CN101875599A - Novel method for synthesizing leaf alcohol - Google Patents
Novel method for synthesizing leaf alcohol Download PDFInfo
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- CN101875599A CN101875599A CN201010005503XA CN201010005503A CN101875599A CN 101875599 A CN101875599 A CN 101875599A CN 201010005503X A CN201010005503X A CN 201010005503XA CN 201010005503 A CN201010005503 A CN 201010005503A CN 101875599 A CN101875599 A CN 101875599A
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Abstract
The invention provides a novel method for synthesizing leaf alcohol. In the method, in catalysis of lewis acid, one of formaldehyde, paraformaldehyde or trioxymethylene performs Alder Ene reaction with 1-amylene at the temperature of minus 40 and 20 DEG C, and the materials after reaction are separated, purified and refined to prepare the target compound conveniently. The method has low-price and easily obtained raw materials, and is particularly applied to industrialized production.
Description
Technical field
The present invention relates to a kind of novel method of synthesizing leaf alcohol.
Background technology
Leaf-alcohol (chemical name is cis-blatter alcohol) is crucial spices, has the natural faint scent of fresh leaf grass, and fragrance is fresh and clean, is fit to directly do spices.Leaf-alcohol and derivative thereof are one of famous and precious spices of pandemic scent type, also become the symbol of world's fragrance industry Green Revolution.Leaf-alcohol and ester thereof still are indispensable blending material during essence is produced, and have contained the leaf-alcohol composition at present at least in synthetic perfume and essence more than 40 kinds.The world demand amount is about 200 tons/year at present.
Leaf-alcohol is present in the multiple green plants.But because boiling point is lower and water-soluble bigger, the leaf-alcohol turnout of natural extract is minimum and production cost is high, and the required leaf-alcohol of China is still by import at present.Therefore biochemical process and chemical synthesis process have commercial value more.
Industrialization at present or the leaf-alcohol synthesis technique with industrial prospect mainly contain following several routes: 3-hexin-1-alcohol is selected the selective hydration method of shortening method, conjugated dienes alcohol, is the synthesis method, biochemical process etc. of raw material with tetrahydrofuran (THF) and derivative thereof.
At present external industrialization technology is crucial with 3-hexin-1-alcohol preparation, and now industrialized 3-hexin-1-alcohol synthetic method has acetylene method, butine method, propiolic alcohol method etc. by the raw material route branch.[referring to (1) " flavor chemistry and technology ", Zhao Yibin, Chemical Industry Press, 2007; (2) flavor chemistry and technology (second edition), Sun Baoguo, He Jian, Chemical Industry Press, 2004; (3) Chinese patent title " a kind of method of synthesizing leaf alcohol ", application for a patent for invention publication number 200410050641.4].
Additive method also has from 1,3-pentadiene, through 2-methyl-5, and the open loop of 6-dihydrofuran, the leaf-alcohol [Chinese patent title " a kind of novel method of synthesizing leaf alcohol ", application for a patent for invention publication number CN1244518A] of reduction preparation at last.
These methods are each has something to recommend him, but have that operation is long, synthesis step is many, complex process or reaction times grows, relates to weak points such as anhydrous and oxygen-free condition more.Therefore the method that needs a kind of reaction conditions gentleness, synthetic route is short, yield is higher synthesizing leaf alcohol.
Summary of the invention
The objective of the invention is defectives such as, complex process many for the method synthesis step that overcomes existing synthesizing leaf alcohol, a kind of novel method of synthesizing leaf alcohol is provided, with a kind of in the 1-amylene of the cheapness that obtains easily and formaldehyde, Paraformaldehyde 96, trioxymethylene or the formalin is raw material, through the Lewis acid catalysis, single step reaction prepares leaf-alcohol, and method is simple.
The technical problem that will solve required for the present invention can be achieved through the following technical solutions:
A kind of novel method of synthesizing leaf alcohol is characterized in that, with two kinds of compositions as raw material, one composition and catalyst dissolution in organic solvent, are stirred down at-40 ℃--20 ℃ slowly add another compositions, are warming up to room temperature behind reinforced the finishing, continue to stir the saturated NaHCO of reaction soln 1-6 hour
3Solution washing, organic phase drying, distillation obtain crude product, and crude product rectifying is obtained leaf-alcohol.
Described two kinds of compositions are respectively a kind of in 1-amylene and formaldehyde, Paraformaldehyde 96, trioxymethylene or the formalin.
Described organic solvent is a kind of in methylene dichloride, the tetracol phenixin.
The mol ratio of described 1-amylene and Paraformaldehyde 96 is 1: 1-6, the mol ratio of described 1-amylene and catalyzer is 1: 0.005-0.4.
Described catalyzer is a lewis acid catalyst, and described lewis acid catalyst is a kind of in aluminum chloride, tin tetrachloride, diethyl aluminum chloride, ethylaluminum dichloride, the alkoxyl group aluminum chloride.
Reaction equation of the present invention is as shown below:
This method generally obtain leaf-alcohol and cis-trans-isomer trans-mixture of blatter alcohol, the two ratio is suitable.Trans-blatter alcohol is present in the green plants equally, also has the natural faint scent of green grass.Therefore, this mixture can directly be used as spices.
Owing to adopted technique scheme, the beneficial effect that the present invention has is, adopt control reaction temperature under cryogenic condition, slowly to add another composition, can controls reaction speed control make it that vigorous reaction not take place, the raw materials used cheapness of the present invention and conveniently being easy to get, only need single step reaction can conveniently obtain target compound, the reaction times is short, is particularly suitable for suitability for industrialized production.
Embodiment
In order to make technique means of the present invention, creation characteristic, to reach purpose and effect is easy to understand,, further set forth the present invention, but embodiments of the present invention are not limited thereto below in conjunction with embodiment.
Embodiment 1
Paraformaldehyde 96 (3g, 0.1mol) and aluminum chloride (0.27g 0.002mol) is dissolved in the methylene dichloride (20ml), start magnetic agitation, the speed of under-40 ℃, dripping with per two seconds 1-2 slowly drip the 1-amylene (3.5g, 0.05mol), be raised to room temperature after dropwising, continue to stir 1 hour.Use saturated NaHCO
3Solution (10ml) washing, the organic phase anhydrous sodium sulfate drying, methylene dichloride is removed in distillation, and remaining crude product obtains the mixture of leaf-alcohol and trans-blatter alcohol, yield 72% through underpressure distillation.Trans-blatter alcohol is present in the green plants equally, also has the natural faint scent of green grass, and therefore, this mixture can directly be used as spices.Mixture rectifying is obtained leaf-alcohol, and yield is 36%.
Embodiment 2
Paraformaldehyde 96 (3g, 0.1mol) and tin tetrachloride (0.32g 0.0012mol) is dissolved in the methylene dichloride (20ml), start magnetic agitation, the speed of under-20 ℃, dripping with per two seconds 1-2 slowly drip the 1-amylene (3.5g, 0.05mol), be raised to room temperature after dropwising, continue to stir 4 hours.Use saturated NaHCO
3Solution (10ml) washing, the organic phase anhydrous sodium sulfate drying, methylene dichloride is removed in distillation, and remaining crude product obtains the mixture of leaf-alcohol and trans-blatter alcohol, yield 85% through underpressure distillation.Mixture rectifying is obtained leaf-alcohol, and yield is 43%.
Embodiment 3
Trioxymethylene (30g, 1mol) and tin tetrachloride (3.2g 0.012mol) is dissolved in the tetracol phenixin (200ml), start magnetic agitation, the speed of under-20 ℃, dripping with per two seconds 1-2 drip the 1-amylene (42g, 0.6mol), be raised to room temperature after dropwising, continue to stir 4 hours.Use saturated NaHCO
3Solution (100ml) washing, the organic phase anhydrous sodium sulfate drying, methylene dichloride is removed in distillation, and remaining crude product obtains the mixture of leaf-alcohol and trans-blatter alcohol, yield 82% through underpressure distillation.Mixture rectifying is obtained leaf-alcohol, and yield is 41%.
Embodiment 4
The 1-amylene (3.5g, 0.05mol) and diethyl aluminum chloride (0.2g 0.0017mol) is dissolved in the methylene dichloride (20ml), start magnetic agitation, feed formaldehyde gas (0.1mol) (by the methanol oxidation on-site preparation) down at-20 ℃, be raised to room temperature behind reinforced the finishing, continue to stir 4 hours.Use saturated NaHCO
3Solution (10ml) washing, the organic phase anhydrous sodium sulfate drying, methylene dichloride is removed in distillation, and remaining crude product obtains the mixture of leaf-alcohol and trans-blatter alcohol, yield 86% through underpressure distillation.Mixture rectifying is obtained leaf-alcohol, and yield is 43%.
Embodiment 5
Paraformaldehyde 96 (3g, 0.1mol) and ethylaluminum dichloride (0.18g, 0.0012mol) be dissolved in the methylene dichloride (20ml), start magnetic agitation, the speed of dripping with per two seconds 1-2 under-20 ℃ slowly drips 1-amylene (3.5g, 0.05mol), be raised to room temperature after dropwising, continue to stir 6 hours.Use saturated NaHCO
3Solution (10ml) washing, the organic phase anhydrous sodium sulfate drying, methylene dichloride is removed in distillation, and remaining crude product obtains the mixture of leaf-alcohol and trans-blatter alcohol, yield 77% through underpressure distillation.Mixture rectifying is obtained leaf-alcohol, and yield is 38%.
Embodiment 6
Paraformaldehyde 96 (3g, 0.1mol) and diethoxy aluminum chloride (0.21g, 0.0012mol) be dissolved in the methylene dichloride (20ml), start magnetic agitation, the speed of dripping with per two seconds 1-2 under-20 ℃ slowly drips 1-amylene (3.5g, 0.05mol), be raised to room temperature after dropwising, continue to stir 6 hours.Use saturated NaHCO
3Solution (10ml) washing, the organic phase anhydrous sodium sulfate drying, methylene dichloride is removed in distillation, and remaining crude product obtains the mixture of leaf-alcohol and trans-blatter alcohol, yield 77% through underpressure distillation.Mixture rectifying is obtained leaf-alcohol, and yield is 31%.
Embodiment 7
Paraformaldehyde 96 (1.5g, 0.05mol) and aluminum chloride (0.033g, 0.25mmol) be dissolved in the methylene dichloride (20ml), start magnetic agitation, the speed of dripping with per two seconds 1-2 under-40 ℃ slowly drips 1-amylene (3.5g, 0.05mol), be raised to room temperature after dropwising, continue to stir 1 hour.Use saturated NaHCO
3Solution (10ml) washing, the organic phase anhydrous sodium sulfate drying, methylene dichloride is removed in distillation, and remaining crude product obtains the mixture of leaf-alcohol and trans-blatter alcohol, yield 60% through underpressure distillation.Trans-blatter alcohol is present in the green plants equally, also has the natural faint scent of green grass, and therefore, this mixture can directly be used as spices.Mixture rectifying is obtained leaf-alcohol, and yield is 30%.
Embodiment 8
Paraformaldehyde 96 (9g, 0.3mol) and aluminum chloride (2.7g 0.02mol) is dissolved in the methylene dichloride (20ml), start magnetic agitation, the speed of under-40 ℃, dripping with per two seconds 1-2 slowly drip the 1-amylene (3.5g, 0.05mol), be raised to room temperature after dropwising, continue to stir 1 hour.Use saturated NaHCO
3Solution (10ml) washing, the organic phase anhydrous sodium sulfate drying, methylene dichloride is removed in distillation, and remaining crude product obtains the mixture of leaf-alcohol and trans-blatter alcohol, yield 80% through underpressure distillation.Trans-blatter alcohol is present in the green plants equally, also has the natural faint scent of green grass, and therefore, this mixture can directly be used as spices.Mixture rectifying is obtained leaf-alcohol, and yield is 40%.
More than show and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in the foregoing description and the specification sheets just illustrates principle of the present invention; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (7)
1. the novel method of a synthesizing leaf alcohol is characterized in that, with two kinds of compositions as raw material, one composition and catalyst dissolution in organic solvent, are stirred down at-40 ℃--20 ℃ slowly add another compositions, are warming up to room temperature behind reinforced the finishing, continue to stir the saturated NaHCO of reaction soln 1-6 hour
3Solution washing, organic phase drying, distillation obtain crude product, and crude product underpressure distillation, rectifying are obtained leaf-alcohol.
2. the novel method of a kind of synthesizing leaf alcohol according to claim 1 is characterized in that, a described composition is a kind of in formaldehyde, Paraformaldehyde 96, trioxymethylene or the formalin, and another composition is the 1-amylene.
3. the novel method of a kind of synthesizing leaf alcohol according to claim 1 is characterized in that, a described composition is the 1-amylene, and another composition is a kind of in formaldehyde, Paraformaldehyde 96, trioxymethylene or the formalin.
4. the novel method of a kind of synthesizing leaf alcohol according to claim 1 is characterized in that, described organic solvent is a kind of in methylene dichloride, the tetracol phenixin.
5. the novel method of a kind of synthesizing leaf alcohol according to claim 1 is characterized in that, the mol ratio of described 1-amylene and formaldehyde is 1: 1-6, the mol ratio of described 1-amylene and catalyzer is 1: 0.005-0.4.
6. the novel method of a kind of synthesizing leaf alcohol according to claim 1 is characterized in that, described catalyzer is a lewis acid catalyst.
7. the novel method of a kind of synthesizing leaf alcohol according to claim 6 is characterized in that, described lewis acid catalyst is a kind of in aluminum chloride, tin tetrachloride, diethyl aluminum chloride, ethylaluminum dichloride, the alkoxyl group aluminum chloride.
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| CN201010005503XA CN101875599A (en) | 2009-04-30 | 2010-01-18 | Novel method for synthesizing leaf alcohol |
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| CN200910050545 | 2009-04-30 | ||
| CN200910050545.2 | 2009-04-30 | ||
| CN201010005503XA CN101875599A (en) | 2009-04-30 | 2010-01-18 | Novel method for synthesizing leaf alcohol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021156870A1 (en) * | 2020-02-06 | 2021-08-12 | Agan Aroma & Fine Chemicals Ltd. | Mixture of 3-hexen-1-ol isomers and a process of preparing same |
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- 2010-01-18 CN CN201010005503XA patent/CN101875599A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021156870A1 (en) * | 2020-02-06 | 2021-08-12 | Agan Aroma & Fine Chemicals Ltd. | Mixture of 3-hexen-1-ol isomers and a process of preparing same |
| CN115210205A (en) * | 2020-02-06 | 2022-10-18 | 阿甘香气及精细化学有限公司 | 3-hexen-1-ol isomer mixture and process for preparing same |
| EP4100383A4 (en) * | 2020-02-06 | 2024-03-20 | Agan Aroma&fine Chemicals Ltd. | Mixture of 3-hexen-1-ol isomers and a process of preparing same |
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Application publication date: 20101103 |