CN101234956A - Ketone and aldehyde condensation method in methyl cis-dihydrojasmonate synthesis - Google Patents
Ketone and aldehyde condensation method in methyl cis-dihydrojasmonate synthesis Download PDFInfo
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- CN101234956A CN101234956A CNA2008100185854A CN200810018585A CN101234956A CN 101234956 A CN101234956 A CN 101234956A CN A2008100185854 A CNA2008100185854 A CN A2008100185854A CN 200810018585 A CN200810018585 A CN 200810018585A CN 101234956 A CN101234956 A CN 101234956A
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Abstract
A ketone-aldehyde condensation method in synthesis of cis-methyl dihydrojasmonate relates to the production technology of a chemical product, in particular to the technical field of ketone-aldehyde condensation methods in synthesis of cis-methyl dihydrojasmonate. Under the catalysis of water solution of sodium hydroxide and substances containing metal cations, condensation reaction occurs between n-valeradehyde and cyclopentanone. In the first procedure of the synthesizing process of the invention, i.e. ketone-aldehyde condensation, sodium hydroxide is adopted as the main catalyst and, at the same time, an auxiliary catalyst is added into the reaction system. Metal cations function for stabilizing aldol condensation products, so the method has powerful control capacity on the product and facilitates inhibition of side reaction. The method can effectively control production of isomers during the process of ketone-aldehyde organic condensation to benefit subsequent production and thereby increase the product purity of cis-methyl dihydrojasmonate to higher than 98 percent.
Description
Technical field
The present invention relates to a kind of production process of chemical product, particularly keto-aldehyde method of condensing technical field in the cis-dihydro jasmine keto-acid methyl ester synthetic method.
Background technology
Cis-methyl jasmonate is a kind of chemical industry synthetic spices, earlier after the organic condensation of keto-aldehyde, isomerization, esterification, oxidizing reaction make, in the organic condensation reaction of former keto-aldehyde, only adds aqueous sodium hydroxide solution as catalyst for reaction.Its defective is: in the organic condensation course of the first step keto-aldehyde, controlled indifferent to resultant can produce more isomer, causes the product purity index of cis-dihydro jasmine keto-acid methyl ester not surpass 92%.Because the content of cis-dihydro jasmine keto-acid methyl ester is on the low side, its practical application is undesirable, makes production end product performance limited.
Summary of the invention
The object of the invention is to invent a kind of at cis-dihydro jasmine keto-acid methyl ester synthetic first step---and be difficult for generating isomer in the organic condensation course of keto-aldehyde, be beneficial to the keto-aldehyde method of condensing that improves the finished product purity.
Present invention resides under the catalysis of aqueous sodium hydroxide solution and material, valeraldehyde and cyclopentanone are carried out condensation reaction with metallic cation.
The present invention is at the first step of synthesis technique---and adopting sodium hydroxide during the keto-aldehyde condensation is Primary Catalysts, adds cocatalyst simultaneously in reaction system.Because metallic cation can work to stablize the aldol condensation product, so this technology is strong to the controlled ability of resultant, help suppressing side reaction, can control the generation of isomer in the organic condensation course of keto-aldehyde effectively, be beneficial to subsequent production, cis-methyl jasmonate product purity can be increased to more than 98%.
Material with metallic cation of the present invention can be the material of calcic, sodium, potassium, magnesium, barium, tungsten, titanium, cobalt, molybdenum, manganese, nickel, copper, iron, aluminium, lead, zine ion.
Among the present invention, described material with metallic cation is preferentially selected zinc chloride for use.Because zinc chloride is done the inhibition side reaction effect height of cocatalyst, and cost keeping is lower.
Among the present invention, aqueous sodium hydroxide solution concentration is 5%～50% in the catalyzer, and aqueous sodium hydroxide solution accounts for 5%～50% of reactant gross weight, and the add-on of zinc chloride accounts for 0.05%～5% of reactant gross weight.
In addition, temperature of reaction of the present invention is controlled at 20 ℃～60 ℃, and the reaction times was controlled at 0.5 hour～8 hours.
When temperature of reaction is higher than 60 ℃,, be unfavorable for suppressing side reaction though speed of response is accelerated; When the reaction times was controlled at 0.5 hour～8 hours, keto-aldehyde condensation resultant was more, can improve yield.
Embodiment
1, allotment concentration is 5%～50% aqueous sodium hydroxide solution.
2, the organic condensation of keto-aldehyde: respectively 10～100kg aqueous sodium hydroxide solution and 1～10kg zinc chloride are added in the reactor, stirring is warmed up to 20 ℃～60 ℃, drips each 100kg of valeraldehyde and cyclopentanone simultaneously, and the reaction times is 1-2 hour, get the cis ketenes, yield is 〉=90%;
In condensation reaction, except zinc chloride, cupric chloride, ferrous sulfate, aluminum nitrate, plumbous oxide etc. can be done cocatalyst, and the add-on of add-on and zinc chloride is suitable.
3, isomerization: at 100 ℃～110 ℃ following distillation dehydrations, isomerization reaction Synthetic 2-amyl cyclopentenone, yield are 〉=95%;
4, esterification: under-10 ℃～-0 ℃, the 2-amyl cyclopentenone is again in 150%～190% ratio and dimethyl malonate condensation, and yield is 〉=60%;
5, oxidizing reaction: under 120 ℃～200 ℃, decarboxylation gets cis-dihydro jasmine keto-acid methyl ester, and yield is 〉=98%.
Claims (5)
1, a kind of keto-aldehyde method of condensing during cis-dihydro jasmine keto-acid methyl ester synthesizes is included under the aqueous sodium hydroxide solution catalysis, and valeraldehyde and cyclopentanone are carried out condensation reaction, it is characterized in that also containing in the catalyzer material with metallic cation.
2, according to the described cis-dihydro jasmine keto-acid methyl ester of claim 1 synthetic in a kind of keto-aldehyde method of condensing, it is characterized in that described material with metallic cation is the material that contains calcium, sodium, potassium, magnesium, barium, tungsten, titanium, cobalt, molybdenum, manganese, nickel, copper, iron, aluminium, lead, zine ion.
3, according to the described cis-dihydro jasmine keto-acid methyl ester of claim 2 synthetic in a kind of keto-aldehyde method of condensing, it is characterized in that described material with metallic cation is a zinc chloride.
4, according to the described cis-dihydro jasmine keto-acid methyl ester of claim 3 synthetic in a kind of keto-aldehyde method of condensing, it is characterized in that aqueous sodium hydroxide solution concentration is 5%～50% in the catalyzer, aqueous sodium hydroxide solution accounts for 5%～50% of reactant gross weight, and the add-on of zinc chloride accounts for 0.05%～5% of reactant gross weight.
5, according to claim 1 or 2 or 3 or 4 described cis-dihydro jasmine keto-acid methyl esters synthetic in a kind of keto-aldehyde method of condensing, it is characterized in that temperature of reaction is controlled at 20 ℃～60 ℃, the reaction times was controlled at 0.5 hour～8 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100185854A CN101234956A (en) | 2008-02-29 | 2008-02-29 | Ketone and aldehyde condensation method in methyl cis-dihydrojasmonate synthesis |
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| CNA2008100185854A CN101234956A (en) | 2008-02-29 | 2008-02-29 | Ketone and aldehyde condensation method in methyl cis-dihydrojasmonate synthesis |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429122B (en) * | 2008-12-11 | 2012-03-21 | 淮安万邦香料工业有限公司 | Decarboxylation method used in synthesis of methyl dihydrojasmonate |
| CN106699528A (en) * | 2016-12-27 | 2017-05-24 | 山东新和成药业有限公司 | Method for one-step synthesis of 2-amyl-2-cyclopentenone |
| CN108569943A (en) * | 2017-03-07 | 2018-09-25 | 中国科学院大连化学物理研究所 | A method of using cyclopentanone as Material synthesis high density aviation fuel |
| CN113929575A (en) * | 2020-06-29 | 2022-01-14 | 上海应用技术大学 | Preparation method of (1R,2S) -methyl dihydrojasmonate |
| CN114478217A (en) * | 2022-02-18 | 2022-05-13 | 山东新和成药业有限公司 | Preparation method of 2-n-pentylcyclopent-2-enone |
| EP4215267A1 (en) * | 2022-01-25 | 2023-07-26 | Centre national de la recherche scientifique | Novel compositions for the sustainable catalysis of organic synthesis reactions |
-
2008
- 2008-02-29 CN CNA2008100185854A patent/CN101234956A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429122B (en) * | 2008-12-11 | 2012-03-21 | 淮安万邦香料工业有限公司 | Decarboxylation method used in synthesis of methyl dihydrojasmonate |
| CN106699528A (en) * | 2016-12-27 | 2017-05-24 | 山东新和成药业有限公司 | Method for one-step synthesis of 2-amyl-2-cyclopentenone |
| CN106699528B (en) * | 2016-12-27 | 2019-07-23 | 山东新和成药业有限公司 | A kind of method of one-step synthesis 2- amyl -2- cyclopentenone |
| CN108569943A (en) * | 2017-03-07 | 2018-09-25 | 中国科学院大连化学物理研究所 | A method of using cyclopentanone as Material synthesis high density aviation fuel |
| CN113929575A (en) * | 2020-06-29 | 2022-01-14 | 上海应用技术大学 | Preparation method of (1R,2S) -methyl dihydrojasmonate |
| CN113929575B (en) * | 2020-06-29 | 2023-05-30 | 上海应用技术大学 | Preparation method of (1R, 2S) -methyl dihydrojasmonate |
| EP4215267A1 (en) * | 2022-01-25 | 2023-07-26 | Centre national de la recherche scientifique | Novel compositions for the sustainable catalysis of organic synthesis reactions |
| CN114478217A (en) * | 2022-02-18 | 2022-05-13 | 山东新和成药业有限公司 | Preparation method of 2-n-pentylcyclopent-2-enone |
| CN114478217B (en) * | 2022-02-18 | 2023-08-08 | 山东新和成药业有限公司 | Preparation method of 2-n-amyl cyclopent-2-enone |
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Open date: 20080806 |