CN1978427A - Method for preparing epsilon-caprolactam by rearrangement of cyclohexanone oxime under ultrasonic wave irradiation - Google Patents
Method for preparing epsilon-caprolactam by rearrangement of cyclohexanone oxime under ultrasonic wave irradiation Download PDFInfo
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- CN1978427A CN1978427A CNA2005101298767A CN200510129876A CN1978427A CN 1978427 A CN1978427 A CN 1978427A CN A2005101298767 A CNA2005101298767 A CN A2005101298767A CN 200510129876 A CN200510129876 A CN 200510129876A CN 1978427 A CN1978427 A CN 1978427A
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Abstract
The invention relates to a method for preparing epsi-Caprolactam by Beckmann rearrangement with a Br phi nsted acidity room temperature ionic liquid as the catalyst and catalyst reaction medium under ultrasonic radiation. The method can produce epsi-caprolactam in a very short response time with a high conversion rate and a high selectivity. In this method, the product will no longer combine with the acidic ionic liquid, and soda will no longer be used to neutralize after the reaction.
Description
Technical field
The present invention relates to a kind of is that the acid ionic liquid at room temperature of Br nsted of cation group is the catalysis of pimelinketone oxime of catalyzer and reaction medium prepares ε-Ji Neixianan through the Beckmann rearrangement reaction a method with the protonated hexanolactam of N-under the ultrasonic wave radiation.
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 is the cationic Br of having nsted tart ionic liquid (Journal of Physical Chemistry with strong Br nsted acid in conjunction with forming with hexanolactam, 2005,19542-19546).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 the product ε-Ji Neixianan and be that the problem that combines between cationic Br nsted acidic ion liquid is resolved owing to existing following running balance to react with ε-Ji Neixianan:
X wherein
-=BF
4 -, CF
3COO
-, ClCH
2COO
-, C
6H
4COO
-, H
2PO
4 -, 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.
The yield and the selectivity of ultrasonic energy quickening chemical reaction velocity, raising feed stock conversion and product are well-known.In alkyl imidazo ion liquid, successfully realized under the ultrasonic wave radiation Suzuki cross-coupling reaction (Chemical Communications, 2002,616-617) and Heck reaction (ChemicalCommunications, 2001,1544-1545).But do not find the report of Beckmann rearrangement reaction ionic liquid-catalyzed under the ultrasonic wave radiation as yet.
Summary of the invention
The object of the present invention is to provide a kind of is that the acid ionic liquid at room temperature of Br nsted of cation group is the catalysis of pimelinketone oxime of catalyzer and reaction medium prepares ε-Ji Neixianan through the Beckmann rearrangement reaction a method with the protonated hexanolactam of N-under the ultrasonic wave radiation.
A kind of method of ultrasonic wave radiation preparing epsilon-caprolactam by rearrangement of cyclohexanone oxime under, it is characterized in that the ultrasonic wave radiation is repeatedly radiation of intermittence, single radiated time, intermittent time, radiation number of times, ultrasonic wave single radiated time is 1-10 second, intermittent time is 2-20 second, the radiation number of times is 40-80 time, and radiation power is the 100-500 watt; With the protonated hexanolactam of N-is that the acid ionic liquid at room temperature of Br nsted of cation group is catalyzer and reaction medium, and the catalysis of pimelinketone oxime prepares ε-Ji Neixianan through the Beckmann rearrangement reaction.
What the present invention was used is chemical structural formula usefulness formula (I) expression of the Br nsted acidic ion liquid of cation group as catalyzer and reaction medium with the protonated hexanolactam of N-:
X wherein
-Be the anionic group of Br nsted acid HX, X
-Be selected from BF
4 -, CF
3COO
-, ClCH
2COO
-, C
6H
4COO
-, H
2PO
4 -, NO
3 -In a kind of.
Cyclohexanone-oxime of the present invention and ion liquid mol ratio are 1: 1-1: 4, and by product only is a spot of pimelinketone.
Method of the present invention, ultrasonic wave single radiated time is 2-7 second preferably; Intermittent time is 5-15 second preferably, and the radiation number of times is 50-70 time preferably; Radiation power is the 200-400 watt preferably.
The mol ratio of the protonated hexanolactam Br of N- nsted acidic ion liquid and cyclohexanone-oxime is 3: 1, ultrasonic wave single radiated time is 5 seconds, intermittent time is 12 seconds, the radiation number of times is 65 times, radiation power is 400 watt-hours, the transformation efficiency of cyclohexanone-oxime is 96.0-100.0%, and the selectivity of hexanolactam is 95.5%-99.0%, and the selectivity of by-product cyclic hexanone is 1.0%-4.5%.
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, hyperacoustic use has been shortened the reaction times greatly, has improved product yield and selectivity;
2, acidic ion liquid be catalyzer be again reaction medium simultaneously, simplified reaction system;
3, 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;
4, ionic liquid at room temperature does not almost have vapour pressure, the environmental pollution of having avoided the conventional organic solvents volatilization to bring;
5, by product is single, only is pimelinketone, at the industrial preparation cyclohexanone-oxime that can be recycled;
6, the 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;
7, do not produce obnoxious flavour, environmental protection more in the reaction process;
8, present method has very strong industrial operability, is suitable for extensive continuous flow prepared ε-Ji Neixianan.
Embodiment
In order to further specify details of the present invention, enumerate some embodiment below, but should not be so limited.
Implementation step of the present invention is: add the protonated hexanolactam Br of 29.6mmol (5.94g) N- nsted acidic ion liquid and a certain amount of ketoxime in the glass test tube of 15ml, react under specified single radiated time, intermittent time, radiation number of times and radiation power.Reaction finishes back gas Chromatographic Determination conversion of raw material and product selectivity.
Embodiment 1-12
The used protonated hexanolactam Br of the N- nsted acidic ion liquid of the embodiment of the invention is (with X
-Expression), the transformation efficiency of cyclohexanone-oxime and the selectivity of product hexanolactam were listed in the table 1 after cyclohexanone-oxime and ion liquid mol ratio, single radiated time, intermittent time, radiation number of times and radiation power and reaction finished.
The catalysis of pimelinketone oxime prepares the method embodiment of hexanolactam under the radiation of table 1 ultrasonic wave through the Beckmann rearrangement reaction
| Embodiment | Ionic liquid X - | Cyclohexanone-oxime/ionic liquid (mol/mol) | Single radiated time (s) | Intermittent time (s) | The radiation number of times | Radiation power (w) | Transformation efficiency (%) | Selectivity (%) |
| 1 | BF 4 - | 1/1 | 2 | 3 | 40 | 200 | 51.2 | 97.5 |
| 2 | NO 3 - | 1/3 | 5 | 8 | 50 | 200 | 61.3 | 90.1 |
| 3 | CF 3COO - | 1/2 | 4 | 20 | 60 | 200 | 71.0 | 92.3 |
| 4 | ClCH 2COO - | 1/2 | 7 | 10 | 70 | 200 | 63.6 | 89.5 |
| 5 | C 6H 4COO - | 1/2 | 10 | 12 | 70 | 200 | 58.6 | 86.5 |
| 6 | H 2PO 4 - | 1/4 | 4 | 8 | 80 | 200 | 67.3 | 88.0 |
| 7 | BF 4 - | 1/3 | 5 | 12 | 65 | 300 | 95.5 | 97.6 |
| 8 | BF 4 - | 1/3 | 5 | 12 | 65 | 400 | 100.0 | 99.0 |
| 9 | BF 4 - | 1/4 | 5 | 12 | 65 | 400 | 100.0 | 98.6 |
| 10 | CF 3COO - | 1/3 | 5 | 12 | 65 | 400 | 96.7 | 97.2 |
| 11 | NO 3 - | 1/3 | 5 | 12 | 65 | 100 | 70.4 | 94.6 |
| 12 | CF 3COO - | 1/4 | 5 | 15 | 70 | 500 | 96.8 | 97.4 |
Claims (4)
1, a kind of method of ultrasonic wave radiation preparing epsilon-caprolactam by rearrangement of cyclohexanone oxime under, it is characterized in that the ultrasonic wave radiation is repeatedly radiation of intermittence, single radiated time, intermittent time, radiation number of times, ultrasonic wave single radiated time is 1-10 second, intermittent time is 2-20 second, the radiation number of times is 40-80 time, and radiation power is the 100-500 watt; With the protonated hexanolactam of N-is that the acid ionic liquid at room temperature of Br nsted of cation group is catalyzer and reaction medium, and the catalysis of pimelinketone oxime prepares ε-Ji Neixianan through the Beckmann rearrangement reaction.
2, the method for claim 1 is characterized in that with the protonated hexanolactam of N-be chemical structural formula usefulness formula (I) expression of the Br nsted acidic ion liquid of cation group as catalyzer and reaction medium:
X wherein
-Be the anionic group of Br nsted acid HX, X
-Be selected from BF
4 -, CF
3COO
-, ClCH
2COO
-, C
6H
4COO
-, H
2PO
4 -, NO
3 -In a kind of.
3, the method for claim 1 is characterized in that cyclohexanone-oxime and ion liquid mol ratio are 1: 1-1: 4.
4, the method for claim 1 is characterized in that ultrasonic wave single radiated time is 2-7 second; Intermittent time is 5-15 second; The radiation number of times is 50-70 time; Radiation power is the 200-400 watt.
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|---|---|---|---|
| CNA2005101298767A CN1978427A (en) | 2005-12-09 | 2005-12-09 | Method for preparing epsilon-caprolactam by rearrangement of cyclohexanone oxime under ultrasonic wave irradiation |
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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 |
| CN101985435A (en) * | 2010-10-28 | 2011-03-16 | 河北科技大学 | Novel eutectic ionic liquid and preparation method thereof |
| 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 |
| CN110002994A (en) * | 2019-05-05 | 2019-07-12 | 河北科技大学 | A kind of eutectic ionic liquid and its preparation method and application |
-
2005
- 2005-12-09 CN CNA2005101298767A patent/CN1978427A/en active Pending
Cited By (7)
| 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 |
| CN101985435A (en) * | 2010-10-28 | 2011-03-16 | 河北科技大学 | Novel eutectic ionic liquid and preparation method thereof |
| CN101985435B (en) * | 2010-10-28 | 2012-05-09 | 河北科技大学 | Novel eutectic ionic liquid and preparation method thereof |
| 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 |
| 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 |
| CN110002994A (en) * | 2019-05-05 | 2019-07-12 | 河北科技大学 | A kind of eutectic ionic liquid and its preparation method and application |
| CN110002994B (en) * | 2019-05-05 | 2021-07-30 | 河北科技大学 | Eutectic ionic liquid and preparation method and application thereof |
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