CN105037455B - The synthetic method of alkyl β D glucopyranosides - Google Patents
The synthetic method of alkyl β D glucopyranosides Download PDFInfo
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- CN105037455B CN105037455B CN201510478565.5A CN201510478565A CN105037455B CN 105037455 B CN105037455 B CN 105037455B CN 201510478565 A CN201510478565 A CN 201510478565A CN 105037455 B CN105037455 B CN 105037455B
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Abstract
The invention discloses a kind of synthetic method of alkyl β D glucopyranosides, comprise the following steps：Full acetylated glucopyranose, alphanol and anhydrous stannic chloride are dissolved in anhydrous methylene chloride, reaction 20-70 minutes are stirred at room temperature, are washed with saturated aqueous sodium carbonate; organic phase is collected, vacuum distillation obtains 1 alkyl 2,3; 4,6 tetra-acetylated β D glucopyranosides；By 1 alkyl 2,3,4,6 tetra-acetylated β D glucopyranosides are dissolved in methanol; sodium methoxide regulation pH to 9 is added, is reacted 1.5 hours at room temperature, is adjusted with storng-acid cation exchange resin to neutrality, filtering; filtrate steams solvent, dries, obtains alkyl β D glucopyranosides.Alkyl is C8‑C12Alkyl.The method of the present invention is simple, and raw material is easy to get, and cost is cheap, and reaction temperature is gently easily-controllable, environment-friendly, and the glucopyranoside purity of the beta comfiguration of preparation is high.
Description
Technical field
The present invention relates to a kind of synthetic method of alkyl-beta-glucosidase, category carbohydrate chemistry field, more particularly to one kind is just
The synthetic method of alkyl-β-D- glucopyranosides.
Background technology
Carbohydrate, be a kind of important organic matter widely distributed in nature, also known as carbohydrate, be polyhydroxy aldehyde or
The general name of polyhydroxyketone and its condensation polymer and some derivatives, typically it is made up of three kinds of carbon, hydrogen, oxygen elements.Sugar is broadly divided into four
Major class：Monosaccharide and disaccharide, oligosaccharide and polysaccharide.Carbohydrate is the most important energy substance of human body, energy needed for substance in vivo transport
70% both be from carbohydrate.What research was more at present is monose and disaccharide.
Glucosides, also referred to as glycocide.It is the hemiacetal hydroxyl of monose or oligosaccharides and hydroxyl, amino or the thiol in another molecule
The dehydrations such as base and produce hydrate.Therefore a glucosides can be divided into two parts.A part is that (sugar removes hemiacetal hydroxyl to sugared residue
Base), another part is aglucon (non-saccharide part), and its key is referred to as glycosidic bond.This carbon atom is become after cyclization as intramolecular
Chiral centre, there are two kinds of possible configurations：If oxygen atom can be above or below plane, one so obtained is chiral
Isomers is referred to as：Anomer.If-OH the substituents on anomeric carbon are with CH2OH groups outside ring into anti-configuration (i.e. not in ring
Side) when, then it is referred to as：α anomers；Both another situations are presented cis-configuration, are then referred to as in the same side of ring：The different heads of β
Thing.Due to ring-type sugar and straight chain sugar in itself can mutual inversion of phases, therefore there is balance for two kinds of anomers.In Fischer projection formula, α
Anomer is expressed as：Different head hydroxyl and CH2OH presentations are trans, and β anomers are then to be cis；The glucosides that nature is widely present
It is β-glucosides mostly, and much there is special bioactivity, so as to is responsible for important physiological function.
The method for being typically prepared glucosides is that fatty alcohol and sugar are reacted under conditions of the concentrated sulfuric acid, due to sugar itself knot
Many hydroxyls in structure be present and also have ethylidene ether structure, so reaction condition is than stronger, such as the concentrated sulfuric acid, 100 degrees Celsius, because
This researcher is modified the hydroxyl on anomeric carbon, and the glycosylation of selectivity is carried out using the different property of anomeric carbon.
K-K methods that Koenigs and Knoor are established synthesize β-glucosides of high-purity and high selectivity, and they pass through full second
Acylated glucose and hydrobromic acid reacts to obtain α-acetyl bromo sugar, because bromine atoms are easy under the conditions of existing for silver ion
Leave away so that other nucleopilic reagents such as alcohols, amine, mercaptan etc., it is easy to which attack anomeric carbon obtains β-glucosides, people
The glucoside compound of numerous monose and disaccharide has been synthesized by this method.
At present, octyl group-β-D- glucopyranosides are mainly existed by 2,3,4,6- tetra-acetylated acetylbromoglycoses and octanol
Under the catalysis of silver salt, then remove what acetyl protection base obtained.This method uses noble silver, and the dosage of silver is bigger,
The price of silver salt is higher and not easy to maintain simultaneously, causes cost height and preparation process is cumbersome, in addition 2,3,4,6- tetra- acetyl
Also costly, industrially prepare 2,3,4,6- tetra-acetylated acetylbromoglycoses needs to use hydrogen bromine base acetylbromoglycose price
Acid, environmental pollution are larger.
Also have and got off synthesis in the catalysis of zinc oxide by 2,3,4,6- tetra-acetylated acetylbromoglycoses and octanol, Ci Zhongfang
Method reacts the use of the expensive silver salt avoided compared to K-K, but still needs 2,3,4,6- tetra-acetylated acetylbromoglycoses, difficult
To avoid environmental pollution, and the injury to experimenter's body.
The content of the invention
The purpose of the present invention is overcome the deficiencies in the prior art, there is provided a kind of simple to operate, cost is cheap, environment-friendly
The synthetic method of alkyl-β-D- glucopyranosides.
Technical scheme is summarized as follows：
A kind of synthetic method of alkyl-β-D- glucopyranosides, comprises the following steps：
1) full acetylated glucopyranose, alkyl alcohol and anhydrous stannic chloride are dissolved in anhydrous methylene chloride, in room
Warm lower stirring reaction 20-70 minutes, to be washed with saturation weak base aqueous solution, collect organic phase, vacuum distillation obtains 1- alkyl -2,
3,4,6- tetra-acetylated-β-D- glucopyranosides；
2) 1- alkyls -2,3,4,6- tetra-acetylated-β-D- glucopyranosides are dissolved in methanol, add sodium methoxide and adjust
PH to 9 is saved, is reacted 1.5 hours at room temperature, is adjusted with storng-acid cation exchange resin to neutrality, filtering, filtrate and steams solvent,
Dry, obtain alkyl-β-D- glucopyranosides.
The mol ratio of full acetylated glucopyranose, alkyl alcohol and anhydrous stannic chloride is preferably 1:1:1.
1- alkyls -2,3, the ratio of 4,6- tetra-acetylated-β-D- glucopyranosides and methanol is preferably 100g：500ml.
Alkyl is preferably C8-C12Alkyl.
The ratio of full acetylated glucopyranose and anhydrous methylene chloride is preferably 100g:500ml.
Storng-acid cation exchange resin specification is preferably Dowex-509 or HCRW-20.
Weak base is preferably sodium carbonate, sodium acid carbonate, potassium carbonate or saleratus.
The full acetylated glucopyranose of raw material of the present invention is cheap, and cost is low, while anhydrous stannic chloride
Can commercially mass purchase, avoid use of the prior art using expensive silver salt and zinc oxide, greatly reduce life
Produce cost.The committed step of the present invention is reacted using full acetylated glucopyranose, and a step is saved compared to traditional handicraft
Reaction, while the use of the hydrogen bromide during synthesis of acetyl base acetylbromoglycose is avoided, reduce to operating personnel's
Actual bodily harm also protects environment, and reaction temperature saves the energy close to normal temperature in experimentation, easy to operate.Because simplify
Synthesis technique before, so the yield of alkyl-β-D- glucopyranosides is also correspondingly improved.
Brief description of the drawings
Fig. 1 is that the hydrogen of n-octyl-β-D- glucopyranosides composes spectrogram.
Fig. 2 is that the carbon of n-octyl-β-D- glucopyranosides composes spectrogram.
Embodiment
All raw materials of the present invention, do not have special limitation to its source, commercially buy.
With reference to specific embodiment, the present invention is further illustrated, and embodiments of the invention are in order that this area
Technical staff better understood when the present invention, but the present invention is not imposed any restrictions.
Embodiment 1
A kind of synthetic method of n-octyl-β-D- glucopyranosides, comprises the following steps：
1) weigh (200g, 0.51mol) full acetylated glucopyranose to be dissolved in 1L anhydrous methylene chlorides, and add just pungent
Alcohol (66.7g, 0.51mol), 0.51mol anhydrous stannic chloride is added, stirring reaction 30 minutes, are satisfied with 500ml*3 at room temperature
Washed with aqueous sodium carbonate, collect organic phase, vacuum distillation obtains pale yellowish oil 1- n-octyls -2,3,4,6- tetra- acetyl
Base-β-D- glucopyranosides；
2) the 1- n-octyls -2,3 that will be obtained, 4,6- tetra-acetylated 237 grams of-β-D- glucopyranosides are dissolved in 1.2L methanol
In, it is stirred at room temperature, adds sodium methoxide regulation pH to 9, react 1.5 hours at room temperature, use strongly acidic cation exchange tree
Fat Dowex-509 is adjusted to neutrality, and filtering, filtrate is spin-dried for, obtain n-octyl-β-D- glucopyranosides (81.9g,
0.28mol), yield 55%, and the product of beta comfiguration>97%.
Fig. 1, Fig. 2 are shown in obtained n-octyl-β-D- glucopyranosides detection.
Embodiment 2
A kind of synthetic method of dodecyl-β-D- glucopyranosides, comprises the following steps：
1) full acetylated glucopyranose, dodecyl alcohol and anhydrous stannic chloride are dissolved in anhydrous methylene chloride,
Reaction 20 minutes is stirred at room temperature, is washed with unsaturated carbonate aqueous solutions of potassium, collects organic phase, vacuum distillation obtains 1- positive 12
Alkyl -2,3,4,6- tetra-acetylated-β-D- glucopyranosides；
The mol ratio of full acetylated glucopyranose, dodecyl alcohol and anhydrous stannic chloride is：1:1.2:1.2；
The ratio of full acetylated glucopyranose and anhydrous methylene chloride is 100g:550ml；
2) 1- dodecyls -2,3,4,6- tetra-acetylated-β-D- glucopyranosides are dissolved in methanol, add methanol
Sodium adjusts pH to 9, reacts 1.5 hours at room temperature, is adjusted with storng-acid cation exchange resin Dowex-509 to neutrality, filtering,
Filtrate steams solvent, dries, is detected through nuclear-magnetism, what is obtained is dodecyl-β-D- glucopyranosides.
1- dodecyls -2,3, the ratio of 4,6- tetra-acetylated-β-D- glucopyranosides and methanol is 100g：520ml.
Yield is 57%.And the product of beta comfiguration>97%.
Embodiment 3
A kind of synthetic method of n-nonyl-β-D- glucopyranosides, comprises the following steps：
1) full acetylated glucopyranose, n-nonyl alcohol and anhydrous stannic chloride are dissolved in anhydrous methylene chloride, in room
The lower stirring reaction of temperature 70 minutes, is washed with saturated sodium bicarbonate aqueous solution, collects organic phase, vacuum distillation obtain 1- n-nonyls-
2,3,4,6- tetra-acetylated-β-D- glucopyranosides；
The mol ratio of full acetylated glucopyranose, n-nonyl alcohol and anhydrous stannic chloride is：1:1.1:1；
The ratio of full acetylated glucopyranose and anhydrous methylene chloride is 100g:450ml；
2) 1- n-nonyls -2,3,4,6- tetra-acetylated-β-D- glucopyranosides are dissolved in methanol, add sodium methoxide and adjust
PH to 9 is saved, is reacted 1.5 hours at room temperature, is adjusted to neutrality, filtering, filtrate and steamed with storng-acid cation exchange resin HCRW-20
Go out solvent, dry, detected through nuclear-magnetism, what is obtained is n-nonyl-β-D- glucopyranosides.
1- nonyls -2,3, the ratio of 4,6- tetra-acetylated-β-D- glucopyranosides and methanol is 100g：500ml.
Yield is 54%.And the product of beta comfiguration>97%.
Claims (7)
1. a kind of synthetic method of alkyl-β-D- glucopyranosides, it is characterised in that comprise the following steps：
1) full acetylated glucopyranose, alkyl alcohol and anhydrous stannic chloride are dissolved in anhydrous methylene chloride, at room temperature
Stirring reaction 20-70 minutes, washed with saturation weak base aqueous solution, collect organic phase, be evaporated under reduced pressure and obtain 1- alkyls -2,3,4,
Tetra-acetylated-β-D- the glucopyranosides of 6-；
2) 1- alkyls -2,3,4,6- tetra-acetylated-β-D- glucopyranosides are dissolved in methanol, add sodium methoxide regulation pH
To 9, react 1.5 hours at room temperature, adjusted with storng-acid cation exchange resin to neutrality, filtering, filtrate and steam solvent, done
It is dry, obtain alkyl-β-D- glucopyranosides.
2. according to the method for claim 1, it is characterized in that the full acetylated glucopyranose, alkyl alcohol and anhydrous four
The mol ratio of stannic chloride is 1:1:1.
3. according to the method for claim 1, it is characterized in that the 1- alkyls -2,3,4,6- tetra-acetylated-β-D- pyrans
The ratio of glucoside and methanol is 100g：500ml.
4. according to the method described in claim 1,2 or 3, it is characterized in that the alkyl is C8-C12Alkyl.
According to the method for claim 1,5. it is characterized in that the full acetylated glucopyranose and anhydrous methylene chloride
Than for 100g:500ml.
6. according to the method for claim 1, it is characterized in that the storng-acid cation exchange resin specification is Dowex-509
Or HCRW-20.
7. according to the method for claim 1, it is characterized in that the weak base is sodium carbonate, sodium acid carbonate, potassium carbonate or carbonic acid
Hydrogen potassium.
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| CN103694279A (en) * | 2013-12-23 | 2014-04-02 | 江西苏克尔新材料有限公司 | Preparation method of 2-deoxy-L-ribose |
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Non-Patent Citations (3)
| Title |
|---|
| SnCl4 induced formation of C7–C16-alkyl D-glucopyranosides.;Stanimir Konstantinovic, et al.,;《J. Serb Chem. Soc.》;20011231;第66卷(第2期);第65-71页. * |
| Synthesis of C7-C16-alkyl glycosides in the presence of tin(IV) chloride as Lewis acid catalyst.;Stanimir Konstantinovic, et al.,;《J. Serb Chem. Soc.》;19991231;第64卷(第3期);第169-171页. * |
| 二聚（1→6）-2-脱氧-β-D-氨基吡喃葡萄糖烷基苷的合成.;王文文，;《中国优秀硕士学位论文全文数据库 医药卫生科技辑》;20110615;第E079-26页. * |
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