CN104177230A - Preparation method of 1,2-cyclopentanediol - Google Patents
Preparation method of 1,2-cyclopentanediol Download PDFInfo
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- CN104177230A CN104177230A CN201410375699.XA CN201410375699A CN104177230A CN 104177230 A CN104177230 A CN 104177230A CN 201410375699 A CN201410375699 A CN 201410375699A CN 104177230 A CN104177230 A CN 104177230A
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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
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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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
- C07D303/06—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms in which the oxirane rings are condensed with a carbocyclic ring system having three or more relevant rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
Abstract
The invention discloses a preparation method of 1,2-cyclopentanediol. The preparation method comprises the following steps: 1) oxidizing reaction, namely adding a certain amount of raw materials, namely cyclopentene, a catalyst, a cocatalyst and hydrogen peroxide to a reaction system, reacting at 35-45 DEG C for 4-6 hours, so as to obtain an oxidative product cyclopentene oxide of cyclopentene; 2) hydrolysis reaction, adding a certain amount of deionized water to the oxidative product cyclopentene oxide, carrying out hydrolysis reaction at 70-90 DEG C for 80-110 hours based on a solid proton acid as the catalyst; and 3) product separation, namely distilling the mixture obtained after hydrolysis reaction at reduced pressure to obtain the product 1,2-cyclopentanediol. According to the preparation method of the 1,2-cyclopentanediol, hydrogen peroxide is adopted as an oxidant; Fu-Cu main catalyst and KCl cocatalyst are adopted to catalyze; the oxidant is easily available and low in cost; the water generated by reaction does not pollute the environment; the catalyst is easily available, low in cost, small in toxicity, high in activity, and strong in stability; the product is high in yield; and the production process is simple and easy to operate.
Description
Technical field
The present invention relates to a kind ofly 1, the preparation method of 2-ring pentanediol, belongs to chemical production field.
Background technology
Ring pentanediol is the important intermediate of preparing cyclopentanedione, and cyclopentanedione has extensive use at chemical industry, medicine etc. aspect a lot, as being used as chemical solvents, spices, medicine intermediate, pesticide intermediate, organic intermediate, foodstuff additive etc.Conventionally by cyclopentenes, the dihydroxylation oxidation by alkene makes ring pentanediol.The catalyzer that alkene dihydroxylation is used has the oxide compound of osmium, ruthenium and manganese, wherein OsO conventionally
4the highest to the selectivity of alkene addition and reliability.But because perosmic anhydride is expensive, toxicity is large, for having little significance of a large amount of organic preparations.Therefore, finding the catalyst system that a kind of excellent catalytic effect, environmental friendliness and cost are low has very important significance.
By cyclopentenes preparation ring pentanediol, generate intermediate product epoxy group(ing) pentamethylene, epoxy group(ing) pentamethylene further hydrolysis just generates ring pentanediol, and wherein the epoxidation reaction of cyclopentenes is crucial.No matter in polarity or non-polar solvent, alkene and peracid effect be easily initial ring oxidation all, and this is considered to a kind of molecular reaction conventionally, and in fact addition is stereospecificity.The epoxidation of cyclopentenes is a catalytic oxidation process, and the selection of catalyzer and oxygenant is crucial.The olefin catalytic epoxidation reaction that oxygen and hydrogen peroxide be oxygen source of take enjoys people's favor.The gas-solid phase reaction that the oxygen of take is oxygen source is produced oxyethane except ethene air direct oxidation method and has been realized industrialization, the air direct oxidation of other alkene seldom succeeds, major cause is that the c h bond of allylic is more easily oxidized, generates a large amount of by products.The homogeneous catalysis system that the oxygen of take is oxygen source also has research, and some systems have also obtained good result, but mostly catalyzer is metal complexes, and stability is low, and reclaims difficulty.By contrast, hydrogen peroxide, owing to having more active oxygen and generating afterwards the water of environmental sound in reaction, is a kind of desirable environmental friendliness oxygen source.In recent years, take the exploitation of the catalyzing expoxidation of olefines system that hydrogen peroxide is oxygen source becomes dominating and having made great progress of epoxidation research field.
Summary of the invention
The object of this invention is to provide under a kind of condition existing at catalyzer and oxygenant, by cyclopentenes oxydrolysis, prepared the production method of 1,2-ring pentanediol.
The present invention solves is existing 1, and the catalyzer cost that exists in the preparation method of 2-ring pentanediol is high, environment friendly is poor, and the oxidation effectiveness of oxygenant is not ideal enough, to defects such as the pollution of environment are large.
The technical scheme that technical solution problem of the present invention adopts is: a kind of 1, the preparation method of 2-ring pentanediol, described preparation method comprises the steps: 1) oxidizing reaction: in reaction system, add a certain amount of raw material cyclopentenes, catalyzer, promotor and hydrogen peroxide, at 35～45 ℃, react 4～6 hours, obtain the oxidation products cyclopentane epoxide of cyclopentenes; In raw material, the mass ratio of cyclopentenes and hydrogen peroxide is 3.5～4.5:1; 2) hydrolysis reaction: add a certain amount of deionized water in aforesaid oxidation products cyclopentane epoxide, using solid proton acid as catalyzer, hydrolysis reaction is 80～110 hours at 70～90 ℃; 3) product separation: the mixture underpressure distillation obtaining after hydrolysis reaction is removed after moisture, and further underpressure distillation obtains product 1, and 2-encircles pentanediol.
Described catalyzer adopts Fe-Cu catalyst system, and in described catalyst system, the mass ratio of Fe and Cu is 49:8.
Described promotor is the mixture of any one or both in Repone K, sodium-chlor.
Further, in described mixed cocatalyst, the mol ratio of Repone K and sodium-chlor is 0.5～2:1.
The mass ratio of described catalyzer, promotor and hydrogen peroxide is 1.0:0.02～0.03:1.5～2.0.
In described hydrolysis reaction, the mass ratio of oxidation products and deionized water is 1:3～5.
Described 1, the preparation method's of 2-ring pentanediol reaction formula is as follows:
The invention has the beneficial effects as follows: compared with prior art, provided by the invention 1, the preparation method of 2-ring pentanediol, adopts hydrogen peroxide as oxygenant, adopts the catalyst system of Fe-Cu Primary Catalysts+KCl promotor; Oxygenant is easy to get and cost is low, water generation reaction can not produce pollution to environment; Catalyzer is easy to get, cost is low, toxicity is little, catalytic activity is high, stability is strong; Product yield is high, and production process is simple to operation.
Embodiment
Embodiment 1
A kind of 1, the preparation method of 2-ring pentanediol, described preparation method comprises the steps:
1) oxidizing reaction: add a certain amount of raw material cyclopentenes, catalyzer, promotor and hydrogen peroxide in reaction system, at 35 ℃, react 6 hours, obtain the oxidation products cyclopentane epoxide of cyclopentenes, described catalyzer adopts Fe-Cu catalyst system, and in described catalyst system, the mass ratio of Fe and Cu is 49:8; Described promotor is sodium-chlor; Described cyclopentenes and the mass ratio of hydrogen peroxide are 4.5:1, and the mass ratio of described catalyzer, promotor and hydrogen peroxide is 1.0:0.02:1.5.The yield of described oxidizing reaction cyclopentane epoxide is 95.3%.
2) hydrolysis reaction: add the deionized water of 5 times of quality in aforesaid oxidation products cyclopentane epoxide, using solid proton acid as catalyzer, hydrolysis reaction is 110 hours at 70 ℃.
3) product separation: the mixture underpressure distillation obtaining after hydrolysis reaction is removed after moisture, and further underpressure distillation obtains product 1, and 2-encircles pentanediol.Described product 1, the yield of 2-ring pentanediol is 88.9%.
Embodiment 2
A kind of 1, the preparation method of 2-ring pentanediol, described preparation method comprises the steps:
1) oxidizing reaction: add a certain amount of raw material cyclopentenes, catalyzer, promotor and hydrogen peroxide in reaction system, at 40 ℃, react 5 hours, obtain the oxidation products cyclopentane epoxide of cyclopentenes, described catalyzer adopts Fe-Cu catalyst system, and in described catalyst system, the mass ratio of Fe and Cu is 49:8; Described promotor is the mixture of Repone K and sodium-chlor, and the mol ratio of Repone K and sodium-chlor is 1:1; Described cyclopentenes and the mass ratio of hydrogen peroxide are 4:1, and the mass ratio of described catalyzer, promotor and hydrogen peroxide is 1.0:0.025:1.9.The yield of described oxidizing reaction cyclopentane epoxide is 96%.
2) hydrolysis reaction: add the deionized water of 4 times of quality in aforesaid oxidation products cyclopentane epoxide, using solid proton acid as catalyzer, hydrolysis reaction is 100 hours at 80 ℃.
3) product separation: the mixture underpressure distillation obtaining after hydrolysis reaction is removed after moisture, and further underpressure distillation obtains product 1, and 2-encircles pentanediol.Described product 1, the yield of 2-ring pentanediol is 90%.
Embodiment 3
A kind of 1, the preparation method of 2-ring pentanediol, described preparation method comprises the steps:
1) oxidizing reaction: add a certain amount of raw material cyclopentenes, catalyzer, promotor and hydrogen peroxide in reaction system, at 45 ℃, react 4 hours, obtain the oxidation products cyclopentane epoxide of cyclopentenes, described catalyzer adopts Fe-Cu catalyst system, and in described catalyst system, the mass ratio of Fe and Cu is 49:8; Described promotor is sodium-chlor; Described cyclopentenes and the mass ratio of hydrogen peroxide are 3.5:1, and the mass ratio of described catalyzer, promotor and hydrogen peroxide is 1.0:0.03:2.0.The yield of described oxidizing reaction cyclopentane epoxide is 95.5%.
2) hydrolysis reaction: add the deionized water of 4 times of quality in aforesaid oxidation products cyclopentane epoxide, using solid proton acid as catalyzer, hydrolysis reaction is 80 hours at 90 ℃.
3) product separation: the mixture underpressure distillation obtaining after hydrolysis reaction is removed after moisture, and further underpressure distillation obtains product 1, and 2-encircles pentanediol.Described product 1, the yield of 2-ring pentanediol is 88.2%.
Claims (6)
1. one kind 1, the preparation method of 2-ring pentanediol, it is characterized in that described preparation method comprises the steps: 1) oxidizing reaction: in reaction system, add a certain amount of raw material cyclopentenes, catalyzer, promotor and hydrogen peroxide, at 35～45 ℃, react 4～6 hours, obtain the oxidation products cyclopentane epoxide of cyclopentenes; In raw material, the mass ratio of cyclopentenes and hydrogen peroxide is 3.5～4.5:1; 2) hydrolysis reaction: add a certain amount of deionized water in aforesaid oxidation products cyclopentane epoxide, using solid proton acid as catalyzer, hydrolysis reaction is 80～110 hours at 70～90 ℃; 3) product separation: the mixture underpressure distillation obtaining after hydrolysis reaction is removed after moisture, and further underpressure distillation obtains product 1, and 2-encircles pentanediol.
2. as claimed in claim 1 a kind of 1, the preparation method of 2-ring pentanediol, is characterized in that described catalyzer adopts Fe-Cu catalyst system, and in described catalyst system, the mass ratio of Fe and Cu is 49:8.
3. as claimed in claim 1 a kind of 1, the preparation method of 2-ring pentanediol, is characterized in that described promotor is the mixture of any one or both in Repone K, sodium-chlor.
4. as claimed in claim 3 a kind of 1, the preparation method of 2-ring pentanediol, is characterized in that in described mixed cocatalyst, the mol ratio of Repone K and sodium-chlor is 0.5～2:1.
5. a kind of 1 as described in claim 1 to 4, the preparation method of 2-ring pentanediol, is characterized in that the mass ratio of described catalyzer, promotor and hydrogen peroxide is 1.0:0.02～0.03:1.5～2.0.
6. as claimed in claim 1 a kind of 1, the preparation method of 2-ring pentanediol, is characterized in that in described hydrolysis reaction, the mass ratio of oxidation products and deionized water is 1:3～5.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008072773A1 (en) * | 2006-12-15 | 2008-06-19 | Sumitomo Chemical Company, Limited | Method for producing (1r,2r)-2-amino-1-cyclopentanol |
| CN101891711A (en) * | 2010-07-23 | 2010-11-24 | 上海化工研究院 | Method for preparing epoxide by utilizing catalytic epoxidation in presence of phase transfer catalyst |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008072773A1 (en) * | 2006-12-15 | 2008-06-19 | Sumitomo Chemical Company, Limited | Method for producing (1r,2r)-2-amino-1-cyclopentanol |
| CN101891711A (en) * | 2010-07-23 | 2010-11-24 | 上海化工研究院 | Method for preparing epoxide by utilizing catalytic epoxidation in presence of phase transfer catalyst |
Non-Patent Citations (2)
| Title |
|---|
| PENG WU ET AL.: "Selective liquid-phase oxidation of cyclopentene over MWW type titanosilicate", 《CATALYSIS TODAY》 * |
| VASILE HULEA ET AL.: "Cyclopentene oxidation with H2O2 over Ti-containing zeolites", 《APPLIED CATALYSIS A: GENERAL》 * |
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