CN1994996A - Process for preparing cyclopropyl methyl ketone - Google Patents
Process for preparing cyclopropyl methyl ketone Download PDFInfo
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- CN1994996A CN1994996A CN 200610098154 CN200610098154A CN1994996A CN 1994996 A CN1994996 A CN 1994996A CN 200610098154 CN200610098154 CN 200610098154 CN 200610098154 A CN200610098154 A CN 200610098154A CN 1994996 A CN1994996 A CN 1994996A
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- methyl ketone
- cyclopropyl methyl
- reaction
- pentanone
- chloro
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Abstract
The invention discloses a making method of cyclopropyl methyl ketone, which comprises the following steps: adding normal aceto propyl alcohol in the alcaine solution; chlorinating; evaporating 5-chloride-2-pentanone; adopting separating coupling technique to do ringed-reaction for 5-chloride-2-pentanone; generating cyclopropyl methyl ketone.
Description
Technical field
The invention belongs to a kind of preparation method of Cyclopropyl Methyl Ketone.
Background technology
The production technique of Cyclopropyl Methyl Ketone, prior art mainly contain three kinds of technological approaches: 1, adopting methyl aceto acetate is that raw material synthesizes Cyclopropyl Methyl Ketone through three steps, thereafter it is prepared cyclopropane-carboxylic acid with the oxidation of hypohalous acid sodium; 2, adopt α-ethanoyl-gamma-butyrolactone halogenating reaction in 10～30 ℃, water medium to generate 5-halo-2 pentanone, 5-halo-2 pentanone carries out the dehydrohalogenation cyclization and generates Cyclopropyl Methyl Ketone; 3, by one or more carboxylic acids, with niobium and catalyzer, prepare ketone under the intensification condition, this technology is particularly useful to preparing Cyclopropyl Methyl Ketone by cyclopropyl-carboxylic acid and acetic acid.4, be raw material with the acetyl n-propyl alcohol,, carry out cyclization again and prepare Cyclopropyl Methyl Ketone with the haloid acid halogenating reaction.This method reduces to two-step reaction with traditional four-step reaction, is convenient to suitability for industrialized production, uses cheap and industrial chemicals commonly used, and overcoming in the conventional procedure with sulfur oxychloride, phosphorus oxychloride or phosphorus pentachloride etc. is chlorizating agent, and byproduct hydrogen chloride contains SO
2, phosphorus trichloride etc. reclaims difficulty, the processing costs height solves the big and unmanageable problem of waste gas, wastewater flow rate of old technology from the source.
Wherein, the 4th kind of method reactions steps is few, is convenient to reaction control.But owing to be hybrid reaction, the easy enolization of product, and at high temperature easily generate polymkeric substance, side reaction is not easy control, and raw material availability is low, and supplies consumption is big, long reaction time, and use KOH, cost height, yield are not high.
Summary of the invention
Purpose of the present invention provides a kind of preparation technology of new Cyclopropyl Methyl Ketone, is starting raw material with the acetyl n-propyl alcohol, by reaction separation coupling technology, building-up process is simple, the purity height of 5-chloro-2 pentanone, yield height use soda-lime to promote the cyclization of 5-chloro-2 pentanone, are beneficial to layering.
The object of the present invention is achieved like this:
The preparation method of Cyclopropyl Methyl Ketone, its reaction formula is:
The preparation method of Cyclopropyl Methyl Ketone may further comprise the steps:
(1), the acetyl n-propyl alcohol is added in the hydrochloric acid soln, chlorination reaction taking place, be heated to 85-105 ℃, generate 5-chloro-2 pentanone, steamed, taken hydrochloric acid out of with material simultaneously, be collected receiving still, tells organic layer and obtain crude product 5-chloro-2 pentanone;
(2), 5-chloro-2 pentanone and soda-lime solution generation ring-closure reaction, generate Cyclopropyl Methyl Ketone, it is main Yan Heshui that hydrochloric acid in the material and alkali reaction generate calcium chloride, and organic layer is told, and just obtains the work in-process Cyclopropyl Methyl Ketone.
Described work in-process Cyclopropyl Methyl Ketone obtains the pure product of Cyclopropyl Methyl Ketone through underpressure distillation.
In the described chlorination reaction, take to adopt separation coupling technology, reaction times 2-5 hour.
Described concentration of hydrochloric acid is 20-30%, and the ring-closure reaction temperature is 65-75 ℃, and soda-lime consists of NaOH and accounts for 5-10%, and CaO accounts for 90-95%.
Concrete innovative point of the present invention is embodied in the following aspects:
1, technology is simple, and adopts separation coupling technology, and production process is shortened greatly, and reduces the generation of by product, improves utilization ratio of raw materials.
2, adopt soda-lime to carry out ring-closure reaction, the reaction conditions gentleness, side reaction is few, and helps the profit two phase stratification.Soda-lime consists of NaOH and accounts for 5-10%, and CaO accounts for 90-95%.
The present invention is because reactions steps is few, and reaction is control easily, uses separation coupling technology, reduces side reaction, improves the generation of main reaction thing, the reaction efficiency height.By product is a salt, meets environmental protection requirement.
Description of drawings
Fig. 1 is the prior art process flow sheet.
Fig. 2 is a process flow diagram of the present invention.
Fig. 3 is a process flow sheet of the present invention.
Embodiment
(1), adopt separation coupling technology, the acetyl n-propyl alcohol is added drop-wise in 30% the hydrochloric acid, be heated to 85-105 ℃, be preferably between 90-100 ℃, chlorination reaction take place, reaction times 1-5 hour, be preferably 2 hours, yield is 75～89%, generates 5-chloro-2 pentanone, steamed simultaneously, be collected at the reception still, layering obtains crude product 5-chloro-2 pentanone, the underpressure distillation dehydration, solved 5-chloro-2 pentanone pyrolytic decomposition polymeric problem, product purity is more than 98.5%.Can blowing air, preferably nitrogen promotes telling of 5-chloro-2 pentanone.
(2), 5-chloro-2 pentanone and soda-lime reactant aqueous solution, cyclization generates Cyclopropyl Methyl Ketone, HCL in the material and alkali effect generate salt and water, organic layer is told, just obtain the work in-process Cyclopropyl Methyl Ketone, obtain the finished product Cyclopropyl Methyl Ketone through underpressure distillation, product purity is more than 99%.
(3), raw and auxiliary material and intermediate specification
| Sequence number | Title | Specification | Detection method |
| 1 | The acetyl n-propyl alcohol | 92％ | Chemical titration |
| 2 | Hydrochloric acid | Content 30% technical grade | Chemical titration |
| 3 | Liquid caustic soda lime | Technical grade | Chemical titration |
| 4 | 5-chloro-2 pentanone | Content 〉=95.5% moisture content≤0.20% | Gas-chromatography karl Fischer aquametry |
Below in conjunction with the embodiment example that describes the present invention:
Example one: 5-chloro-2 pentanone is synthetic
In the there-necked flask of 1000ml, add the HCl (the amount 1.5mol of HCl) of 193g30%, be heated with stirring to 90 ℃, begin to drip the acetyl n-propyl alcohol of 102g (1mol), dropwise in one hour.Continue constant temperature 2h, organic layer is told in cooling, and vacuum distilling gets light yellow transparent liquid product 105 grams (yield 87.4%), GC purity assay 98.2%.
Example two: Cyclopropyl Methyl Ketone is synthetic
120.6g (purity 98.2%, 1mol) 5-chloro-2 pentanone is added in the solution of 70.6g soda-lime and 50g water composition, heat to 65-75 ℃ (being preferably 70 ℃), behind the stirring 1h, insulation 2h, layering, tell thick product 90 grams of organic layer, handle back 86 grams, distill to such an extent that pure product 72 restrain (yield 86.6%), GC purity assay 99.4%, colourless transparent liquid.Soda-lime consists of NaOH and accounts for 5-10%, and CaO accounts for 90-95%.
Claims (4)
1, the preparation method of Cyclopropyl Methyl Ketone is characterized in that may further comprise the steps:
(1), the acetyl n-propyl alcohol is added in the hydrochloric acid soln, chlorination reaction taking place, be heated to 85-105 ℃, generate 5-chloro-2 pentanone, steamed, taken hydrochloric acid out of with material simultaneously, be collected receiving still, tells organic layer and obtain crude product 5-chloro-2 pentanone;
(2), 5-chloro-2 pentanone and soda-lime solution generation ring-closure reaction, generate Cyclopropyl Methyl Ketone, it is main Yan Heshui that hydrochloric acid in the material and alkali reaction generate calcium chloride, and organic layer is told, and just obtains the work in-process Cyclopropyl Methyl Ketone.
2, method according to claim 1 is characterized in that described work in-process Cyclopropyl Methyl Ketone obtains the pure product of Cyclopropyl Methyl Ketone through underpressure distillation.
3, method according to claim 1 is characterized in that taking to adopt separation coupling technology in the described chlorination reaction reaction times 2-5 hour.
4, method according to claim 1 is characterized in that described concentration of hydrochloric acid is 20-30%, and the ring-closure reaction temperature is 65-75 ℃, and soda-lime consists of NaOH and accounts for 5-10%, and CaO accounts for 90-95%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100981544A CN100494146C (en) | 2006-12-05 | 2006-12-05 | Process for preparing cyclopropyl methyl ketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100981544A CN100494146C (en) | 2006-12-05 | 2006-12-05 | Process for preparing cyclopropyl methyl ketone |
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| CN1994996A true CN1994996A (en) | 2007-07-11 |
| CN100494146C CN100494146C (en) | 2009-06-03 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106467457A (en) * | 2016-08-30 | 2017-03-01 | 淄博益利化工新材料有限公司 | A kind of continuous method producing 5 chlorine 2 pentanone |
| CN110862310A (en) * | 2019-12-05 | 2020-03-06 | 上海生农生化制品股份有限公司 | Synthesis method of cyclopropyl methyl ketone |
| CN113582824A (en) * | 2021-08-26 | 2021-11-02 | 江苏清泉化学股份有限公司 | Preparation method of high-purity cyclopropyl methyl ketone |
| CN113816841A (en) * | 2021-10-12 | 2021-12-21 | 瑞孚信江苏药业股份有限公司 | Preparation method of cyclopropyl methyl ketone |
-
2006
- 2006-12-05 CN CNB2006100981544A patent/CN100494146C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106467457A (en) * | 2016-08-30 | 2017-03-01 | 淄博益利化工新材料有限公司 | A kind of continuous method producing 5 chlorine 2 pentanone |
| CN106467457B (en) * | 2016-08-30 | 2020-10-27 | 淄博齐塑环保科技有限公司 | Method for continuously producing 5-chloro-2-pentanone |
| CN110862310A (en) * | 2019-12-05 | 2020-03-06 | 上海生农生化制品股份有限公司 | Synthesis method of cyclopropyl methyl ketone |
| CN113582824A (en) * | 2021-08-26 | 2021-11-02 | 江苏清泉化学股份有限公司 | Preparation method of high-purity cyclopropyl methyl ketone |
| CN113582824B (en) * | 2021-08-26 | 2024-01-30 | 江苏清泉化学股份有限公司 | Preparation method of high-purity cyclopropyl methyl ketone |
| CN113816841A (en) * | 2021-10-12 | 2021-12-21 | 瑞孚信江苏药业股份有限公司 | Preparation method of cyclopropyl methyl ketone |
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| Publication number | Publication date |
|---|---|
| CN100494146C (en) | 2009-06-03 |
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