CN104327033B - Molecularly-selective preparation method of 3'-ester group catechin and 4'-ester group catechin - Google Patents
Molecularly-selective preparation method of 3'-ester group catechin and 4'-ester group catechin Download PDFInfo
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- CN104327033B CN104327033B CN201410521387.5A CN201410521387A CN104327033B CN 104327033 B CN104327033 B CN 104327033B CN 201410521387 A CN201410521387 A CN 201410521387A CN 104327033 B CN104327033 B CN 104327033B
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- catechin
- ester group
- ester base
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- group catechin
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
- C07D311/60—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with aryl radicals attached in position 2
- C07D311/62—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with aryl radicals attached in position 2 with oxygen atoms directly attached in position 3, e.g. anthocyanidins
Abstract
The invention discloses a molecularly-selective preparation method of 3'-ester group catechin and 4'-ester group catechin. The method comprises following steps: dissolving catechin in acetonitrile, adding acyl chloride and a tertiary amine, performing stirring to carry out a reaction, and performing post-treatment after the reaction finished to obtain the 4'-ester group catechin and the 3'-ester group catechin. The method has following beneficial effects: (1) the preparation method is good in selectivity and purities of obtained 3'-ester group catechin and 4'-ester group catechin are high and the preparation method has a good application prospect; and (2) the preparation method is simple in operation, is free of toxic and stimulating organic solvents during the whole process, is free of environmental pollution and is suitable for industrialized production.
Description
Technical field
The invention belongs to functional food or medicament research and development technical field are and in particular to a kind of 3 ' and 4 ' -ester base catechins are divided
The preparation method of son.
Background technology
Polyphenol is that a class is widely present in the polyhydroxy aldehydes matter in plant.They are in the leaf of plant, wood, skin, shell
With all have certain content in sarcocarp, all containing higher plant polyphenol in fruit, corn epidermis.Polyphenol has excellent antioxygen and is turned into
With this is the basis of its all physiologically active.Substantial amounts of internal and experiment in vitro and epidemiologic data show, eat a certain amount of
Plant polyphenol disease is had prevention and inhibitory action.Polyphenol has the cardiovascular such as arteriosclerosis, prevention and treatment of coronary heart disease and apoplexy
Disease and antiinflammatory, anti-allergic effects and antivirus action.With polyphenol chemical and pharmacological development, people gradually recognize many
Phenol is the natural product that a class has unique physiologically active and pharmacologically active.Emerging with current " pursuit nature " consumption idea
Rise, polyphenol has broad application prospects in high-tech areas such as pharmacy, biochemistry, daily use chemicals, food and fine chemistry industries.Catechin
For a kind of important natural plant polyphenols, in Folium Camelliae sinensis etc., there is abundant distribution, its active function is notable, recently induces one to look steadily
Mesh.Research shows that catechin has significant antioxidation, mutation, anti-radiation and antibacterial disinfective action；Immune system can be strengthened
Function, the growth of suppression metabolism of lipid and cholesterol.
Catechin has been achieved for larger progress in terms of basic and applied research, but due to the multiple hydroxyl of catechin
Presence make its water solublity more fat-soluble relatively low, therefore limit its application in grease system it is difficult to reach effectively
Antioxidation concentration threshold.In addition relatively low fat-soluble also results in catechin molecule be difficult through cell membrane lipid double-deck so that
Its bioavailability relatively low it is difficult to reach target spot and substantially reduce its due activity.Due to these problems, to catechin molecule
Structure is modified has become current study hotspot to optimize its physicochemical property and biological activity.On the one hand pass through molecular modification
The active of catechin can be improved, on the other hand introduce new physiologically active also by introducing other active groups, real
Now various active is integrated.Catechin structural modification method mainly has the derivatization methods such as esterification, etherificate.It is exactly profit that esterification is modified
With the method for biological or chemical synthesis, by the process of the hydroxy esterification at some for catechin molecular structure positions.Although it is existing at present
The preparation method of mixing ester group catechin, but also it is not specifically designed for the effective ways that ad-hoc location is esterified.In order to enter
The property of one-step optimization catechin, develops its specific esterification process essential.
Content of the invention
The invention provides a kind of 3 ' and 4 ' -ester base catechin molecule method for selective production, the method selectivity height, behaviour
Make simple, be suitable to industrialized production.
A kind of 3 ' and 4 ' -ester base catechin molecule method for selective production, comprising: catechin is dissolved in acetonitrile, plus
Enter acyl chlorides and tertiary amine, stirring is reacted, reaction end carries out post processing and obtains 4 ' -ester base catechins and 3 ' -ester base catechu
Element.
The structure of described 4 ' -ester base catechins is shown below:
The structure of described 3 ' -ester base catechins is shown below:
In formula (i) and formula (ii), r is alkane acyl group；More preferably benzoyl, substituted benzoyl, c1-c18
Alkane acyl group；It is still more preferably benzoyl, c10-c13 alkane acyl group, with being more preferably benzoyl, c12
Alkane acyl group；
Described acyl chlorides is selected from one of chloro-formate, alkyl acyl chloride；More preferably benzyl chloroformate, chloro-carbonic acid
One of substituted benzene methyl ester, alkyl acyl chloride of c1-c18；It is still more preferably benzyl chloroformate, c10-c13 alkane acyl chlorides
One of；Much further preferably from benzyl chloroformate, lauroyl chloride；During from benzyl chloroformate, lauroyl chloride, selectivity is relatively
High.
Described tertiary amine is triethylamine, tripropyl amine (TPA), tri-n-butylamine, n, at least one in n- diisopropylethylamine.This examination
Agent is conducive to the acidity coupling with catechin 3 ', 4 '-phenolic hydroxyl group for alkali, realizes the high selectivity of 3 ', 4 '-phenolic hydroxyl group.As excellent
Choosing, described tertiary amine is triethylamine, n, n- diisopropylethylamine, low price, and selectivity height is it is easy to operate.
Described acetonitrile is advantageously implemented high selectivity as reaction dissolvent.
Preferably, the mol ratio of described catechin, acyl chlorides and tertiary amine is 1:1-3:1-3.It is still more preferably
1:1-1.3:1-1.4；This molar ratio range is conducive to abundant conversion and the high selectivity of raw material；4 ' -ester base catechins and 3 ' -ester
Base catechin significantly improves.
Preferably, described post processing includes:
(1) add organic solvents in the reaction system after the completion of reaction, extraction product is in organic faciess；
(2) organic faciess after extraction are concentrated, obtain sterling through chromatographic isolation.
As further, preferably, described organic solvent includes ethyl acetate, ether, chloroform, dichloromethane, oil
One of ether, normal hexane, t-butyl methyl ether, these organic solvents are preferable to the solubility property of product, and are easy to volatilize
Remove.
The reaction of the present invention is carried out at room temperature.
The invention has the advantages that and effect:
(1) preparation method of the present invention has preferable selectivity, 3 ' the -ester base catechins obtaining and 4 ' -ester base catechins
The purity of molecule is high, has preferable application prospect.
(2) preparation method of the present invention is simple to operate, and overall process avoids using poisonous organic solvent excitatory, acyclic
Border pollution is it is adaptable to industrialized production is applied.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1
Catechin (29mg), benzyl chloroformate (20mg) and triethylamine (12mg) are stirred at room temperature reaction 2 hours, treat anti-
Should be extracted with ethyl acetate after terminating, obtain after post Layer Chromatography 4 '-benzyloxycarbonyl group ester catechin (yield: 40%, eluting
Agent be chloroform and methanol mixed solvent), 3 '-benzyloxycarbonyl group ester catechin (yield: 40%, eluant be chloroform and methanol mixed
Solvent).
3 '-benzyloxycarbonyl group ester catechin:1h nmr(400mhz,dmso)δ9.89(s,1h),9.20(s,1h),8.95(s,
1h), 7.48-7.36 (m, 5h), 7.11 (dd, j=8.4,2.0hz, 1h), 7.10 (d, j=1.6hz, 1h), 6.93 (d, j=
8.0hz, 1h), 5.91 (d, j=2.4hz, 1h), 5.71 (d, j=2.4hz, 1h), 5.26 (s, 2h), 4.96 (d, j=5.2hz,
1h), 4.54 (d, j=8.0hz, 1h), 3.88-3.81 (m, 1h), 2.74-2.65 (m, 1h), 2.44-2.35 (m, 1h).
4 '-benzyloxycarbonyl group ester catechin:1h nmr(400mhz,dmso)δ9.88(s,1h),9.21(s,1h),8.97(s,
1h), 7.48-7.36 (m, 5h), 7.09 (d, j=8.0hz, 1h), 6.95 (d, j=2.0hz, 1h), 6.81 (dd, j=8.4,
2.0hz, 1h), 5.92 (d, j=2.4hz, 1h), 5.73 (d, j=2.4hz, 1h), 5.26 (s, 2h), 5.04 (d, j=5.6hz,
1h), 4.60 (d, j=7.6hz, 1h), 3.88-3.81 (m, 1h), 2.74-2.65 (m, 1h), 2.44-2.35 (m, 1h).
Embodiment 2
Catechin (29mg), benzyl chloroformate (34mg) and tripropyl amine (TPA) (36mg) are stirred at room temperature reaction 2 hours, treat anti-
Should be extracted with ethyl acetate after terminating, obtain after post Layer Chromatography 4 '-benzyloxycarbonyl group ester catechin (yield: 36%), 3 '-
Benzyloxycarbonyl group ester catechin (yield: 36%).Detection data is with embodiment 1.
Embodiment 3
Catechin (29mg), lauroyl chloride (22mg) and n, n- diisopropylethylamine (17mg) is stirred at room temperature reaction 2
Hour, question response is extracted with ethyl acetate after terminating, obtain after post Layer Chromatography 4 '-dodecanoyl ester catechin (yield:
42%, eluant be chloroform and methanol mixed solvent), 3 '-dodecanoyl ester catechin (yield: 42%, eluant be chloroform and
Methanol mixed solvent).
3 '-dodecanoyl catechin:1h nmr(400mhz,dmso)δ9.62(s,1h),9.21(s,1h),8.96(s,
1h), 7.07 (dd, j=8.4,2.0hz, 1h), 6.96 (d, j=1.6hz, 1h), 6.89 (d, j=8.0hz, 1h), 5.91 (d, j
=2.4hz, 1h), 5.70 (d, j=2.0hz, 1h), 4.96 (d, j=5.2hz, 1h), 4.53 (d, j=8.0hz, 1h), 3.89-
3.80(m,1h),2.77-2.65(m,1h),2.58-2.49(m,2h),2.43-2.32(m,1h),1.68-1.58(m,2h),
1.32–1.14(m,16h),0.91-0.82(m,3h).
4 '-dodecanoyl catechin:1h nmr(400mhz,dmso)δ9.61(s,1h),9.22(s,1h),8.98(s,
1h), 6.94 (d, j=8.4hz, 1h), 6.91 (d, j=2.0hz, 1h), 6.79 (dd, j=8.4,2.0hz, 1h), 5.92 (d, j
=2.4hz, 1h), 5.73 (d, j=2.0hz, 1h), 5.05 (d, j=4.8hz, 1h), 4.59 (d, j=7.6hz, 1h), 3.89-
3.80(m,1h),2.77-2.65(m,1h),2.58-2.49(m,2h),2.43-2.32(m,1h),1.68-1.58(m,2h),
1.32–1.14(m,16h),0.91-0.82(m,3h.
Claims (3)
1. one kind 3 ' and 4 ' -ester base catechin molecule method for selective production, comprising: catechin is dissolved in acetonitrile, adds
Acyl chlorides and tertiary amine, stirring is reacted, and reaction end carries out post processing and obtains 4 ' -ester base catechins and 3 ' -ester base catechins；
The structure of described 4 ' -ester base catechins is shown below:
The structure of described 3 ' -ester base catechins is shown below:
In formula (i) and formula (ii), r is benzoyl, c12 alkane acyl group；
The mol ratio of described catechin, acyl chlorides and tertiary amine is 1:1-1.3:1-1.4；
Described acyl chlorides is benzyl chloroformate, lauroyl chloride；
Described tertiary amine is triethylamine, n, n- diisopropylethylamine.
2. according to claim 13 ' and 4 ' -ester base catechin molecule method for selective production are it is characterised in that described
Post processing include:
(1) add organic solvents in the reaction system after the completion of reaction, extraction product is in organic faciess；
(2) organic faciess after extraction are concentrated, obtain sterling through chromatographic isolation.
3. according to claim 23 ' and 4 ' -ester base catechin molecule method for selective production are it is characterised in that described
Organic solvent include one of ethyl acetate, ether, chloroform, dichloromethane, petroleum ether, normal hexane, t-butyl methyl ether.
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| CN201410521387.5A CN104327033B (en) | 2014-09-30 | 2014-09-30 | Molecularly-selective preparation method of 3'-ester group catechin and 4'-ester group catechin |
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| CN201410521387.5A CN104327033B (en) | 2014-09-30 | 2014-09-30 | Molecularly-selective preparation method of 3'-ester group catechin and 4'-ester group catechin |
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| CN104327033B true CN104327033B (en) | 2017-02-01 |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1575004A (en) * | 1976-03-23 | 1980-09-17 | Iverni Della Beffa Spa | Pharmacologically active polyphenolic substances |
| CN1231277A (en) * | 1999-01-18 | 1999-10-13 | 余姚市四明茶叶生物制品有限公司 | Fat-soluble tea polyphenol and esterfication method productive process thereof |
| CN1448395A (en) * | 2003-04-03 | 2003-10-15 | 浙江大学 | Antioxidant EGCG aliphatic ester and prep. thereof |
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