CN102391215A - Synthesis method of chiral gamma-dodecalactone - Google Patents
Synthesis method of chiral gamma-dodecalactone Download PDFInfo
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- CN102391215A CN102391215A CN2011103275731A CN201110327573A CN102391215A CN 102391215 A CN102391215 A CN 102391215A CN 2011103275731 A CN2011103275731 A CN 2011103275731A CN 201110327573 A CN201110327573 A CN 201110327573A CN 102391215 A CN102391215 A CN 102391215A
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- dodecalactone
- nonyl alcohol
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Abstract
The invention discloses a synthesis method of chiral gamma-dodecalactone. The method comprises the following steps of: synthesizing a lactone molecule with optical activity from a reactant under the environment and induction of a chiral molecule; proportionally mixing nonanol, acrylic acid and peroxide, and adding a certain amount of chiral alpha-phenylethylamine zinc acetate ruthenium or copper chromium organic complex into the reaction backing material; and synthesizing the gamma-dodecalactone with optical cavity under the action of silica-alumina mixed catalyst and the induction of D or L tartaric acid. Through the invention, the problems that the gamma-dodecalactone spice is mainly made by chemical synthesis in the prior art, the lactone spices synthesized from a substance without optical activity under general conditions are all racemic mixtures with turbid aroma, lots of foreign gases and relatively obvious artificial traces; and the synthesis method of chiral gamma-dodecalactone provided by the invention is easy to operate, has a relatively good use effect; and the synthesized product has a relatively high enantiomeric excess value and the aroma of the spice is more fresh.
Description
Technical field
The present invention relates to a kind of preparation method of chirality synthetic perfume, particularly relate to the compound method of a kind of chirality γ-dodecalactone.
Background technology
Natural lactone spice is present in the fruit of all kinds of fruit more, all extensively is present in the fruit such as peach, almond, strawberry like γ-decalactone, γ-Shi Yineizhi, γ-dodecalactone.Be called peach aldehyde again like γ-Shi Yineizhi, have intensive peach fragrance, outward appearance is colourless to light yellow thick liquid, and water insoluble and glycerine is dissolved in organic flux such as ethanol.Their a large amount of being used in the prescription of food flavour and daily cosmetics essence.
Lactone spice in the market is mainly derived from chemosynthesis.With the non-optically active substance lactone spice that obtains of compound method under general condition, be racemic modification.The synthetic spices fragrance of raceme is relatively more muddy, and foreign gas is more, and artificial trace is comparatively obvious, and the effect of use is bad, often can not satisfy the demand of use.And mostly the lactone in the natural food is asymmetric lactone, and its fragrance is purer than the synthetic perfume fragrance of racemic modification, and simultaneously, equally also there is evident difference in the fragrance between asymmetric lactone dextrorotatory form, levo form.And also more pure through its fragrance of asymmetric lactone after splitting than the fragrance of racemic lactone spice, more lay particular stress on natural style, its added value is higher.For example: (R)-(+)-γ-dodecalactone contains the strong fragrance of a flower, and the sweet fruity of essential fragrance color can be applicable in the fruit flavor.(S)-(-)-and γ-dodecalactone has the sweet fruity of fat, and the milk flavor a little less than the strength ratio R type enantiomorph, can be applied in the dairy products essence.
The acquisition of chiral molecules has chemical resolution method, asymmetric synthesis method, biological enzyme, chromatography etc.The importance of chiral molecules, the living things system mid point according to very important position.The lactone spice chiral molecules splits research; Existing a lot of report; The open 2001-11063 of Japanese Patent Laid and Shanghai likes that general spices CN1872849A has reported and uses optically active α-Ben Yian as resolving agent, and the fractionation lactone spice is ((R)-(+)-gamma lactone) and (S)-(-)-gamma lactone.To the compound method of lactone spice chiral molecules, report fewer.
Summary of the invention
Be mainly derived from chemosynthesis in order to solve γ in the prior art-dodecalactone spices,, be racemic modification with the non-optically active substance lactone spice that obtains of compound method under general condition; Spices fragrance is relatively more muddy, and foreign gas is more, and artificial trace is comparatively obvious; The problem that result of use is bad; The invention provides a kind of simple to operately, the synthetic product enantiomeric excess value is higher, and spices fragrance is more pure; Result of use is better, more lays particular stress on the compound method of the chirality γ-dodecalactone of natural style.
In order to address the above problem, the technical scheme that the present invention taked is:
The compound method of a kind of chirality γ-dodecalactone is characterized in that: in the four-hole boiling flask of 2000mL, add the 1000g nonyl alcohol; Add 20gR-(+)-α-Ben Yian zinc acetate ruthenium organic coordination compound; Be stirred and heated to 175 ℃, drip in nonyl alcohol 100g: vinylformic acid 110g:L-tartrate 2g: behind the nonyl alcohol and vinylformic acid proportioning liquid of superoxide 3g ratio proportioning, the reactor drum that reactant warp one is equipped with the silica-alumina mixed catalyst reacts; The reaction mixture that must contain (S)-(-)-γ-dodecalactone; This reaction mixture gets (S)-(-)-γ-dodecalactone bullion after thick the steaming, after negative pressure rectifying, get (S)-(-)-γ-dodecalactone 123g; Enantiomeric excess value is 90%, and product yield is 44.8%.
The compound method of aforesaid a kind of chirality γ-dodecalactone is characterized in that: the mass ratio of silicon-dioxide and aluminum oxide is 1:2 in the said silica-alumina mixed catalyst.
The compound method of a kind of chirality γ-dodecalactone is characterized in that: in the four-hole boiling flask of 2000mL, add the 1350g nonyl alcohol; Add 18gS-(-)-α-Ben Yian neutralized verdigris chromium organic coordination compound; Be stirred and heated to 180 ℃, drip in nonyl alcohol 134g: vinylformic acid 120g:D-tartrate 2g: behind the nonyl alcohol and vinylformic acid proportioning liquid of superoxide 3g ratio proportioning, the reactor drum that reactant warp one is equipped with the silica-alumina mixed catalyst reacts; The reaction mixture that must contain (R)-(+)-γ-dodecalactone; This reaction mixture gets (R)-(+)-γ-dodecalactone bullion after thick the steaming, after negative pressure rectifying, get (R)-(+)-γ-dodecalactone 108g; Enantiomeric excess value is 91%, and product yield is 39.4%.
The compound method of aforesaid a kind of chirality γ-dodecalactone is characterized in that: the mass ratio of silicon-dioxide and aluminum oxide is 1:2 in the said silica-alumina mixed catalyst.
The invention has the beneficial effects as follows: reactant of the present invention the environment of chiral molecules and induce synthetic optically active down in ester molecule.With nonyl alcohol and vinylformic acid and superoxide by a certain percentage after the proportioning; In the reaction bed material, add a certain amount of chirality α-Ben Yian zinc acetate ruthenium or copper chromium organic coordination compound; Under the effect of silica-alumina mixed catalyst; Inducing down synthetic optically active γ-dodecalactone by D or L are tartaric.Synthetic product enantiomorph output is high, and process operation is simple, and spices fragrance is more pure, and result of use is better, more lays particular stress on natural style, and its added value is also higher.
Embodiment
Below in conjunction with specific embodiment the present invention is done more detailed description.
Embodiment one
Be equipped with in the 2000mL four-hole boiling flask of whisking appliance one; Add the 1000g nonyl alcohol; Add 20gR-(+)-α-Ben Yian zinc acetate ruthenium organic coordination compound, be stirred and heated to 175 ℃, drip in nonyl alcohol 100g: vinylformic acid 110g:L tartrate 2g: behind the nonyl alcohol and vinylformic acid proportioning liquid of superoxide 3g ratio proportioning; It is that the reactor drum of the silica-alumina mixed catalyst of 1:2 reacts that reactant is equipped with mass ratio through one, must contain the reaction mixture of (S)-(-)-γ-dodecalactone.This reaction mixture gets (S)-(-)-γ-dodecalactone bullion after thick the steaming, after negative pressure rectifying, get (S)-(-)-γ-dodecalactone 123g, and enantiomeric excess value is 90%.Product yield is 44.8%
Embodiment two
Be equipped with in the 2000mL four-hole boiling flask of whisking appliance one; Add the 1350g nonyl alcohol; Add 18gS-(-)-α-Ben Yian neutralized verdigris chromium organic coordination compound, be stirred and heated to 180 ℃, drip in nonyl alcohol 134g: vinylformic acid 120g:D tartrate 2g: behind the nonyl alcohol and vinylformic acid proportioning liquid of superoxide 3g ratio proportioning; It is that the reactor drum of the silica-alumina mixed catalyst of 1:2 reacts that reactant is equipped with mass ratio through one, must contain the reaction mixture of (R)-(+)-γ-dodecalactone.This reaction mixture gets (R)-(+)-γ-dodecalactone bullion after thick the steaming, after negative pressure rectifying, get (R)-(+)-γ-dodecalactone 108g, and enantiomeric excess value is 91%.Product yield is 39.4%.
More than show and described ultimate principle of the present invention, principal character and advantage.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 explains principle of the present invention; Under the prerequisite that does not break away from spirit and scope of the invention, the present invention also has various changes and modifications, and these variations and improvement all fall in the scope of the invention that requires protection.The present invention requires protection domain by appending claims and equivalent circle thereof.
Claims (4)
1. the compound method of a chirality γ-dodecalactone is characterized in that: in the four-hole boiling flask of 2000mL, add the 1000g nonyl alcohol; Add 20gR-(+)-α-Ben Yian zinc acetate ruthenium organic coordination compound; Be stirred and heated to 175 ℃, drip in nonyl alcohol 100g: vinylformic acid 110g:L-tartrate 2g: behind the nonyl alcohol and vinylformic acid proportioning liquid of superoxide 3g ratio proportioning, the reactor drum that reactant warp one is equipped with the silica-alumina mixed catalyst reacts; The reaction mixture that must contain (S)-(-)-γ-dodecalactone; This reaction mixture gets (S)-(-)-γ-dodecalactone bullion after thick the steaming, after negative pressure rectifying, get (S)-(-)-γ-dodecalactone 123g; Enantiomeric excess value is 90%, and product yield is 44.8%.
2. the compound method of a kind of chirality γ according to claim 1-dodecalactone is characterized in that: the mass ratio of silicon-dioxide and aluminum oxide is 1:2 in the said silica-alumina mixed catalyst.
3. the compound method of a chirality γ-dodecalactone is characterized in that: in the four-hole boiling flask of 2000mL, add the 1350g nonyl alcohol; Add 18gS-(-)-α-Ben Yian neutralized verdigris chromium organic coordination compound; Be stirred and heated to 180 ℃, drip in nonyl alcohol 134g: vinylformic acid 120g:D-tartrate 2g: behind the nonyl alcohol and vinylformic acid proportioning liquid of superoxide 3g ratio proportioning, the reactor drum that reactant warp one is equipped with the silica-alumina mixed catalyst reacts; The reaction mixture that must contain (R)-(+)-γ-dodecalactone; This reaction mixture gets (R)-(+)-γ-dodecalactone bullion after thick the steaming, after negative pressure rectifying, get (R)-(+)-γ-dodecalactone 108g; Enantiomeric excess value is 91%, and product yield is 39.4%.
4. the compound method of a kind of chirality γ according to claim 3-dodecalactone is characterized in that: the mass ratio of silicon-dioxide and aluminum oxide is 1:2 in the said silica-alumina mixed catalyst.
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| CN2011103275731A CN102391215A (en) | 2011-10-25 | 2011-10-25 | Synthesis method of chiral gamma-dodecalactone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108794432A (en) * | 2017-04-28 | 2018-11-13 | 山东新和成药业有限公司 | A kind of method that photosensitizer catalysis prepares the third butyrolactone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1872849A (en) * | 2005-06-03 | 2006-12-06 | 上海爱普香料有限公司 | Method for synthesizing (S)(-)-gamma-lactone |
| CN101016311A (en) * | 2007-03-09 | 2007-08-15 | 合肥工业大学 | Novel use of chiral (R/S)-a-phenethylamine(+/-)-tartrate |
| CN101830919A (en) * | 2010-05-17 | 2010-09-15 | 合肥工业大学 | Zinc nitride and copper nitride compound of chiral alpha-phenylethylamine and use thereof |
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- 2011-10-25 CN CN2011103275731A patent/CN102391215A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1872849A (en) * | 2005-06-03 | 2006-12-06 | 上海爱普香料有限公司 | Method for synthesizing (S)(-)-gamma-lactone |
| CN101016311A (en) * | 2007-03-09 | 2007-08-15 | 合肥工业大学 | Novel use of chiral (R/S)-a-phenethylamine(+/-)-tartrate |
| CN101830919A (en) * | 2010-05-17 | 2010-09-15 | 合肥工业大学 | Zinc nitride and copper nitride compound of chiral alpha-phenylethylamine and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《江西化工》 20021231 蔡明沂等 gamma-丁内酯类化合物的合成与应用 5-10 , 第4期 * |
| 蔡明沂等: "γ-丁内酯类化合物的合成与应用", 《江西化工》, no. 4, 31 December 2002 (2002-12-31), pages 5 - 10 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108794432A (en) * | 2017-04-28 | 2018-11-13 | 山东新和成药业有限公司 | A kind of method that photosensitizer catalysis prepares the third butyrolactone |
| CN108794432B (en) * | 2017-04-28 | 2020-04-21 | 山东新和成药业有限公司 | Method for preparing gamma lactone by photosensitization catalysis |
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Application publication date: 20120328 |