CN103012094B - Synthesis method of ionone-type spice intermediate products - Google Patents
Synthesis method of ionone-type spice intermediate products Download PDFInfo
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- CN103012094B CN103012094B CN201210580431.0A CN201210580431A CN103012094B CN 103012094 B CN103012094 B CN 103012094B CN 201210580431 A CN201210580431 A CN 201210580431A CN 103012094 B CN103012094 B CN 103012094B
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- dehydrolinalool
- propyl
- ionone
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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 organic synthesis field, specifically relate to the synthetic method of a kind of jononeionone system fragrance intermediates.
Background technology
Citrylideneacetone, methyl citrylideneacetone are the important intermediate of synthesis 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 perfume industry; The alpha, beta-lonone simultaneously synthesized is the important intermediate of synthesise vitamins A and β-carotene.
During the linguistic term of Chinese scholars to the synthesis technique of citrylideneacetone and homologue is continuing to carry out always for a long time.Its main synthetic method be by citral in the basic conditions with acetone through Aldol condensation system to, and citral obtains primarily of litsea cubeba oil rectification and purification with via dehydrolinalool catalytically rearranging.
Obtained by litsea cubeba oil rectification and purification method that citral yield is low, raw material resources are limited, production cost is high.
Patent EP0947492(1999) describe a kind of with the method for molybdenum compound catalytically rearranging lemarome, reaction times 20 hours, yield about 90%.The method there is the shortcoming of low-down space-time yield and catalyzer cost is higher.
Patent US7141698B2(2003) describe a kind of 20 ~ 120 DEG C, the method for serialization synthesis of pseudo-ionone and methyl citrylideneacetone under 1 ~ 10MPa.The method is because reacting at high temperature under high pressure, very high to equipment requirements, obtains the yield about 90% of citrylideneacetone, methyl citrylideneacetone yield about 92%.
Summary of the invention
The object of this invention is to provide a kind of with the method for the direct synthesis of pseudo-ionone of dehydrolinalool or methyl citrylideneacetone.
The present invention take dehydrolinalool as raw material, react through Carlow, again through isomerization synthesis of pseudo-ionone or methyl citrylideneacetone, compared with synthesizing with traditional citral method, the present invention take directly dehydrolinalool as Material synthesis citrylideneacetone or methyl citrylideneacetone, and reactions steps is few, and yield is high, pollute few, meet the idea of development of green chemical industry.
For realizing goal of the invention, the present invention adopts following technical scheme:
A) there is Carlow reaction in compound shown in dehydrolinalool and formula I under the effect of catalyzer, the company's of generation ketene compounds;
B) the described ketene compounds that connects obtains jononeionone system fragrance intermediates pseudo ionone or methyl pseudoionone through isomerization reaction under the effect of alkaline catalysts;
Wherein, R
1for 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 can by the corresponding alcohol removing will generated after generation alcoholysis reaction by the method for rectifying.
As preferably, R in formula I of the present invention
1for hydrogen and/or R
2for methyl.
Wherein, catalyzer described in described step a is aluminum isopropylate.
Particularly, in step a of the present invention, the mol ratio of compound and catalyzer shown in dehydrolinalool, formula I is 1:1 ~ 1.5:0.01 ~ 0.1, 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 DEG C, and the reaction times is 1.25 ~ 3.2h; Preferred reaction pressure is 0.5 ~ 2Mpa, and temperature of reaction is 60 ~ 120 DEG C, and the reaction times is 1.5 ~ 3h, and more preferably reaction pressure is 1 ~ 1.5Mpa, and temperature of reaction is 80 ~ 90 DEG C, and the reaction times is 2h.
Synthetic method of the present invention, described step b is specially:
After step a) reaction terminates, inflated with nitrogen, to normal pressure, cools to 0 ~ 50 DEG C, and dropping mass concentration is that the alcoholic solution of the alkaline catalysts of 0.1 ~ 1% carries out isomerization, the complete acetic acid adjust ph that adds of isomerization, 6 ~ 7, is separated to obtain pseudo ionone or methyl pseudoionone.
Wherein, the alkaline catalysts described in described step b is alkali metal hydroxide, and preferred described alkali metal hydroxide is one or more in lithium hydroxide, sodium hydroxide or potassium hydroxide; Be more preferably sodium hydroxide.
Wherein, the alcohol described in described step b be in the formula I selected with R
2corresponding alcohol R
2oH, as methyl alcohol, ethanol, Virahol etc.
Synthetic method of the present invention, in described step b, the mol ratio of dehydrolinalool and alkaline catalysts is 1:0.002 ~ 0.02.
In described step b isomerization reaction, temperature of reaction is 0 ~ 50 DEG C, and the reaction times is 1 ~ 2 hour, preferably 1.5 hours.
It should be noted that technical scheme involved in the present patent application file, except making concrete restriction, those skilled in the art will envision that and adopt conventional means disclosed in prior art to realize the present invention.
As a kind of preferred forms, synthetic method of the present invention preferably includes following steps:
A) compound shown in the dehydrolinalool being 1:1.2:0.03 by amount ratio, formula I and aluminum isopropylate mixing make it that Carlow reaction occur, the company's of generation ketene compounds, and wherein, reaction pressure is 1.2Mpa, and temperature of reaction is 85 DEG C, and the reaction times is 2 hours;
B) after step a) reaction terminates, inflated with nitrogen, to normal pressure, cools to 15 DEG C, and dropping mass concentration is that the alcoholic solution of the alkali metal hydroxide of 0.5% carries out isomerization 1 hour, and wherein, the mol ratio of dehydrolinalool and alkaline catalysts is 1:0.01., the complete acetic acid adjust ph that adds of isomerization 6 ~ 7, by reaction solution with R
2oH makes solvent and filters in the pillar that super-cell is housed, and filtrate is carried out rectifying and obtained pseudo ionone or methyl pseudoionone;
Synthetic method of the present invention is specially: put in withstand voltage reactor by compound shown in dehydrolinalool and formula I, catalyzer, carry out magnetic agitation and oil bath is warmed up to 40 ~ 170 DEG C, vapor-phase chromatography monitoring dehydrolinalool residual quantity, reaction pressure is 0 ~ 3Mpa, reacts 1.25 ~ 3.2 hours.After having reacted, inflated with nitrogen, to normal pressure, cools to 0 ~ 50 DEG C, drips certain density alkali metal hydroxide alcoholic solution and carries out isomerization reaction.The complete acetic acid adjust ph that adds of isomerization is 6 ~ 7.By reaction solution with R
2oH makes solvent and filters in the pillar that super-cell is housed, and filtrate is carried out rectifying and obtained product.
Adopt technique scheme, the present invention take directly dehydrolinalool as Material synthesis citrylideneacetone or methyl citrylideneacetone, and reactions steps is few, and yield is high, pollutes few, 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 more than 91% under the reaction conditions of gentleness, high purity 97%, is a kind of desirable synthetic method promoted.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
By 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 interior temperature 85 DEG C with oil bath, reaction pressure is kept to be that 1.2MPa reacts 2 hours, gas chromatographic analysis dehydrolinalool transformation efficiency 98.8%.After having reacted, inflated with nitrogen, to normal pressure, cools to 15 DEG C, drips the sodium hydrate methanol solution 50ml of 0.5%, drips Bi Baowen 1.5 hours.Acetic acid adjust ph is added 6 ~ 7 after isomerization.Filtered in the pillar that super-cell is housed with methanol as solvent by reaction solution, filtrate is carried out rectifying and is obtained 97.5%(cis-trans sum) citrylideneacetone product 117.3g.Citrylideneacetone yield about 93.1%
Embodiment 2
According to the method for embodiment 1, distinctive points is only, 91.0g methyl acetoacetate changes into and drops into 83.5g methyl acetoacetate by the present embodiment, and other conditions are constant.Dehydrolinalool transformation efficiency is 97.6%, obtains the citrylideneacetone product 114.5g of content 98.1%.Citrylideneacetone yield about 92.5%
Embodiment 3
According to the method for embodiment 1, distinctive points is only, 91.0g methyl acetoacetate changes into and drops into 98.5g methyl acetoacetate by the present embodiment, and other conditions are constant.Dehydrolinalool transformation efficiency is 99.2%, obtains the citrylideneacetone product 114.3g of content 97.8%.Citrylideneacetone yield about 92.1%.
Embodiment 4 ~ 6
According to the method for embodiment 1, distinctive points is only, reacts during the reaction of Carlow with 60 DEG C, 90 DEG C, 120 DEG C, and gas-chromatography monitoring dehydrolinalool transformation efficiency more than 97.5%, other conditions are constant.Test-results (wherein the reaction times is the Carlow reaction times, lower same) as shown in table 1:
Table 1:
Embodiment 7 ~ 8
According to the method for embodiment 1, distinctive points is only, reacts during the reaction of Carlow at 0MPa, 3MPa, and gas-chromatography monitoring dehydrolinalool transformation efficiency more than 97.5%, other conditions are constant.Test-results is as shown in table 2:
Table 2:
Embodiment 9 ~ 10
According to embodiment 1, react unlike replacing methyl acetoacetate (being respectively 1.2:1 and 1.1:1 with dehydrolinalool mol ratio) with 102.2g and 93.7g2-methyl-3-oxobutyrate respectively, other conditions are constant, synthesizing methyl citrylideneacetone.Test-results is as shown in table 3:
Table 3:
Embodiment 11 ~ 12
According to embodiment 1, unlike reacting with 101.2g methyl aceto acetate and 112g ISOPROPYL ACETOACETATE (with dehydrolinalool mol ratio for 1.2:1) respectively, other conditions are constant, synthesis of pseudo-ionone.Test-results is as shown in table 4:
Table 4:
Test-results shows, and use method described in the invention, the yield of synthesis of pseudo-ionone and methyl citrylideneacetone can reach more than 91% under proper condition.Use method described in the invention, take directly dehydrolinalool as Material synthesis citrylideneacetone or methyl citrylideneacetone, reactions steps is few, and yield is high, pollutes few, meets the idea of development of green chemical industry.
Although above with general explanation, embodiment and test, the present invention is described in detail, and on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (1)
1. a synthetic method for jononeionone system fragrance intermediates, comprises the steps:
A) compound shown in the dehydrolinalool being 1:1.2:0.03 by amount ratio, formula I and aluminum isopropylate mixing make it that Carlow reaction occur, the company's of generation ketene compounds, wherein, reaction pressure is 1.2Mpa, temperature of reaction is 85 DEG C, and the reaction times is 2 hours;
B) after step a) is reacted and is terminated, inflated with nitrogen is to normal pressure, cool to 15 DEG C, dropping mass concentration is that the alcoholic solution of the alkali metal hydroxide of 0.5% carries out isomerization 1 hour, wherein, the mol ratio of dehydrolinalool and alkali metal hydroxide is 1:0.01, and isomerization is complete adds acetic acid adjust ph to 6 ~ 7, by reaction solution with R
2oH makes solvent and filters in the pillar that super-cell is housed, and filtrate is carried out rectifying and obtained pseudo ionone or methyl pseudoionone;
Wherein, R
1for hydrogen or methyl, R
2for methyl, ethyl, n-propyl, sec.-propyl, butyl, isobutyl-, 2-methyl-propyl, n-pentyl, isopentyl, 2-methyl butyl or benzyl.
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| CN108530279B (en) * | 2018-05-21 | 2021-06-01 | 浙江新和成股份有限公司 | Synthesis method of pseudo ionone |
| 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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| US6051741A (en) * | 1997-10-17 | 2000-04-18 | Basf Aktiengesellschaft | Preparation of γ,δ-unsaturated ketones by the Carroll reaction, novel catalysts therefor and the preparation thereof |
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| 假性紫罗兰酮合成的研究进展;张建斌等;《2006年中国香料香精学术研讨会论文集》;20060501;第109-114页 * |
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