CN106892807B - A kind of preparation method of the isophorone using organic imidazoles system quaternary ammonium strong base catalyst - Google Patents
A kind of preparation method of the isophorone using organic imidazoles system quaternary ammonium strong base catalyst Download PDFInfo
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- CN106892807B CN106892807B CN201710082672.5A CN201710082672A CN106892807B CN 106892807 B CN106892807 B CN 106892807B CN 201710082672 A CN201710082672 A CN 201710082672A CN 106892807 B CN106892807 B CN 106892807B
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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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Abstract
The invention discloses a kind of preparation methods of isophorone using organic imidazoles system quaternary ammonium strong base catalyst, using acetone as starting material, under the catalytic action of the organic imidazoles system quaternary ammonium highly basic of catalyst, liquid phase condensations reaction occurs for acetone, obtains isophorone 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 as in the acetone of reaction medium and starting material, can make reaction go on smoothly.Using the preparation method of isophorone provided by the invention, synthesis of isophorone, technique is synthesized using organic catalysis, and conversion per pass is greater than 60%, and selectivity is greater than 70%.The features such as preparation method of isophorone of the invention has new technology, and step is few, and reaction condition is mild.
Description
Technical field
The present invention relates to the technical fields of organic chemical synthesis, more particularly, to a kind of preparation for catalyzing and synthesizing isophorone
Method.
Background technique
Isophorone (CAS:78-59-1) is a kind of important fine chemical material.It is in Polymeric Industry, medical industry
In have a wide range of applications, annual output is up to tens of thousands of tons.
The compound is synthesized in 19th-century, during nineteen sixties Polymeric Industry is fast-developing
Start to industrialize, then the demand growth with the whole world to industries such as high performance material, medicine intermediate, pesticides, market
Rapid growth, annual requirement is up to tens of thousands of tons at present.
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.Since inorganic strong alkali is not readily dissolved in acetone, in order to enable reaction is suitable
Benefit carries out, and generally to add a small amount of water.Since reaction condensate is not soluble in water, system gradually forms two-phase, needs strong stir
It mixes.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 passes through metal oxygen at high temperature (200-300 degrees Celsius)
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 energy consumption is high, catalyst preparation is at high cost, and catalyst life is short.
In conclusion no matter the technique for the synthesis of isophorone reported at present, use liquid phase synthesis or vapor- phase synthesis,
The disadvantages of it is not satisfied enough that there are yield and conversion ratios, at high cost.
Summary of the invention
In view of the deficiencies of the prior art, to improve low isophorone conversion ratio, poor selectivity, expensive catalyst the problem of,
The present invention provides a kind of preparation methods of isophorone using organic imidazoles system quaternary ammonium strong base catalyst, by using organic miaow
Azoles quaternary ammonium base carries out the liquid phase synthesis of isophorone as catalyst.
The present invention realizes by the following technical programs:
A kind of preparation method of organic catalysis isophorone, using acetone as starting material, in catalyst organic imidazoles system season
Under the catalytic action of ammonium highly basic, liquid phase condensations reaction occurs for acetone, obtains isophorone by distillation.Specifically include following step
It is rapid:
(1) synthesis of organic imidazoles system quaternary ammonium highly basic:
,
(2) synthesis of isophorone:
；
X as described in step (1)-For the anion of imidazoles quaternary ammonium salt, including Cl-、Br-, I-One kind；In step (1)
Reaction dissolvent used is the initial reactant acetone of next step.The reaction dissolvent of step (1) is that the starting of step (2) reaction is former
Material, can be avoided the influence of other solvents and reaction substrate.
Alkali used in step (1) is one kind of sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, preferably sodium methoxide.
Wherein, the temperature of exchange reaction is 0~30 DEG C, preferably 10~20 DEG C；The time of exchange reaction be 1~8 h, preferably 2~4
h。
Wherein, organic imidazoles system quaternary ammonium highly basic of above-mentioned condensation reaction has a structure that
,
R1 and R2 in structural formula are respectively the fatty chain substituent for being less than or equal to 6 carbon.Organic imidazoles system quaternary ammonium is strong
Alkali can be dissolved in as in the acetone of reaction medium and starting material, can make reaction go on smoothly, and do not have to addition water,
The technical issues of avoiding " reaction condensate is not soluble in water, and system gradually forms two-phase, needs strong stirring ".Meanwhile by
W-response is formed in organic imidazoles system quaternary ammonium highly basic and reactant, improves the conversion ratio and selectivity of condensation reaction.
As a kind of preferred embodiment of experimental program of the invention, the R1 be methyl, ethyl, n-propyl, isopropyl,
One kind of tert-butyl, normal-butyl；The R2 is one kind of methyl, ethyl, n-propyl, isopropyl, tert-butyl, normal-butyl.
In above-mentioned step (2), reaction medium and starting material are acetone, the organic imidazoles system of the catalyst being added
The catalytic amount of quaternary ammonium highly basic is 0.1 ~ 10mol%, and condensation reaction carries out in a high pressure reaction kettle, setting-up point is 140 ~
180 DEG C, condensation reaction time be 5 ~ for 24 hours.After the completion of reaction under high pressure, to the purification of isophorone can continuously or interval
Carry out to ground, single phase or multistage.Purification is preferably realized by distillation, according to principal product isophorone and by-product boiling point
Difference, separating-purifying obtains isophorone.
As advanced optimizing for experimental program of the invention, the organic imidazoles system quaternary ammonium highly basic of the catalyst being added is urged
Change dosage is 0.5 ~ 2mol%, and condensation reaction carries out in a high pressure reaction kettle, and setting-up point is 150 ~ 170 DEG C, condensation reaction
Time is 7 ~ 12h.
Based on above-mentioned technical solution, technical effect that the present invention has are as follows:
(1) using the preparation method of isophorone provided by the invention, synthesis of isophorone, technique is using organic catalysis conjunction
At conversion per pass is greater than 60%, and selectivity is greater than 70%.With the features such as new technology, step is few, and reaction condition is mild.
(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
Control at a temperature of carry out after a certain period of time, the selectivity of isophorone reaches basicly stable, and the by-product 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, and does not need strict control
Reaction end；Finally by distillation, separating-purifying obtains principal product isophorone.
(3) preparation method of a kind of isophorone using organic imidazoles system quaternary ammonium strong base catalyst provided by the invention is led to
Cross using organic imidazoles system quaternary ammonium highly basic, make condensation of acetone at isophorone, substantially improve conversion per pass, and achieve compared with
Good selectivity, and convenient operation and control, to equipment without particular/special requirement, reaction efficiency is high, and large-scale production is suitble to promote.
Specific embodiment
For the ease of it will be understood by those skilled in the art that, the present invention is further explained in the light of specific embodiments,
The content that embodiment refers to is not delimit the scope of the invention.
Embodiment 1
(1) organic imidazoles Quaternary Ammonium Alkali Catalyst is prepared
One 100 mL three-neck flasks are taken, sequentially add chlorination 1,3- methylimidazole (1.33 thereto under nitrogen protection
G, 0.01 mol), acetone (100 mL, 1.71 mol), then be added 30% methanol solution of sodium methylate (1.8 g, 0.01
Mol), control reaction temperature is 15 DEG C.After reacting 4h, reaction solution is filtered, filtrate is packed into 250 mL autoclaves.
(2) synthesis of isophorone
Autoclave is installed, is heated to 180 degrees Celsius, is reacted 5 hours.After cooling, sample is taken to carry out GC analysis, acetone turns
Rate is 62%, and selectivity is 71%.After air-distillation removes acetone, product carries out rectification under vacuum, obtains 30 g of isophorone, receives
Rate is 40%.
Embodiment 2
(1) organic imidazoles Quaternary Ammonium Alkali Catalyst is prepared
One 100 mL three-neck flasks are taken, sequentially add chlorination 1,3- di-t-butyl imidazoles thereto under nitrogen protection
(4.30 g, 0.02 mol), acetone (100 mL, 1.71 mol), then be added 50% sodium hydrate aqueous solution (1.6 g,
0.02 mol), control reaction temperature is 20 DEG C.After reacting 6h, reaction solution is filtered, filtrate is packed into 250 mL high pressures
Kettle.
(2) synthesis of isophorone
Autoclave is installed, is heated to 150 degrees Celsius, is reacted 6 hours.After cooling, sample is taken to carry out GC analysis, acetone turns
Rate is 67%, and selectivity is 69%.After air-distillation removes acetone, product carries out rectification under vacuum, obtains isophorone 28g, receives
Rate is 38%.
Embodiment 3
(1) organic imidazoles Quaternary Ammonium Alkali Catalyst is prepared
One 100 mL three-neck flasks are taken, sequentially add chlorination 1,3- di-n-butyl imidazoles thereto under nitrogen protection
(3.22 g, 0.015 mol), acetone (100 mL, 1.71 mol), then be added 30% methanol solution of sodium methylate (1.8 g,
0.01 mol), control reaction temperature is 18 DEG C.After reacting 6h, reaction solution is filtered, filtrate is packed into 250 mL high pressures
Kettle.
(2) synthesis of isophorone
Autoclave is installed, is heated to 160 degrees Celsius, is reacted 7 hours.After cooling, sample is taken to carry out GC analysis, acetone turns
Rate is 68%, and selectivity is 71%.After air-distillation removes acetone, product carries out rectification under vacuum, obtains isophorone 29.8g,
Yield is 39%.
The above description is only a preferred embodiment of the present invention and oneself, the implementation model that should not be considered as limiting the invention
It encloses, although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still
It is possible to modify the technical solutions described in the foregoing embodiments, or part of technical characteristic is equally replaced
It changes.All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in the present invention
Protection scope within.
Claims (6)
1. a kind of preparation method of the isophorone using organic imidazoles system quaternary ammonium strong base catalyst, which is characterized in that starting material
Acetone occurs condensation reaction and generates isophorone, specifically include under the catalytic action of the organic imidazoles system quaternary ammonium highly basic of catalyst
Following steps:
(1) synthesis of organic imidazoles system quaternary ammonium highly basic:
,
The X-For the anion of imidazoles quaternary ammonium salt, including Cl-、Br-, I-One kind；
(2) synthesis of isophorone:
；
Organic imidazoles system quaternary ammonium highly basic has a structure that
,
R1 and R2 in structural formula are respectively the fatty chain substituent for being less than or equal to 6 carbon.
2. the preparation method of the isophorone according to claim 1 using organic imidazoles system quaternary ammonium strong base catalyst, special
Sign is that the R1 is one kind of methyl, ethyl, n-propyl, isopropyl, tert-butyl；The R2 is methyl, ethyl, just
One kind of propyl, isopropyl, tert-butyl.
3. the preparation method of the isophorone according to claim 1 using organic imidazoles system quaternary ammonium strong base catalyst, special
Sign is that the catalytic amount of organic imidazoles system quaternary ammonium highly basic is 0.1 ~ 10mol%.
4. the preparation method of the isophorone according to claim 3 using organic imidazoles system quaternary ammonium strong base catalyst, special
Sign is that the catalytic amount of organic imidazoles system quaternary ammonium highly basic is 0.5 ~ 2mol%.
5. the preparation method of the isophorone according to claim 1 using organic imidazoles system quaternary ammonium strong base catalyst, special
Sign is that the condensation reaction of the step (2) carries out in a high pressure reaction kettle, and the setting-up point is 140 ~ 180
DEG C, the condensation reaction time is 5 ~ for 24 hours.
6. the preparation method of the isophorone according to claim 5 using organic imidazoles system quaternary ammonium strong base catalyst, special
Sign is that the setting-up point is 150 ~ 170 DEG C, and the condensation reaction time is 7 ~ 12h.
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Citations (2)
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102010062587A1 (en) * | 2010-12-08 | 2012-06-14 | Evonik Degussa Gmbh | Process for the preparation of isophorone |
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Patent Citations (2)
| 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 |
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