CN104130237A - Styrene cyclic carbonate preparation method - Google Patents
Styrene cyclic carbonate preparation method Download PDFInfo
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- CN104130237A CN104130237A CN201410335628.7A CN201410335628A CN104130237A CN 104130237 A CN104130237 A CN 104130237A CN 201410335628 A CN201410335628 A CN 201410335628A CN 104130237 A CN104130237 A CN 104130237A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings 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
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- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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Abstract
The invention relates to a styrene cyclic carbonate preparation method. The method comprises the following steps: mandelic acid is dissolved in a solvent; an acid catalyst is added and the materials are mixed, such that methyl mandelate is obtained; methyl mandelate is dissolved in the solvent again; the solution is mixed with sodium borohydride, such that 1-phenyl-1,2-ethanediol is obtained; 1-phenyl-1,2-ethanediol is dissolved in diethyl carbonate; an alkali catalyst is added, and the materials are mixed, such that the styrene cyclic carbonate is obtained. The method provided by the invention can also be used for preparing chiral styrene cyclic carbonate. The technical route of the method has the advantages of mild reaction conditions, easy-to-operate reaction process, simple post-treatment, easy-to-separate product, and the like.
Description
Technical field:
The present invention relates to a kind of preparation method of Styrene carbonate, belong to chemical intermediate fabricating technology field.
Background technology:
Cyclic carbonate is of many uses, can be used as the good medium of solvent (as decarbonization solvent) and high tension battery and electrical condenser, for the production of products such as paint remover and biodegradable wrapping material, is also expected for the production of novel, efficient knock-compound etc.Styrene carbonate (formula 4) is important in cyclic organic carbonate ester " green chemical ", and it has higher boiling point, is clean polar aprotic solvent, has very large using value and market potential.At present, industrial general application is by CO
2cycloaddition epoxide or prepared by methods such as alkene direct oxidation phosphinylidynes, but these methods can not be used for preparing efficiently cyclic carbonate, particularly cannot prepare the R-Styrene carbonate (formula 8) with chirality.
Summary of the invention:
The present invention is directed to above-mentioned shortcoming, a kind of preparation method of reliable, efficient Styrene carbonate is provided, a kind of preparation method of reliable, efficient R-Styrene carbonate is particularly also provided.
Therefore an object of the present invention is to provide the preparation method of a kind of Styrene carbonate (formula 1).
For achieving the above object, the technical scheme of taking is:
The preparation method of Styrene carbonate (formula 1), comprises the following steps:
(a) acid of amygdalic acid (formula 1) and methyl alcohol and catalytic amount is mixed, obtain methyl mandelate (formula 2);
(b) methyl mandelate (formula 2) and sodium borohydride are mixed, obtain 1-phenyl-1，2-ethandiol (formula 3);
(c) alkali of 1-phenyl-1，2-ethandiol (formula 3) and diethyl carbonate and catalytic amount is mixed, obtain described Styrene carbonate (formula 4).
Described preparation method, is characterized in that, in step (a), mixing temperature is 25 ℃ to 80 ℃, preferably 65 ℃.
Described preparation method, is characterized in that, in step (a), acid catalyst is selected the vitriol oil.
Described preparation method, is characterized in that, in step (b), mixing temperature is 0 ℃ to 25 ℃.
Described preparation method, is characterized in that, in step (b), the solvent of hybrid reaction is chosen as methyl alcohol.
Described preparation method, is characterized in that, in step (c), mixing temperature is 100 ℃ to 140 ℃, and preferably temperature is 133 ℃.
Another object of the present invention is to provide a kind of (R)-Styrene carbonate (formula 8), described in it, preparation method comprises the following steps:
(a) acid of D-amygdalic acid (formula 5) and methyl alcohol and catalytic amount is mixed, obtain D-methyl mandelate (formula 6);
(b) D-methyl mandelate (formula 6) and sodium borohydride are mixed, obtain (R)-1-phenyl-1，2-ethandiol (formula 7);
(c) alkali of (R)-1-phenyl-1，2-ethandiol (formula 7) and diethyl carbonate and catalytic amount is mixed, obtain described (R)-Styrene carbonate (formula 8).
Described preparation method, is characterized in that, in step (a), mixing temperature is 25 ℃ to 80 ℃, preferably 65 ℃.
Described preparation method, is characterized in that, in step (a), acid catalyst is selected the vitriol oil.
Described preparation method, is characterized in that, in step (b), mixing temperature is 0 ℃ to 25 ℃.
Described preparation method, is characterized in that, in step (b), the solvent of hybrid reaction is chosen as methyl alcohol.Described preparation method, is characterized in that, in step (c), mixing temperature is 100 ℃ to 140 ℃, and preferably temperature is 133 ℃.
Compared with prior art, the present invention has the following advantages:
1, provide a kind of new technological line of preparing Styrene carbonate.
2, this technological line has that synthesis technique is simple, the reaction times is short, reaction conditions is gentle, react easy to operate, and reaction intermediate or finished product can be by purifying such as simple crystallizations.
3, in this technological line, the enantiomorph configuration of initiator D-amygdalic acid is well kept in reaction.
4, the present invention is can be for the highly purified chirality Styrene carbonate of a large amount of preparation.
Embodiment:
Through deep research, contriver has found the new technological line for the synthesis of Styrene carbonate and chirality Styrene carbonate first.
The invention provides structure suc as formula 4 and formula 8 shown in compound.
Compound provided by the invention is stereomeric racemic mixture or a kind of mixture of normal dominant stereoisomeric forms in any ratio wherein.
Preparation method:
The invention provides a kind of Styrene carbonate (formula 4), described in it, preparation method comprises the following steps:
(a) acid of DL-amygdalic acid (formula 1) and methyl alcohol and catalytic amount is mixed, obtain methyl mandelate (formula 2);
(b) methyl mandelate (formula 2) and sodium borohydride are mixed, obtain 1-phenyl-1，2-ethandiol (formula 3);
(c) alkali of 1-phenyl-1，2-ethandiol (formula 3) and diethyl carbonate and catalytic amount is mixed, obtain described Styrene carbonate (formula 4).
The invention provides a kind of (R)-Styrene carbonate (formula 8), described in it, preparation method is consistent with the method for Styrene carbonate (formula 4):
Below in conjunction with specific embodiment, further set forth the present invention.These embodiment only, for the present invention is described, limit the scope of the invention and be not used in.As non-definition separately, the familiar same meaning of all specialties used and scientific words and one skilled in the art in literary composition.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The effect that only presents a demonstration of better implementation method described in literary composition and material.
Embodiment 1
DL-amygdalic acid (formula 1) is prepared DL-methyl mandelate (formula 2):
Under room temperature, DL-amygdalic acid (95g) is dissolved in anhydrous methanol (300mL), adds the methanol solution (0.95g is dissolved in 10mL methyl alcohol) of the vitriol oil, and 2h refluxes when temperature is 65 ℃.Reaction system is cooled to after room temperature, steams solvent, add 100mL ethyl acetate, use 20mL water washing, then use saturated NaHCO
3solution washing organic phase.By organic phase solution anhydrous sodium sulfate drying.Concentrate and obtain crude product DL-methyl mandelate, 104g, productive rate 100%, product characters is colourless liquid, can directly carry out next step reaction.
Embodiment 2
D-amygdalic acid (formula 5) is prepared D-methyl mandelate (formula 6):
Under room temperature, D-amygdalic acid (95g) is dissolved in anhydrous methanol (300mL), adds the methanol solution (0.95g is dissolved in 10mL methyl alcohol) of the vitriol oil, and 2h refluxes when temperature is 65 ℃.Reaction system is cooled to after room temperature, steams solvent, add 100mL ethyl acetate, use 20mL water washing, then use saturated NaHCO
3solution washing organic phase.By organic phase solution anhydrous sodium sulfate drying.Concentrate and obtain crude product D-methyl mandelate, 104g, productive rate 100%, product characters is colourless liquid, can directly carry out next step reaction.
Embodiment 3
DL-methyl mandelate (formula 2) is prepared racemization 1-phenyl-1,2 ethylene glycol (formula 3):
DL-methyl mandelate (104g) is dissolved in to anhydrous methanol (500mL), at 0 ℃, adds NaBH in batches
4(36.0g), at this temperature, react after 1h, be warming up to room temperature, after half an hour, TLC detection reaction finishes.Steam solvent, obtain a large amount of white solids, add a small amount of water (50mL), to system, pour 1N HCl in batches, until white solid dissolves, reaction system is acid (PH～4-5), continues to stir 1 hour to clarification.Ethyl acetate extraction 3 times, TLC detects water does not have product substantially.Merge organic phase, dry, concentrate and just obtain 1-phenyl-1, the racemic mixture of 2 ethylene glycol, 77.0g, productive rate 90%, white solid.Can directly carry out next step reaction.
Embodiment 4
D-methyl mandelate (formula 6) preparation (R)-1-phenyl-1,2 ethylene glycol (formula 7):
D-methyl mandelate (104g) is dissolved in to anhydrous methanol (500mL), at 0 ℃, adds NaBH in batches
4(36.0g), at this temperature, react after 1h, be warming up to room temperature, after half an hour, TLC detection reaction finishes.Steam solvent, obtain a large amount of white solids, add a small amount of water (50mL), to system, pour 1N HCl in batches, until white solid dissolves, reaction system is acid (PH～4-5), continues to stir 1 hour to clarification.Ethyl acetate extraction 3 times, TLC detects water does not have product substantially.Merge organic phase, dry, concentrated (R)-1-phenyl-1,2 ethylene glycol, 77.0g, productive rate 90%, the white solid of just obtaining.Can directly carry out next step reaction.
Embodiment 5
Racemization 1-phenyl-1，2-ethandiol (formula 3) is prepared Styrene carbonate (formula 4):
Under room temperature, racemization 1-phenyl-1,2-ethylene glycol (77g) is dissolved in diethyl carbonate (133mL, 2.0eq), add Anhydrous potassium carbonate (7.7g), stir 10 minutes, put into and be heated in advance the oil bath of 133 ℃, on reaction flask, connect a common water distilling apparatus, the ethanol that reaction is produced directly steams reaction system, guarantees that molecular balance moves to product direction.React after approximately 1 hour, almost do not have ethanol to steam, TLC detects raw material completely dissolve.Remove water distilling apparatus, reaction system is cooled to room temperature, and decompression steams diethyl carbonate, adds water (200mL) in residue, and dichloromethane extraction (3x100mL) merges organic phase, and uses anhydrous sodium sulfate drying.Dried organic phase is concentrated and obtains more micro-yellow solid.The product that the thick product obtaining obtains through recrystallization (petrol ether/ethyl acetate system), 85.0g, productive rate 93%, proterties is white crystal.
Embodiment 6
(R)-1-phenyl-1，2-ethandiol (formula 7) preparation (R)-Styrene carbonate (formula 8):
Under room temperature, racemization 1-phenyl-1,2-ethylene glycol (77g) is dissolved in diethyl carbonate (133mL, 2.0eq), add Anhydrous potassium carbonate (7.7g), stir 10 minutes, put into and be heated in advance the oil bath of 133 ℃, on reaction flask, connect a common water distilling apparatus, the ethanol that reaction is produced directly steams reaction system, guarantees that molecular balance moves to product direction.React after approximately 1 hour, almost do not have ethanol to steam, TLC detects raw material completely dissolve.Remove water distilling apparatus, reaction system is cooled to room temperature, and decompression steams diethyl carbonate, adds water (200mL) in residue, and dichloromethane extraction (3x100mL) merges organic phase, and uses anhydrous sodium sulfate drying.Dried organic phase is concentrated and obtains more micro-yellow solid.The product that the thick product obtaining obtains through recrystallization (petrol ether/ethyl acetate system), 85.0g, productive rate 93%, HPLC detects purity >99%, and proterties is white crystal, fusing point: 49 ℃-52 ℃, [α] 2
5 d=-24 (c=1.0, CHCl
3);
1h NMR (400MHz, CDCl
3) δ 7.46-7.43 (m, 3H), 7.39-7.36 (m, 2H), 5.69 (t, J=8.0Hz, 1H), 4.81 (t, J=8.4Hz, 1H), 4.35 (t, J=8.0Hz, 1H).
13c NMR (100MHz, CDCl
3) δ 154.8,135.8,129.7,129.2,125.8,77.9,71.1.
Claims (10)
1. a preparation method for Styrene carbonate, is characterized in that, said method comprising the steps of:
A is dissolved in amygdalic acid in solvent, then adds acid catalyst to mix, and obtains methyl mandelate;
B is dissolved in methyl mandelate in solvent again, and sodium borohydride mixing, obtains 1-phenyl-1，2-ethandiol;
C is dissolved in 1-phenyl-1，2-ethandiol in diethyl carbonate, then adds alkaline catalysts to mix, and obtains Styrene carbonate.
2. a preparation method for (R)-Styrene carbonate, is characterized in that, said method comprising the steps of:
A is dissolved in D-amygdalic acid in solvent, then adds acid catalyst to mix, and obtains D-methyl mandelate;
B is dissolved in D-methyl mandelate in solvent again, and sodium borohydride mixing, obtains (R)-1-phenyl-1，2-ethandiol;
C is dissolved in (R)-1-phenyl-1，2-ethandiol in diethyl carbonate, then adds alkaline catalysts to mix, and obtains (R)-Styrene carbonate.
3. any one preparation method as claimed in claim 1 or 2, is characterized in that, in step a, mixing temperature is 25 ℃-80 ℃.
4. any one preparation method as claimed in claim 1 or 2, is characterized in that, in step a, acid catalyst is the vitriol oil.
5. any one preparation method as claimed in claim 1 or 2, is characterized in that, in step a and b, solvent is methyl alcohol.
6. any one preparation method as claimed in claim 1 or 2, is characterized in that, in step c, mixing temperature is 100 ℃-140 ℃.
7. any one preparation method as claimed in claim 1 or 2, is characterized in that, in step c, alkaline catalysts is salt of wormwood.
8. any one preparation method as claimed in claim 1 or 2, is characterized in that, step a specifically comprises: amygdalic acid is dissolved in anhydrous methanol, then adds the vitriol oil, the mixed methanol solution 2h that refluxes when temperature is 65 ℃; Reaction system is cooled to after room temperature, steams solvent, add ethyl acetate, wash with water, then use saturated NaHCO
3solution washing organic phase; By organic phase solution anhydrous sodium sulfate drying; The concentrated crude product methyl mandelate that obtains.
9. any one preparation method as claimed in claim 1 or 2, is characterized in that, step b specifically comprises: methyl mandelate is dissolved in to anhydrous methanol, adds NaBH at 0 ℃ in batches
4, at this temperature, react after 1h, be warming up to room temperature, after half an hour, TLC detection reaction finishes; Steam solvent, obtain a large amount of white solids, add a small amount of water, to system, pour 1N HCl in batches, until white solid dissolves, it is acid that reaction system is, and continues to stir 1 hour to clarification; Ethyl acetate extraction 3 times, TLC detects water does not have product substantially; Merge organic phase, dry, concentrated 1-phenyl-1,2 ethylene glycol of just obtaining.
10. any one preparation method as claimed in claim 1 or 2, it is characterized in that, step c specifically comprises: under room temperature, 1-phenyl-1，2-ethandiol is dissolved in diethyl carbonate, adds Anhydrous potassium carbonate, stir 10 minutes, put into and be heated in advance the oil bath of 133 ℃, connect a common water distilling apparatus on reaction flask, the ethanol that reaction is produced directly steams reaction system; React after approximately 1 hour, almost do not have ethanol to steam, TLC detects raw material completely dissolve; Remove water distilling apparatus, reaction system is cooled to room temperature, and decompression steams diethyl carbonate, adds water in residue, and dichloromethane extraction merges organic phase, and with anhydrous sodium sulfate drying; Dried organic phase is concentrated, and the thick product obtaining obtains product through recrystallization.
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| CN201410335628.7A CN104130237A (en) | 2014-07-15 | 2014-07-15 | Styrene cyclic carbonate preparation method |
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| CN201410335628.7A CN104130237A (en) | 2014-07-15 | 2014-07-15 | Styrene cyclic carbonate preparation method |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0816316A1 (en) * | 1995-03-10 | 1998-01-07 | Nitto Chemical Industry Co., Ltd. | Process for producing 1,2-ethanediol derivatives |
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2014
- 2014-07-15 CN CN201410335628.7A patent/CN104130237A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0816316A1 (en) * | 1995-03-10 | 1998-01-07 | Nitto Chemical Industry Co., Ltd. | Process for producing 1,2-ethanediol derivatives |
Non-Patent Citations (1)
| Title |
|---|
| LEI CHANG ET AL.: "Highly enantioselective hydrolysis of phenyl-1,2-ethanediol cyclic carbonates by newly isolated Bacillus sp. ECU0015", 《JOURNAL OF MOLECULAR CATALYSIS B: ENZYMATIC》 * |
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