CN103193570B - High-selectivity protection method of hydroxy - Google Patents
High-selectivity protection method of hydroxy Download PDFInfo
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- CN103193570B CN103193570B CN201310121510.XA CN201310121510A CN103193570B CN 103193570 B CN103193570 B CN 103193570B CN 201310121510 A CN201310121510 A CN 201310121510A CN 103193570 B CN103193570 B CN 103193570B
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Abstract
The invention provides a high-selectivity protection method of hydroxyl. The method comprises the following steps of: dissolving an organic compound containing two or more hydroxys into proper aprotic solvents; adding an acylation reagent which has the molar weight equal to that of the hydroxy requiring protection; adding anionic salt which is of catalytic amount and is low in price and easy to gain; and reacting for sufficient time at proper temperature, thus protecting one or two hydroxys in a two-hydroxy or multi-hydroxy compound along with high selectivity. The high-selectivity protection method of the hydroxyl has the characteristics of being environment-friendly, mid in reaction condition, simple and convenient in operation and high in yield, and the adopted agents are green, environment-friendly, low in price, easy to gain, high in efficiency, etc.
Description
Technical field
The invention belongs to fine chemicals and carbohydrate chemistry synthesis technical field, relating to is the method for specific hydroxyl in a kind of selective protection sugar of simple and effective or polyol.
Background technology
In organic synthesis technology, for the reactant that has a plurality of similar reactive behavioies site, selective protection is a kind of important and conventional skill often.Particularly, in carbohydrate chemistry is synthetic, there are two or more hydroxyls that reactive behavior is close in glycan molecule conventionally, and for the sugared building block of preparing valuable sugar compounds intermediate and synthesizing for oligosaccharides, the selective protection of sugared hydroxyl is always one of focus of research.Example in Application in Chemical Engineering is as the synthesis of Sucralose by using monoesterification (Chinese patent 01106626.1).Wherein the preparation of sucrose 6-monoesters intermediate has adopted the method for 6 hydroxyls of selective esterification sucrose.The high-purity mono-glycerides of the most widely used emulsifying agent in food chemistry, its molecular structure is also that a primary hydroxyl of glycerine is by lipid acid selective esterification.
To carry out the protection of highly selective to the close hydroxyl of a plurality of reactive behavioies of sugar, often need to utilize solid and stereoelectronic effect (Dong, the H. of glycan molecule itself; Zhou, Y.X.; Pan, X.L.; Cui, F.C.; Liu, W.Liu, J.Y.;
o.J.Org.Chem.2012,77,1457), and rely on some special reagent.Wherein modal class methods are by using organotin reagent (Grindley, T.B., Adv.Carbohyd.Chem.Bi.1998,53,17), for a certain site or a plurality of sites highly selective of the glycan molecule of isomorphism type are not introduced blocking group.Its reaction relating to comprises the multiclass protective reactions such as the acylations, ether, silicon ether, sulfonylation of sugared hydroxyl.The organotin reagent using is mainly tributyltin oxide and Dibutyltin oxide.As everyone knows, for the severe poisonous chemicals that country keeps under strict control, there is serious environmental hazard problem ， developed country in butyl tin compounds, and the use of organotin is strictly controlled especially.So more green method, comprises the organoboron reagent (Lee, the D. that use catalytic amount; Taylor, M.S.J.Am.Chem.Soc.2011,133,3724), use organosilicon reagent (Zhou, the Y.X. of nontoxic or micro-poison; Ramstrom, O.; Dong, H., Chem.Commun.2012,48,5370), etc. method, in succession developed.Yet still there is such or such shortcoming in these methods on the ease for use of reaction conditions, reaction and cost.Although used the organoboron reagent of catalytic amount as organic boron method, must use a large amount of organic basess to be used as acid binding agent simultaneously.Organosilicon method operational condition is harsh.So develop a kind of green, the existing important scientific research value of easy, efficient selectivity hydroxyl protection method, have again great actual application value.
Summary of the invention
Task of the present invention is to provide the guard method of a kind of hydroxyl highly selective, makes that it has environmental friendliness, reaction conditions is gentle, easy and simple to handle, yield is high, and agents useful for same not only environmental protection but also the feature such as cheap and easy to get, efficient.
Realizing technical scheme of the present invention is:
This hydroxyl highly selective provided by the invention guard method comprises the following steps:
Step 1: the organic compound that contains two above hydroxyls is dissolved in to aprotic solvent, and containing two above organic compound of hydroxyl and the amount ratio of aprotic solvent is 2-4 milliliter/mmole;
Step 2: add acylating reagent, acylating reagent is 1.0～1.5:1 with needing the hydroxyl mol ratio of protection, is preferably 1.1:1;
Step 3: adding anion salt is catalyzer again; anion salt is 0.1-0.6:1 with needing the hydroxyl mol ratio of protection; be preferably 0.3:1; in 0～50 ° of C, be preferably in room temperature reaction after 6～24 hours, decompression desolventizes; be isolated to the product that hydroxyl is protected by highly selective; the described concrete grammar that is isolated to the product that hydroxyl protected by highly selective is: solvent evaporated, crystallization in methyl alcohol, the separated dry product that hydroxyl is protected by highly selective that obtains.
Aprotic solvent described in above-mentioned steps one can be C
1～C
4alkyl chloride, acetonitrile, benzene, toluene, tetrahydrofuran (THF), acetone, dimethyl formamide, dimethyl sulfoxide (DMSO) in a kind of or mixed solvent of two kinds wherein, be preferably acetonitrile or tetrahydrofuran (THF).
Acylating reagent described in above-mentioned steps two can be Acetyl Chloride 98Min., diacetyl oxide, chloroacetyl chloride, Benzoyl chloride or benzoyl oxide, is preferably diacetyl oxide.
Anion salt described in above-mentioned steps three is the compound with following chemical general formula:
M
+X
-
In formula:
M
+can be sodium ion, potassium ion, strontium ion, tetramethyl-amine ion, tetraethyl-amine ion, tetrapropyl amine ion or 4-butyl amine ion; Be preferably 4-butyl amine ion;
X
-can be fluorion, chlorion, bromide anion, acetate ion, benzoate anion ion or cryanide ion, be preferably acetate ion.
The contriver of patent application of the present invention finds under study for action; a kind of substrate that contains two adjacent hydroxyls is dissolved in a kind of aprotic solvent; add with the molar weight of substrate and compare excessive a little acylating reagent; and then add a kind of anion salt of catalytic amount; through room temperature to 40 ° C reaction after 12 hours, our high yield obtained a kind of specific hydroxyl by the product of highly selective acidylate.Because this method reaction conditions is gentle, easy and simple to handle, selectivity is good, yield is high, and not only environmental protection but also cheap and easy to get of agents useful for same, impel us to the method, to carry out extensive and deep research.
In the inventive method, the object that adds anion salt is to utilize negatively charged ion and hydroxyl to generate hydrogen bond, thereby activate this hydroxyl, makes it to occur acylation reaction, and its mechanism is as follows:
Based on above-mentioned mechanism, anion salt must have good solvability in selected solvent, so in acetonitrile and tetrahydrofuran solution, preferably select the tetrabutyl amine salt of fluorion, chlorion, bromide anion, acetic acid ion.And in DMF, also can select the metallic cation salt such as Potassium monofluoride, Sodium Fluoride, cesium fluoride, sodium-chlor, Repone K, sodium-acetate, Potassium ethanoate.The electronegativity of negatively charged ion is stronger, and the hydrogen bond that itself and hydroxyl generate is just stronger, and its acylation reaction of the hydroxyl being activated by hydrogen bond is active just higher.So use fluorion when improving reactive behavior, also reduced the selectivity of reaction; Use bromide anion reactive behavior lower, therefore must at high temperature react just, can carry out.
Aspect the selection of substrate, we had both selected the multiple substrate that contains two adjacent hydroxyls, had also selected multiple poly-hydroxy substrate.Selecting of aprotic solvent is the accessibility of considering when it desolventizes the solvability of selected substrate and aftertreatment.Although DMF has better solvability to reaction substrate, post-reaction treatment is inconvenient.The result considering, reaction solvent is preferably acetonitrile and tetrahydrofuran (THF).
The acylating reagent adding in the inventive method can be Acetyl Chloride 98Min., diacetyl oxide, chloroacetyl chloride, Benzoyl chloride or benzoyl oxide, and acylating reagent is 1.0-1.5 with the molar ratio of the hydroxyl of protecting, and is preferably 1.1.In the time of acylating reagent protection hydroxyl, can discharge the negatively charged ion identical with used catalyst, so the anion salt adding and sugared molar ratio can be between 0.1-1.0, molar ratio is preferably 0.3-0.6.
In the present invention, selected multiple sugar and polyol to carry out testing (in Table 1); select acetonitrile as reaction solvent; 1.1 times will be protected the diacetyl oxide of hydroxyl molar weight is acylating reagent; the tetrabutylphosphoniuacetate acetate amine of 0.6 molar equivalent is catalyzer; 40 ° of C reactions 6～24 hours, reaction result saw the following form:
Table 1: the hydroxyl highly selective acylation test-results that the acetate ion that the present invention carries out promotes:
More than the yield of test is shown in the reactant of sequence number 11 row except compound 21(), yield, all more than 85%, illustrates that the inventive method has versatility and higher selectivity.
In sum, the invention reside in the hydroxyl selective protection method who discloses a kind of environmental friendliness, reaction conditions gentleness, simple and effective.According to the present invention; the organic compound that contains two or more hydroxyls is dissolved in to aprotic solvent; the consumption of solvent is 2～4 milliliters/mmole substrate; then add acylating reagent, acylating reagent is 1.1:1 with needing the hydroxyl mol ratio of protection, then to add anion salt be catalyzer; anion salt is 0.3～0.6:1 with needing the hydroxyl mol ratio of protection; 0～50 ° of C reacts 6～24 hours, then desolventizes through decompression, and product can obtain through separation the product that hydroxyl is protected by highly selective.The inventive method has environmental friendliness, reaction conditions is gentle, easy and simple to handle, yield is high, and agents useful for same not only environmental protection but also the advantage such as cheap and easy to get, efficient.
Accompanying drawing explanation
Fig. 1: the mechanism of negatively charged ion activation acylated hydroxy reaction.
Embodiment
The invention will be further described for following embodiment, but scope involved in the present invention is not limited to following cited mode.
Example 1 to 7 is the embodiment of the selective protection containing two adjacent oxy-compound
Example 1: reaction solvent is acetonitrile, catalyzer is tetrabutylphosphoniuacetate acetate amine
Take 1 gram of methyl-4,6-benzylidene-alpha-D-glucose glycosides is dissolved in 10 milliliters of acetonitriles, add 0.64 gram of tetrabutylammonium acetate amine and 0.37 milliliter of acetyl acid anhydride, at 40 ℃, react 12 hours, solvent evaporated, crystallization in methyl alcohol, separated pure methyl-2-acetic ester-4 that are dried to obtain, 1 gram of 6-benzylidene-alpha-D-glucose glycosides, yield 87%.
Example 2: reaction solvent is acetonitrile, catalyzer is bromination 4-butyl amine
Take 1 gram of methyl-4,6-benzylidene-alpha-D-glucose glycosides is dissolved in 10 milliliters of acetonitriles, add 0.64 gram of four butyl bromation amine and 0.37 milliliter of acetyl acid anhydride, reflux 24 hours, solvent evaporated, crystallization in methyl alcohol, separated pure methyl-2-acetic ester-4 that are dried to obtain, 0.6 gram of 6-benzylidene-alpha-D-glucose glycosides, yield 52%.
Example 3: reaction solvent is acetonitrile, and catalyzer is for fluoridizing 4-butyl amine
Take 1 gram of methyl-4,6-benzylidene-alpha-D-glucose glycosides is dissolved in 9 milliliters of acetonitriles, the tetrabutyl fluoride amine tetrahydrofuran solution and the 0.37 milliliter of acetyl acid anhydride that add 1 milliliter of 1M, 0 ° of C reacts 8 hours, solvent evaporated, crystallization in methyl alcohol, separated pure methyl-2-acetic ester-4 that are dried to obtain, 0.7 gram of 6-benzylidene-alpha-D-glucose glycosides, yield 61%.
Example 4: reaction solvent is tetrahydrofuran (THF), catalyzer is tetrabutylphosphoniuacetate acetate amine
Take 1 gram of methyl-4,6-benzylidene-alpha-D-glucose glycosides is dissolved in 6 milliliters of tetrahydrofuran (THF)s, add 0.4 gram of tetrabutylammonium acetate amine and 0.37 milliliter of acetyl acid anhydride, at 40 ℃, react 12 hours, solvent evaporated, crystallization in methyl alcohol, separated pure methyl-2-acetic ester-4 that are dried to obtain, 0.95 gram of 6-benzylidene-alpha-D-glucose glycosides, yield 83%.
Example 5: reaction solvent is acetonitrile, catalyzer is tetrabutylphosphoniuacetate acetate amine
Take 1 gram of methyl-4,6-benzylidene-β-D-Glucose glycosides is dissolved in 10 milliliters of acetonitriles, add 0.64 gram of tetrabutylammonium acetate amine and 0.37 milliliter of acetyl acid anhydride, at 40 ℃, react 12 hours, solvent evaporated, crystallization in methyl alcohol, separated pure methyl-2-acetic ester-4 that are dried to obtain, 0.94 gram of 6-benzylidene-β-D-Glucose glycosides, yield 82%.
Example 6: reaction solvent is tetrahydrofuran (THF), catalyzer is tetrabutylphosphoniuacetate acetate amine
Take 1 gram of phenylglycol and be dissolved in 10 milliliters of tetrahydrofuran (THF)s, add 1 gram of tetrabutylammonium acetate amine and 0.76 milliliter of acetyl acid anhydride, at 40 ℃, react 12 hours, solvent evaporated, rectification under vacuum obtains 1.1 grams of phenylglycol-2-acetic ester, yield 84%.
Example 7: reaction solvent is dimethyl formamide, catalyzer is sodium-acetate
Take 1 gram of methyl-4,6-benzylidene-β-D-Glucose glycosides is dissolved in 4 milliliters of dimethyl formamides, add 0.1 gram of sodium-acetate and 0.37 milliliter of acetyl acid anhydride, at 40 ℃, react 12 hours, solvent evaporated, crystallization in methyl alcohol, separated pure methyl-2-acetic ester-4 that are dried to obtain, 0.9 gram of 6-benzylidene-β-D-Glucose glycosides, yield 78%.
The embodiment of the selective protection that example 8 to embodiment 12 is polyol
Example 8: reaction solvent is dimethyl formamide, catalyzer is Potassium monofluoride
Take 1 gram of methyl-alpha-D-glucose glycosides and be dissolved in 5 milliliters of dimethyl formamides, add 1 gram of Potassium monofluoride and 1.5 milliliters of Benzoyl chlorides, at 40 ℃, react 12 hours, solvent evaporated, crystallization in methyl alcohol, separation is dried and obtains pure methyl-3,1.5 grams of 6-dibenzoate glucosides, yield 73%.
Example 9: reaction solvent is dimethyl formamide, catalyzer is potassium benzoate
Take 1 gram of anhydrous glycerol and be dissolved in 5 milliliters of dimethyl formamides, add 0.5 gram of potassium benzoate and 1.5 milliliters of Benzoyl chlorides, at 50 ℃, react 12 hours; solvent evaporated, crystallization in methyl alcohol, directly separated with chromatography column after concentrating under reduced pressure; obtain 1-benzoyl monoglyceride 1.3g, yield 90%.
Example 10: reaction solvent is tetrahydrofuran (THF), catalyzer is tetrabutylphosphoniuacetate acetate amine
Take 1 gram of methyl-β-D-Glucose glycosides and be dissolved in 10 milliliters of tetrahydrofuran (THF)s, add 0.9 gram of tetrabutylphosphoniuacetate acetate amine and 1 ml acetic anhydride, at 40 ℃, react 12 hours, solvent evaporated, crystallization in methyl alcohol, separation is dried and obtains pure methyl-3,1.1 grams of 6-diacetate esters glucosides, yield 82%.
Example 11: reaction solvent is acetonitrile, catalyzer is tetrabutylphosphoniuacetate acetate amine
Take 1 gram of methyl-β-D-galactoside and be dissolved in 10 milliliters of acetonitriles, add 0.9 gram of tetrabutylphosphoniuacetate acetate amine and 1 ml acetic anhydride, at 40 ℃, react 16 hours, solvent evaporated, crystallization in methyl alcohol, separation is dried and obtains pure methyl-3,1.1 grams of 6-diacetate esters galactosides, yield 82%.
Example 12: reaction solvent is mixed solvent, catalyzer is tetrabutylphosphoniuacetate acetate amine
Taking 1 gram of methyl-β-D-xyloside is dissolved in the mixed solvent of 2 milliliters of dimethyl formamides and 8 milliliters of acetonitriles, add 0.6 gram of tetrabutylphosphoniuacetate acetate amine and 0.6 ml acetic anhydride, room temperature reaction 16 hours, solvent evaporated, crystallization in methyl alcohol, 1.1 grams of separated dry pure methyl-3-acetic ester xylosides, yield 88%.
Claims (9)
1. a hydroxyl highly selective guard method, comprises the following steps:
Step 1: the organic compound that contains two above hydroxyls is dissolved in to aprotic solvent, and aprotic solvent is 2-4 milliliter/mmole with the amount ratio of the compound that contains two above hydroxyls;
Step 2: add acylating reagent, acylating reagent is 1.0-1.5 with needing the hydroxyl mol ratio of protection
﹕1;
Step 3: adding anion salt is catalyzer again, anion salt is 0.1-0.6 with needing the hydroxyl mol ratio of protection
﹕1, in 0～50
oc reaction is after 6～24 hours, and decompression desolventizes, and is isolated to the product that hydroxyl is protected by highly selective;
Anion salt described in step 3 is the compound with following chemical general formula:
M
+ X
-
In above formula:
M
+ sodium ion, potassium ion, strontium ion, tetramethyl-amine ion, tetraethyl-amine ion, tetrapropyl amine ion or 4-butyl amine ion;
X
-fluorion, chlorion, bromide anion, acetate ion, benzoate anion ion or cryanide ion.
2. hydroxyl highly selective according to claim 1 guard method; it is characterized in that; the concrete grammar that is isolated to the product that hydroxyl protected by highly selective described in step 3 is: solvent evaporated, crystallization in methyl alcohol, the separated dry product that hydroxyl is protected by highly selective that obtains.
3. hydroxyl highly selective according to claim 1 guard method, is characterized in that, the aprotic solvent described in step 1 is C
1～C
4alkyl chloride, acetonitrile, benzene, toluene, tetrahydrofuran (THF), acetone, dimethyl formamide, dimethyl sulfoxide (DMSO) in a kind of or mixed solvent of two kinds wherein.
4. method according to claim 1, is characterized in that, the aprotic solvent described in step 1 is acetonitrile or tetrahydrofuran (THF).
5. method according to claim 1, is characterized in that, the acylating reagent described in step 2 is Acetyl Chloride 98Min., diacetyl oxide, chloroacetyl chloride, Benzoyl chloride or benzoyl oxide.
6. method according to claim 1, is characterized in that, the acylating reagent described in step 2 is diacetyl oxide.
7. method according to claim 1, is characterized in that, in step 3: anion salt is 0.3 with needing the hydroxyl mol ratio of protection
﹕1, temperature of reaction is room temperature.
8. method according to claim 1, is characterized in that, the anion salt described in step 3 is the compound with following chemical general formula:
M
+ X
-
In above formula: M
+ it is 4-butyl amine; X
-it is acetate ion.
9. method according to claim 1, is characterized in that, in step 2, acylating reagent is 1.1 with needing the hydroxyl mol ratio of protection
﹕1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245058A (en) * | 1999-06-11 | 2008-08-20 | 沃泰克斯药物股份有限公司 | Inhibitors of aspartyl protease |
| CN101402619A (en) * | 2008-11-21 | 2009-04-08 | 中国药科大学 | Novel 2-deoxidizedfructofuranose derivative, preparation method and medical uses thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245058A (en) * | 1999-06-11 | 2008-08-20 | 沃泰克斯药物股份有限公司 | Inhibitors of aspartyl protease |
| CN101402619A (en) * | 2008-11-21 | 2009-04-08 | 中国药科大学 | Novel 2-deoxidizedfructofuranose derivative, preparation method and medical uses thereof |
Non-Patent Citations (2)
| Title |
|---|
| Geraldine Blatter.the use of 2-deoxy-2-trichloroacetamido-D-glucopyranose derivatives in synthesess of oligosaccharides.《Carbohydrate Research》.1994,(第260期), |
| the use of 2-deoxy-2-trichloroacetamido-D-glucopyranose derivatives in synthesess of oligosaccharides;Geraldine Blatter;《Carbohydrate Research》;19941231(第260期);全文 * |
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Application publication date: 20130710 Assignee: Hubei Laifeng Tengshen Flavor Chemical Co., Ltd. Assignor: Huazhong University of Science and Technology Contract record no.: 2015420000091 Denomination of invention: High-selectivity protection method of hydroxy Granted publication date: 20140122 License type: Exclusive License Record date: 20150603 |
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