CN103387558A - Method for synthesizing lactone compound through catalyzing and oxidizing cyclic ketones - Google Patents
Method for synthesizing lactone compound through catalyzing and oxidizing cyclic ketones Download PDFInfo
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- CN103387558A CN103387558A CN2013103175624A CN201310317562A CN103387558A CN 103387558 A CN103387558 A CN 103387558A CN 2013103175624 A CN2013103175624 A CN 2013103175624A CN 201310317562 A CN201310317562 A CN 201310317562A CN 103387558 A CN103387558 A CN 103387558A
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Abstract
The invention discloses a method for synthesizing a lactone compound through catalyzing and oxidizing cyclic ketones. The method comprises the steps of adding cyclic ketones into a vessel, dropwise adding a hydrogen peroxide solution, adding a phosphotungstate catalyst after the dropwise adding process is completed, and then, carrying out stirring reaction; and after the reaction is ended, filtering, washing, extracting and distilling so as to obtain a target product. The method has the advantages that phosphotungstate is used as a catalyst, the preparation is simple, the conversion ratio of 2-heptyl cyclopentanone, cyclopentanone and cyclohexanone is increased, and the atom utilization of the reaction is increased; the phosphotungstate catalyst can be reused; solvents and acid accelerators are not required to be added, so that economic and environmental benefits are improved; waste acid treatment and strong acid corrosiveness do not exist, energy is saved, emission is reduced, and the safety is high; and the method has the characteristics of good selectivity, high atom efficiency, mild reaction conditions, clean environment and the like, and is suitable for industrial engineering application.
Description
Technical field
The present invention relates to a kind of a kind of method of synthetic method of lactone compound, particularly catalyzing cyclone oxide to synthesizing lactone, belong to the organic chemistry preparation field.
Background technology
The Baeyer-Villiger oxidizing reaction is cyclic ketones or chain oxidation of ketones to be become the reaction of lactone or ester.The Baeyer-Villiger oxidizing reaction, according to the difference of the oxygenant of application in reaction, mainly can be divided into peroxy acid oxidation, hydrogen peroxide oxidation, dioxygen oxidation and other oxygenant oxidation etc.Use the earliest in this four large class oxygenant and industrialized be the peroxy acid oxidation; But now general with the use of hydrogen peroxide and oxygen, be mainly because they are easy to the large-scale industrialization application and are conducive to environment protection.
Although peroxy acid oxidation Baeyer-Villiger reaction has been opened a method that is prepared the different structure ester by ketone compounds for the research worker, but with peroxy acid, as oxygenant, have following shortcoming: the preparation of (1) this type of oxygenant need be used the superoxol of high density, and there are many danger in the superoxol of high density in transportation with in processing; (2) can formation wait the organic carboxyl acid of amount of substance or the refuse of carboxylate salt after the reaction, need to reclaim or process; (3) in use danger is larger for organic peroxide acid, and transportation and storage are also inconvenient, thereby have limited its application in industrial production.The shortcoming such as (4) low, the difficult separation of reaction product of selectivity and environment be unfriendly.
Though oxygen is a kind of convenience, cheapness, be easy to get, the oxygenant of safety, but selectivity and transformation efficiency in the Baeyer-Villiger oxidizing reaction are all very low, usually will make co-oxidants with aldehyde, also need simultaneously suitable catalyzer to exist.Aldehyde first is oxidized to peroxy acid at oxygen or in containing oxygen system, and then with substrate ketone or cyclic ketones generation oxidizing reaction, generate ester or lactone, the peroxy acid that is generated by aldehyde in oxidising process is reduced to carboxylic acid, so the co-oxidation process of molecular oxygen and aldehyde is actually and has consumed more expensive aldehyde and the carboxylic acid of by-product cheapness.
The superoxol of lower concentration is a kind of safe, economic oxygenant, and oxidation products is exactly water except target product, and free from environmental pollution, aftertreatment is easier to, and meets the idea of development of green chemical industry, thereby more and more is subject to vast chemical research person's favor.From the angle of large-scale commercial production, using the superoxol of lower concentration is a kind of desirable selection as oxygenant.But the superoxol oxidation capacity of lower concentration a little less than, himself is difficult to the ketone compounds direct oxidation, catalyzer elder generation and hydrogen peroxide effect that needs are special,, to increase its nucleophilic performance, thereby more be conducive to it, ketone carbonyl generation nucleophilic addition(Adn) in substrate is generated corresponding ester compound; Perhaps manage to activate the ketone carbonyl in substrate, with this, increase positive polarity on carbonyl carbon.Thereby reach the purpose of catalysis Baeyer-Villiger oxidizing reaction.Therefore exploitation is cheap, catalyzer is imperative efficiently.
Common catalyst system is divided into homogeneous catalysis, enzyme catalysis and heterogeneous catalyst three major types in the reaction of the Baeyer-Villiger take superoxol as oxygenant.Use more homogeneous catalyst that Lewis acid catalyst and metal complex catalysts etc. are arranged, although thereby they have preferably catalytic effect and separate and can not reuse the researching value that has reduced this type of catalyzer from product owing to being difficult to; The biological enzyme agent receives much concern because it has high efficiency, selectivity and narrow spectrum characteristics.Baeyer-Villiger oxidizing reaction take enzyme as the derivative of catalyst different substituents ketone particularly shows the research in the Baeyer-Villiger oxidizing reaction of beta-unsaturated ketone, enzyme has very high chemo-selective, the selectivity of regioselectivity and corresponding isomery.But enzymic catalytic reaction parameter such as temperature, ionic strength etc. must accurately be controlled, and, in case rangeability surpasses its permissible value, will cause the loss of activity of enzyme.Enzyme shows the highest catalytic activity usually in the aqueous solution, and the synthetic organic compound of great majority often the solubleness in the aqueous solution is poor, in addition, the shortcoming that also exists catalyzer to be difficult to recycle and reuse.Study hotspot mainly concentrates on heterogeneous catalyst at present, compare homogeneous catalysis and enzyme catalysis, heterogeneous catalyst has following obvious advantage: heterogeneous catalyst can be high temperature resistant, and can select the raw material preparation according to actual requirement, be easy to remove from reaction system, reusable edible, and can be easily in reaction process the catalytic performance to catalyzer monitor, be applied at present heterogeneous catalyst in the Baeyer-Villiger reaction and mostly be solid acid catalyst, the preparation of this type of catalyzer is complicated, and needs, at higher temperature, catalytic effect is arranged.
Summary of the invention
The purpose of this invention is to provide a kind of take alismone, cyclopentanone or pimelinketone as raw material, take the superoxol of lower concentration as oxidising agent, with Suanphosphotungstate (K
3-xH
xPW, Ag
3-xH
xPW) be catalyzer, prepare the novel method of lactone under condition of no solvent, to overcome the deficiency on prior art.
The technical solution that realizes the object of the invention is: a kind of method of catalyzing cyclone oxide to synthesizing lactone comprises the following steps:
Step 1, cyclic ketones is joined in container, drip superoxol, drip to finish and add stirring reaction after the Suanphosphotungstate catalyzer;
After step 2, reaction finish, obtain target product after filtration, washing, extraction, distillation.
Cyclic ketones described in step 1 is a kind of in alismone, cyclopentanone or pimelinketone; Described Suanphosphotungstate catalyzer is K
3-xH
xPW or Ag
3-xH
xPW; Described catalyst quality is 5% ~ 20% of cyclic ketones quality; Described temperature of reaction is 25 ~ 75 ℃, and the stirring reaction time is 2 ~ 24h.
Superoxol massfraction described in step 1 is 30%; The mol ratio of described hydrogen peroxide and cyclic ketones is 2.5/1.
Compared with prior art, its remarkable advantage is in the present invention: (1) the present invention uses Suanphosphotungstate to be catalyzer, and its preparation is simple, has improved the transformation efficiency of alismone, cyclopentanone and pimelinketone, has improved the atom utilization of reaction.(2) the Suanphosphotungstate catalyzer of the present invention's use is reusable.(3) the present invention need not to add solvent and sour promotor, has improved economic benefit and environmental benefit.(4) the present invention processes without spent acid and without strong acid corrodibility, and energy-saving and emission-reduction are safe.(5) superoxol of the present invention's application lower concentration is oxidising agent, replaces superoxol or the peroxy acid oxygenant of high density, and the spatter property and the security that have improved industrial preparation feedback, reduced environmental pollution.(6) room temperature of the present invention namely has higher speed of reaction, and is energy-conservation, improved economic benefit and environmental benefit.
Embodiment
Below with specific embodiment, carry out process in detail, example does not represent the invention scope of restriction this patent.
In the present invention, phosphate-tungstic acid salt adopts the volumetry preparation, concrete steps are: the solution of potassium carbonate of certain mass (silver nitrate solution) is added drop-wise to stirring at room 1h in the Salkowski's solution of certain mass under intense agitation it is fully precipitated, filter, drying obtains catalyzer K
3-xH
xPW(Ag
3-xH
xPW).
Reagent source and detecting instrument model used:
Alismone, industrial goods, Yangzhou precious magnificent chemical science and technology Development Co., Ltd; Cyclopentanone, industrial goods, Yangzhou precious magnificent chemical science and technology Development Co., Ltd; Pimelinketone, industrial goods, Yangzhou precious magnificent chemical science and technology Development Co., Ltd; Phospho-wolframic acid, SILVER REAGENT, Chemical Reagent Co., Ltd., Sinopharm Group; 30% superoxol, SILVER REAGENT, Chemical Reagent Co., Ltd., Sinopharm Group; Gas chromatograph, Angilent6820, Anjelen Sci. ﹠ Tech. Inc.
Embodiment 1
In 50 mL there-necked flasks, add the 0.91g alismone, the dropping massfraction is 30% superoxol, the mol ratio of hydrogen peroxide and alismone is 2.5/1, then adds catalyzer K
3-xH
xPW, its quality is 5% of alismone quality, magnetic agitation, reaction is 24 hours under 40 ℃.Mixture filters with glass funnel, the elimination catalyzer.The filtrate standing separation goes out organic phase.The sodium bicarbonate aqueous solution of getting 2 mL 5% washs organic phase three times, be washed with distilled water to again organic phase for neutral, regulate water to weakly alkaline and use ethyl acetate extraction with the sodium bicarbonate aqueous solution that massfraction is 5%, acetic acid ethyl acetate extract and organic phase are merged, the rotary evaporation in vacuo solvent, the promoting the circulation of qi analysis of hplc of going forward side by side of weighing.The transformation efficiency of alismone is 74%, and the productive rate of δ-dodecalactone is 49%.
Embodiment 2
In 50 mL there-necked flasks, add 0.91 g alismone, the dropping massfraction is 30% hydrogen peroxide, the mol ratio of hydrogen peroxide and alismone is 2.5/1, then adds catalyzer K
3-xH
xPW, its quality is 10% of alismone quality, magnetic agitation, and reaction is 12 hours under 40 ℃.Mixture filters with glass funnel, the elimination catalyzer.The filtrate standing separation goes out organic phase.The sodium bicarbonate aqueous solution of getting 2 mL 5% washs organic phase three times, be washed with distilled water to again organic phase for neutral, regulate water to weakly alkaline and use ethyl acetate extraction with the sodium bicarbonate aqueous solution that massfraction is 5%, acetic acid ethyl acetate extract and organic phase are merged, the rotary evaporation in vacuo solvent, the promoting the circulation of qi analysis of hplc of going forward side by side of weighing.The transformation efficiency of alismone is 85%.The productive rate of δ-dodecalactone is 68%.
Embodiment 3
In 50 mL there-necked flasks, add 0.91 g alismone, the dropping massfraction is 30% hydrogen peroxide, the mol ratio of hydrogen peroxide and alismone is 2.5/1, then adds catalyzer K
3-xH
xPW, its quality is 15% of alismone quality, magnetic agitation, reaction is 12 hours under 40 ℃.Mixture filters with glass funnel, the elimination catalyzer.The filtrate standing separation goes out organic phase.The sodium bicarbonate aqueous solution of getting 2 mL 5% washs organic phase three times, be washed with distilled water to again organic phase for neutral, regulate water to weakly alkaline and use ethyl acetate extraction with the sodium bicarbonate aqueous solution that massfraction is 5%, acetic acid ethyl acetate extract and organic phase are merged, rotary evaporation in vacuo, the rotary evaporation in vacuo solvent, the promoting the circulation of qi analysis of hplc of going forward side by side of weighing.The transformation efficiency of alismone is 90%.The productive rate of δ-dodecalactone is 74%.
Embodiment 4
In 50 mL there-necked flasks, add 0.91 g alismone, the dropping massfraction is 30% hydrogen peroxide, the mol ratio of hydrogen peroxide and alismone is 2.5/1, then adds catalyzer K
3-xH
xPW, its quality is 20% of alismone quality, magnetic agitation, reaction is 8 hours under 40 ℃.Mixture filters with glass funnel, the elimination catalyzer.The filtrate standing separation goes out organic phase.The sodium bicarbonate aqueous solution of getting 2 mL 5% washs organic phase three times, be washed with distilled water to again organic phase for neutral, regulate water to weakly alkaline and use ethyl acetate extraction with the sodium bicarbonate aqueous solution that massfraction is 5%, acetic acid ethyl acetate extract and organic phase are merged, the rotary evaporation in vacuo solvent, the promoting the circulation of qi analysis of hplc of going forward side by side of weighing.The transformation efficiency of alismone is 98%.The productive rate of δ-dodecalactone is 90%.
Embodiment 5
In 50 mL there-necked flasks, add 0.91 g alismone, the dropping massfraction is 30% hydrogen peroxide, the mol ratio of hydrogen peroxide and alismone is 2.5/1, then adds catalyzer K
3-xH
xPW, its quality is 20% of alismone quality, magnetic agitation, reaction is 24 hours under 25 ℃.Mixture filters with glass funnel, the elimination catalyzer.The filtrate standing separation goes out organic phase.The sodium bicarbonate aqueous solution of getting 2 mL 5% washs organic phase three times, be washed with distilled water to again organic phase for neutral, regulate water to weakly alkaline and use ethyl acetate extraction with the sodium bicarbonate aqueous solution that massfraction is 5%, acetic acid ethyl acetate extract and organic phase are merged, the rotary evaporation in vacuo solvent, the promoting the circulation of qi analysis of hplc of going forward side by side of weighing.The transformation efficiency of alismone is 79%.The productive rate of δ-dodecalactone is 71%.
Embodiment 6
In 50 mL there-necked flasks, add 0.91 g alismone, the dropping massfraction is 30% hydrogen peroxide, the mol ratio of hydrogen peroxide and alismone is 2.5/1, then adds catalyst A g
3-xH
xPW, its quality is 20% of alismone quality, magnetic agitation, reaction is 12 hours under 40 ℃.Mixture filters with glass funnel, the elimination catalyzer.The filtrate standing separation goes out organic phase.The sodium bicarbonate aqueous solution of getting 2 mL 5% washs organic phase three times, be washed with distilled water to again organic phase for neutral, regulate water to weakly alkaline and use ethyl acetate extraction with the sodium bicarbonate aqueous solution that massfraction is 5%, acetic acid ethyl acetate extract and organic phase are merged, the rotary evaporation in vacuo solvent, the promoting the circulation of qi analysis of hplc of going forward side by side of weighing.The transformation efficiency of alismone is 87%.The productive rate of δ-dodecalactone is 71%.
Embodiment 7
In 50 mL there-necked flasks, add 0.84 g cyclopentanone, the dropping massfraction is 30% hydrogen peroxide, the mol ratio of hydrogen peroxide and cyclopentanone is 2.5/1, then adds catalyzer K
3-xH
xPW, its quality is 20% of cyclopentanone quality, magnetic agitation, reaction is 2 hours under 75 ℃.Mixture filters with glass funnel, the elimination catalyzer.The filtrate standing separation goes out organic phase.The sodium bicarbonate aqueous solution of getting 2 mL 5% washs organic phase three times, be washed with distilled water to again organic phase for neutral, regulate water to weakly alkaline and use ethyl acetate extraction with the sodium bicarbonate aqueous solution that massfraction is 5%, acetic acid ethyl acetate extract and organic phase are merged, the rotary evaporation in vacuo solvent, the promoting the circulation of qi analysis of hplc of going forward side by side of weighing.The transformation efficiency of cyclopentanone is 98%.The productive rate of δ-valerolactone is 40%.
Embodiment 8
In 50 mL there-necked flasks, add 0.98 g pimelinketone, the dropping massfraction is 30% hydrogen peroxide, the mol ratio of hydrogen peroxide and pimelinketone is 2.5/1, then adds catalyzer K
3-xH
xPW, its quality is 20% of pimelinketone quality, magnetic agitation, reaction is 3 hours under 75 ℃.Mixture filters with glass funnel, the elimination catalyzer.The filtrate standing separation goes out organic phase.The sodium bicarbonate aqueous solution of getting 2 mL 5% washs organic phase three times, be washed with distilled water to again organic phase for neutral, regulate water to weakly alkaline and use ethyl acetate extraction with the sodium bicarbonate aqueous solution that massfraction is 5%, acetic acid ethyl acetate extract and organic phase are merged, the rotary evaporation in vacuo solvent, the promoting the circulation of qi analysis of hplc of going forward side by side of weighing.The transformation efficiency of pimelinketone is 87%.The productive rate of 6-caprolactone is 42%.
Claims (5)
1. the method for a catalyzing cyclone oxide to synthesizing lactone is characterized in that comprising the following steps:
Step 1, cyclic ketones is joined in container, drip superoxol, drip to finish and add stirring reaction after the Suanphosphotungstate catalyzer;
After step 2, reaction finish, obtain target product after filtration, washing, extraction, distillation.
2. the method for catalyzing cyclone oxide to synthesizing lactone according to claim 1, is characterized in that the cyclic ketones described in step 1 is a kind of in alismone, cyclopentanone or pimelinketone.
3. the method for catalyzing cyclone oxide to synthesizing lactone according to claim 1, is characterized in that the Suanphosphotungstate catalyzer described in step 1 is K
3-xH
xPW or Ag
3-xH
xPW; Described catalyst quality is 5% ~ 20% of cyclic ketones quality.
4. the method for catalyzing cyclone oxide to synthesizing lactone according to claim 1, is characterized in that the temperature of reaction described in step 1 is 25 ~ 75 ℃, and the stirring reaction time is 2 ~ 24h.
5. the method for catalyzing cyclone oxide to synthesizing lactone according to claim 1, is characterized in that in step 1, the superoxol massfraction described in step 1 is 30%; The mol ratio of described hydrogen peroxide and cyclic ketones is 2.5/1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602516A (en) * | 2017-10-17 | 2018-01-19 | 青岛科技大学 | The method that amino acid ion liquid catalyzes and synthesizes δ ring valerolactones |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336734A (en) * | 2010-07-15 | 2012-02-01 | 中国石油化工股份有限公司 | Method for catalytic oxidation preparation of lactone from cycloalkane |
| CN102942548A (en) * | 2012-11-20 | 2013-02-27 | 南京理工大学 | Delta-dodecalactone synthesis method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336734A (en) * | 2010-07-15 | 2012-02-01 | 中国石油化工股份有限公司 | Method for catalytic oxidation preparation of lactone from cycloalkane |
| CN102942548A (en) * | 2012-11-20 | 2013-02-27 | 南京理工大学 | Delta-dodecalactone synthesis method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602516A (en) * | 2017-10-17 | 2018-01-19 | 青岛科技大学 | The method that amino acid ion liquid catalyzes and synthesizes δ ring valerolactones |
| CN107602516B (en) * | 2017-10-17 | 2021-05-18 | 青岛科技大学 | Method for synthesizing delta-cyclopentanolide under catalysis of amino acid ionic liquid |
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