CN105152902A - Method for preparing 1-cyclohexenylacetic acid - Google Patents
Method for preparing 1-cyclohexenylacetic acid Download PDFInfo
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- CN105152902A CN105152902A CN201510507808.3A CN201510507808A CN105152902A CN 105152902 A CN105152902 A CN 105152902A CN 201510507808 A CN201510507808 A CN 201510507808A CN 105152902 A CN105152902 A CN 105152902A
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- naoh
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- acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/08—Preparation of carboxylic acids or their salts, halides or anhydrides from nitriles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 1-cyclohexenylacetic acid. The method comprises steps as follows: (1) cyclohexanone and acetonitrile are placed in a reaction container containing a Na-NaOH/gamma-Al2O3 solid mixture to be stirred for a reaction at the controlled reaction temperature of 180-220 DEG C and under the reaction pressure of 5-10 kg/cm<2> for 3-5 h, and 1-cyclohexenylacetonitrile is obtained; (2) the 1-cyclohexenylacetonitrile prepared in Step (1) is placed in a reaction container containing an acid and high-temperature liquid water for a hydrolysis reaction, and the 1-cyclohexenylacetic acid is obtained. The 1-cyclohexenylacetonitrile is prepared with the Na-NaOH/gamma-Al2O3 solid mixture serving as a catalyst for cyclohexanone and acetonitrile, so that the conversion rate and the yield of the 1-cyclohexenylacetonitrile are high; the prepared 1-cyclohexenylacetonitrile has the hydrolysis reaction with the acid and the high-temperature liquid water, the 1-cyclohexenylacetic acid is obtained, the conversion rate and the yield of the 1-cyclohexenylacetic acid are increased by the aid of the high-temperature liquid water, and the usage amount of the acid is obviously reduced.
Description
Technical field
The present invention relates to the technical field of 1-cyclohexenyl acetic acid, particularly relate to a kind of method preparing 1-cyclohexenyl acetic acid.
Background technology
1-cyclohexenyl acetic acid has another name called 1-cyclohexenyl-1-acetic acid, molecular weight 139.2, and No. CAS is 18294-87-6, and be a kind of colourless to yellowish transparent liquid, its fusing point is 26 ~ 28 DEG C, and boiling point is 252.4 DEG C, and flash-point is 149.7 DEG C.In prior art there is the technological deficiency that product yield is lower and yield is lower in the preparation method of 1-cyclohexenyl acetic acid.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of method preparing 1-cyclohexenyl acetic acid, the product yield that this preparation method obtains is high, yield is high.
For reaching this object, the present invention by the following technical solutions:
Prepare a method for 1-cyclohexenyl acetic acid, comprise the steps:
(1) pimelinketone and acetonitrile are inserted Na-NaOH/ γ-Al is housed
2o
3stir in the reaction vessel of solid mixture and react, controlling temperature of reaction is 180 ~ 220 DEG C, reaction pressure 5 ~ 10kg/cm
2, the reaction times is 3 ~ 5h, obtains 1-cyclohexenylacetonitriles;
(2) the 1-cyclohexenylacetonitriles that step (1) prepares is inserted be equipped with acid and high temperature liquid water reaction vessel in there is hydrolysis reaction, obtain 1-cyclohexenyl acetic acid.
With Na-NaOH/ γ-Al in step (1)
2o
3solid mixture makees catalyzer, γ-Al
2o
3water insoluble, strong acid or strong base solution can be dissolved in, it is the solid materials of a kind of porousness, high degree of dispersion, there is very large specific surface area, its micropore surface has that adsorptivity is high, the advantage of Heat stability is good, as catalyzer and carrier thereof, mix with solid Na, NaOH, Na, NaOH provide the alkaline condition of reaction, and meanwhile, the water produced in reaction process and Na react, accelerated reaction while absorbing a part of aquatic products heat-dissipating amount, continue to provide alkaline condition with NaOH simultaneously, improve transformation efficiency, and Na-NaOH/ γ-Al
2o
3consumption very little when, the speed of reaction and transformation efficiency are all higher, described Na-NaOH/ γ-Al
2o
3solid mixture accounts for 5 ~ 20% of pimelinketone and acetonitrile total mass; Described Na-NaOH/ γ-Al
2o
3γ-Al in solid mixture
2o
3account for Na-NaOH/ γ-Al
2o
320 ~ 30% of solid mixture total mass; Described Na-NaOH/ γ-Al
2o
3in solid mixture, the mass ratio of Na and NaOH is 1:(1 ~ 4).
Wherein, the mass ratio of described pimelinketone and acetonitrile is 1:(4 ~ 6).
1-cyclohexenylacetonitriles described in step (2) is 1:(1 ~ 3 with the mol ratio of acid), described acid is with the molar basis of hydrogen.Acid can the acid commonly used by this area such as hydrochloric acid, sulfuric acid.
High temperature liquid water, typically refer to temperature at the compressed liquid water of 200 ~ 350 DEG C, because high temperature liquid water self has the function of acid catalysis and base catalysis, the characteristic of dissolved organic matter and inorganics while of energy, have broad application prospects in fields such as reaction, separation, waste renewable resources, can the use even eliminating mineral acid, alkali be reduced.So the use of high temperature liquid water significantly reduces the usage quantity of acid.The temperature of the high temperature liquid water described in step (2) is 200 ~ 240 DEG C.
Hydrolysis reaction described in step (2) is 1 ~ 3h.
Compared with prior art, beneficial effect of the present invention is: with Na-NaOH/ γ-Al
2o
3solid mixture does the catalyst preparing 1-cyclohexenylacetonitriles of pimelinketone and acetonitrile, make the transformation efficiency of 1-cyclohexenylacetonitriles and yield high; By the 1-cyclohexenylacetonitriles of preparation and acid and high temperature liquid water generation hydrolysis reaction, obtain 1-cyclohexenyl acetic acid, the use of high temperature liquid water improves transformation efficiency and the yield of 1-cyclohexenyl acetic acid, and significantly reduces the usage quantity of acid.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.
As no specific instructions, various raw material of the present invention all can commercially availablely be buied, or prepares according to the ordinary method of this area.
Embodiment 1
Pimelinketone and acetonitrile are inserted Na-NaOH/ γ-Al is housed
2o
3stir in the reactor of solid mixture and react, wherein, the mass ratio of pimelinketone and acetonitrile is 1:4, Na-NaOH/ γ-Al
2o
3γ-Al in solid mixture
2o
3account for Na-NaOH/ γ-Al
2o
320%, Na-NaOH/ γ-Al of solid mixture total mass
2o
3in solid mixture, the mass ratio of Na and NaOH is 1:3, and the temperature controlling reactor is 200 DEG C, reaction pressure 6kg/cm
2, maintaining nitrogen purge reaction 3h, by the mixture of reactant removing solid mixture, Distillation recovery obtains 1-cyclohexenylacetonitriles.
The above-mentioned 1-cyclohexenylacetonitriles prepared is inserted in the reactor that hydrochloric acid and high temperature liquid water are housed, wherein, the mol ratio of 1-cyclohexenylacetonitriles and hydrochloric acid is 1:2, and the temperature of high temperature liquid water is 220 DEG C, and after reaction 2h, Distillation recovery obtains 1-cyclohexenyl acetic acid.
Embodiment 2
Pimelinketone and acetonitrile are inserted Na-NaOH/ γ-Al is housed
2o
3stir in the reactor of solid mixture and react, wherein, the mass ratio of pimelinketone and acetonitrile is 1:5, Na-NaOH/ γ-Al
2o
3γ-Al in solid mixture
2o
3account for Na-NaOH/ γ-Al
2o
325%, Na-NaOH/ γ-Al of solid mixture total mass
2o
3in solid mixture, the mass ratio of Na and NaOH is 1:2, and the temperature controlling reactor is 190 DEG C, reaction pressure 8kg/cm
2, maintaining nitrogen purge reaction 4h, by the mixture of reactant removing solid mixture, Distillation recovery obtains 1-cyclohexenylacetonitriles.
The above-mentioned 1-cyclohexenylacetonitriles prepared is inserted in the reactor that hydrochloric acid and high temperature liquid water are housed, wherein, the mol ratio of 1-cyclohexenylacetonitriles and hydrochloric acid is 1:3, and the temperature of high temperature liquid water is 230 DEG C, and after reaction 2h, Distillation recovery obtains 1-cyclohexenyl acetic acid.
Embodiment 3
Pimelinketone and acetonitrile are inserted Na-NaOH/ γ-Al is housed
2o
3stir in the reactor of solid mixture and react, wherein, the mass ratio of pimelinketone and acetonitrile is 1:6, Na-NaOH/ γ-Al
2o
3γ-Al in solid mixture
2o
3account for Na-NaOH/ γ-Al
2o
325%, Na-NaOH/ γ-Al of solid mixture total mass
2o
3in solid mixture, the mass ratio of Na and NaOH is 1:4, and the temperature controlling reactor is 190 DEG C, reaction pressure 10kg/cm
2, maintaining nitrogen purge reaction 4h, by the mixture of reactant removing solid mixture, Distillation recovery obtains 1-cyclohexenylacetonitriles.
The above-mentioned 1-cyclohexenylacetonitriles prepared is inserted in the reactor that hydrochloric acid and high temperature liquid water are housed, wherein, the mol ratio of 1-cyclohexenylacetonitriles and hydrochloric acid is 1:2, and the temperature of high temperature liquid water is 240 DEG C, and after reaction 3h, Distillation recovery obtains 1-cyclohexenyl acetic acid.
Embodiment 4
Pimelinketone and acetonitrile are inserted Na-NaOH/ γ-Al is housed
2o
3stir in the reactor of solid mixture and react, wherein, the mass ratio of pimelinketone and acetonitrile is 1:4, Na-NaOH/ γ-Al
2o
3γ-Al in solid mixture
2o
3account for Na-NaOH/ γ-Al
2o
322%, Na-NaOH/ γ-Al of solid mixture total mass
2o
3in solid mixture, the mass ratio of Na and NaOH is 1:3, and the temperature controlling reactor is 190 DEG C, reaction pressure 10kg/cm
2, maintaining nitrogen purge reaction 5h, by the mixture of reactant removing solid mixture, Distillation recovery obtains 1-cyclohexenylacetonitriles.
The above-mentioned 1-cyclohexenylacetonitriles prepared is inserted in the reactor that sulfuric acid and high temperature liquid water are housed, wherein, the mol ratio of 1-cyclohexenylacetonitriles and sulfuric acid is 1:2, and the temperature of high temperature liquid water is 240 DEG C, and after reaction 2h, Distillation recovery obtains 1-cyclohexenyl acetic acid.
1-cyclohexenyl acetic acid embodiment 1 ~ 4 obtained carries out transformation efficiency and yield is tested, and what deserves to be explained is, these tests the means of testing be familiar with by those skilled in the art, concrete test technology does not repeat at this.Its test result is as table 1:
Table 1
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (8)
1. prepare a method for 1-cyclohexenyl acetic acid, it is characterized in that, comprise the steps:
(1) pimelinketone and acetonitrile are inserted Na-NaOH/ γ-Al is housed
2o
3stir in the reaction vessel of solid mixture and react, controlling temperature of reaction is 180 ~ 220 DEG C, reaction pressure 5 ~ 10kg/cm
2, the reaction times is 3 ~ 5h, obtains 1-cyclohexenylacetonitriles;
(2) the 1-cyclohexenylacetonitriles that step (1) prepares is inserted be equipped with acid and high temperature liquid water reaction vessel in there is hydrolysis reaction, obtain 1-cyclohexenyl acetic acid.
2. the method preparing 1-cyclohexenyl acetic acid according to claim 1, is characterized in that, Na-NaOH/ γ-Al described in step (1)
2o
3solid mixture accounts for 5 ~ 20% of pimelinketone and acetonitrile total mass.
3. the preparation method of 1-cyclohexenyl acetic acid according to claim 2, is characterized in that, described γ-Al
2o
3account for Na-NaOH/ γ-Al
2o
320 ~ 30% of solid mixture total mass.
4. the preparation method of 1-cyclohexenyl acetic acid according to claim 2, is characterized in that, described Na-NaOH/ γ-Al
2o
3in solid mixture, the mass ratio of Na and NaOH is 1:(1 ~ 4).
5. the preparation method of 1-cyclohexenyl acetic acid according to claim 1, is characterized in that, described in step (1), the mass ratio of pimelinketone and acetonitrile is 1:(4 ~ 6).
6. the preparation method of 1-cyclohexenyl acetic acid according to claim 1, is characterized in that, 1-cyclohexenylacetonitriles described in step (2) is 1:(1 ~ 3 with the mol ratio of acid), described acid is with the molar basis of hydrogen.
7. the preparation method of 1-cyclohexenyl acetic acid according to claim 1, is characterized in that, the temperature of the high temperature liquid water described in step (2) is 200 ~ 240 DEG C.
8. the preparation method of 1-cyclohexenyl acetic acid according to claim 1, is characterized in that, the hydrolysis reaction described in step (2) is 1 ~ 3h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510507808.3A CN105152902A (en) | 2015-08-18 | 2015-08-18 | Method for preparing 1-cyclohexenylacetic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510507808.3A CN105152902A (en) | 2015-08-18 | 2015-08-18 | Method for preparing 1-cyclohexenylacetic acid |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161626A (en) * | 2007-11-15 | 2008-04-16 | 浙江大学 | Method for preparing phenylacetic acid by non-catalyzed hydrolysis of benzene acetonitrile in near-critical water medium |
| CN104230698A (en) * | 2014-08-28 | 2014-12-24 | 太仓运通生物化工有限公司 | Synthesis method of 1-cyclohexenylacetic acid |
| CN104262197A (en) * | 2014-08-28 | 2015-01-07 | 太仓运通生物化工有限公司 | Synthesis method of 1-cyclohexenylacetonitrile |
-
2015
- 2015-08-18 CN CN201510507808.3A patent/CN105152902A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161626A (en) * | 2007-11-15 | 2008-04-16 | 浙江大学 | Method for preparing phenylacetic acid by non-catalyzed hydrolysis of benzene acetonitrile in near-critical water medium |
| CN104230698A (en) * | 2014-08-28 | 2014-12-24 | 太仓运通生物化工有限公司 | Synthesis method of 1-cyclohexenylacetic acid |
| CN104262197A (en) * | 2014-08-28 | 2015-01-07 | 太仓运通生物化工有限公司 | Synthesis method of 1-cyclohexenylacetonitrile |
Non-Patent Citations (1)
| Title |
|---|
| 刘洪润等: "固体超强碱催化环己酮羟醛缩合反应的研究", 《化学试剂》 * |
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Application publication date: 20151216 |