CN104177230B - A kind of preparation method of 1,2-ring pentanediol - Google Patents
A kind of preparation method of 1,2-ring pentanediol Download PDFInfo
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- CN104177230B CN104177230B CN201410375699.XA CN201410375699A CN104177230B CN 104177230 B CN104177230 B CN 104177230B CN 201410375699 A CN201410375699 A CN 201410375699A CN 104177230 B CN104177230 B CN 104177230B
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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 kind of 1, the preparation method of 2-ring pentanediol, comprise the steps: 1) oxidizing reaction: in reaction system, add a certain amount of raw material cyclopentenes, catalyzer, promotor and hydrogen peroxide, react 4 ~ 6 hours at 35 ~ 45 DEG C, obtain the oxidation products cyclopentane epoxide of cyclopentenes; 2) hydrolysis reaction: add a certain amount of deionized water in aforesaid oxidation products cyclopentane epoxide, using solid proton acid as catalyzer, hydrolysis reaction 80 ~ 110 hours at 70 ~ 90 DEG C; 3) product separation: the mixture underpressure distillation obtained after hydrolysis reaction is obtained product 1,2-ring pentanediol.The preparation method of 1,2-ring pentanediol provided by the invention, adopts hydrogen peroxide as oxygenant, adopts Fe-Cu Primary Catalysts+KCl promotor to carry out catalysis; Oxygenant is easy to get, cost is low, water generation reaction can not produce pollution to environment; Catalyzer is easy to get, cost is low, toxicity is little, activity is high, stability is strong; Product yield is high, and production process is simple to operation.
Description
Technical field
The present invention relates to a kind of preparation method of 1,2-ring pentanediol, belong to chemical production field.
Background technology
Ring pentanediol is the important intermediate preparing cyclopentanedione, and cyclopentanedione has extensive use in chemical industry, medicine etc. are a lot, as being used as chemical solvents, spices, medicine intermediate, pesticide intermediate, organic intermediate, foodstuff additive etc.Ring pentanediol is oxidized obtained by cyclopentenes by the dihydroxylation of alkene usually.The catalyzer that alkene dihydroxylation uses has the oxide compound of osmium, ruthenium and manganese usually, wherein OsO
4to the selectivity of alkene addition and reliability the highest.But because perosmic anhydride is expensive, toxicity large, for having little significance of a large amount of organic preparation.Therefore, find a kind of excellent catalytic effect, environmental friendliness and the low catalyst system of cost have very important significance.
Prepare ring pentanediol by cyclopentenes, generate intermediate product epoxy group(ing) pentamethylene, epoxy group(ing) pentamethylene is hydrolyzed further and 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 all easily initial ring are oxidized, and this is considered to a kind of molecular reaction usually, 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 being oxygen source with oxygen and hydrogen peroxide enjoys the favor of people.With oxygen be oxygen source gas-solid phase reaction except ethene air direct oxidation method produce oxyethane realized except 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.Be that the homogeneous catalysis system of oxygen source also has research with oxygen, and some systems also achieve good result, but mostly catalyzer is metal complexes, stability is low, and reclaims difficulty.By contrast, hydrogen peroxide, owing to having more active oxygen and generating the water of environmental sound after the reaction, is a kind of desirable environmental friendliness oxygen source.In recent years, be that the exploitation of catalyzing expoxidation of olefines system of oxygen source becomes dominating of epoxidation research field and has made great progress with hydrogen peroxide.
Summary of the invention
The object of this invention is to provide a kind of under catalyzer and oxygenant existent condition, be hydrolyzed the production method of preparation 1,2-ring pentanediol by oxidation of cyclopentene.
What the present invention solved is that the catalyzer cost existed in the preparation method of existing 1,2-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, react 4 ~ 6 hours at 35 ~ 45 DEG C, 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 80 ~ 110 hours at 70 ~ 90 DEG C; 3) product separation: after the mixture underpressure distillation obtained after hydrolysis reaction is removed moisture, further underpressure distillation obtains product 1,2-ring 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.
The reaction formula of the preparation method of 1,2-described ring pentanediol is as follows:
The invention has the beneficial effects as follows: compared with prior art, the preparation method of 1,2-ring pentanediol provided by the invention, adopt hydrogen peroxide as oxygenant, adopt 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 preparation method of 1,2-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, react 6 hours at 35 DEG C, 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: the deionized water adding 5 times of quality in aforesaid oxidation products cyclopentane epoxide, using solid proton acid as catalyzer, hydrolysis reaction 110 hours at 70 DEG C.
3) product separation: after the mixture underpressure distillation obtained after hydrolysis reaction is removed moisture, further underpressure distillation obtains product 1,2-ring pentanediol.The yield of described product 1,2-ring pentanediol is 88.9%.
Embodiment 2
A kind of preparation method of 1,2-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, react 5 hours at 40 DEG C, 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: the deionized water adding 4 times of quality in aforesaid oxidation products cyclopentane epoxide, using solid proton acid as catalyzer, hydrolysis reaction 100 hours at 80 DEG C.
3) product separation: after the mixture underpressure distillation obtained after hydrolysis reaction is removed moisture, further underpressure distillation obtains product 1,2-ring pentanediol.The yield of described product 1,2-ring pentanediol is 90%.
Embodiment 3
A kind of preparation method of 1,2-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, react 4 hours at 45 DEG C, 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: the deionized water adding 4 times of quality in aforesaid oxidation products cyclopentane epoxide, using solid proton acid as catalyzer, hydrolysis reaction 80 hours at 90 DEG C.
3) product separation: after the mixture underpressure distillation obtained after hydrolysis reaction is removed moisture, further underpressure distillation obtains product 1,2-ring pentanediol.The yield of described product 1,2-ring pentanediol is 88.2%.
Claims (4)
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, react 4 ~ 6 hours at 35 ~ 45 DEG C, 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 80 ~ 110 hours at 70 ~ 90 DEG C; 3) product separation: after the mixture underpressure distillation obtained after hydrolysis reaction is removed moisture, further underpressure distillation obtains product 1,2-ring 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.
2. the preparation method of a kind of 1,2-ring pentanediol as claimed in claim 1, is characterized in that the mol ratio of Repone K and sodium-chlor in described mixed cocatalyst is 0.5 ~ 2:1.
3. the preparation method of a kind of 1,2-ring pentanediol as claimed in claim 1 or 2, 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.
4. the preparation method of a kind of 1,2-ring pentanediol as claimed in claim 1, it 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008169204A (en) * | 2006-12-15 | 2008-07-24 | Sumitomo Chemical Co Ltd | Method for preparing (1r, 2r)-2-amino-1-cyclopentanol |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|
| Cyclopentene oxidation with H2O2 over Ti-containing zeolites;Vasile Hulea et al.;《Applied Catalysis A: General》;19981231;第170卷;169-175 * |
| Selective liquid-phase oxidation of cyclopentene over MWW type titanosilicate;Peng Wu et al.;《Catalysis Today》;20060612;第117卷;199-205 * |
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