
In conjunction with Fig. 1, Fig. 2, the preparation method of vinyl ethers compound benzyloxy vinyl ether of the present invention may further comprise the steps:
The first step, catalyzer [Ir (COD) Cl]
2Preparation, reaction equation is as follows:
Specifically may further comprise the steps:
1) with 1 of the iridous chloride of 0.1g (0.00028mol), 0.12mL (0.001mol), 5 cyclooctadiene are added in the reaction unit, then add the mixture of 3.5mL (0.194mol) water and 1.6mL (0.021mol) Virahol in the reaction unit, stirring obtains reaction solution;
2) vacuumize after the reaction unit sealing, inflated with nitrogen, make reaction solution in the atmosphere of nitrogen, heat 80～100 ℃ of backflows and react 10～14h;
3) after reaction finishes, make reaction solution be cooled to room temperature and filtration, the gained solid is dry with the methanol wash final vacuum, [Ir (COD) Cl] of the redness of generation
2About 0.0723g, filtrate decompression is distilled to 50% rear gained solid also with methanol wash and vacuum-drying, and the product of twice drying is required catalyzer, merges stand-byly, and productive rate is about 83.2%;
Second step adds the resulting catalyzer of 0.0067g (0.01mmol) the first step [Ir (COD) Cl] in there-necked flask
2, the phenylcarbinol of 0.11ml (1mmol), the vinyl acetate of 1ml (1mmol), the yellow soda ash of 0.005g (0.06mmol), the toluene that then adds 1ml in the there-necked flask evenly obtains reaction mixture as stirring solvent;
The 3rd step vacuumized after the there-necked flask sealing, inflated with nitrogen, made reaction mixture in the nitrogen atmosphere of anhydrous and oxygen-free, heat 80 ℃ of backflows and react, after the reaction 20min, the color of the solution becomes burgundy from yellow, sustained reaction 8h, solution becomes Vandyke brown;
The 4th step after reaction finishes, made reaction mixture be cooled to room temperature, added the ethyl acetate of 3mL in the reaction mixture and the deionized water of 1mL extracts, and separated organic phase a;
The 5th step, separate to the 4th step and to add the saturated sodium chloride solution of 1mL among the organic phase a obtain and extract, then separate organic phase b;
The 6th step, with organic phase b with anhydrous magnesium sulfate drying after, underpressure distillation organic phase b by silica gel column chromatography and take sherwood oil and ethyl acetate as elutriant separates, obtains target product benzyloxy vinyl ether again, productive rate is 85.6%.
Wherein, catalyzer [Ir (COD) Cl]
2Results of elemental analyses shown in table 1.1:
Table 1.1[Ir (COD) Cl]
2Ultimate analysis
Ultimate analysis condition: m.p.＞200 ℃
Embodiment 2: reactions steps is identical with embodiment 1, and difference is:
With the first step 1) in reaction use 1, the volume of 5-cyclooctadiene changes respectively 0.067mL (0.00056mol), 0.15mL (0.00125mol), 0.21mL (0.0017mol) into, all the other conditions are constant, catalyzer in the first step [Ir (COD) Cl]
2Productive rate be respectively 65.1%, 77.1% and 78.2%.
Embodiment 3: reactions steps is identical with embodiment 1, and difference is:
With the first step 1) in the Virahol that uses of reaction be changed to respectively ethanol, propyl carbinol, constancy of volume, all the other conditions are constant, catalyzer in the first step [Ir (COD) Cl]
2Productive rate be respectively 79.1% and 53.2%.
Embodiment 4: reactions steps is identical with embodiment 1, and difference is:
With the first step 1) in the volume of water used of reaction be changed to respectively 1.6mL (0.088mol), 3.2mL (0.177mol) and 4.8mL (0.266mol), all the other conditions are constant, catalyzer in the first step [Ir (COD) Cl]
2Productive rate be respectively 68.2%, 78.2%, 57.7%.
Embodiment 5: reactions steps is identical with embodiment 1, and difference is:
With the first step 2) in the reflux temperature be set to respectively 100～110 ℃, 110～130 ℃, all the other conditions are constant, catalyzer in the first step [Ir (COD) Cl]
2Productive rate be respectively 71.2%, 57.7%.
Embodiment 6: reactions steps is identical with embodiment 1, and difference is:
Change respectively the consumption of the vinyl acetate of second step into 1.2mL (1.2mmol), 1.5mL (1.5mmol), 2mL (2mmol), all the other steps are constant, and target product benzyloxy vinyl ether productive rate is for being respectively 66.9%, 85.8%, 89.7%.
Embodiment 7: reactions steps is identical with embodiment 1, and difference is:
Change respectively the consumption of the yellow soda ash of second step into 0.00083g (0.01mmol), 0.03g (0.036mmol), 0.08g (0.096mmol), 0.017g (0.2mmol), all the other steps are constant, and target product benzyloxy vinyl ether productive rate is for being respectively 11.5%, 36.9%, 65.8%, 89.7%.
Embodiment 8: reactions steps is identical with embodiment 1, and difference is:
Solvent in the second step is changed to respectively benzene, p-Xylol or does not add organic solvent, and all the other steps are constant, and target product benzyloxy vinyl ether productive rate is for being respectively 88.2%, 59.5%, 86.2%.
Embodiment 9: reactions steps is identical with embodiment 1, and difference is:
Reflux temperature in the 3rd step is set to respectively 90 ℃, 100 ℃, 120 ℃, and all the other steps are constant, and target product benzyloxy vinyl ether productive rate is for being respectively 84.2%, 89.5%, 88.2%.
Embodiment 10: reactions steps is identical with embodiment 1, and difference is:
Change respectively the sustained reaction time in the 3rd step into 6h, 10h, 14h, 18h, all the other steps are constant, and target product benzyloxy vinyl ether productive rate is for being respectively 45.7%, 75.3%, 89.5%, 89.7%.
Embodiment 11: take the triethylene glycol divinyl ether as example, chemical equation is as follows:
In conjunction with Fig. 1, Fig. 2, the preparation method of vinyl ethers compound triethylene glycol divinyl ether of the present invention may further comprise the steps:
The first step, catalyzer [Ir (COD) Cl]
2Preparation, reaction equation is as follows:
Specifically may further comprise the steps:
1) iridous chloride of 0.1g (0.00028mol), 1,5 cyclooctadiene of 0.12mL (0.001mol) are added in the reaction unit, then add the mixture of 3.5mL water and 1.6mL Virahol in the reaction unit, stirring obtains reaction solution;
2) vacuumize after the reaction unit sealing, inflated with nitrogen, make reaction solution in the atmosphere of nitrogen, heat 80～100 ℃ of backflows and react 10～14h;
3) after reaction finishes, make reaction solution be cooled to room temperature and filtration, the gained solid is dry with the methanol wash final vacuum, [Ir (COD) Cl] of the redness of generation
2About 0.0723g, filtrate decompression is distilled to 50% rear gained solid also with methanol wash and vacuum-drying, and the product of twice drying is required catalyzer, merges stand-byly, and productive rate is about 83.2%;
Second step adds the resulting catalyzer of 0.0124g (0.02mmol) the first step [Ir (COD) Cl] in there-necked flask
2, the triethylene glycol of 0.12ml (1mmol), the vinyl acetate of 2ml (2mmol), the yellow soda ash of 0.01g (0.012mmol), the toluene that then adds 1ml in the there-necked flask evenly obtains reaction mixture as stirring solvent;
The 3rd step vacuumized after the there-necked flask sealing, inflated with nitrogen, made reaction mixture in the nitrogen atmosphere of anhydrous and oxygen-free, heat 80 ℃ of backflows and react, after the reaction 20min, the color of the solution becomes burgundy from yellow, sustained reaction 8h, solution becomes Vandyke brown;
The 4th step after reaction finishes, made reaction mixture be cooled to room temperature, added the ethyl acetate of 3mL in the reaction mixture and the deionized water of 1mL extracts, and separated organic phase a;
The 5th step, separate to the 4th step and to add the saturated sodium chloride solution of 1mL among the organic phase a obtain and extract, then separate organic phase b;
The 6th step, with organic phase b with anhydrous magnesium sulfate drying after, underpressure distillation organic phase b by silica gel column chromatography and take sherwood oil and ethyl acetate as elutriant separates, obtains target product triethylene glycol divinyl ether again, productive rate is 45.6%.
Embodiment 12: reactions steps is identical with embodiment 11, and difference is:
Change respectively the consumption of the yellow soda ash of second step into 0.00083g (0.01mmol), 0.03g (0.036mmol), 0.08g (0.096mmol), 0.017g (0.2mmol), all the other steps are constant, and target product triethylene glycol divinyl ether productive rate is for being respectively 8.7%, 19.7%, 47.8%, 20.3%.
Embodiment 13: reactions steps is identical with embodiment 11, and difference is:
Reflux temperature in the 3rd step is set to respectively 90 ℃, 100 ℃, 120 ℃, and all the other steps are constant, and target product triethylene glycol divinyl ether productive rate is for being respectively 38.6%, 43.6%, 40.5%.
Embodiment 14: reactions steps is identical with embodiment 11, and difference is:
The kind of catalyzer will be changed in the second step, use respectively the catalyzer such as iridous chloride, triphenylphosphine palladium chloride, 1.5 cyclooctadiene rhodium chloride dimers, 1.5 cyclooctadiene Palladous chlorides, all the other steps are constant, and target product triethylene glycol divinyl ether productive rate is for being respectively 0.0%, 1.1%, 0.0%, 0.0%.
Embodiment 15: reactions steps is identical with embodiment 11, and difference is:
Change respectively the sustained reaction time in the 3rd step into 6h, 10h, 14h, 18h, all the other steps are constant, and target product triethylene glycol divinyl ether productive rate is for being respectively 18.579%, 33.6%, 40.5%, 42.5%.
Embodiment 16: reactions steps is identical with embodiment 11, and difference is:
With catalyzer in the second step [Ir (COD) Cl]
2Consumption change respectively 0.008g (0.012mmol), 0.036g (0.05mmol), 0.0603g (0.09mmol) 0.067 (0.1mmol) into, all the other steps are constant, and target product triethylene glycol divinyl ether productive rate is for being respectively 4.6%, 23.6%, 41.4%, 42.0%.
In conjunction with Fig. 3, the nuclear-magnetism of gained target product triethylene glycol divinyl ether characterizes collection of illustrative plates, and the chemical shift of hydrogen is as follows:
H-NMR (CDCl
3, 500MHz) δ=6.495ppm (s, 2H), δ=4.206ppm (m, 2H), δ=4.020ppm (m, 2H), δ=3.856ppm (m, 4H), δ=3.7598ppm (m, 4H), δ=3.657ppm (m, 4H), the chemical shift of all hydrogen has proved the structure of product triethylene glycol divinyl ether all in the position of correspondence.
Claims (7)
1. the preparation method of a vinyl ethers compound, described vinyl ethers compound is benzyloxy vinyl ether or triethylene glycol divinyl ether, it is characterized in that, the method for preparing described vinyl ethers compound may further comprise the steps:
The first step, catalyzer [Ir (COD) Cl]
2Preparation, specifically may further comprise the steps:
1) with iridous chloride, 1, the 5-cyclooctadiene is added in the reaction unit, then adds entry and pure mixture in reaction unit, and stirring obtains reaction solution;
2) vacuumize after the reaction unit sealing, inflated with nitrogen, reaction solution reflux in the atmosphere of nitrogen is reacted;
3) after reaction finishes, make reaction solution be cooled to room temperature and filtration, filter residue is dry with the methanol wash final vacuum, and the gained solid is also with methanol wash and vacuum-drying after the filtrate decompression distillation, and the product of twice drying is required catalyzer, merges stand-by;
Second step, catalyzer, raw alcohol, vinyl acetate, yellow soda ash that the first step is prepared are added to reactor, then add organic solvent in reactor, and stirring obtains reaction mixture, and described raw alcohol is triethylene glycol or phenylcarbinol;
The 3rd step vacuumized after the reactor sealing, inflated with nitrogen, and reaction mixture reflux in the atmosphere of nitrogen is reacted;
The 4th step after reaction finishes, made reaction mixture be cooled to room temperature, added ethyl acetate in the reaction mixture and water extracts, and separated organic phase a;
The 5th step, the 4th step separated add saturated sodium chloride solution among the organic phase a obtain and extract, then separate organic phase b;
The 6th step, with after the organic phase b underpressure distillation by silica gel column chromatography and take sherwood oil and ethyl acetate as elutriant separates, obtain target product triethylene glycol divinyl ether.
2. the preparation method of vinyl ethers compound according to claim 1 is characterized in that: the first step 1) described in the mol ratio of iridous chloride and 1,5-cyclooctadiene be 1: 2～1: 6.
3. the preparation method of vinyl ethers compound according to claim 1 is characterized in that: the first step 1) described in alcohol be Virahol, ethanol or propyl carbinol, and the volume ratio of described water and alcohol is 1: 1～3: 1.
4. the preparation method of vinyl ethers compound according to claim 1 is characterized in that: the first step 2) described in reflux to carry out temperature of reaction be 80～130 ℃, the time is 10～14h.
5. the preparation method of vinyl ethers compound according to claim 1 is characterized in that: described in the second step in the raw alcohol mol ratio of hydroxyl and vinyl acetate be 1: 1～1: 2; The mol ratio of hydroxyl and catalyzer is 1: 0.006～1: 0.05 in the raw alcohol; The mol ratio of hydroxyl and yellow soda ash is 1: 0.01～1: 0.2 in the raw alcohol.
6. the preparation method of vinyl ethers compound according to claim 1, it is characterized in that: organic solvent described in the second step is toluene, benzene, p-Xylol or does not add organic solvent.
7. the preparation method of vinyl ethers compound according to claim 1 is characterized in that: the reflux temperature is 80～120 ℃ described in the 3rd step, and the time is 6～18h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380490A (en) * | 2016-09-09 | 2017-02-08 | 昆明理工大学 | One-step synthesis method of (1,5-cyclooctadiene)-dichloro iridium dipolymer |
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| EP1288186A2 (en) * | 2001-08-30 | 2003-03-05 | Daicel Chemical Industries, Ltd. | Vinyl ether compounds and preparation process thereof |
| JP2006045089A (en) * | 2004-08-02 | 2006-02-16 | Daicel Chem Ind Ltd | METHOD FOR PRODUCING DI-mu-CHLOROBIS(1,5-CYCLOOCTADIENE) DIIRIDIUM(I) |
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| EP1288186A2 (en) * | 2001-08-30 | 2003-03-05 | Daicel Chemical Industries, Ltd. | Vinyl ether compounds and preparation process thereof |
| JP2006045089A (en) * | 2004-08-02 | 2006-02-16 | Daicel Chem Ind Ltd | METHOD FOR PRODUCING DI-mu-CHLOROBIS(1,5-CYCLOOCTADIENE) DIIRIDIUM(I) |
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| J.L.HERDE, ET AL.: "5.CYCLOOCTENE AND 1,5-CYCLOOCTADIENE COMPLEXES OF IRIDIUM(Ⅰ)", 《INORGANIC SYNTHESIS》 * |
| NARI-AKI HARADA,ET AL.: "Vinyl polymerization versus [1,3] O to C rearrangement in the ruthenium-catalyzed reactions of vinyl ethers with hydrosilanes", 《TETRAHEDRON》 * |
| YOSHIO OKIMOTO, ET AL.: "Development of a Highly Efficient Catalytic Method for Synthesis of Vinyl Ethers", 《 J.AM.CHEM.SOC.》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106380490A (en) * | 2016-09-09 | 2017-02-08 | 昆明理工大学 | One-step synthesis method of (1,5-cyclooctadiene)-dichloro iridium dipolymer |
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