CN106892807A - A kind of preparation method of isophorone - Google Patents
A kind of preparation method of isophorone Download PDFInfo
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- CN106892807A CN106892807A CN201710082672.5A CN201710082672A CN106892807A CN 106892807 A CN106892807 A CN 106892807A CN 201710082672 A CN201710082672 A CN 201710082672A CN 106892807 A CN106892807 A CN 106892807A
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- isophorone
- quaternary ammonium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a kind of preparation method of organic catalysis isophorone, with acetone as initiation material, under the catalytic action of the organic imidazoles system quaternary ammonium highly basic of catalyst, there is liquid phase condensations reaction in acetone, isophorone is obtained by distillation.Specifically include the synthesis of organic imidazoles system quaternary ammonium highly basic and the synthesis of isophorone.Organic imidazoles system quaternary ammonium highly basic can be dissolved in the middle of the acetone as reaction medium and initiation material, can cause that reaction is smoothed out.The preparation method of the isophorone provided using the present invention, synthesis of isophorone, technique is synthesized using organic catalysis, and conversion per pass is more than 60%, and selectivity is more than 70%.The preparation method of isophorone of the invention has new technology, and step is few, the features such as reaction condition is gentle.
Description
Technical field
The present invention relates to the technical field of organic chemical synthesis, more particularly, to a kind of preparation for catalyzing and synthesizing isophorone
Method.
Background technology
Isophorone（CAS：78-59-1）It is a kind of important fine chemical material.It is in Polymeric Industry, medical industry
In have a wide range of applications, annual production is up to tens thousand of tons.
The compound is synthesized in 19th-century, during the fast development of nineteen sixties Polymeric Industry
Start industrialization, the then demand growth with the whole world to industries such as high performance material, medicine intermediate, agricultural chemicals, its market
Rapid growth, current annual requirement is up to tens thousand of tons.
The current industrial product route of isophorone is acetone condensation method, is specifically divided into liquid phase condensations and vapour phase condensation.
The liquid phase condensations of reported in literature are in high-pressure bottle, with inorganic strong alkali such as Sodamide, calcium hydride, alkali metal or alkaline-earth metal
Hydroxide is heated to high temperature and is condensed as catalyst.Because inorganic strong alkali is not readily dissolved in acetone, in order that must react suitable
Profit is carried out, and typically to add a small amount of water.Because reaction condensate is water insoluble, system gradually forms two-phase, it is necessary to strong stirs
Mix.The drawbacks of this kind of synthesis is that conversion ratio and selectivity are all low.
The vapour phase condensation of reported in literature is that at high temperature, acetone gas are in high temperature（200-300 degrees Celsius）By metal oxygen
The solid-phase catalysts such as compound, metal hydroxides, calcium aluminium compound, magnalium complexes are reacted.The advantage of this kind of synthesis is
Conversion ratio and selectivity are slightly good.Disadvantage is however that high energy consumption, catalyst preparation high cost, catalyst life is short.
In sum, the technique of the synthesis of isophorone of report at present, no matter using liquid phase synthesis or vapor- phase synthesis,
There are yield and conversion ratio to be not enough satisfied with, the shortcomings of high cost.
The content of the invention
In view of the shortcomings of the prior art, to improve low isophorone conversion ratio, poor selectivity, the problem of expensive catalyst,
The invention provides a kind of preparation method of isophorone, by using organic imidazoles quaternary ammonium base as catalyst, different Buddhist is carried out
The liquid phase synthesis of your ketone.
The present invention is realized by the following technical programs：
A kind of preparation method of organic catalysis isophorone is strong in the organic imidazoles system quaternary ammonium of catalyst with acetone as initiation material
Under the catalytic action of alkali, there is liquid phase condensations reaction in acetone, isophorone is obtained by distillation.Specifically include following steps：
（1）The synthesis of organic imidazoles system quaternary ammonium highly basic：
,
（2）The synthesis of isophorone：
；
Step（1）Described in X-It is the anion of imidazoles quaternary ammonium salt, including Cl-、Br-, I-One kind；Step（1）In it is used
Reaction dissolvent for next step initial reactant acetone.Step（1）Reaction dissolvent be step（2）The initiation material of reaction,
Can be avoided the influence of other solvents and reaction substrate.
Step（1）Alkali used is NaOH, sodium methoxide, caustic alcohol, preferably one kind of sodium tert-butoxide, sodium methoxide.
Wherein, the temperature of exchange reaction is 0~30 DEG C, preferably 10~20 DEG C；The time of exchange reaction is 1~8 h, preferably 2~4
h。
Wherein, organic imidazoles system quaternary ammonium highly basic of above-mentioned condensation reaction has following structure：
,
R1 and R2 in structural formula are respectively the fatty chain substituent less than or equal to 6 carbon.Organic imidazoles system quaternary ammonium highly basic energy
It is dissolved in the middle of the acetone as reaction medium and initiation material, can causes that reaction is smoothed out, and without adding water, it is to avoid
The technical problem of " reaction condensate is water insoluble, and system gradually forms two-phase, it is necessary to strong stirring ".Simultaneously as having
Machine imidazoles system quaternary ammonium highly basic and reactant form W-response, improve the conversion ratio and selectivity of condensation reaction.
As a kind of preferred embodiment of experimental program of the invention, described R1 is methyl, ethyl, n-propyl, isopropyl,
One kind of the tert-butyl group, normal-butyl；Described R2 is methyl, ethyl, n-propyl, isopropyl, the tert-butyl group, one kind of normal-butyl.
In above-mentioned step（2）In, reaction medium and initiation material are acetone, the organic imidazoles system of the catalyst for being added
The catalytic amount of quaternary ammonium highly basic is 0.1 ~ 10mol%, and condensation reaction carries out in autoclave, setting-up point is 140 ~
180 DEG C, condensation reaction time is 5 ~ 24h.After the completion of reaction under high pressure, can continuously or interval to the purification of isophorone
Carry out to ground, single phase or multistage.Purification is preferably realized by distillation, according to principal product isophorone and accessory substance boiling point
Difference, separating-purifying obtains isophorone.
Used as the further optimization of experimental program of the invention, the organic imidazoles system quaternary ammonium highly basic of catalyst for being added is urged
Change consumption is 0.5 ~ 2mol%, and condensation reaction is carried out in autoclave, and setting-up point is 150 ~ 170 DEG C, condensation reaction
Time is 7 ~ 12h.
Based on above-mentioned technical scheme, the technique effect that the present invention has is：
（1）The preparation method of the isophorone provided using the present invention, synthesis of isophorone, technique is synthesized using organic catalysis,
Conversion per pass is more than 60%, and selectivity is more than 70%.With new technology, step is few, the features such as reaction condition is gentle.
（2）Acetone and organic imidazoles system quaternary ammonium highly basic are carried out condensation reaction by the present invention in same dicyandiamide solution, are reacted
After certain hour is carried out at a temperature of the control, the selectivity of isophorone reaches basicly stable, and the accessory substance for reacting generation is different
Propylidene acetone and isopropyl keto-alcohol are few, do not have polymolecular polymerizate substantially, and reaction is easier to control, it is not necessary to strict control
Reaction end；Finally by distillation, separating-purifying obtains principal product isophorone.
（3）The preparation method of the isophorone that the present invention is provided, by using organic imidazoles system quaternary ammonium highly basic, makes acetone contract
Synthesis of isophorone, substantially improves conversion per pass, and achieves preferable selectivity, and convenient operation and control, pair sets
Standby without particular/special requirement, reaction efficiency is high, is adapted to large-scale production and promotes.
Specific embodiment
For the ease of it will be understood by those skilled in the art that, with reference to specific embodiment, the invention will be further described,
The content that implementation method is referred to not delimit the scope of the invention.
Embodiment 1
（1）Prepare organic imidazoles Quaternary Ammonium Alkali Catalyst
One 100 mL three-neck flasks are taken, chlorination 1,3- methylimidazoles is sequentially added thereto under nitrogen protection（1.33 g,
0.01 mol）, acetone（100 mL, 1.71 mol）, it is subsequently adding 30% methanol solution of sodium methylate（1.8 g, 0.01 mol）,
Controlling reaction temperature is 15 DEG C.After question response 4h, reaction solution is filtered, filtrate loads 250 mL autoclaves.
（2）The synthesis of isophorone
Autoclave is installed, 180 degrees Celsius are heated to, reacted 5 hours.After cooling, taking sample carries out GC analyses, acetone conversion
It is 62%, selectivity is 71%.After air-distillation removes acetone, product carries out rectification under vacuum, obtains the g of isophorone 30, and yield is
40%。
Embodiment 2
（1）Prepare organic imidazoles Quaternary Ammonium Alkali Catalyst
One 100 mL three-neck flasks are taken, chlorination 1,3- di-t-butyl imidazoles is sequentially added thereto under nitrogen protection（4.30 g
, 0.02 mol）, acetone（100 mL, 1.71 mol）, it is subsequently adding 50% sodium hydrate aqueous solution（1.6 g, 0.02 mol）,
Controlling reaction temperature is 20 DEG C.After question response 6h, reaction solution is filtered, filtrate loads 250 mL autoclaves.
（2）The synthesis of isophorone
Autoclave is installed, 150 degrees Celsius are heated to, reacted 6 hours.After cooling, taking sample carries out GC analyses, acetone conversion
It is 67%, selectivity is 69%.After air-distillation removes acetone, product carries out rectification under vacuum, obtains isophorone 28g, and yield is
38%。
Embodiment 3
（1）Prepare organic imidazoles Quaternary Ammonium Alkali Catalyst
One 100 mL three-neck flasks are taken, chlorination 1,3- di-n-butyl imidazoles is sequentially added thereto under nitrogen protection（3.22 g
, 0.015 mol）, acetone（100 mL, 1.71 mol）, it is subsequently adding 30% methanol solution of sodium methylate（1.8 g, 0.01
mol）, controlling reaction temperature is 18 DEG C.After question response 6h, reaction solution is filtered, filtrate loads 250 mL autoclaves.
（2）The synthesis of isophorone
Autoclave is installed, 160 degrees Celsius are heated to, reacted 7 hours.After cooling, taking sample carries out GC analyses, acetone conversion
It is 68%, selectivity is 71%.After air-distillation removes acetone, product carries out rectification under vacuum, obtains isophorone 29.8g, yield
It is 39%.
The foregoing is only the preferred embodiments of the present invention and oneself, it is impossible to be considered as limiting implementation model of the invention
Enclose, although being described in detail to the present invention with reference to the foregoing embodiments, for a person skilled in the art, it is still
Technical scheme described in foregoing embodiments can be modified, or which part technical characteristic is equally replaced
Change.All any modification, equivalent substitution and improvements within the spirit and principles in the present invention, made etc., should be included in the present invention
Protection domain within.
Claims (6)
1. a kind of preparation method of isophorone, it is characterised in that initiation material acetone is strong in the organic imidazoles system quaternary ammonium of catalyst
Under the catalytic action of alkali, there is condensation reaction generation isophorone, specifically include following steps：
（1）The synthesis of organic imidazoles system quaternary ammonium highly basic：
,
Described X-It is the anion of imidazoles quaternary ammonium salt, including Cl-、Br-, I-One kind；
（2）The synthesis of isophorone：
；
Described organic imidazoles system quaternary ammonium highly basic has following structure：
,
R1 and R2 in structural formula are respectively the fatty chain substituent less than or equal to 6 carbon.
2. the preparation method of isophorone according to claim 1, it is characterised in that described R1 is methyl, ethyl, just
Propyl group, isopropyl, one kind of the tert-butyl group；Described R2 is methyl, ethyl, n-propyl, isopropyl, one kind of the tert-butyl group.
3. the preparation method of isophorone according to claim 1, it is characterised in that described organic imidazoles system quaternary ammonium is strong
The catalytic amount of alkali is 0.1 ~ 10mol%.
4. the preparation method of isophorone according to claim 3, it is characterised in that described organic imidazoles system quaternary ammonium is strong
The catalytic amount of alkali is 0.5 ~ 2mol%.
5. the preparation method of isophorone according to claim 1, it is characterised in that described step（2）Condensation it is anti-
Should be carried out in autoclave, described setting-up point is 140 ~ 180 DEG C, described condensation reaction time is 5 ~ 24h.
6. the preparation method of isophorone according to claim 5, it is characterised in that described setting-up point is
150 ~ 170 DEG C, described condensation reaction time is 7 ~ 12h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2016110025697 | 2016-11-15 | ||
| CN201611002569 | 2016-11-15 |
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| Publication Number | Publication Date |
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| CN106892807A true CN106892807A (en) | 2017-06-27 |
| CN106892807B CN106892807B (en) | 2019-05-03 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903180A (en) * | 2019-12-18 | 2020-03-24 | 万华化学集团股份有限公司 | Preparation method and device of isophorone |
| CN116178119A (en) * | 2022-11-23 | 2023-05-30 | 江苏宏邦化工科技有限公司 | Method for preparing alpha-isophorone by taking 3, 5-trimethyl-2-cyclohexene-1-subunit acetone as raw material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3981918A (en) * | 1974-05-15 | 1976-09-21 | Bp Chemicals International Limited | Isophorone production using a potassium hydroxide catalyst |
| CN101648877A (en) * | 2009-09-03 | 2010-02-17 | 南京大学 | Preparation method of quaternary ammonium carboxylate ion liquid with low halogen |
| US20130261343A1 (en) * | 2010-12-08 | 2013-10-03 | Evonik Degussa Gmbh | Method for producing isophorone |
-
2017
- 2017-02-16 CN CN201710082672.5A patent/CN106892807B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3981918A (en) * | 1974-05-15 | 1976-09-21 | Bp Chemicals International Limited | Isophorone production using a potassium hydroxide catalyst |
| CN101648877A (en) * | 2009-09-03 | 2010-02-17 | 南京大学 | Preparation method of quaternary ammonium carboxylate ion liquid with low halogen |
| US20130261343A1 (en) * | 2010-12-08 | 2013-10-03 | Evonik Degussa Gmbh | Method for producing isophorone |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903180A (en) * | 2019-12-18 | 2020-03-24 | 万华化学集团股份有限公司 | Preparation method and device of isophorone |
| CN110903180B (en) * | 2019-12-18 | 2022-11-08 | 万华化学集团股份有限公司 | Preparation method and device of isophorone |
| CN116178119A (en) * | 2022-11-23 | 2023-05-30 | 江苏宏邦化工科技有限公司 | Method for preparing alpha-isophorone by taking 3, 5-trimethyl-2-cyclohexene-1-subunit acetone as raw material |
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