CN1033577C - Process for preparing unsaturated carbonyl compound by reaction of olefinic alcohol and enol ether - Google Patents
Process for preparing unsaturated carbonyl compound by reaction of olefinic alcohol and enol ether Download PDFInfo
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- CN1033577C CN1033577C CN 92109831 CN92109831A CN1033577C CN 1033577 C CN1033577 C CN 1033577C CN 92109831 CN92109831 CN 92109831 CN 92109831 A CN92109831 A CN 92109831A CN 1033577 C CN1033577 C CN 1033577C
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- reaction
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- enol
- unsaturated carbonyl
- alkene ether
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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
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a method for preparing gamma, sigma unsaturated aldehyde ketone by the reaction of olefinic alcohol and olefinic ether. The method divides the reaction into two stages, wherein the temperature of the first stage is low and time is long; the temperature of the second state is high and time is short; an unexpected result is obtained, the yield is increased by 30%, and the feeding sequence is altered. The present invention has the advantage of simple and convenient operation, and the present invention is suitable for industrial production.
Description
The invention belongs to the reaction of enol and alkene ether and produce the method for γ, the unsaturated aldehyde ketone of σ.
Enol and alkene ether prepared in reaction γ, the unsaturated aldehyde ketone of σ have research and report external morning, and its structural formula is as follows:
R1 is alkyl or H in the formula, also can be oxy radical, and R2, R4, R5 are alkyl or H, lower paraffin hydrocarbons, alkene, naphthenic hydrocarbon, cycloolefin and aromatic hydrocarbon.Above-mentioned beta-unsaturated carbonyl compounds is the important intermediate of synthesise vitamins A, vitamin-E, but also synthetic perfume.
Belg patent 634,738, and same Patent USPatent 3,574,715 has narrated enol and alkene ether prepared in reaction γ, σ beta-unsaturated carbonyl compounds, is 125 ℃ of fixed temperatures, reacts yield about 60% 16 hours.Above-mentioned patent is that (0-10 ℃) adds alkene ether with catalyzer at low temperatures, adds solvent, enol again, and a large amount of refrigerants of charging process consumption are uneconomical like this.
The objective of the invention is to make the reaction of enol and alkene ether to generate the unsaturated aldehyde ketone yield of γ, σ and improve, change charging process, earlier enol is added reactor, can save the energy in ambient operation, easy and simple to handle, be suitable for the preparation of industrialization beta-unsaturated carbonyl compounds.
The object of the present invention is achieved like this: enol and alkene ether reaction generation γ, the reaction of σ unsaturated aldehyde ketone compound are divided into two stages, earlier enol is added reactor in room temperature, add catalyzer, back adding organic solvent stirs, add alkene ether again, react fs temperature 80-170 ℃, reacted 8-40 hour, heat up then; The subordinate phase temperature of reaction is than the high 50-100 of fs temperature of reaction ℃, and the subordinate phase reaction times is 1/100 to 1/7 of reaction times fs.
The present invention generates the reaction mechanism of γ, the unsaturated aldehyde ketone of σ according to enol and alkene ether reaction, adopted unique zone heating method, because enol and alkene ether reaction fs have generated acetal in the presence of an acidic catalyst, continue reaction with this understanding and take off a part alcohol.Fs optimum reacting time 16-30 hour, can finish for 110-150 ℃.The two keys of subordinate phase carry out transposition, and isomerization reaction needs high temperature, and the time is short.Go out above-mentioned two sections heating means by test and Selection, obtain beyond thought effect.The unsaturated aldehyde ketone yield of γ, σ that generates has improved 30%, need not be freezing when reinforced, and save energy, easy and simple to handle, be suitable for suitability for industrialized production.
The enol of reaction usefulness has: 3-methyl-1-butene-3-alcohol, 2,3-dimethyl-1-butylene-3-alcohol, 3-Methyl-1-pentene-3-alcohol, 3,7-dimethyl-1.6-diene triol (Linalool), 3,7,11-trimethylammonium-1.6,100 two carbon triolefin-3-alcohol (nerolidol), different vegetable alcohol, 3,7-dimethyl-7-methoxyl group-1-butylene triol (that alcohol of methoxy methyl); Alkene ether commonly used has: isopropyl methyl ether, 2-oxyethyl group-1-butylene base ether, 2-oxyethyl group-3-or alkene ether, 2-oxyethyl group-2.5-hexadienyl ether, 1-tetrahydrobenzene butyl ether, catalysts adopts acid catalyst, as H3PO4, or tosic acid, also useful hydrogen sulfate first, action solvent is generally used hydrocarbon, hexanaphthene, normal hexane, octane-iso, benzene, toluene and their mixture, sherwood oil, flux wet goods.
In order to understand the present invention, as follows for embodiment:
Embodiment 1:
In the 100ml autoclave, add 15 grams 3,7-dimethyl-1.6-octadiene-3-alcohol (Linalool), add 0.1 gram 85%H3PO4, add 6-7 gram 120# solvent oil, cover the high pressure kettle cover, stirred 2-5 minute, and stopped to stir, be evacuated to 260mmHg, logical N2 gas three times and so forth, adds the different propylene methyl ether of 30 grams to normal pressure, feed the N2 gas lift and be depressed into 2 kg/cm, open stirring, be rapidly heated 120 ℃, reacted 30 hours, and improved temperature then fast, reacted 15 hours to 180 ℃ of interior temperature.Cooling, exhaust move into matrass with material, add triethylamine and are neutralized to PH=7.The air distillation foreshot is different propylene methyl ether, and middle fraction is a Propanal dimethyl acetal, and after cut is the 120# solvent oil.The cold slightly back underpressure distillation of remaining material.＜68 ℃/2mmHg is a foreshot, can be inserted in down batch reaction liquid.68-75 ℃/2mmHg is positive fraction, geranyl acetone, purity 〉=95%, yield 92% (to Linalool).
Embodiment 2
In the 100ml autoclave, add 20 grams 3,7-11-trimethylammonium-1.6,10-12 carbon triolefin-3-alcohol (nerolidol), 0.15 gram 85%H3PO4,8-9 gram 120# solvent oil covers the high pressure kettle cover, stirred 2-3 minute, stop to stir, be evacuated to 260mmHg, logical N2 gas is to normal pressure, three times and so forth, add different propylene methyl ether, feed the N2 gas lift and be depressed into 2 kg/cm, start stirring, temperature is 145 ℃ in rising to fast, reaction is 36 hours under this temperature, and temperature is 195 ℃ in rising to fast then, reacts 4 hours.Cooling, exhaust move into matrass with material, add triethylamine and are neutralized to PH=7.Air distillation, foreshot are different propylene methyl ether, and middle fraction is a Propanal dimethyl acetal, and after cut is the 120# solvent oil.The cold slightly back underpressure distillation of remaining material.＜120 ℃/0.5mmHg is a foreshot, can be inserted in down batch reaction liquid.120-165 ℃/0.5mmHg is positive fraction farnesyl acetone, purity 〉=92%, yield 83-86% (to nerolidol).
Claims (2)
1, the method for a kind of enol and alkene ether preparing unsaturated carbonyl compound by reaction, it is characterized in that enol and alkene ether reaction generation γ, the reaction of σ unsaturated aldehyde ketone compound are divided into two stages, earlier enol is added reactor in room temperature, add catalyzer, add organic solvent after stirring, add alkene ether again, react fs temperature 80-170 ℃, reacted 8-40 hour, and heated up then; The subordinate phase temperature of reaction is than the high 50-100 of fs temperature of reaction ℃, and the subordinate phase reaction times is 1/100 to 1/7 of reaction times fs.
2, method according to claim 1, the best that it is characterized in that reacting the fs temperature is 110-150 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92109831 CN1033577C (en) | 1992-08-18 | 1992-08-18 | Process for preparing unsaturated carbonyl compound by reaction of olefinic alcohol and enol ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92109831 CN1033577C (en) | 1992-08-18 | 1992-08-18 | Process for preparing unsaturated carbonyl compound by reaction of olefinic alcohol and enol ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1069963A CN1069963A (en) | 1993-03-17 |
| CN1033577C true CN1033577C (en) | 1996-12-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 92109831 Expired - Fee Related CN1033577C (en) | 1992-08-18 | 1992-08-18 | Process for preparing unsaturated carbonyl compound by reaction of olefinic alcohol and enol ether |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| BRPI0920620A2 (en) * | 2008-10-21 | 2015-12-22 | Dsm Ip Assets Bv | manufacture of unsaturated gamma-delta ketones |
| KR101861665B1 (en) | 2011-07-20 | 2018-05-28 | 엘지전자 주식회사 | Refrigerator |
| CN108299171B (en) * | 2018-02-11 | 2021-03-16 | 浙江新和成股份有限公司 | Method for synthesizing methyl heptenone from 2-methyl-3-butene-2-ol |
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- 1992-08-18 CN CN 92109831 patent/CN1033577C/en not_active Expired - Fee Related
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