CN106831377B - A kind of preparation method of the isophorone using organic methenamine system quaternary ammonium strong base catalyst - Google Patents
A kind of preparation method of the isophorone using organic methenamine system quaternary ammonium strong base catalyst Download PDFInfo
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- CN106831377B CN106831377B CN201710082671.0A CN201710082671A CN106831377B CN 106831377 B CN106831377 B CN 106831377B CN 201710082671 A CN201710082671 A CN 201710082671A CN 106831377 B CN106831377 B CN 106831377B
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- 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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Abstract
The invention discloses a kind of preparation methods of isophorone using organic methenamine system quaternary ammonium strong base catalyst, using acetone as starting material, under the catalytic action of the organic methenamine system quaternary ammonium highly basic of catalyst, liquid phase condensations reaction occurs for acetone, obtains isophorone by distillation.Specifically include the synthesis of organic methenamine system quaternary ammonium highly basic and the synthesis of isophorone.Organic methenamine 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 50%, and selectivity is greater than 60%.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 method of isophorone using organic methenamine system quaternary ammonium strong base catalyst, by using having
Machine methenamine 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 the isophorone using organic methenamine system quaternary ammonium strong base catalyst is that starting is former with acetone
Material, under the catalytic action of the organic methenamine system quaternary ammonium highly basic of catalyst, liquid phase condensations reaction occurs for acetone, by distilling
To isophorone.Specifically includes the following steps:
(1) synthesis of organic methenamine system quaternary ammonium highly basic:
,
(2) synthesis of isophorone:
；
X as described in step (1)-For the anion of methenamine quaternary ammonium salt, including Cl-、Br-, I-One kind；Step
(1) reaction dissolvent used in is the initial reactant acetone of next step.The reaction dissolvent of step (1) is step (2) reaction
Starting 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 methenamine system quaternary ammonium highly basic of above-mentioned condensation reaction has a structure that
,
R in structural formula is the fatty chain substituent or benzyl less equal than 6 carbon.Organic methenamine system season
Ammonium highly basic 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 add
The technical issues of adding water, avoiding " reaction condensate is not soluble in water, and system gradually forms two-phase, needs strong stirring ".Together
When, since organic methenamine system quaternary ammonium highly basic and reactant form W-response, improve conversion ratio and the choosing of condensation reaction
Selecting property.
As a kind of preferred embodiment of experimental program of the invention, the R be methyl, ethyl, n-propyl, isopropyl,
One kind of tert-butyl, normal-butyl, benzyl.
In above-mentioned step (2), reaction medium and starting material are acetone, the organic Wu Luotuo of the catalyst being added
The catalytic amount of strain quaternary ammonium highly basic is 0.1 ~ 10mol%, and condensation reaction carries out in a high pressure reaction kettle, and 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
Intermittently, it carries out to single phase or multistage.Purification is preferably realized by distillation, according to principal product isophorone and by-product
The difference of boiling point, separating-purifying obtain isophorone.
As advanced optimizing for experimental program of the invention, the organic methenamine system quaternary ammonium highly basic of the catalyst being added
Catalytic amount be 0.5 ~ 2mol%, 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, technique is synthesized using organic catalysis, conversion per pass
The features such as greater than 50%, selectivity is greater than 60%, has new technology, and step is few, and reaction condition is mild.
(2) acetone and organic methenamine system quaternary ammonium highly basic are carried out condensation reaction by the present invention in same dicyandiamide solution,
React control at a temperature of carry out after a certain period of time, the selectivity of isophorone reaches basicly stable, reacts the by-product of generation
Object is few, does not have polymolecular polymerizate substantially, and reaction is easier to control, and does not need strict control reaction end；Finally lead to
Distillation is crossed, separating-purifying obtains principal product isophorone.
(3) preparation method of isophorone provided by the invention makes third by using organic methenamine system quaternary ammonium highly basic
Ketone is condensed into isophorone, substantially improves conversion per pass, and achieves preferable 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 methenamine Quaternary Ammonium Alkali Catalyst is prepared
One 100 mL three-neck flasks are taken, sequentially add methyl chloride methenamine (1.90 g thereto under nitrogen protection
, 0.01 mol), acetone (100 mL, 1.71 mol), then be added 30% methanol solution of sodium methylate (1.8 g, 0.01 mol),
Controlling 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 55%, and selectivity is 63%.After air-distillation removes acetone, product carries out rectification under vacuum, obtains 24 g of isophorone, receives
Rate is 31%.
Embodiment 2
(1) organic methenamine Quaternary Ammonium Alkali Catalyst is prepared
One 100 mL three-neck flasks are taken, sequentially add zephiran chloride methenamine (5.34 g thereto under nitrogen protection
, 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 autoclaves.
(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 59%, and selectivity is 65%.After air-distillation removes acetone, product carries out rectification under vacuum, obtains isophorone 26g, receives
Rate is 36%.
Embodiment 3
(1) organic methenamine Quaternary Ammonium Alkali Catalyst is prepared
One 100 mL three-neck flasks are taken, sequentially add chlorination tert-butyl methenamine (3.12 thereto under nitrogen protection
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 autoclaves.
(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 60%, and selectivity is 66%.After air-distillation removes acetone, product carries out rectification under vacuum, obtains isophorone 27g, receives
Rate is 38%.
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 methenamine system quaternary ammonium strong base catalyst, which is characterized in that starting
Raw material acetone occurs condensation reaction and generates isophorone under the catalytic action of the organic methenamine system quaternary ammonium highly basic of catalyst,
Specifically includes the following steps:
(1) synthesis of organic methenamine system quaternary ammonium highly basic:
,
The X-For the anion of methenamine quaternary ammonium salt, including Cl-、Br-, I-One kind；
(2) synthesis of isophorone:
；
Organic methenamine system quaternary ammonium highly basic has a structure that
,
R in structural formula is the fatty chain substituent or benzyl less equal than 6 carbon.
2. the preparation method of the isophorone according to claim 1 using organic methenamine system quaternary ammonium strong base catalyst,
It is characterized in that, the R is one kind of methyl, ethyl, n-propyl, isopropyl, tert-butyl, benzyl.
3. the preparation method of the isophorone according to claim 1 using organic methenamine system quaternary ammonium strong base catalyst,
It is characterized in that, the catalytic amount of organic methenamine system quaternary ammonium highly basic is 0.1 ~ 10mol%.
4. the preparation method of the isophorone according to claim 3 using organic methenamine system quaternary ammonium strong base catalyst,
It is characterized in that, the catalytic amount of organic methenamine system quaternary ammonium highly basic is 0.5 ~ 2mol%.
5. the preparation method of the isophorone according to claim 1 using organic methenamine system quaternary ammonium strong base catalyst,
It is characterized in that, the condensation reaction of the step (2) carries out in a high pressure reaction kettle, the setting-up point is 140 ~
180 DEG C, the condensation reaction time be 5 ~ for 24 hours.
6. the preparation method of the isophorone according to claim 5 using organic methenamine system quaternary ammonium strong base catalyst,
It is characterized in that, the setting-up point is 150 ~ 170 DEG C, the condensation reaction time is 7 ~ 12h.
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| CN201611002628 | 2016-11-15 | ||
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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 |
| CN101519406A (en) * | 2009-03-25 | 2009-09-02 | 浙江工业大学 | Novel synthetic method of alkyl formamine villaumite |
| CN102976910A (en) * | 2011-09-05 | 2013-03-20 | 张锦碧 | Environment-friendly and simple preparation method for synthesizing isophorone from acetone |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010062587A1 (en) * | 2010-12-08 | 2012-06-14 | Evonik Degussa Gmbh | Process for the preparation of isophorone |
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- 2017-02-16 CN CN201710082671.0A patent/CN106831377B/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 |
| CN101519406A (en) * | 2009-03-25 | 2009-09-02 | 浙江工业大学 | Novel synthetic method of alkyl formamine villaumite |
| CN102976910A (en) * | 2011-09-05 | 2013-03-20 | 张锦碧 | Environment-friendly and simple preparation method for synthesizing isophorone from acetone |
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