CN103012094A - Synthesis method of ionone-type spice intermediate products - Google Patents
Synthesis method of ionone-type spice intermediate products Download PDFInfo
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- CN103012094A CN103012094A CN2012105804310A CN201210580431A CN103012094A CN 103012094 A CN103012094 A CN 103012094A CN 2012105804310 A CN2012105804310 A CN 2012105804310A CN 201210580431 A CN201210580431 A CN 201210580431A CN 103012094 A CN103012094 A CN 103012094A
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Abstract
The invention discloses a synthesis method of ionone-type spice intermediate products, namely pseudoionone and methyl pseudoionone, wherein the pseudoionone and the methyl pseudoionone are prepared by taking dehydrogenated linalool as a raw material, reacting with a compound represented as the formula I under an appropriate catalyst condition, and implementing an isomerization reaction. The method disclosed by the invention, in preparing the ionone-type spice intermediate products, is few in reaction steps, high in yield and low in pollution, wherein the R1 represents either -H or -CH3; and R2 represents methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, 2-methyl propyl, n-amyl, isoamyl, 2-methyl butyl, benzyl or other groups.
Description
Technical field
The present invention relates to a kind of synthetic method of compound, belong to the organic synthesis field, specifically relate to the synthetic method that a kind of jononeionone is the spices intermediate.
Background technology
Citrylideneacetone, methyl citrylideneacetone are the important intermediate of synthetic jononeionone, are widely used in spices, medicine, foodstuff additive industry.A kind of rare spice with banksia rose type fragrance of jononeionone is one of maximum and of paramount importance spices of output in the perfume industry; Synthetic alpha, beta-lonone is the important intermediate of synthesise vitamins A and β-carotene simultaneously.
During Chinese scholars is continuing to carry out to the improvement of the synthesis technique of citrylideneacetone and homologue research always for a long time.Its main synthetic method be by citral under alkaline condition with acetone through Aldol condensation system to, and citral mainly obtains by the litsea cubeba oil rectification and purification with via the dehydrolinalool catalytically rearranging.
Obtained by litsea cubeba oil rectification and purification method that the citral yield is low, raw material resources are limited, production cost is high.
Patent EP0947492(1999) a kind of method with molybdenum compound catalytically rearranging lemarome has been described, about 20 hours reaction times, yield approximately 90%.The method exists the shortcoming of low-down space-time yield and catalyzer cost higher.
Patent US7141698B2(2003) described a kind of under 20～120 ℃, 1～10MPa the method for serialization synthesis of pseudo-ionone and methyl citrylideneacetone.The method is because reacting under High Temperature High Pressure, and is very high to equipment requirements, the yield that obtains citrylideneacetone approximately 90%, methyl citrylideneacetone yield approximately 92%.
Summary of the invention
The purpose of this invention is to provide a kind of method with the direct synthesis of pseudo-ionone of dehydrolinalool or methyl citrylideneacetone.
The present invention is take dehydrolinalool as raw material, react through the Carlow, again through isomerization synthesis of pseudo-ionone or methyl citrylideneacetone, compare with traditional citral method is synthetic, the present invention is directly take dehydrolinalool as the raw material synthesis of pseudo-ionone or the methyl citrylideneacetone, and reactions steps is few, and yield is high, pollute and lack, meet the idea of development of green chemical industry.
For realizing goal of the invention, the present invention adopts following technical scheme:
A) the Carlow reaction occurs in compound shown in dehydrolinalool and the formula I under the effect of catalyzer, the company's of generation ketene compounds;
B) describedly connect ketene compounds to make jononeionone through isomerization reaction under the effect of alkaline catalysts be spices intermediate pseudo ionone or methyl pseudoionone;
Wherein, R
1Be hydrogen or methyl, R
2For groups such as methyl, ethyl, n-propyl, sec.-propyl, butyl, isobutyl-, 2-methyl-propyl, n-pentyl, isopentyl, 2-methyl butyl or benzyls, to such an extent as to the corresponding alcohol that can will occur by the method with rectifying to generate after the alcoholysis reaction is removed.
As preferably, R in the formula I of the present invention
1Be hydrogen and/or R
2Be methyl.
Wherein, catalyzer described in the described step a is aluminum isopropylate.
Particularly, the mol ratio of compound shown in dehydrolinalool, the formula I and catalyzer is 1:1～1.5:0.01～0.1 among the step a of the present invention, is preferably 1:1.05～1.3:0.02～0.05.
In the reaction of described step a Carlow, reaction pressure is 0～3Mpa; Temperature of reaction is 40～170 ℃, and the reaction times is 1.25～3.2h; Preferred reaction pressure is 0.5～2Mpa, and temperature of reaction is 60～120 ℃, and the reaction times is 1.5～3h, and more preferably reaction pressure is 1～1.5Mpa, and temperature of reaction is 80～90 ℃, and the reaction times is 2h.
Synthetic method of the present invention, described step b is specially:
After the step a) reaction finishes, inflated with nitrogen cools to 0～50 ℃ to normal pressure, and the alcoholic solution that drips mass concentration and be 0.1～1% alkaline catalysts carries out isomerization, isomerization complete with the vinegar acid for adjusting pH value 6～7, separate to get pseudo ionone or methyl pseudoionone.
Wherein, the alkaline catalysts described in the described step b is alkali metal hydroxide, and preferred described alkali metal hydroxide is one or more in lithium hydroxide, sodium hydroxide or the potassium hydroxide; Sodium hydroxide more preferably.
Wherein, the alcohol described in the described step b be in the formula I of selecting with R
2Corresponding pure R
2OH is such as methyl alcohol, ethanol, Virahol etc.
Synthetic method of the present invention, the mol ratio of dehydrolinalool and alkaline catalysts is 1:0.002～0.02 among the described step b.
In the described step b isomerization reaction, temperature of reaction is 0～50 ℃, and the reaction times is 1～2 hour, preferred 1.5 hours.
It should be noted that technical scheme related in the present patent application file, except make concrete restriction, those skilled in the art will envision that and adopt the disclosed conventional means of prior art to realize the present invention.
As a kind of preferred forms, synthetic method of the present invention preferably includes following steps:
A) be that compound shown in the dehydrolinalool, formula I of 1:1.2:0.03 and aluminum isopropylate mix and make it that Carlow reaction occur with amount ratio, the company's of generation ketene compounds, wherein, reaction pressure is 1.2Mpa, and temperature of reaction is 85 ℃, and the reaction times is 2 hours;
B) after step a) reaction finished, inflated with nitrogen cooled to 15 ℃ to normal pressure, and the alcoholic solution that drips mass concentration and be 0.5% alkali metal hydroxide carried out isomerization 1 hour, and wherein, the mol ratio of dehydrolinalool and alkaline catalysts is 1:0.01., isomerization complete with the vinegar acid for adjusting pH value 6～7, with reaction solution with R
2OH makes solvent and filters in the pillar of super-cell is housed, and filtrate is carried out rectifying and got pseudo ionone or methyl pseudoionone;
Synthetic method of the present invention is specially: compound shown in dehydrolinalool and the formula I, catalyzer are put in the withstand voltage reactor, carry out magnetic agitation and oil bath and be warmed up to 40～170 ℃, vapor-phase chromatography monitoring dehydrolinalool residual quantity, reaction pressure is 0～3Mpa, reacts 1.25～3.2 hours.After reaction was finished, inflated with nitrogen cooled to 0～50 ℃ to normal pressure, drips certain density alkali metal hydroxide alcoholic solution and carries out isomerization reaction.Isomerization complete with the vinegar acid for adjusting pH value 6～7.With reaction solution with R
2OH makes solvent and filters in the pillar of super-cell is housed, and filtrate is carried out rectifying and obtained product.
Adopt technique scheme, the present invention is directly take dehydrolinalool as the raw material synthesis of pseudo-ionone or the methyl citrylideneacetone, and reactions steps is few, and yield is high, pollutes fewly, meets the idea of development of green chemical industry.In addition, the yield of synthesis of pseudo-ionone of the present invention and methyl citrylideneacetone can reach under the reaction conditions of gentleness more than 91%, and purity is a kind of desirable synthetic method promoted up to 97%.
Embodiment
Following examples are used for explanation the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
With 100g(content 98.5%) dehydrolinalool and 91.0g methyl acetoacetate, 4.0g aluminum isopropylate put in the withstand voltage reaction flask of 500ml, carry out magnetic agitation and be heated to 85 ℃ of interior temperature with oil bath, keeping reaction pressure is 1.2MPa reaction 2 hours, gas chromatographic analysis dehydrolinalool transformation efficiency 98.8%.After reaction was finished, inflated with nitrogen cooled to 15 ℃ to normal pressure, dripped 0.5% sodium hydrate methanol solution 50ml, dripped Bi Baowen 1.5 hours.After isomerization is complete with the vinegar acid for adjusting pH value 6～7.Reaction solution is made solvent with methyl alcohol filter in the pillar of super-cell is housed, filtrate is carried out rectifying and is obtained 97.5%(cis-trans sum) citrylideneacetone product 117.3g.Citrylideneacetone yield approximately 93.1%
Embodiment 2
According to the method for embodiment 1, distinctive points only is, the present embodiment changes the 91.0g methyl acetoacetate into and drops into the 83.5g methyl acetoacetate, and other conditions are constant.The dehydrolinalool transformation efficiency is 97.6%, obtains the citrylideneacetone product 114.5g of content 98.1%.Citrylideneacetone yield approximately 92.5%
Embodiment 3
According to the method for embodiment 1, distinctive points only is, the present embodiment changes the 91.0g methyl acetoacetate into and drops into the 98.5g methyl acetoacetate, and other conditions are constant.The dehydrolinalool transformation efficiency is 99.2%, obtains the citrylideneacetone product 114.3g of content 97.8%.Citrylideneacetone yield approximately 92.1%.
Embodiment 4～6
According to the method for embodiment 1, distinctive points only is, reacts with 60 ℃, 90 ℃, 120 ℃ during the reaction of Carlow, and gas-chromatography monitoring dehydrolinalool transformation efficiency is more than 97.5%, and other conditions are constant.Test-results (wherein the reaction times is the Carlow reaction times, and is lower same) as shown in table 1:
Table 1:
Embodiment 7～8
According to the method for embodiment 1, distinctive points only is, reacts at 0MPa, 3MPa during the reaction of Carlow, and gas-chromatography monitoring dehydrolinalool transformation efficiency is more than 97.5%, and other conditions are constant.Test-results is as shown in table 2:
Table 2:
Embodiment 9 ~ 10
According to embodiment 1, different is to replace methyl acetoacetate (being respectively 1.2:1 and 1.1:1 with the dehydrolinalool mol ratio) with 102.2g and 93.7g2-methyl-3-ketobutyric acid methyl esters respectively to react, and other conditions are constant, the synthesizing methyl citrylideneacetone.Test-results is as shown in table 3:
Table 3:
Embodiment 11 ~ 12
According to embodiment 1, different is respectively take 101.2g methyl aceto acetate and 112g ISOPROPYL ACETOACETATE (with the dehydrolinalool mol ratio as 1.2:1) react, other conditions are constant, synthesis of pseudo-ionone.Test-results is as shown in table 4:
Table 4:
Method described in the invention is used in the test-results demonstration, and the yield of synthesis of pseudo-ionone and methyl citrylideneacetone can reach more than 91% under proper condition.Use method described in the invention, directly take dehydrolinalool as the raw material synthesis of pseudo-ionone or the methyl citrylideneacetone, reactions steps is few, and yield is high, pollutes fewly, meets the idea of development of green chemical industry.
Although, above used general explanation, embodiment and test, the present invention is described in detail, on basis of the present invention, can make some modifications or improvements it, and this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. the synthetic method that jononeionone is the spices intermediate comprises the steps:
A) the Carlow reaction occurs in compound shown in dehydrolinalool and the formula I under the effect of catalyzer, the company's of generation ketene compounds;
B) describedly connect ketene compounds to make jononeionone through isomerization reaction under the effect of alkaline catalysts be spices intermediate pseudo ionone or methyl pseudoionone;
Wherein, R
1Be hydrogen or methyl, R
2Be methyl, ethyl, n-propyl, sec.-propyl, butyl, isobutyl-, 2-methyl-propyl, n-pentyl, isopentyl, 2-methyl butyl or benzyl.
2. method according to claim 1 is characterized in that, catalyzer described in the step a is aluminum isopropylate.
3. method according to claim 1 and 2 is characterized in that, the mol ratio of compound shown in dehydrolinalool, the formula I and catalyzer is 1:1～1.5:0.01～0.1 among the described step a, is preferably 1:1.05～1.3:0.02～0.05.
4. method according to claim 1 and 2 is characterized in that, reaction pressure is 0～3Mpa among the described step a; Temperature of reaction is 40～170 ℃, and the reaction times is 1.25～3.2h; Preferred reaction pressure is 0.5～2Mpa, and temperature of reaction is 60～120 ℃, and the reaction times is 1.5～3h, and more preferably reaction pressure is 1～1.5Mpa, and temperature of reaction is 80～90 ℃, and the reaction times is 2h.
5. method according to claim 1, it is characterized in that, described step b is specially: after the step a) reaction finishes, inflated with nitrogen is to normal pressure, cool to 0～50 ℃, the alcoholic solution that drips mass concentration and be 0.1～1% alkaline catalysts carries out isomerization, and the complete pH adjusting agent that adds of isomerization is regulated pH value to 6～7, separates to get pseudo ionone or methyl pseudoionone.
6. method according to claim 5 is characterized in that, the alkaline catalysts described in the step b is alkali metal hydroxide, is preferably in lithium hydroxide, sodium hydroxide or the potassium hydroxide one or more; Sodium hydroxide more preferably.
7. method according to claim 5 is characterized in that, the alcohol described in the step b be in the formula I with R
2Corresponding pure R
2OH.
8. method according to claim 1 or 5 is characterized in that, employed alkaline catalysts measures with dehydrolinalool among the described step b, and the mol ratio of dehydrolinalool and alkaline catalysts is 1:0.002～0.02.
9. method according to claim 1 or 5 is characterized in that, among the described step b, temperature of reaction is 0～50 ℃, and the reaction times is 1～2 hour, preferred 1.5 hours.
10. method according to claim 1 is characterized in that, comprises the steps:
A) be that compound shown in the dehydrolinalool, formula I of 1:1.2:0.03 and aluminum isopropylate mix and make it that Carlow reaction occur with amount ratio, the company's of generation ketene compounds, wherein, reaction pressure is 1.2Mpa, and temperature of reaction is 85 ℃, and the reaction times is 2 hours;
B) after the step a) reaction finishes, inflated with nitrogen is to normal pressure, cool to 15 ℃, the alcoholic solution that drips mass concentration and be 0.5% alkali metal hydroxide carried out isomerization 1 hour, wherein, the mol ratio of dehydrolinalool and alkaline catalysts is 1:0.01, and isomerization is complete with vinegar acid for adjusting pH value to 6～7, with reaction solution with R
2OH makes solvent and filters in the pillar of super-cell is housed, and filtrate is carried out rectifying and got pseudo ionone or methyl pseudoionone.
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| CN201210580431.0A CN103012094B (en) | 2012-12-28 | 2012-12-28 | Synthesis method of ionone-type spice intermediate products |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108530279A (en) * | 2018-05-21 | 2018-09-14 | 浙江新和成股份有限公司 | A kind of synthetic method of pseudo ionone |
| CN109534977A (en) * | 2018-12-12 | 2019-03-29 | 万华化学集团股份有限公司 | One kind synthesizing α, γ-unsaturation dienone method and the catalyst for this method by propargyl alcohol |
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| US3860655A (en) * | 1967-02-04 | 1975-01-14 | Basf Ag | Production of 6,10-dimethylundecatrien-(3,5,10)-one-(2) |
| CN1218792A (en) * | 1997-10-17 | 1999-06-09 | Basf公司 | Process for preparing gamma, delta unsaturated ketone by carroll reaction and novel catalyst used in said method and its preparation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108530279A (en) * | 2018-05-21 | 2018-09-14 | 浙江新和成股份有限公司 | A kind of synthetic method of pseudo ionone |
| CN108530279B (en) * | 2018-05-21 | 2021-06-01 | 浙江新和成股份有限公司 | Synthesis method of pseudo ionone |
| CN109534977A (en) * | 2018-12-12 | 2019-03-29 | 万华化学集团股份有限公司 | One kind synthesizing α, γ-unsaturation dienone method and the catalyst for this method by propargyl alcohol |
| CN109534977B (en) * | 2018-12-12 | 2022-04-22 | 万华化学集团股份有限公司 | Method for synthesizing alpha, gamma-unsaturated dienone from propargyl alcohol and catalyst used in method |
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