CN103204829A - A kind of preparation method of organic acid glycidyl ester - Google Patents
A kind of preparation method of organic acid glycidyl ester Download PDFInfo
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- CN103204829A CN103204829A CN2013101197845A CN201310119784A CN103204829A CN 103204829 A CN103204829 A CN 103204829A CN 2013101197845 A CN2013101197845 A CN 2013101197845A CN 201310119784 A CN201310119784 A CN 201310119784A CN 103204829 A CN103204829 A CN 103204829A
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- -1 organic acid glycidyl ester Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 150000002895 organic esters Chemical class 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims abstract description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940095102 methyl benzoate Drugs 0.000 claims abstract description 5
- VEZIKIAGFYZTCI-UHFFFAOYSA-N methyl 3-(4-methoxyphenyl)prop-2-enoate Chemical compound COC(=O)C=CC1=CC=C(OC)C=C1 VEZIKIAGFYZTCI-UHFFFAOYSA-N 0.000 claims abstract description 4
- DYUWQWMXZHDZOR-UHFFFAOYSA-N methyl 4-iodobenzoate Chemical compound COC(=O)C1=CC=C(I)C=C1 DYUWQWMXZHDZOR-UHFFFAOYSA-N 0.000 claims abstract description 4
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 13
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 8
- 238000005809 transesterification reaction Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims 2
- JPGRSTBIEYGVNO-UHFFFAOYSA-N methyl 4-ethynylbenzoate Chemical compound COC(=O)C1=CC=C(C#C)C=C1 JPGRSTBIEYGVNO-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- YOJAHJGBFDPSDI-UHFFFAOYSA-N methyl 4-nitrobenzoate Chemical compound COC(=O)C1=CC=C([N+]([O-])=O)C=C1 YOJAHJGBFDPSDI-UHFFFAOYSA-N 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 150000002148 esters Chemical group 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000000741 silica gel Substances 0.000 description 12
- 229910002027 silica gel Inorganic materials 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 238000010828 elution Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- XRQKARZTFMEBBY-UHFFFAOYSA-N oxiran-2-ylmethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1CO1 XRQKARZTFMEBBY-UHFFFAOYSA-N 0.000 description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 3
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical compound C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- 125000003232 p-nitrobenzoyl group Chemical group [N+](=O)([O-])C1=CC=C(C(=O)*)C=C1 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- CIXFJOIWHPRYJT-UHFFFAOYSA-N oxiran-2-ylmethyl formate Chemical compound O=COCC1CO1 CIXFJOIWHPRYJT-UHFFFAOYSA-N 0.000 description 1
- AFDXODALSZRGIH-UHFFFAOYSA-N p-coumaric acid methyl ether Natural products COC1=CC=C(C=CC(O)=O)C=C1 AFDXODALSZRGIH-UHFFFAOYSA-N 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of organic acid glycidyl ester, which belongs to the field of organic synthesis, wherein a catalyst is used for catalyzing ester exchange reaction of organic ester and glycidyl ester, wherein the organic ester is methyl acrylate, methyl benzoate, 4-nitrobenzoic acid methyl ester, p-iodobenzoic acid methyl ester, 4-acetylenyl methyl benzoate or p-methoxy methyl cinnamate; the catalyst is 4-dimethylaminopyridine, and the method has the beneficial effects that the 4-dimethylaminopyridine is used as the catalyst, so that the reaction time is effectively shortened, and the energy conservation and emission reduction are facilitated.
Description
Technical field
The present invention relates to a kind of organic acid glycidyl ester preparation method, belong to the organic synthesis field.
Background technology
Transesterification reaction between ester and the alcohol can be used dissimilar catalyzer.JP55011542 uses KOH as the catalyzer of condensation reaction, yet this strong alkaline substance can make Racemic glycidol in the short period of time polymerization take place, and produces potentiality danger such as blast.DE2423405 uses the stronger lithium methoxide of alkalescence as catalyzer, brings very big danger to aftertreatment.The use of weakly alkaline catalyzer also has report, has used potassium cyanide as catalyzer as DE2525026, and it can cause the appearance of addition by product, not only makes reaction process complicated, and product purity is reduced.JP55094381 has used the less Potassium ethanoate of toxicity as catalyzer, but in the still-process of aftertreatment, has significantly reduced the purity of product.Also have one piece of Japanese Patent to make catalyzer with triethylamine, use normal hexane that methyl alcohol is taken out of, obtain the very high product of purity.Triethylamine has suppressed the addition of methyl alcohol to methacrylic acid, has reduced the generation of by product.But triethylamine may be sneaked in the product, has influenced quality product, and the recovery of normal hexane is also pretty troublesome.JP55094379 has reported that also use N-Methylimidazole is as the Preparation of Catalyst glycidyl methacrylate.In transesterification reaction, by-product carbinol is that the existence by negative pressure separates from reaction system and removes, and the separation of target product is then realized by underpressure distillation.
Summary of the invention
The object of the invention is to provide the novel process of a kind of 4-of utilization Dimethylamino pyridine as Catalyst Production organic acid glycidyl ester, and synthesizes six kinds of fine-chemical intermediate compounds.The present invention utilizes the transesterification reaction principle, and single step reaction obtains needed product, simplifies technical process, reduces production costs.
The invention provides a kind of organic acid glycidyl ester preparation method, utilize the transesterification reaction of catalyst organic ester and Racemic glycidol, described organic ester is methyl acrylate, methyl benzoate, 4-nitrobenzoic acid methyl esters, 4-Iodobenzoic acid methyl esters, 4-acetylenylbenzene methyl-formiate or p-methoxycinnamic acid methyl esters; Described catalyzer is the 4-Dimethylamino pyridine.
Catalyzer in the transesterification reaction of the prior art is strong alkali catalyst, catalyzer in the transesterification reaction of the present invention is the 4-Dimethylamino pyridine, the 4-Dimethylamino pyridine is a kind of organic weak base, does not react with two keys, triple bond and iodine in the reactant, effectively suppresses the generation of side reaction.
The mass ratio of catalyzer of the present invention and organic ester is preferably 1:1～10.
The mass ratio of organic ester of the present invention and Racemic glycidol is preferably 1:1～10.
Preparation method of the present invention is for to join organic ester, Racemic glycidol, 4-Dimethylamino pyridine and stopper in the reactor, and the control temperature of reaction is 30～60 ℃, reaction 1～5h;
Described stopper is MEHQ.
Beneficial effect of the present invention is:
1. the 4-Dimethylamino pyridine is a kind of effective catalyst, and with catalyzer ratio of the prior art, in the identical reaction times, temperature of reaction obviously reduces; Identical temperature of reaction, the reaction times obviously shortens, and is beneficial to energy-saving and emission-reduction;
2. the 4-Dimethylamino pyridine is a kind of catalyzer of gentleness, can reduce the generation of side reaction;
3. the present invention utilizes transesterification reaction, and single step reaction obtains Chemicals, has simplified production process, has reduced production cost.
Embodiment
Following non-limiting example can make those of ordinary skill in the art more fully understand the present invention, but does not limit the present invention in any way.
Embodiment 1
4-Iodobenzoic acid methyl esters with 131mg, the Racemic glycidol of 221mg, 2.7g ethyl acetate solvent join successively in the there-necked flask that is provided with water trap and thermometer, again the 4-Dimethylamino pyridine of 60mg and the MEHQ of 30mg are joined in the reactor, the control temperature of reaction is 60 ℃, reaction 2h, constantly blast nitrogen in the reaction process, methyl alcohol except the dereaction generation, the normal-phase chromatography condition is 200～300 order silica gel, 4-Iodobenzoic acid glycidyl ester crude product and silica gel mass ratio are 1:30, moving phase is normal hexane/ether=4/1, elution volume is 4 column volumes, collection contains the cut of 4-Iodobenzoic acid glycidyl ester, evaporate to dryness obtains 0.098g 4-Iodobenzoic acid glycidyl ester faint yellow solid, and yield is 65%.
Embodiment 2
4-nitrobenzoic acid methyl esters with 90mg, the Racemic glycidol of 221mg, 2.7g ethyl acetate solvent join successively in the there-necked flask that is provided with water trap and thermometer, again the 4-Dimethylamino pyridine of 60mg and the MEHQ of 30mg are joined in the reactor, the control temperature of reaction is 50 ℃, reaction 2h, constantly blast nitrogen in the reaction process, methyl alcohol except the dereaction generation, the normal-phase chromatography condition is 200～300 order silica gel, 4-nitrobenzoyl acid glycidyl ester crude product and silica gel mass ratio are 1:30, moving phase is normal hexane/ether=4/1, elution volume is 4 column volumes, collection contains the cut of 4-nitrobenzoyl acid glycidyl ester, evaporate to dryness obtains 0.084g4-nitrobenzoyl acid glycidyl ester colourless liquid, and yield is 75%.
Embodiment 3
Methyl acrylate with 43mg, the Racemic glycidol of 221mg joins in the there-necked flask that is provided with water trap and thermometer successively, again the 4-Dimethylamino pyridine of 60mg and the MEHQ of 30mg are joined in the reactor, the control temperature of reaction is 60 ℃, reaction 2h, constantly blast nitrogen in the reaction process, methyl alcohol except the dereaction generation, the normal-phase chromatography condition is 200～300 order silica gel, glycidyl acrylate crude product and silica gel mass ratio are 1:30, moving phase is normal hexane/ether=4/1, and elution volume is 4 column volumes, collects the cut that contains glycidyl acrylate, evaporate to dryness obtains 0.047g glycidyl acrylate colourless liquid, and yield is 74%.
Embodiment 4
Methyl benzoate with 68mg, the Racemic glycidol of 221mg, 2.7g ethyl acetate solvent join successively in the there-necked flask that is provided with water trap and thermometer, again the 4-Dimethylamino pyridine of 60mg and the MEHQ of 30mg are joined in the reactor, the control temperature of reaction is 50 ℃, reaction 2h, constantly blast nitrogen in the reaction process, methyl alcohol except the dereaction generation, the normal-phase chromatography condition is 200～300 order silica gel, phenylformic acid glycidyl ester crude product and silica gel mass ratio are 1:30, moving phase is normal hexane/ether=4/1, elution volume is 4 column volumes, collection contains the cut of phenylformic acid glycidyl ester, evaporate to dryness obtains 0.064g phenylformic acid glycidyl ester colourless liquid, and yield is 72%.
Embodiment 5
P-methoxycinnamic acid methyl esters with 96mg, the Racemic glycidol of 221mg, 2.7g ethyl acetate solvent join successively in the there-necked flask that is provided with water trap and thermometer, again the 4-Dimethylamino pyridine of 60mg and the MEHQ of 30mg are joined in the reactor, the control temperature of reaction is 60 ℃, reaction 2h, constantly blast nitrogen in the reaction process, methyl alcohol except the dereaction generation, the normal-phase chromatography condition is 200～300 order silica gel, p-methoxycinnamic acid glycidyl ester crude product and silica gel mass ratio are 1:30, moving phase is normal hexane/ether=4/1, elution volume is 4 column volumes, collection contains the cut of p-methoxycinnamic acid glycidyl ester, evaporate to dryness obtains 0.073g p-methoxycinnamic acid glycidyl ester colourless liquid, and yield is 62%.
Embodiment 6
4-acetylenylbenzene methyl-formiate with 80mg, the Racemic glycidol of 221mg, 2.7g ethyl acetate solvent join successively in the there-necked flask that is provided with water trap and thermometer, again the 4-Dimethylamino pyridine of 60mg and the MEHQ of 30mg are joined in the reactor, the control temperature of reaction is 30 ℃, reaction 2h, constantly blast nitrogen in the reaction process, methyl alcohol except the dereaction generation, the normal-phase chromatography condition is 200～300 order silica gel, 4-acetylenylbenzene formic acid glycidyl ester crude product and silica gel mass ratio are 1:30, moving phase is normal hexane/ether=4/1, elution volume is 4 column volumes, collection contains the cut of 4-acetylenylbenzene formic acid glycidyl ester, evaporate to dryness obtains 0.069g4-acetylenylbenzene formic acid glycidyl ester colourless liquid, and yield is 68%.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2013101197845A CN103204829A (en) | 2013-04-08 | 2013-04-08 | A kind of preparation method of organic acid glycidyl ester |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2013101197845A CN103204829A (en) | 2013-04-08 | 2013-04-08 | A kind of preparation method of organic acid glycidyl ester |
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| CN103204829A true CN103204829A (en) | 2013-07-17 |
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| CN2013101197845A Pending CN103204829A (en) | 2013-04-08 | 2013-04-08 | A kind of preparation method of organic acid glycidyl ester |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030216587A1 (en) * | 2002-05-13 | 2003-11-20 | Saudi Basic Industries Corporation (Sabic) | Process for the conversion of aldehydes to esters |
| CN101528938A (en) * | 2006-10-26 | 2009-09-09 | 巴斯夫欧洲公司 | Process for producing of epoxy-containing (meth)acrylic esters, using lipases |
| CN101570537A (en) * | 2009-06-18 | 2009-11-04 | 浙江师范大学 | Preparation method of panipenem |
-
2013
- 2013-04-08 CN CN2013101197845A patent/CN103204829A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030216587A1 (en) * | 2002-05-13 | 2003-11-20 | Saudi Basic Industries Corporation (Sabic) | Process for the conversion of aldehydes to esters |
| CN101528938A (en) * | 2006-10-26 | 2009-09-09 | 巴斯夫欧洲公司 | Process for producing of epoxy-containing (meth)acrylic esters, using lipases |
| CN101570537A (en) * | 2009-06-18 | 2009-11-04 | 浙江师范大学 | Preparation method of panipenem |
Non-Patent Citations (2)
| Title |
|---|
| 庞灏等: "《一种新型高效阻聚剂－对羟基苯甲醚》", 《江苏化工》 * |
| 廖联安等: "《4-二甲氨基吡啶的合成及其催化的有机反应》", 《合成化学》 * |
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Application publication date: 20130717 |