CN103254253B - A kind of method preparing diacetone-D-allose - Google Patents
A kind of method preparing diacetone-D-allose Download PDFInfo
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- CN103254253B CN103254253B CN201310223010.7A CN201310223010A CN103254253B CN 103254253 B CN103254253 B CN 103254253B CN 201310223010 A CN201310223010 A CN 201310223010A CN 103254253 B CN103254253 B CN 103254253B
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Abstract
The present invention relates to sugar compounds field, be specifically related to a kind of method preparing diacetone-D-allose.Dissolve Tetrabutyl amonium bromide, Potassium Bromide, tetramethyl piperidine oxynitride, adds organic solvent, diacetoneglucose and hydrogen peroxide, is obtained by reacting 1,2; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose solution, aftertreatment obtains 1, and 2; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose; Dissolve, add sodium borohydride and stir, be obtained by reacting 1,2:5,6-bis--oxygen-Ya isopropyl-α-D-allofuranose solution, obtains 1,2:5 through aftertreatment, 6-bis--oxygen-Ya isopropyl-α-D-allofuranose.The inventive method, by one-step synthesis method diacetone-D-allose, improves purity and the yield of product effectively; Simple to operate, raw material is easy to get, and has saved running cost and material.
Description
Technical field
The present invention relates to sugar compounds field, be specifically related to a kind of method preparing diacetone-D-allose.
Background technology
Diacetone-D-allose, also known as 1,2:5,6-bis--oxygen-Ya isopropyl-α-D-allofuranose, English name: 1,2:5,6-Di-O-isopropylidene-alpha-D-allofuranose, No. CAS: 2595-05-3, molecular formula: C
12h
20o
6, structural formula is as follows:
In the prior art, the polite oxidation of general employing (Swern oxidation) reaction, such as: oxalyl chloride, methyl-sulphoxide reacts and diacetoneglucose is oxidized generation 1,2 in methylene dichloride; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose, then adopt reductive agent by 1,2; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose is reduced into 1,2:5,6-bis--oxygen-Ya isopropyl-α-D-allofuranose.As patent CN102268048A, all existence condition is harsher for above-mentioned this method, such as temperature requirement-78 DEG C, step complex operation, the required treatment time and step many, the shortcomings such as productive rate is low, and by product is many.
Summary of the invention
In order to solve the step complex operation existed in the preparation of diacetone-D-allose in above prior art, required treatment time and step is many, productive rate is low problem, the invention provides and a kind ofly adopt single stage method, the method preparing diacetone-D-allose that simple to operate, raw material is easy to get.
The present invention is achieved by the following measures:
Prepare a method for diacetone-D-allose, comprise the following steps:
A) use water dissolution Tetrabutyl amonium bromide, Potassium Bromide, tetramethyl piperidine oxynitride, add organic solvent, stir after add diacetoneglucose, 5-10 DEG C adds hydrogen peroxide, is obtained by reacting 1,2 at 10-15 DEG C; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose solution, aftertreatment obtains 1, and 2; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose;
B) by 1,2; 5,6-bis--bis-isopropylidene-α-D-3-hexanone ribofuranose dissolves, be divided into 10 batches at 10-16 DEG C and add sodium borohydride stirring, often criticize interval 5 minutes, be obtained by reacting 1,2:5,6-bis--oxygen-Ya isopropyl-α-D-allofuranose solution, 1,2:5 is obtained, 6-bis--oxygen-Ya isopropyl-α-D-allofuranose through aftertreatment.
Described method, described diacetoneglucose: Tetrabutyl amonium bromide: tetramethyl piperidine oxynitride: the mol ratio of hydrogen peroxide is 1:0.01-0.1:0.02:1.5-2.0.
Described method, the mol ratio of diacetoneglucose and sodium borohydride is 1:0.1-0.4.
Described method, the mol ratio of tetramethyl piperidine oxynitride and Potassium Bromide is 20:87.
Described method, in step a, the reaction times is 2-4 hour, and in step b, the reaction times is 0.5-2 hour.
Described method, in step a, aftertreatment is for being separated organic phase, aqueous phase organic solvent extraction, merges organic phase, evaporate to dryness.
Described method, in step b, aftertreatment is evaporate to dryness 1,2:5,6-bis--oxygen-Ya isopropyl-α-D-allofuranose solution, and add water and organic solvent extraction, organic phase carries out drying, adds mixed solvent crystallization, dry.
Described method, in step a, described organic solvent is methylene dichloride or chloroform.
Described method, organic solvent is methylene dichloride or chloroform, and water and organic solvent mol ratio are 1:1.
Described method, mixed solvent is mol ratio is the ethyl acetate of 2:8-9 and the solvent mixture of isohexane.
Beneficial effect: the inventive method adopts different reaction systems, comprises catalyzer etc., by means of only one-step synthesis method diacetone-D-allose, improves purity and the yield of product effectively; Simple to operate, raw material is easy to get, and has saved running cost and material.
Embodiment
In order to further understand the present invention, be described below in conjunction with the process of specific embodiment to this programme, but should be appreciated that these describe just in order to further instruction the features and advantages of the present invention, instead of limiting to the claimed invention.
embodiment 1
A) with 300mol water dissolution 0.05mol Tetrabutyl amonium bromide, 0.087mol Potassium Bromide, 0.02mol tetramethyl piperidine oxynitride; add 70mol methylene dichloride, add 1mol diacetoneglucose after stirring, 10 DEG C add 1.5mol hydrogen peroxide; within 2 hours, 1 is obtained, 2 10-15 DEG C of reaction; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose solution, aftertreatment obtains 1, and 2; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose;
B) by 1,2; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose is dissolved in Virahol, stirs and is cooled to 10 DEG C, be divided into 10 batches and add the stirring of 0.2mol sodium borohydride, often criticize 0.02mol, often criticize interval 5 minutes, add rear stirring 1h, TLC display reaction to complete, obtain 1,2:5,6-bis--oxygen-Ya isopropyl-α-D-allofuranose solution, obtains 0.743mol1 through aftertreatment, 2:5,6-bis--oxygen-Ya isopropyl-α-D-allofuranose, purity 98.74%, yield is 74.3%.
In step a, aftertreatment for being separated organic phase, can extracting aqueous phase with organic solvent 70mol methylene dichloride, merging organic phase, evaporate to dryness.Also can be other post processing mode, as long as can the above results be reached, just can use.
In step b, aftertreatment is 40 DEG C of solvent evaporated, adds 25mol water and 25mol dichloromethane extraction, dry organic phase, evaporate to dryness organic phase, adds 2mol ethyl acetate and 8mol isohexane stirring and crystallizing, filtration drying after 2h.
embodiment 2
A) with 300mol water dissolution 0.06mol Tetrabutyl amonium bromide, 0.087mol Potassium Bromide, 0.02mol tetramethyl piperidine oxynitride; add 70mol methylene dichloride, add 1mol diacetoneglucose after stirring, 10 DEG C add 1.5mol hydrogen peroxide; within 2 hours, 1 is obtained, 2 10-15 DEG C of reaction; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose solution, aftertreatment obtains 1, and 2; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose;
B) by 1,2; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose is dissolved in Virahol, stirs and is cooled to 10 DEG C, be divided into 10 batches and add the stirring of 0.2mol sodium borohydride, often criticize 0.02mol, often criticize interval 5 minutes, add rear stirring 1h, TLC display reaction to complete, obtain 1,2:5,6-bis--oxygen-Ya isopropyl-α-D-allofuranose solution, obtains 0.747mol1 through aftertreatment, 2:5,6-bis--oxygen-Ya isopropyl-α-D-allofuranose, purity 98.96%, yield is 74.7%.
In step a, aftertreatment for being separated organic phase, can extracting aqueous phase with organic solvent 70mol methylene dichloride, merging organic phase, evaporate to dryness.Also can be other post processing mode, as long as can the above results be reached, just can use.
In step b, aftertreatment is 40 DEG C of solvent evaporated, adds 25mol water and 25mol dichloromethane extraction, dry organic phase, evaporate to dryness organic phase, adds 2mol ethyl acetate and 9mol isohexane stirring and crystallizing, filtration drying after 2h.
embodiment 3
A) with 3000mol water dissolution 0.6mol Tetrabutyl amonium bromide, 0.87mol Potassium Bromide, 0.2mol tetramethyl piperidine oxynitride; add 700mol methylene dichloride, add 10mol diacetoneglucose after stirring, 10 DEG C add 15mol hydrogen peroxide; within 2 hours, 1 is obtained, 2 10-15 DEG C of reaction; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose solution, aftertreatment obtains 1, and 2; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose;
B) by 1,2; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose is dissolved in Virahol, stirs and is cooled to 10 DEG C, be divided into 10 batches and add the stirring of 2mol sodium borohydride, often criticize 0.2mol, often criticize interval 5 minutes, add rear stirring 1h, TLC display reaction to complete, obtain 1,2:5,6-bis--oxygen-Ya isopropyl-α-D-allofuranose solution, obtains 7.51mol1 through aftertreatment, 2:5,6-bis--oxygen-Ya isopropyl-α-D-allofuranose, purity 98.88%,, yield is 75.1%.
In step a, aftertreatment for being separated organic phase, can extracting aqueous phase with organic solvent 700mol methylene dichloride, merging organic phase, evaporate to dryness.Also can be other post processing mode, as long as can the above results be reached, just can use.
In step b, aftertreatment is 40 DEG C of solvent evaporated, adds 250mol water and 250mol dichloromethane extraction, dry organic phase, evaporate to dryness organic phase, adds 20mol ethyl acetate and 80mol isohexane stirring and crystallizing, filtration drying after 2h.
embodiment 4
A) with 3000mol water dissolution 0.1mol Tetrabutyl amonium bromide, 0.87mol Potassium Bromide, 0.2mol tetramethyl piperidine oxynitride; add 700mol methylene dichloride, add 10mol diacetoneglucose after stirring, 10 DEG C add 20mol hydrogen peroxide; within 2 hours, 1 is obtained, 2 10-15 DEG C of reaction; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose solution, aftertreatment obtains 1, and 2; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose;
B) by 1,2; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose is dissolved in Virahol, stirs and is cooled to 10 DEG C, be divided into 10 batches and add the stirring of 2mol sodium borohydride, often criticize 0.2mol, often criticize interval 5 minutes, add rear stirring 1h, TLC display reaction to complete, obtain 1,2:5,6-bis--oxygen-Ya isopropyl-α-D-allofuranose solution, obtains 7.46mol1 through aftertreatment, 2:5,6-bis--oxygen-Ya isopropyl-α-D-allofuranose, yield is 74.6%.
In step a, aftertreatment for being separated organic phase, can extracting aqueous phase with organic solvent 700mol methylene dichloride, merging organic phase, evaporate to dryness.Also can be other post processing mode, as long as can the above results be reached, just can use.
In step b, aftertreatment is 40 DEG C of solvent evaporated, adds 250mol water and 250mol dichloromethane extraction, dry organic phase, evaporate to dryness organic phase, adds 20mol ethyl acetate and 80mol isohexane stirring and crystallizing, filtration drying after 2h.
embodiment 5
A) with 3000mol water dissolution 1mol Tetrabutyl amonium bromide, 0.87mol Potassium Bromide, 0.2mol tetramethyl piperidine oxynitride; add 700mol methylene dichloride, add 10mol diacetoneglucose after stirring, 10 DEG C add 20mol hydrogen peroxide; within 2 hours, 1 is obtained, 2 10-15 DEG C of reaction; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose solution, aftertreatment obtains 1, and 2; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose;
B) by 1,2; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose is dissolved in Virahol, stirs and is cooled to 10 DEG C, be divided into 10 batches and add the stirring of 2.2mol sodium borohydride, often criticize 0.2mol, often criticize interval 5 minutes, add rear stirring 1h, TLC display reaction to complete, obtain 1,2:5,6-bis--oxygen-Ya isopropyl-α-D-allofuranose solution, obtains 7.63mol1 through aftertreatment, 2:5,6-bis--oxygen-Ya isopropyl-α-D-allofuranose, purity 98.93%, yield is 76.3%.
In step a, aftertreatment for being separated organic phase, can extracting aqueous phase with organic solvent 700mol methylene dichloride, merging organic phase, evaporate to dryness.Also can be other post processing mode, as long as can the above results be reached, just can use.
In step b, aftertreatment is 40 DEG C of solvent evaporated, adds 250mol water and 250mol dichloromethane extraction, dry organic phase, evaporate to dryness organic phase, adds 20mol ethyl acetate and 80mol isohexane stirring and crystallizing, filtration drying after 2h.
Claims (5)
1. prepare a method for diacetone-D-allose, it is characterized in that comprising the following steps:
A) use water dissolution Tetrabutyl amonium bromide, Potassium Bromide, tetramethyl piperidine oxynitride, add methylene dichloride or chloroform, stir after add diacetoneglucose, 5-10 DEG C adds hydrogen peroxide, is obtained by reacting 1,2 at 10-15 DEG C; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose solution, aftertreatment obtains 1, and 2; 5,6-, bis--bis-isopropylidene-α-D-3-hexanone ribofuranose;
B) by 1,2; 5,6-bis--bis-isopropylidene-α-D-3-hexanone ribofuranose dissolves, be divided into 10 batches at 10-16 DEG C and add sodium borohydride stirring, often criticize interval 5 minutes, be obtained by reacting 1,2:5,6-bis--oxygen-Ya isopropyl-α-D-allofuranose solution, 1,2:5 is obtained, 6-bis--oxygen-Ya isopropyl-α-D-allofuranose through aftertreatment;
Described diacetoneglucose: Tetrabutyl amonium bromide: tetramethyl piperidine oxynitride: the mol ratio of hydrogen peroxide is 1:0.01-0.1:0.02:1.5-2.0, the mol ratio of diacetoneglucose and sodium borohydride is 1:0.2-0.22, and the mol ratio of tetramethyl piperidine oxynitride and Potassium Bromide is 20:87.
2. method according to claim 1, is characterized in that in step a, and the reaction times is 2-4 hour, and in step b, the reaction times is 0.5-2 hour.
3. method according to claim 1, is characterized in that in step a, aftertreatment, for being separated organic phase, aqueous phase methylene dichloride or chloroform extraction, merges organic phase, evaporate to dryness.
4. method according to claim 1, it is characterized in that in step b, aftertreatment is evaporate to dryness 1,2:5,6-bis--oxygen-Ya isopropyl-α-D-allofuranose solution, add water and organic solvent extraction, organic phase carries out drying, adds mixed solvent crystallization, dry;
Organic solvent is methylene dichloride or chloroform, and water and organic solvent mol ratio are 1:1.
5. method according to claim 4, is characterized in that, mixed solvent is mol ratio is the ethyl acetate of 2:8-9 and the solvent mixture of isohexane.
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