CN1781908A - Process for preparing epsilon-hexanolactam by catalyzing cyclohexanone-oxime rearranging - Google Patents
Process for preparing epsilon-hexanolactam by catalyzing cyclohexanone-oxime rearranging Download PDFInfo
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- CN1781908A CN1781908A CN 200410100908 CN200410100908A CN1781908A CN 1781908 A CN1781908 A CN 1781908A CN 200410100908 CN200410100908 CN 200410100908 CN 200410100908 A CN200410100908 A CN 200410100908A CN 1781908 A CN1781908 A CN 1781908A
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- hexanolactam
- oxime
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Abstract
The present invention relates to catalytic Beckmann rearrangement process of cyclohexanone-oxime by using the Bronsted acid ion liquid with N-protonated hexanolactam as cationic group serving as the catalyst and reaction medium to prepare epsilon-hexanolactam. The present invention produces epsilon-hexanolactam in mild reaction temperature, short reaction period, high conversion rate and high selectivity, and the acid ion liquid may be reused. The product is no longer combined with the acid ion liquid and needs no alkali neutralization, and the reaction system is simple, without environmental pollution, no corrosion on the apparatus, low cost of the acid ion liquid, and excellent industrial application foreground.
Description
Technical field
The present invention relates to a kind of method of preparing epsilon-hexanolactam by catalyzing cyclohexanone-oxime rearranging, concretely, the present invention relates to a kind of is that the acid ionic liquid at room temperature of Br nsted of cation group is that the catalysis of pimelinketone oxime of catalyzer and reaction medium is reset the method for preparing ε-Ji Neixianan through Beckmann with the protonated hexanolactam of N-.
Background technology
ε-Ji Neixianan is a kind of important chemical material, mainly as the polymerization single polymerization monomer of nylon 6 fiber and production of resins, in industries such as weaving, plastics and leatheroids extensive use is arranged.The traditional processing technology of ε-Ji Neixianan is that cyclohexanone-oxime is reset the preparation ε-Ji Neixianan through Beckmann.Reset to adopt and contain 30%SO
3Oleum under 100-130 ℃, carry out, reaction finishes the back and adds a large amount of ammoniacal liquor and make with vitriol oil bonded hexanolactam and dissociate out.But this technology has many shortcomings: a large amount of low value-added ammonium sulfate (2-4 ton/ton hexanolactam) of (1) by-product; (2) equipment corrosion is serious; (3) Fu Za follow-up hexanolactam purifying process; (4) produce a large amount of acid water pollution environment.Therefore develop a kind of environmental friendliness, pollution-free, do not produce solid waste, easily and the isolating clean catalysis technology of reaction system become chemical researchist research and development object for a long time.Though with solid acids such as molecular sieve and metal oxides is that the gas phase Beckmann of catalyzer is rearranged in and has solved the problems referred to above to a certain extent, harsh reaction conditions (350-500 ℃ of high temperature) and rapid catalyst inactivation make in the rearrangement product the more and catalyzer of by product need frequent regeneration.Recently have report (J.Org.Chem.1998,63,9100) can realize in supercritical water that rearrangement of cyclohexanone-oxime is a hexanolactam, but reaction conversion ratio is very low, adds that supercritical water needs High Temperature High Pressure, the industrial application difficulty is very big.Therefore seeking reaction conditions gentleness, eco-friendly liquid phase Beckmann rearrangement reaction catalyst system and technology still is necessary.
Ionic liquid at room temperature be fully by certain cationic and negatively charged ion constitute in room temperature or be bordering on the material that is in a liquid state under the room temperature.Compare with solid matter, it is liquid; Compare with traditional fluent meterial, it is an ionic.Thereby, to compare with other solids or fluent material, ionic liquid often shows unique physicochemical property and functions peculiar.From the early 1980s, successively has carried out since the ionic liquid research countries in the world etc., ionic liquid at room temperature with its liquid temperature wide ranges, almost do not have vapour pressure, thermal capacitance is big, thermostability is high, excellent physical chemistry such as reusable obtains broad research in organic synthesis, catalytic chemistry, electrochemistry, compartment analysis, friction and every field such as lubricated.Studies show that, the first step of the catalytic Beckmann rearrangement reaction of protonic acid is that the nitrogen-oxygen bond part of oxime is protonated, then form epimino positive ion intermediate, and the inner strong coulombic force of ionic liquid, can strengthen the stability of this positive charge intermediate, and ion liquid weak coordination ability might strengthen the hydrogen ion degree of freedom that dissociates from protonic acid, makes it show more strongly-acid.Therefore, in ionic liquid, carry out the Beckmann rearrangement reaction than usual vehicle is preferably.Calendar year 2001 Deng You congruence (Tetrahedron Letters, 2001,42, in the imidazolyl ionic liquid at room temperature be that catalyzer has realized that successfully the high highly selective Beckmann that transforms of cyclohexanone-oxime resets the preparation ε-Ji Neixianan 403-405) with the phosphorus compound, but catalyzer can not be reused, product and catalyst system separation difficulty.Task-specific ionic liquid was subject to people's attention because of the response characteristic of its high reactivity, highly selective in recent years.Bibliographical information (Tetrahedron Letters was arranged in 2004,2004,45,2681-2683) use the ionic liquid of imidazoles cationic functionalization can carry out effective Beckmann rearrangement as reaction medium and catalyzer, but weakly alkaline product hexanolactam still has combining of certain degree with acidic ion liquid, cause the separation difficulty of product and catalyzer, thereby limited its prospects for commercial application.Therefore develop a kind of efficient, with easily separated, the reusable ionic liquid at room temperature catalyst system of product hexanolactam, be to realize in the ionic liquid at room temperature that the clean catalysis Beckmann rearrangement of cyclohexanone oxime is equipped with the key of ε-Ji Neixianan.
What deserves to be mentioned is that the ε-Ji Neixianan molecule has tertiary amine structure like same imidazoles, the pyridines, if be the cationic Br of having nsted tart ionic liquid in conjunction with forming with hexanolactam with strong Br nsted acid.If this type of ionic liquid is reset the preparation ε-Ji Neixianan as catalyzer and reaction medium catalysis of pimelinketone oxime through Beckmann, can imagine that the product ε-Ji Neixianan is resolved owing to existing following running balance to react with the problem that combines that with ε-Ji Neixianan is cationic Br nsted acidic ionic liquid catalysts and medium:
X wherein
-=BF
4 -, CF
3COO
-, ClCH
2COO
-, C
6H
4COO
-, C
6H
4CH
2COO
-, NO
3 -The product ε-Ji Neixianan be that cationic ionic-liquid catalyst and reaction medium can be separated by suitable separating and extracting method with hexanolactam, no longer produce a large amount of solid by-products, and ionic-liquid catalyst and reaction medium can reuse.
Summary of the invention
The object of the present invention is to provide a kind of is that the Br nsted acidic ion liquid of cation group is catalyzer and reaction medium catalysis of pimelinketone oxime prepare ε-Ji Neixianan through the Beckmann rearrangement reaction a method with the protonated hexanolactam of N-.
A kind of method of preparing epsilon-hexanolactam by catalyzing cyclohexanone-oxime rearranging, it is characterized in that with the protonated hexanolactam of N-be the Br nsted acidic ion liquid of cation group as catalyzer and reaction medium, its chemical structural formula is with formula (I) expression:
X wherein
-Be the anionic group of Br nsted acid HX, X
-Be selected from BF
4 -, CF
3COO
-, ClCH
2COO
-, C
6H
4COO
-, C
6H
4CH
2COO
-, NO
3 -In a kind of; Control reaction temperature 50-120 ℃, reaction times 1-6 hour, preparing epsilon-hexanolactam by catalyzing cyclohexanone-oxime rearranging.
Cyclohexanone-oxime of the present invention and ion liquid mol ratio are 1: 1-1: 4.
The preferable temperature of reaction of the present invention is 70-100 ℃, and the preferable reaction times is 3-5 hour, and the by product of reaction only is a pimelinketone.
When the mol ratio of the protonated hexanolactam Br of N- nsted acidic ion liquid and cyclohexanone-oxime is 3: 1, reacted 4 hours down at 90-100 ℃, the transformation efficiency of cyclohexanone-oxime is 93.0%-97.3%, the selectivity of hexanolactam is 87.0%-95.0%, and the selectivity of corresponding by-product cyclic hexanone is 13.0%-5.0%.
The present invention compares with the catalytic process of P contained compound in the ionic liquid at room temperature with existing industrial widely used Beckmann rearrangement reaction process, is characterized in:
(1) acidic ion liquid be catalyzer be again reaction medium simultaneously, simplified reaction system;
(2) ingenious product ε-Ji Neixianan and the inorganic or organic acid synthetic acidic ionic liquid at room temperature that utilizes this reaction, the product that reaction is generated no longer combines with acidic ion liquid, thereby need not to add the alkali neutralization, and do not produce solid waste, help the isolation and purification of product;
(3) ionic liquid at room temperature does not almost have vapour pressure, the environmental pollution of having avoided the conventional organic solvents volatilization to bring;
(4) by product is single, only is pimelinketone, at the industrial preparation cyclohexanone-oxime that can be recycled;
(5) preparation of the protonated hexanolactam Br of N- nsted acidic ion liquid is simple, and raw materials used hexanolactam is more cheap than the general synthetic used Methylimidazole of ionic liquid, greatly reduces production cost;
(6) do not produce obnoxious flavour, environmental protection more in the reaction process;
(7) present method has very strong industrial operability, is suitable for the mass preparation ε-Ji Neixianan.
Embodiment
In order to further specify details of the present invention, enumerate some embodiment below, but should not be so limited.
Embodiment 1
Get hexanolactam fluoroboric acid ionic liquid 15mmol, place the 100ml round-bottomed flask to add the 5mmol cyclohexanone-oxime, stir and be warming up to 50 ℃ of maintenances 3 hours down gradually, reactant is chilled to room temperature and obtains a homogeneous phase liquid form mixt, gets its 1ml and adds 6ml acetone, and is fully mixed, stratographic analysis, transformation efficiency is 13%, and product ε-Ji Neixianan selectivity is 65%, and by product is a pimelinketone.
Embodiment 2
Get hexanolactam fluoroboric acid ionic liquid 20mmol, place the 100ml round-bottomed flask to add the 5mmol cyclohexanone-oxime, stir and be warming up to 60 ℃ of maintenances 3 hours down gradually, reactant is chilled to room temperature and obtains a homogeneous phase liquid form mixt, get its 1ml and add 6ml acetone, fully mixed, gas chromatographic analysis, transformation efficiency is 61%, and the selectivity of product ε-Ji Neixianan is 81%.
Embodiment 3
Get hexanolactam fluoroboric acid ionic liquid 10mmol, place the 100ml round-bottomed flask to add the 5mmol cyclohexanone-oxime, stir and be warming up to 90 ℃ of maintenances 6 hours down gradually, reactant is chilled to room temperature and obtains a homogeneous phase liquid form mixt, get its 1ml and add 6ml acetone, fully mixed, gas chromatographic analysis, transformation efficiency is 90%, and selectivity is 84%.
Embodiment 4
Get hexanolactam fluoroboric acid ionic liquid 15mmol, place the 100ml round-bottomed flask to add the 5mmol cyclohexanone-oxime, stir and be warming up to 90 ℃ of maintenances 4 hours down gradually, reactant is chilled to room temperature and obtains a homogeneous phase liquid form mixt, get its 1ml and add 6ml acetone, fully mixed, gas chromatographic analysis, transformation efficiency is 95.8%, and selectivity is 89.4%.
Embodiment 5
Same with embodiment 4, but the ion liquid consumption of hexanolactam fluoroboric acid is amplified to 1.0mol, the consumption of cyclohexanone-oxime is amplified to 0.33mol, reacts in the 500ml round-bottomed flask, stirs and is warming up to 90 ℃ of maintenances 4 hours down gradually, reactant is chilled to room temperature and obtains a homogeneous phase liquid form mixt, get its 1ml and add 6ml acetone, fully mixed, gas chromatographic analysis, transformation efficiency is 95.0%, and selectivity is 87.0%.
Embodiment 6
Get hexanolactam trifluoroacetic acid ionic liquid 15mmol, place the 100ml round-bottomed flask to add the 5mmol cyclohexanone-oxime, stir and be warming up to 100 ℃ of maintenances 4 hours down gradually, reactant is chilled to room temperature and obtains a homogeneous phase liquid form mixt, get its 1ml and add 6ml acetone, fully mixed, gas chromatographic analysis, transformation efficiency is 97.3%, and selectivity is 93.5%.
Embodiment 7
Get hexanolactam phenylformic acid ionic liquid 15mmol, place the 100ml round-bottomed flask to add the 5mmol cyclohexanone-oxime, stir and be warming up to 100 ℃ of maintenances 4 hours down gradually, reactant is chilled to room temperature and obtains a homogeneous phase liquid form mixt, get its 1ml and add 6ml acetone, fully mixed, gas chromatographic analysis, transformation efficiency is 94.6%, and selectivity is 92.7%.
Embodiment 8
Get hexanolactam Mono Chloro Acetic Acid ionic liquid 15mmol, place the 100ml round-bottomed flask to add the 5mmol cyclohexanone-oxime, stir and be warming up to 100 ℃ of maintenances 4 hours down gradually, reactant is chilled to room temperature and obtains a homogeneous phase liquid form mixt, get its 1ml and add 6ml acetone, fully mixed, gas chromatographic analysis, transformation efficiency is 93.7%, and selectivity is 94.6%.
Embodiment 9
Get hexanolactam toluylic acid ionic liquid 15mmol, place the 100ml round-bottomed flask to add the 5mmol cyclohexanone-oxime, stir and be warming up to 100 ℃ of maintenances 4 hours down gradually, reactant is chilled to room temperature and obtains a homogeneous phase liquid form mixt, get its 1ml and add 6ml acetone, fully mixed, gas chromatographic analysis, transformation efficiency is 93.0%, and selectivity is 95.0%.
Claims (3)
1, a kind of method of preparing epsilon-hexanolactam by catalyzing cyclohexanone-oxime rearranging, it is characterized in that with the protonated hexanolactam of N-be the Br nsted acidic ion liquid of cation group as catalyzer and reaction medium, its chemical structural formula is with formula (I) expression:
X wherein
-Be the anionic group of Br nsted acid HX, X
-Be selected from BF
4 -, CF
3COO
-, ClCH
2COO
-, C
6H
4COO
-, C
6H
4CH
2COO
-, NO
3 -In a kind of; Control reaction temperature 50-120 ℃, reaction times 1-6 hour, preparing epsilon-hexanolactam by catalyzing cyclohexanone-oxime rearranging.
2, the method for claim 1 is characterized in that cyclohexanone-oxime and ion liquid mol ratio are 1: 1-1: 4.
3, the method for claim 1 is characterized in that temperature of reaction is 70-100 ℃, and the reaction times is 3-5 hour.
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|---|---|---|---|
| CN 200410100908 CN1305855C (en) | 2004-12-02 | 2004-12-02 | Process for preparing epsilon-hexanolactam by catalyzing cyclohexanone-oxime rearranging |
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|---|---|---|---|
| CN 200410100908 CN1305855C (en) | 2004-12-02 | 2004-12-02 | Process for preparing epsilon-hexanolactam by catalyzing cyclohexanone-oxime rearranging |
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| CN1781908A true CN1781908A (en) | 2006-06-07 |
| CN1305855C CN1305855C (en) | 2007-03-21 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008145312A1 (en) * | 2007-05-25 | 2008-12-04 | Dsm Ip Assets B.V. | Method of making a lactam in an ionic liquid |
| CN103288734A (en) * | 2012-02-29 | 2013-09-11 | 北京安耐吉能源工程技术有限公司 | Catalyst system for Beckmann rearrangement and method for preparing caprolactam thereof |
| CN103288735A (en) * | 2012-02-29 | 2013-09-11 | 北京安耐吉能源工程技术有限公司 | Catalyst system for Beckmann rearrangement and method for preparing caprolactam thereof |
| CN113461614A (en) * | 2021-06-30 | 2021-10-01 | 青岛科技大学 | Preparation method of caprolactam |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101985435B (en) * | 2010-10-28 | 2012-05-09 | 河北科技大学 | Novel eutectic ionic liquid and preparation method thereof |
-
2004
- 2004-12-02 CN CN 200410100908 patent/CN1305855C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008145312A1 (en) * | 2007-05-25 | 2008-12-04 | Dsm Ip Assets B.V. | Method of making a lactam in an ionic liquid |
| CN103288734A (en) * | 2012-02-29 | 2013-09-11 | 北京安耐吉能源工程技术有限公司 | Catalyst system for Beckmann rearrangement and method for preparing caprolactam thereof |
| CN103288735A (en) * | 2012-02-29 | 2013-09-11 | 北京安耐吉能源工程技术有限公司 | Catalyst system for Beckmann rearrangement and method for preparing caprolactam thereof |
| CN103288735B (en) * | 2012-02-29 | 2015-03-04 | 北京安耐吉能源工程技术有限公司 | Catalyst system for Beckmann rearrangement and method for preparing caprolactam thereof |
| CN103288734B (en) * | 2012-02-29 | 2015-04-29 | 北京安耐吉能源工程技术有限公司 | Catalyst system for Beckmann rearrangement and method for preparing caprolactam thereof |
| CN113461614A (en) * | 2021-06-30 | 2021-10-01 | 青岛科技大学 | Preparation method of caprolactam |
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|---|---|
| CN1305855C (en) | 2007-03-21 |
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