CN103992207A - Method for preparing vicinal diol by catalytic oxidation of alkene in hydrogen peroxide/cationic resin system - Google Patents

Method for preparing vicinal diol by catalytic oxidation of alkene in hydrogen peroxide/cationic resin system Download PDF

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Publication number
CN103992207A
CN103992207A CN201410193122.7A CN201410193122A CN103992207A CN 103992207 A CN103992207 A CN 103992207A CN 201410193122 A CN201410193122 A CN 201410193122A CN 103992207 A CN103992207 A CN 103992207A
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type
reaction
alkene
karb
zeo
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CN103992207B (en
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宋国强
张文楠
黄险峰
曹引梅
姚昶旭
罗九艳
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Changzhou University
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Changzhou University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
    • C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
    • C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention relates to a method for preparing vicinal diol by catalytic oxidation of alkene in a hydrogen peroxide/cationic resin system and belongs to the field of organic synthesis. The method is carried out by the following steps: adding alkene and cation exchange resin into a single-ported round-bottom flask; stirring and heating with a constant temperature oil bath pan at the temperature of 0-90 DEG C; measuring a hydrogen dioxide solution with a constant voltage dropping funnel according to the dosage of the added alkene; slowly adding a reaction solution after reaching a set temperature and reacting for 0.1-10h; adding a few amount of Na2S2O3 to quench the reaction after the end of the reaction; filtering out the cation exchange resin, cleaning with methanol and recovering; and extracting a reaction solution with ethyl acetate and water, putting a water phase into a refrigerator, and precipitating white crystals, namely a vicinal diol compound. The method requires no solvent; a catalyst can be recycled; a reaction system is mild; environmental pollutants are few; the method has a wide application range; and production cost is low. By optimizing reaction conditions, product purity is higher than 92%, and yield can reach 89%. The method has a strong industrial application prospect.

Description

The method of the adjacent glycol of hydrogen peroxide/resin cation (R.C.) system catalyzed oxidation alkene system
technical field
The present invention relates to a kind of preparation method of adjacent glycols compound, belong to organic synthesis field.
Background technology
Adjacent glycols compound (as 1,2-cyclohexanediol, 1,2-hexylene glycol), as a large amount of synthetic important intermediate of Chemicals, is widely used in the production of the fine chemical products such as medicine, agricultural chemicals, polyester.And with 1,2-cyclohexanediol for raw material, pyrocatechol prepared by dehydroaromatizationof is also widely used in fields such as spices, agricultural chemicals, medicine, chemical assistants.At present, the domestic large-scale production about vicinal diol compound is less, its synthetic route mainly contains two kinds: the one, and, although this method step is simple, there is the restriction industrialization development factors such as expensive, the poisonous and product yield of required catalyzer is low in the direct oxidation method taking alkene as raw material; The 2nd, taking epoxy compounds as raw material, the adjacent glycols compound of hydrolysis preparation under acidic conditions, this synthetic route is easy to realize, but the suitable height of required cost.Therefore, be starting raw material by alkene, in same system, its epoxidation process of catalysis and epoxy compounds hydrolytic process simultaneously, the route of preparing adjacent glycol can improve reaction efficiency greatly, reduces production costs simultaneously.In recent years, along with the raising of environment protection requirement, hydrogen peroxide is the most frequently used oxygenant of this type of system, and it is nontoxic, reaction conditions is gentle, and reaction later by-product only has water, is a kind of desirable cleaning oxidizer.But hydrogen peroxide is during as oxygenant, and oxidation activity is lower, generally all needs catalyzer.Therefore, select a kind of new catalyst system to make hydrogen peroxide activation, can make reaction conditions become gentle, improve selectivity and the yield of reaction product, for industrialization provides favourable reference, there is higher economic and social benefit.
 
Summary of the invention
Its reaction formula of the present invention is as schemed:
R 1, R 2, R 3, R 4can be identical or different be selected from hydrogen, saturated fatty base.
The synthetic method of the adjacent glycols compound of the present invention, carry out in the steps below:
(1) in single necked round bottom flask, add alkene, Zeo-karb, stir and use the heating of thermostatical oil bath, temperature is 0-90 DEG C;
(2) according to adding the consumption of alkene, measure superoxol with constant pressure funnel, slowly add reaction solution, reaction 0.1-10h after reaching design temperature;
(3) after reaction finishes, add a small amount of Na 2s 2o 3the essence reaction of going out.Leach Zeo-karb, use the washed with methanol that is more than or equal to 1:1 with its mol ratio, reclaim.Reaction solution is with after ethyl acetate and water extraction, and water is put into refrigerator, separates out white crystal, is adjacent glycols compound, and purity is 92% ~ 100%, and yield is 70% ~ 89%.Recovery resin is added to next batch reaction, and reactions steps is identical.Through 1-15 revision test, product purity all reaches 92% ~ 100%, and productive rate all remains on 70% ~ 89%.
Wherein in step (1), the mol ratio of alkene and Zeo-karb is 1:0.1-1:5.
Wherein in step (2), the mol ratio of alkene and superoxol is 1:0.5-1:30.
Wherein the alkene structures formula described in step (1) is , R 1, R 2, R 3, R 4can be identical or different be selected from hydrogen, saturated fatty base, comprise the combination of straight-chain paraffin, branched paraffin, naphthenic hydrocarbon and these three kinds of alkane.
Described resin is modification strongly acidic cation-exchange, can be selected from Ag type, Mn type, K type, Ni type, Co type, Fe type, Zr type etc., preferably Ag type, Mn type.
Wherein, Zeo-karb described in step (1) is preferably Ag type, the Mn type Zeo-karb of modification, and its preparation method is: pack commercially available Na type Zeo-karb into ion exchange column with after washed with de-ionized water 3 times; Preparation 10% hydrochloric acid soln, slowly adds ion exchange column, keeps the flow velocity of drip/min of 2-3 to carry out ion-exchange, and after repeated exchanged 2-3 time, use deionized water rinsing, until solution PH=7; Prepare respectively 10% AgNO 3solution and 10% MnCl 2solution, slowly adds ion exchange column again, keeps the flow velocity of 2-3 drip/min to carry out ion-exchange, and after repeated exchanged 2-3 time, use deionized water rinsing, until solution PH=7.The Ag type, the Mn type Zeo-karb that have exchanged can use after drying.
Agents useful for same of the present invention and raw material be commercially available obtaining all.
Positive progressive effect of the present invention is: the present invention proposes a kind of clean preparation method of synthetic adjacent glycols compound, the method is without solvent, catalyzer recoverable, and reaction system gentleness, low in the pollution of the environment, scope on probation is wide, and production cost is low.Through optimizing reaction conditions, product purity is all higher than 92%, and productive rate can reach 89%, has very strong industrial applications prospect.
 
Embodiment
Describe the present invention with specific embodiment.Protection scope of the present invention is not limited with embodiment, but is limited by claim.
embodiment 1
2.00g tetrahydrobenzene (0.024mol), 2g Mn type D001 resin catalyst are joined in single necked round bottom flask, maintain the temperature at 70 DEG C, slowly drip the hydrogen peroxide of 2.04g (0.012mol) 20%, reaction 0.1-10h, adds a small amount of Na 2s 2o 3the essence reaction of going out.Remove by filter resin, with layering after 10mL × 4 ethyl acetate and the extraction of 10mL × 3 water, water low temperature crystallization, suction filtration obtains the white crystal 2.34g of 1,2-cyclohexanediol, yield 84.0%.
embodiment 2
2.00g tetrahydrobenzene (0.024mol), 10g Ag type D001 resin catalyst are joined in single necked round bottom flask, maintain the temperature at 70 DEG C, slowly drip the hydrogen peroxide of 81.62 (0.72mol) 30%, reaction 0.1-10h, adds a small amount of Na 2s 2o 3the essence reaction of going out.Remove by filter resin, with layering after 100mL × 4 ethyl acetate and the extraction of 100mL × 3 water, water low temperature crystallization, suction filtration obtains the white crystal 2.01g of 1,2-cyclohexanediol, yield 72.12%.
embodiment 3
2.00g tetrahydrobenzene (0.024mol), 2gMn type D001 resin catalyst are joined in single necked round bottom flask, maintain the temperature at 70 DEG C, slowly drip the hydrogen peroxide of 2.72g (0.024mol) 30%, reaction 0.1-10h, adds a small amount of Na 2s 2o 3the essence reaction of going out.Remove by filter resin, with layering after 10mL × 4 ethyl acetate and the extraction of 10mL × 3 water, water low temperature crystallization, suction filtration obtains the white crystal 2.48g of 1,2-cyclohexanediol, yield 89.0%.
embodiment 4
2.00g tetrahydrobenzene (0.024mol), 2g Ag type D001 resin catalyst are joined in single necked round bottom flask, maintain the temperature at 0 DEG C, slowly drip the hydrogen peroxide of 8.16g (0.024mol) 10%, reaction 0.1-10h, adds a small amount of Na 2s 2o 3the essence reaction of going out.Remove by filter resin, with layering after 10mL × 4 ethyl acetate and the extraction of 10mL × 3 water, water low temperature crystallization, suction filtration obtains the white crystal 1.95g of 1,2-cyclohexanediol, yield 70.0%.
embodiment 5
2.00g tetrahydrobenzene (0.024mol), 2g Mn type D001 resin catalyst are joined in single necked round bottom flask, maintain the temperature at 90 DEG C, slowly drip the hydrogen peroxide of 4.08g (0.024mol) 20%, reaction 0.1-10h, adds a small amount of Na 2s 2o 3the essence reaction of going out.Remove by filter resin, with layering after 10mL × 4 ethyl acetate and the extraction of 10mL × 3 water, water low temperature crystallization, suction filtration obtains the white crystal 2.37g of 1,2-cyclohexanediol, yield 85.23%.
embodiment 6
2.00g 1-hexene (0.024mol), 2g Mn type D001 resin catalyst are joined in single necked round bottom flask, maintain the temperature at 70 DEG C, slowly drip the hydrogen peroxide of 2.04g (0.012mol) 20%, reaction 0.1-10h, adds a small amount of Na 2s 2o 3the essence reaction of going out.Remove by filter resin, with layering after 10mL × 4 ethyl acetate and the extraction of 10mL × 3 water, water low temperature crystallization, suction filtration obtains the white crystal 2.19g of 1,2-hexylene glycol, yield 77.56%.
embodiment 7
2.00g 1-hexene (0.024mol), 2g Ag type D001 resin catalyst are joined in single necked round bottom flask, maintain the temperature at 70 DEG C, slowly drip the hydrogen peroxide of 81.62 (0.72mol) 30%, reaction 0.1-10h, adds a small amount of Na 2s 2o 3the essence reaction of going out.Remove by filter resin, with layering after 100mL × 4 ethyl acetate and the extraction of 100mL × 3 water, water low temperature crystallization, suction filtration obtains the white crystal 1.99g of 1,2-hexylene glycol, yield 70.32%.
embodiment 8
2.00g 1-hexene (0.024mol), 2g Mn type D001 resin catalyst are joined in single necked round bottom flask, maintain the temperature at 70 DEG C, slowly drip the hydrogen peroxide of 4.08g (0.024mol) 20%, reaction 0.1-10h, adds a small amount of Na 2s 2o 3the essence reaction of going out.Remove by filter resin, with layering after 10mL × 4 ethyl acetate and the extraction of 10mL × 3 water, water low temperature crystallization, suction filtration obtains the white crystal 2.30g of 1,2-hexylene glycol, yield 81.11%.
embodiment 9
2.00g tetrahydrobenzene (0.024mol), 2g Mn type D001 resin catalyst are joined in single necked round bottom flask, maintain the temperature at 60 DEG C, slowly drip the hydrogen peroxide of 2.72g (0.024mol) 30%, reaction 0.1-10h, adds a small amount of Na 2s 2o 3the essence reaction of going out.Remove by filter resin, with being incorporated to solution after the washed with methanol resin of 5mL × 2, resin reclaims.
embodiment 10
The Mn type D001 resin catalyst of recycling use in 2.00g tetrahydrobenzene (0.024mol), 2g embodiment 61 time is joined in single necked round bottom flask, maintain the temperature at 60 DEG C, slowly drip the hydrogen peroxide of 2.72g (0.024mol) 30%, reaction 0.1-10h, adds a small amount of Na 2s 2o 3the essence reaction of going out.Remove by filter resin, with being incorporated to solution after the washed with methanol resin of 5mL × 2, resin reclaims.Layering after 10mL for reaction solution × 4 ethyl acetate and the extraction of 10mL × 3 water, water low temperature crystallization, suction filtration obtains the white crystal 2.27g of 1,2-cyclohexanediol, yield 81.44%.
embodiment 11
The Mn type D001 resin catalyst of recycling use in 2.00g tetrahydrobenzene (0.024mol), 2g embodiment 7 15 times is joined in single necked round bottom flask, maintain the temperature at 60 DEG C, slowly drip the hydrogen peroxide of 2.72g (0.024mol) 30%, reaction 0.1-10h, adds a small amount of Na 2s 2o 3the essence reaction of going out.Layering after 10mL for reaction solution × 4 ethyl acetate and the extraction of 10mL × 3 water, water low temperature crystallization, suction filtration obtains the white crystal 2.05g of 1,2-cyclohexanediol, yield 73.51%.

Claims (7)

1. the synthetic method of adjacent glycols compound, is characterized in that carrying out in the steps below:
(1) in single necked round bottom flask, add alkene, Zeo-karb, stir and use the heating of thermostatical oil bath, temperature is 0-90 DEG C;
(2) according to adding the consumption of alkene, measure superoxol with constant pressure funnel, slowly add reaction solution, reaction 0.1-10h after reaching design temperature;
(3) after reaction finishes, add a small amount of Na 2s 2o 3the essence reaction of going out;
Leach Zeo-karb, use the washed with methanol that is more than or equal to 1:1 with its mol ratio, reclaim.
2. reaction solution is with after ethyl acetate and water extraction, and water is put into refrigerator, separates out white crystal, is adjacent glycols compound.
3. the synthetic method of adjacent glycols compound according to claim 1, is characterized in that in step (1) wherein, the mol ratio of alkene and Zeo-karb is 1:0.1-1:5.
4. the synthetic method of adjacent glycols compound according to claim 1, is characterized in that in step (2) wherein, the mol ratio of alkene and superoxol is 1:0.5-1:30.
5. the synthetic method of adjacent glycols compound according to claim 1, is characterized in that wherein the alkene structures formula described in step (1) is , R 1, R 2, R 3, R 4can be identical or different be selected from hydrogen, saturated fatty base, comprise the combination of straight-chain paraffin, branched paraffin, naphthenic hydrocarbon and these three kinds of alkane.
6. the synthetic method of adjacent glycols compound according to claim 1, is characterized in that described resin is modification strongly acidic cation-exchange, is Ag type, Mn type, K type, Ni type, Co type, Fe type, Zr type.
7. the synthetic method of adjacent glycols compound according to claim 5, it is characterized in that Ag type, Mn type Zeo-karb that wherein described in step (1), Zeo-karb is modification, its preparation method is: pack commercially available Na type Zeo-karb into ion exchange column with after washed with de-ionized water 3 times; Preparation 10% hydrochloric acid soln, slowly adds ion exchange column, keeps the flow velocity of drip/min of 2-3 to carry out ion-exchange, and after repeated exchanged 2-3 time, use deionized water rinsing, until solution PH=7; Prepare respectively 10% AgNO 3solution and 10% MnCl 2solution, slowly adds ion exchange column again, keeps the flow velocity of 2-3 drip/min to carry out ion-exchange, and after repeated exchanged 2-3 time, use deionized water rinsing, until solution PH=7;
The Ag type, the Mn type Zeo-karb that have exchanged can use after drying.
CN201410193122.7A 2014-05-09 2014-05-09 Method for preparing vicinal diol by catalytic oxidation of alkene in hydrogen peroxide/cationic resin system Expired - Fee Related CN103992207B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110724116A (en) * 2018-07-16 2020-01-24 东营市海科新源化工有限责任公司 Preparation method and production system of vicinal diol compound
CN112441882A (en) * 2019-09-02 2021-03-05 中国石油化工股份有限公司 Stabilizer for refining ethylene glycol and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2145076A (en) * 1983-08-13 1985-03-20 Ciba Geigy Ag A process for producing 1,2-alkanediols
CN1887424A (en) * 2006-07-14 2007-01-03 哈尔滨工业大学 Modified ion exchange resin catalyst and its application
CN1923777A (en) * 2005-08-31 2007-03-07 中国科学院大连化学物理研究所 Preparation method of 1,2-aliphatic glycol
CN101967082A (en) * 2010-04-12 2011-02-09 宁波中化化学品有限公司 Method for preparing 1,2-pentadiol

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2145076A (en) * 1983-08-13 1985-03-20 Ciba Geigy Ag A process for producing 1,2-alkanediols
CN1923777A (en) * 2005-08-31 2007-03-07 中国科学院大连化学物理研究所 Preparation method of 1,2-aliphatic glycol
CN1887424A (en) * 2006-07-14 2007-01-03 哈尔滨工业大学 Modified ion exchange resin catalyst and its application
CN101967082A (en) * 2010-04-12 2011-02-09 宁波中化化学品有限公司 Method for preparing 1,2-pentadiol

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110724116A (en) * 2018-07-16 2020-01-24 东营市海科新源化工有限责任公司 Preparation method and production system of vicinal diol compound
CN110724116B (en) * 2018-07-16 2023-10-24 东营市海科新源化工有限责任公司 Preparation method and production system of vicinal diol compound
CN112441882A (en) * 2019-09-02 2021-03-05 中国石油化工股份有限公司 Stabilizer for refining ethylene glycol and preparation method thereof
CN112441882B (en) * 2019-09-02 2023-04-07 中国石油化工股份有限公司 Stabilizer for refining ethylene glycol and preparation method thereof

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