CN105111044A - Method for synthesizing isopentenol from butenol - Google Patents
Method for synthesizing isopentenol from butenol Download PDFInfo
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- CN105111044A CN105111044A CN201510504493.7A CN201510504493A CN105111044A CN 105111044 A CN105111044 A CN 105111044A CN 201510504493 A CN201510504493 A CN 201510504493A CN 105111044 A CN105111044 A CN 105111044A
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- methyl
- butene
- solid super
- butenol
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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
- C07C29/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by isomerisation
Abstract
The invention is suitable for the technical field of a synthetic method for isopentenol and provides a method for synthesizing isopentenol from butenol. The method is a method for isomerizing double bonds of 3-methyl-3-butenol under the catalytic action of a catalyst composed of solid super base and aluminium isopropoxide, wherein the solid super base is Na-Na2CO3/gamma-Al2O3, the dosage of the catalyst is 0.2-12% of 3-methyl-3-butenol, and the mass ratio of the solid super base and aluminium isopropoxide in the catalyst is 1: 1 to 1: 2. The reaction pressure is 0.5-4MPa, the temperature is 100-140 DEG C and the time is 2-3 hours. The method provided by the invention is mild in reaction condition, the catalyst is high in activity and easy to separate and can be repeatedly used, the method is low in production cost, environmental-friendly and safe in production, and the product is high in purity and selectivity and green and environmental-friendly, so that the cost is greatly lowered, and the method is an efficient and economical synthetic method and has a wide prospect.
Description
Technical field
The present invention relates to the synthetic method technical field of prenol, particularly relate to a kind of method of being synthesized prenol by butenol.
Background technology
Super base reagent is a kind of metallization reaction reagent by organometallic compound and activator mix, is widely used in the fields such as basic organic synthesis, pharmaceutical synthesis, electronic material research and development.Compared with single metalating reagent, it has many superior performances, and its preparation method is easy, not only has very high base strength, but also makes metallization reaction have regioselectivity and the stereochemistry selectivity of height.As the environmentally friendly catalyzer of one, solid base catalyst has a wide range of applications in organic synthesis, in technological innovation, have consequence.Solid base catalyst receives and grant ligand by electronics and forms carbanion thus reaction is occurred, and the investigation and application of solid base catalyst achieves huge progress up to now.
Prenol, being i.e. commonly called as of 3-methyl-3-butene-1-alcohol are colourless oil liquid, be widely used in producing various medicine intermediate, can be used for the synthesis of benzene permethrin sterilant and other fine chemicals, be the important source material of producing medicine or agricultural chemicals, the market requirement is huge.At present, the synthetic method of prenol is mainly isoprene method: be namely raw material with isoprene, product prenol is obtained through processes such as chlorination, esterification, alkaline solution saponification, the method operational path is long, raw material consumption amount is large, by product is many, production cost is higher and seriously polluted, and its prospect causes anxiety.
In nearest prior art, the popular method that prenol is research is now generated with the isomerization of 3-methyl-3-butene-1-alcohol, the normal Pd catalyzer using Se or Te of such reaction, wherein Se, Te and Pd are rare metal, price is high, large-scale promotion use cost is high, and the method that the Chinese patent that such as application number is 200810035295.0 is introduced take aluminum oxide as carrier, its activeconstituents Pd; The loaded catalyst that it is carrier that method described in US Patent No. 4310709 employs with C, active ingredient is Pd and Se.These methods all will use rare metal, and utilize the characteristic of rare metal to improve catalytic activity, price is high, and access times are few.Obviously, in these class methods, isomerization reaction is committed step, therefore finds the key that a kind of cheap, active high, reused catalyzer becomes research.
In summary, obviously there is inconvenience and defect in actual use in prior art, so be necessary to be improved.
Summary of the invention
For above-mentioned defect, the object of the present invention is to provide a kind of method of being synthesized prenol by butenol, its reaction conditions is gentle, catalyst activity is high, be easy to be separated and reusable, product purity and selectivity high, environmental protection, greatly reduces cost, be a kind of synthetic method of efficient economy, have a extensive future.
To achieve these goals, the invention provides a kind of method of being synthesized prenol by butenol, it is for raw material with 3-methyl-3-butene-1-alcohol, under the katalysis of the catalyzer be made up of solid super base and aluminum isopropylate, 3-methyl-3-butene-1-alcohol double-bond isomerization is made to generate prenol; Described solid super base is Na-Na
2cO
3/ γ-Al
2o
3; The consumption of described catalyzer is 0.2% ~ 12% of 3-methyl-3-butene-1-alcohol quality, and in described catalyzer, the mass ratio of solid super base and aluminum isopropylate is 1:1 ~ 1:2; The pressure of building-up reactions is 0.5MPa ~ 4MPa, and temperature of reaction is 100 DEG C ~ 140 DEG C, and the reaction times is 2 ~ 3h.
According to method of being synthesized prenol by butenol of the present invention, the consumption of described catalyzer is 0.5% ~ 8% of 3-methyl-3-butene-1-alcohol quality, and in described catalyzer, the mass ratio of solid super base and aluminum isopropylate is 1:2; The pressure of building-up reactions is 1MPa ~ 3MPa, and temperature of reaction is 110 DEG C ~ 140 DEG C, and the reaction times is 3h.
According to method of being synthesized prenol by butenol of the present invention, the consumption of described catalyzer is 0.5% ~ 5% of 3-methyl-3-butene-1-alcohol quality, and in described catalyzer, the mass ratio of solid super base and aluminum isopropylate is 1:2; The pressure of building-up reactions is 2.5MPa, and temperature of reaction is 110 DEG C ~ 140 DEG C, and the reaction times is 3h.
One provided by the invention with 3-methyl-3-butene-1-alcohol for raw material, under the katalysis of the catalyzer be made up of solid super base and aluminum isopropylate, make 3-methyl-3-butene-1-alcohol double-bond isomerization generate the method for prenol, described solid super base is Na-Na
2cO
3/ γ-Al
2o
3, the consumption of described catalyzer is 0.2% ~ 12% of 3-methyl-3-butene-1-alcohol quality, and in described catalyzer, the mass ratio of solid super base and aluminum isopropylate is 1:1 ~ 1:2; The pressure of building-up reactions is 0.5MPa ~ 4MPa, and temperature of reaction is 100 DEG C ~ 140 DEG C, and the reaction times is 2 ~ 3h.By method of being synthesized prenol by butenol of the present invention, its reaction conditions is gentle, catalyst activity is high, be easy to be separated and reusable, and production cost is low, environmental friendliness, production safety, product purity and selectivity high, environmental protection, greatly reduces cost, be a kind of synthetic method of efficient economy, have a extensive future.
After reaction terminates, catalyzer after filtration or reusablely after centrifugation also can to use continuously, reduces if reuse the activity of catalyzer for several times, re-uses after catalyzer can being stirred activity recovery in a nitrogen environment.
Chemical synthesis route of the present invention is as follows:
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
To achieve these goals, the invention provides a kind of method of being synthesized prenol by butenol, it is for raw material with 3-methyl-3-butene-1-alcohol, under the katalysis of the catalyzer be made up of solid super base and aluminum isopropylate, 3-methyl-3-butene-1-alcohol double-bond isomerization is made to generate prenol; Described solid super base is Na-Na
2cO
3/ γ-Al
2o
3; The consumption of described catalyzer is 0.2% ~ 12% of 3-methyl-3-butene-1-alcohol quality, and in described catalyzer, the mass ratio of solid super base and aluminum isopropylate is 1:1 ~ 1:2; The pressure of building-up reactions is 0.5MPa ~ 4MPa, and temperature of reaction is 100 DEG C ~ 140 DEG C, and the reaction times is 2 ~ 3h.
Embodiment 1
Under the nitrogen environment of 0.5MPa, in reactor, add 650.0 grams of 3-methyl-3 butene-1-ols, add 0.65 gram of aluminum isopropylate, 0.65 gram of Na-Na
2cO
3/ γ-Al
2o
3solid super base, control temperature is 110 DEG C, and reaction times 3h, filters, and is detected by chromatographic instrument, and 3-methyl-3 butene-1-ol participating in reaction is 468.0 grams, generates end product prenol 442.6 grams, transformation efficiency 72.0%, selectivity 94.5%, yield 68.1%.
Embodiment 2
Under the nitrogen environment of 1MPa, in reactor, add 650.0 grams of 3-methyl-3 butene-1-ols, add 0.43 gram of aluminum isopropylate, 0.87 gram of Na-Na
2cO
3/ γ-Al
2o
3solid super base, control temperature is 120 DEG C, and reaction times 2h, filters, and is detected by chromatographic instrument, and 3-methyl-3 butene-1-ol participating in reaction is 483.5 grams, generates end product prenol 439.9 grams, transformation efficiency 74.4%, selectivity 91.0%, yield 67.7%.
Embodiment 3
Under the nitrogen environment of 4MPa, in reactor, add 650.0 grams of 3-methyl-3 butene-1-ols, add 13.5 grams of aluminum isopropylates, 26.5 grams of Na-Na
2cO
3/ γ-Al
2o
3solid super base, control temperature is 120 DEG C, and reaction times 2.1h, filters, detected by chromatographic instrument, 3-methyl-3 butene-1-ol participating in reaction is 475.5 grams, generates end product prenol 445.3 grams, selectivity 93.6%, transformation efficiency 73.2%, yield 68.5%.
Embodiment 4
Under the nitrogen environment of 3MPa, in reactor, add 650.0 grams of 3-methyl-3 butene-1-ols, add 17.3 grams of aluminum isopropylates, 21.6 grams of Na-Na
2cO
3/ γ-Al
2o
3solid super base, control temperature is 140 DEG C, and reaction times 2.5h, filters, detected by chromatographic instrument, 3-methyl-3 butene-1-ol participating in reaction is 461.0 grams, generates end product prenol 428.8 grams, selectivity 93.0%, transformation efficiency 70.9%, yield 66.0%.
Embodiment 5
Under the nitrogen environment of 2.5MPa, in reactor, add 650.0 grams of 3-methyl-3 butene-1-ols, add 5.6 grams of aluminum isopropylates, 10.2 grams of Na-Na
2cO
3/ γ-Al
2o
3solid super base, control temperature is 130 DEG C, and reaction times 3h, filters, and is detected by chromatographic instrument, and 3-methyl-3 butene-1-ol participating in reaction is 481.5 grams, generates end product prenol 457.2 grams, selectivity 95.0%, transformation efficiency 74.1%, yield 70.3%.
Embodiment 6
Under the nitrogen environment of 2MPa, in reactor, add 650.0 grams of 3-methyl-3 butene-1-ols, add 2.2 grams of aluminum isopropylates, 3.8 grams of Na-Na
2cO
3/ γ-Al
2o
3solid super base, control temperature is 100 DEG C, and reaction times 2.6h, filters, detected by chromatographic instrument, 3-methyl-3 butene-1-ol participating in reaction is 477.0 grams, generates end product prenol 446.3 grams, selectivity 93.6%, transformation efficiency 73.4%, yield 68.7%.
Controlled trial 1:
Under the nitrogen environment of 2.5MPa, in reactor, add 650.0 grams of 3-methyl-3 butene-1-ols, add 10.2 grams of Na-Na
2cO
3/ γ-Al
2o
3solid super base, control temperature is 130 DEG C, and reaction times 3h, filters, and is detected by chromatographic instrument, and 3-methyl-3 butene-1-ol participating in reaction is 298.5 grams, generates end product prenol 200.5 grams, selectivity 67.2%, transformation efficiency 45.9%, yield 30.8%.
Controlled trial 2:
Under the nitrogen environment of 2.5MPa, in reactor, add 650.0 grams of 3-methyl-3 butene-1-ols, add 5.6 grams of aluminum isopropylates, control temperature is 130 DEG C, reaction times 3h, filter, detected by chromatographic instrument, 3-methyl-3 butene-1-ol participating in reaction is 238.0 grams, generate end product prenol 92.1 grams, selectivity 38.7%, transformation efficiency 36.6%, yield 14.2%.
In sum, one provided by the invention with 3-methyl-3-butene-1-alcohol for raw material, under the katalysis of the catalyzer be made up of solid super base and aluminum isopropylate, make 3-methyl-3-butene-1-alcohol double-bond isomerization generate the method for prenol, described solid super base is Na-Na
2cO
3/ γ-Al
2o
3, the consumption of described catalyzer is 0.2% ~ 12% of 3-methyl-3-butene-1-alcohol quality, and in described catalyzer, the mass ratio of solid super base and aluminum isopropylate is 1:1 ~ 1:2; The pressure of building-up reactions is 0.5MPa ~ 4MPa, and temperature of reaction is 100 DEG C ~ 140 DEG C, and the reaction times is 2 ~ 3h.By method of being synthesized prenol by butenol of the present invention, its reaction conditions is gentle, catalyst activity is high, be easy to be separated and reusable, and production cost is low, environmental friendliness, production safety, product purity and selectivity high, environmental protection, greatly reduces cost, be a kind of synthetic method of efficient economy, have a extensive future.
Certainly; the present invention also can have other various embodiments; when not deviating from the present invention's spirit and essence thereof; those of ordinary skill in the art are when making various corresponding change and distortion according to the present invention, but these change accordingly and are out of shape the protection domain that all should belong to the claim appended by the present invention.
Claims (3)
1. one kind is synthesized the method for prenol by butenol, it is characterized in that, it is with 3-methyl-3-butene-1-alcohol for raw material, under the katalysis of the catalyzer be made up of solid super base and aluminum isopropylate, makes 3-methyl-3-butene-1-alcohol double-bond isomerization generate prenol;
Described solid super base is Na-Na
2cO
3/ γ-Al
2o
3;
The consumption of described catalyzer is 0.2% ~ 12% of 3-methyl-3-butene-1-alcohol quality, and in described catalyzer, the mass ratio of solid super base and aluminum isopropylate is 1:1 ~ 1:2;
The pressure of building-up reactions is 0.5MPa ~ 4MPa, and temperature of reaction is 100 DEG C ~ 140 DEG C, and the reaction times is 2 ~ 3h.
2. method of being synthesized prenol by butenol according to claim 1, it is characterized in that, the consumption of described catalyzer is 0.5% ~ 8% of 3-methyl-3-butene-1-alcohol quality, and in described catalyzer, the mass ratio of solid super base and aluminum isopropylate is 1:2; The pressure of building-up reactions is 1MPa ~ 3MPa, and temperature of reaction is 110 DEG C ~ 140 DEG C, and the reaction times is 3h.
3. method of being synthesized prenol by butenol according to claim 1, it is characterized in that, the consumption of described catalyzer is 0.5% ~ 5% of 3-methyl-3-butene-1-alcohol quality, and in described catalyzer, the mass ratio of solid super base and aluminum isopropylate is 1:2; The pressure of building-up reactions is 2.5MPa, and temperature of reaction is 110 DEG C ~ 140 DEG C, and the reaction times is 3h.
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|---|---|---|---|
| CN201510504493.7A CN105111044B (en) | 2015-08-17 | 2015-08-17 | The method that prenol is synthesized by butenol |
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|---|---|---|---|
| CN201510504493.7A CN105111044B (en) | 2015-08-17 | 2015-08-17 | The method that prenol is synthesized by butenol |
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| CN105111044A true CN105111044A (en) | 2015-12-02 |
| CN105111044B CN105111044B (en) | 2018-02-16 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175230A (en) * | 2015-09-08 | 2015-12-23 | 山东成泰化工有限公司 | Method of synthesizing isopentenol from butenol |
| CN109721470A (en) * | 2018-12-29 | 2019-05-07 | 中触媒新材料股份有限公司 | A kind of method that serialization prepares prenol |
| CN111099994A (en) * | 2019-11-18 | 2020-05-05 | 名畔科技(镇江)有限公司 | Preparation method of surfactant |
Citations (3)
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| WO2009106622A1 (en) * | 2008-02-28 | 2009-09-03 | Basf Se | Method for isomerizing olefinically unsaturated alcohols |
| CN102675048A (en) * | 2012-04-20 | 2012-09-19 | 山东新和成药业有限公司 | Method for synthesizing prenol by composite catalyst |
| CN102701910A (en) * | 2012-05-24 | 2012-10-03 | 南开大学 | Method for preparing prenol by isomerizing 3-methyl-3-butene-1-ethanol |
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2015
- 2015-08-17 CN CN201510504493.7A patent/CN105111044B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009106622A1 (en) * | 2008-02-28 | 2009-09-03 | Basf Se | Method for isomerizing olefinically unsaturated alcohols |
| CN102675048A (en) * | 2012-04-20 | 2012-09-19 | 山东新和成药业有限公司 | Method for synthesizing prenol by composite catalyst |
| CN102701910A (en) * | 2012-05-24 | 2012-10-03 | 南开大学 | Method for preparing prenol by isomerizing 3-methyl-3-butene-1-ethanol |
Non-Patent Citations (1)
| Title |
|---|
| 丁元生等: "Na-Na2CO3/γ-Al2O3型固体超强碱催化剂的制备及表征", 《精细石油化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175230A (en) * | 2015-09-08 | 2015-12-23 | 山东成泰化工有限公司 | Method of synthesizing isopentenol from butenol |
| CN109721470A (en) * | 2018-12-29 | 2019-05-07 | 中触媒新材料股份有限公司 | A kind of method that serialization prepares prenol |
| CN109721470B (en) * | 2018-12-29 | 2022-03-25 | 中触媒新材料股份有限公司 | Method for continuously preparing isopentenol |
| CN111099994A (en) * | 2019-11-18 | 2020-05-05 | 名畔科技(镇江)有限公司 | Preparation method of surfactant |
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| CN105111044B (en) | 2018-02-16 |
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Inventor after: Han Haibin Inventor after: Wen Bin Inventor after: Liu Mingjiu Inventor before: Zhang Guohua Inventor before: Ji Ke Inventor before: Jiang Lixin Inventor before: Geng Guangli Inventor before: Yu Shuhua |
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Effective date of registration: 20190704 Address after: 261300 Chengtai Road, Binhai (Xiaying) Economic Development Zone, Changyi City, Weifang City, Shandong Province Patentee after: Shandong Chengtai New Materials Co., Ltd. Address before: 261313 Binhai (Xiaying) Economic Development Zone, Weifang City, Shandong Province Patentee before: Shandong Cheng Tai Chemical Co., Ltd. |
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