CN101462930B - Preparation of beta-dione - Google Patents
Preparation of beta-dione Download PDFInfo
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- CN101462930B CN101462930B CN2008102418435A CN200810241843A CN101462930B CN 101462930 B CN101462930 B CN 101462930B CN 2008102418435 A CN2008102418435 A CN 2008102418435A CN 200810241843 A CN200810241843 A CN 200810241843A CN 101462930 B CN101462930 B CN 101462930B
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Abstract
The present invention relates to a preparation method of beta-diketone; Claisen condensation reaction is adopted; the chemical general expression of the beta-diketone is R1COCH2COR2, wherein, R1 is C6-C12 alkyl, and R2 is phenyl or alkylphenyl; the method comprises the following steps: ester, phenyl ketone and partial solvent are pre-mixed for spare; a condensating agent and remaining solvent are added in a reactor, and the temperature is raised under nitrogen atmosphere; during the period when the temperature of the reactor is raised to the needed temperature of the condensation reaction, the pre-mixed material is dropwise added in the reactor for carrying out the condensation reaction with a system which is composed of the condensating agent and the remaining solvent under an infinite reflux condition; after the pre-mixed material is dropwise added, heat-preserving condensation reaction is carried out continuously under the infinite reflux condition. The ester and the condensating agent in the raw material are contacted when the reacting condition is achieved, and acylation reaction is slow reaction, relative to the Claisen condensation reaction, thus being capable of better solving the acidylation problem of the ester, and reducing the effect of the acylation reaction to the minimum; the yield of the beta-diketone is more than or equal to 90 percent.
Description
Technical field
The present invention relates to the acyclic or isocyclic compound of condensation, especially relate to a kind of preparation method of beta-diketon.
Background technology
The extraction ability of beta-diketon shows that it is effective copper extractant.When the preparation beta-diketone compounds, take claisen (Claisen) condensation reaction usually, under the katalysis of condensing agent, synthesize.For example earlier ester and unreactive hydrocarbons solvent and condensing agent are added in the reactor, elevated temperature to condensation reaction temperature required during, drip the ketone or derivatives thereof again.That Chinese invention patent CN1046498C has announced is a kind of " improving one's methods of preparation beta-diketon ", comprising following steps:
(A) phenyl methyl ketone and ester are reacted in the presence of basic catalyst in unreactive hydrocarbons solvent under the reflux temperature of organic solvent, thereby form the diketone condensation product of described phenyl methyl ketone and ester;
(B) make the reaction of this mixture of reaction products and aqueous acids, form organic solvent phase and aqueous acids mutually, thus an alkali metal salt in the acidified reaction mixture;
(C) washing contains the organic solvent phase of diketone product, so that remove salt and any excess acid;
(D) under the elevated temperature condition, stripping is through the volatile matter of organic solvent in mutually of washing;
(E) underpressure distillation resistates is so that reclaim the diketone product.
Wherein improvements comprise one or more the following steps:
(I) phenyl methyl ketone is added in the reaction mixture being as short as in the time that is enough to reduce to greatest extent degraded product in the reaction mixture and increases diketone product productive rate to greatest extent;
(II) carry out completely constantly in reaction, additionally add solvent,, thereby reduce the productive rate that falls product in the mixture of reaction products and improve the diketone product to greatest extent to greatest extent so that reduce the temperature of mixture of reaction products rapidly;
(III) aqueous acids is mixed mutually and ask when sufficiently long, thereby the alkali metal concn that organic solvent is kept in mutually is substantially zero;
(IV) step (A) is finished constantly and the time between zero hour of step (B), shortened to the time limit that is enough to reduce to greatest extent degraded product in the reaction mixture and improves diketone product productive rate to greatest extent.
Also there is following defective in aforesaid method: in the elevated temperature process, part ester and condensing agent produce acylation, have changed the initial material ratio, and its result causes yield to reduce.If the increasing material proportion improves yield then loses more than gain.
Summary of the invention
Technical problem to be solved by this invention is to remedy above-mentioned the deficiencies in the prior art, proposes a kind of preparation method of beta-diketon.
Technical problem of the present invention is solved by the following technical solutions:
The preparation method of this beta-diketon takes the claisen condensation reaction, synthesizes under the katalysis of condensing agent, and the chemical general formula of described beta-diketon is R
1COCH
2COR
2, R wherein
1Be C
6～C
12Alkyl, R
2Be phenyl or alkyl phenyl.
The preparation method's of this beta-diketon characteristics are may further comprise the steps:
Ester, phenyl ketone and partial solvent pre-mixing is standby;
Condensing agent and residual solvent are added in the reactor elevated temperature under nitrogen atmosphere;
During the reactor elevated temperature is temperature required to condensation reaction, described premixed material is added drop-wise to the system of forming with condensing agent and residual solvent in the reactor carries out condensation reaction under the total reflux condition;
After described premixed material dropping finishes, continue under the total reflux condition, to carry out heat-preserving condensation reaction.
The dropping time is bigger to the synthesis yield influence.The dropping time is too short to be that rate of addition is too fast, and the alcohols that condensation produces can not be absorbed by condensing agent fully, and unabsorbed alcohols material will form hemiketal with methyl phenyl ketone, causes yield to reduce.Dripping overlong time is that rate of addition is slow excessively, can increase beta-diketon product cracked risk again.The dropping time that present method adopts is 1～3 hour, and preferably the dropping time is 2 hours.Do not get rid of when carrying out industrial production, because the restriction of material flow, the dropping time may change.And take under the total reflux condition, to react, can prevent losing of low boiling point solvent, because the sodium salt of the resulting beta-diketon of condensation only in rarer solution, just can not separated out, be convenient to carry out follow-up acidification reaction when low temperature.
Technical problem of the present invention adopts following further technical scheme to be solved.
Described condensing agent is a strong alkali catalyst.
Described strong alkali catalyst is sodium methylate, sodium hydride or sodium amide.
Described solvent is low-pole inert solvent or nonpolar inert solvent.They neither can carry out proton transfer reaction, also not with solute generation solvation.
Described low-pole inert solvent is dimethylbenzene or toluene.
Described nonpolar inert solvent is a solvent oil.
Described ester is a fatty acid ester.
Described fatty acid ester is C
6～C
12Alkyl fatty acid methyl esters or alkyl fatty acetoacetic ester.
Described alkyl fatty acid methyl esters is methyl caproate, methyl caprylate, different methyl pelargonate or methyl caprate.
Described alkyl fatty acetoacetic ester is an oil of cognac.
Described ketone or derivatives thereof is an arone compounds.
Described arone compounds is methyl phenyl ketone or phenylacetyl ethane.
Described condensation reaction is temperature required to be 125～150 ℃.
The heat-preserving condensation reaction time after described the dropwising is 4～8 hours, and the preferred heat-preserving condensation reaction time is 5 hours.
After described heat-preserving condensation reaction finishes, following steps are arranged successively also:
The mother liquor temperature is arrived room temperature at 1 hour internal cooling;
Add rubble ice in the mother liquor, the temperature of mother liquor is reduced to below 0 ℃;
Be in the sulfuric acid of 50% concentration with mass ratio and mother liquor, add trash ice simultaneously and keep the mother liquor temperature, after neutralization finishes, leave standstill, remove water below 0 ℃;
Being lower than in the mother liquor temperature under 10 ℃ the condition, is that the sulfuric acid of 50% concentration carries out the acidifying collection to mother liquor and washed 20～40 minutes with mass ratio, removes water once more; Lower temperature and reasonable time can guarantee to transform fully and avoid the cracking of beta-diketon;
Mother liquor is handled by the strong-acid ion exchange resin post after washing through three times again, to remove the sodium ion in the mother liquor, avoids reducing because of remaining beta-diketon sodium causes productive rate;
By the low boiling point solvent in the air distillation removal mother liquor;
Under the condition of vacuum tightness≤100mmHg, distill out most of lower boiling unreacted ester compounds in the mother liquor;
Under the condition under vacuum tightness≤5mmHg, collect 160～200 ℃ of cuts at last, be the beta-diketon product.
The beneficial effect that the present invention is compared with the prior art is:
The present invention is to being improved by the process of organic acid acetic and methyl phenyl ketone condensation prepared beta-diketon; because the ester in the raw material is just to contact when reaching reaction conditions with condensing agent; acylation reaction is to be long response time with respect to the claisen condensation reaction; can solve the acidylate problem of ester preferably; reduce to the influence of acylation reaction minimum; adopt productive rate 〉=90% of the synthetic beta-diketon of improving one's methods of the present invention, and adopt productive rate≤50% of conventional claisen condensation method.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment one
A kind of preparation method of beta-diketon is as follows:
In the 1000ml four footpath flasks that are equipped with agitator, thermometer, nitrogen ingress pipe, reflux exchanger and constant pressure funnel, add 16g sodium amide and 100ml dimethylbenzene.Open nitrogen, start and stir, heat elevated temperature immediately.
When temperature is increased to 135 ℃, begin to drip being pre-mixed uniform liquid by 110g methyl caprylate, 30g methyl phenyl ketone and 50ml dimethylbenzene, dripped the process required time about 1.5 hours.
Under 140 ℃, heat-preserving condensation reaction 5 hours, stopped reaction.
Reaction mother liquor was cooled to room temperature rapidly in 30 minutes.Adding rubble ice again makes the mother liquor temperature continue to drop to below 0 ℃.
Under agitation, be that the sulfuric acid of 50% concentration is neutralized to neutrality with mother liquor with mass ratio, continue to add rubble ice simultaneously and keep solution temperature to be lower than 0 ℃.After neutralization finishes, leave standstill, remove water.
Be that the sulfuric acid 100ml acidifying collection of 50% concentration was washed 15 minutes with mass ratio again, divide the phase of anhydrating, wash three times.
Mother liquor passes through strongly-acid deionization plastic resin treatment again.
Mother liquor at first adopts air distillation, removes removal xylene.Be decompressed to the 100mm mercury column then, unreacted reactant such as methyl caprylate and other by products are removed in distillation.Be decompressed at last and collect 160～180 ℃ of cuts under vacuum tightness 1～2mm mercury column, promptly get beta-diketon, its purity 〉=95%, productive rate 96%.
Embodiment two
The preparation method of another beta-diketon is as follows:
In the 1000ml four footpath flasks that are equipped with agitator, thermometer, nitrogen ingress pipe, reflux exchanger and constant pressure funnel, add
27The dimethylbenzene of g methyl alcohol and 100ml.Open nitrogen and stirring, immediately elevated temperature.
When temperature is increased to 135 ℃, begin to drip being pre-mixed uniform liquid by the methyl caprate of 110g, methyl phenyl ketone and the 50ml dimethylbenzene of 30g, dripped the process required time about 2.0 hours.
Subsequent process is identical with embodiment one.Make the purity 95% of beta-diketon, productive rate 93%.
Above content be in conjunction with concrete preferred implementation to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention; under the prerequisite that does not break away from the present invention/inventive concept, make some alternative or obvious modification that are equal to; and performance or purposes are identical, then should be considered as belonging to the protection domain that the present invention is determined by claims of being submitted to.
Claims (7)
1. the preparation method of a beta-diketon takes the claisen condensation reaction, synthesizes under the katalysis of condensing agent, and the chemical general formula of described beta-diketon is R
1COCH
2COR
2, R wherein
1Be C
6～C
12Alkyl, R
2Be phenyl or alkyl phenyl, it is characterized in that:
May further comprise the steps:
Ester, phenyl ketone and partial solvent pre-mixing is standby, and described solvent is low-pole inert solvent or nonpolar inert solvent, and described low-pole inert solvent is dimethylbenzene or toluene, and described nonpolar inert solvent is a solvent oil;
Condensing agent and residual solvent are added in the reactor, elevated temperature under nitrogen atmosphere, described condensing agent is a strong alkali catalyst, described strong alkali catalyst is sodium methylate, sodium hydride or sodium amide;
During the reactor elevated temperature is temperature required to condensation reaction, described premixed material is added drop-wise to the system of forming with condensing agent and residual solvent in the reactor carries out condensation reaction under the total reflux condition, described condensation reaction is temperature required to be 125～150 ℃;
After described premixed material dropping finishes, continue under the total reflux condition, to carry out heat-preserving condensation reaction.
2. the preparation method of beta-diketon as claimed in claim 1 is characterized in that:
Described ester is a fatty acid ester; Described fatty acid ester is C
6～C
12Alkyl fatty acid methyl esters or alkyl fatty acetoacetic ester.
3. the preparation method of beta-diketon as claimed in claim 2 is characterized in that:
Described alkyl fatty acid methyl esters is methyl caproate, methyl caprylate, different methyl pelargonate or methyl caprate.
4. the preparation method of beta-diketon as claimed in claim 2 is characterized in that:
Described alkyl fatty acetoacetic ester is an oil of cognac.
5. as the preparation method of claim 3 or 4 described beta-diketons, it is characterized in that:
Described phenyl ketone is an arone compounds; Described arone compounds is methyl phenyl ketone or phenylacetyl ethane.
6. the preparation method of beta-diketon as claimed in claim 5 is characterized in that:
The heat-preserving condensation reaction time after described the dropwising is 4～8 hours.
7. the preparation method of beta-diketon as claimed in claim 1 is characterized in that:
After described lasting condensation reaction finishes, following steps are arranged successively also:
The mother liquor temperature is arrived room temperature at 1 hour internal cooling;
Add rubble ice in the mother liquor, the temperature of mother liquor is reduced to below 0 ℃;
Be in the sulfuric acid of 50% concentration with mass ratio and mother liquor, add trash ice simultaneously and keep the mother liquor temperature, after neutralization finishes, leave standstill, remove water below 0 ℃;
Being lower than in the mother liquor temperature under 10 ℃ the condition, is that the sulfuric acid of 50% concentration carries out the acidifying collection to mother liquor and washed 20～40 minutes with mass ratio, removes water once more;
Mother liquor is handled by the strong-acid ion exchange resin post after washing through three times again;
By the low boiling point solvent in the air distillation removal mother liquor;
Under the condition of vacuum tightness≤100mmHg, distill out most of lower boiling unreacted ester compounds in the mother liquor;
Under the condition under vacuum tightness≤5mmHg, collect 160～200 ℃ of cuts at last, be the beta-diketon product.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102418435A CN101462930B (en) | 2008-12-22 | 2008-12-22 | Preparation of beta-dione |
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|---|---|---|---|
| CN2008102418435A CN101462930B (en) | 2008-12-22 | 2008-12-22 | Preparation of beta-dione |
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| CN101462930A CN101462930A (en) | 2009-06-24 |
| CN101462930B true CN101462930B (en) | 2011-09-14 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274916B (en) * | 2013-04-28 | 2015-03-11 | 温州大学 | Alkyl and aryl ketone compound preparation method |
| CN103265420B (en) * | 2013-05-03 | 2015-09-02 | 温州大学 | A kind of preparation method of aromatic diketone compound |
| CN105218388B (en) * | 2015-10-26 | 2017-07-11 | 西北农林科技大学 | β carbonyls olefinic amine compound and it is used as the application for preparing antibacterial agents for pathogenic bacteria |
| CN106478387B (en) * | 2016-01-14 | 2019-02-01 | 大连理工大学 | A kind of preparation method of the two arone compound containing Alpha-Naphthyl |
| CN105712851B (en) * | 2016-01-21 | 2018-08-21 | 大连理工大学 | A kind of preparation method of the two arone compound containing betanaphthyl |
| CN113943216A (en) * | 2020-07-15 | 2022-01-18 | 太原市小店区巨龙福利加工厂 | Process for preparing beta-diketone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1232014A (en) * | 1992-11-06 | 1999-10-20 | 罗狄亚化学公司 | Processes for making beta-diketones |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1232014A (en) * | 1992-11-06 | 1999-10-20 | 罗狄亚化学公司 | Processes for making beta-diketones |
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Effective date of registration: 20130530 Address after: Qin Feng Road, Qiandeng Town, Kunshan city of Suzhou City, Jiangsu province 215341 Patentee after: Kunshan City Banming Electronic Science & Technology Co., Ltd. Address before: 518067 Guangdong city of Shenzhen province Nanshan District Shekou Industrial Road. Three Arts crafts emporium, the first floor of B block Patentee before: Shenzhen Board Technology Co., Ltd. |