CN105330704B - The preparation method of 2-deoxy-D-glucose - Google Patents

The preparation method of 2-deoxy-D-glucose Download PDF

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CN105330704B
CN105330704B CN201510780244.0A CN201510780244A CN105330704B CN 105330704 B CN105330704 B CN 105330704B CN 201510780244 A CN201510780244 A CN 201510780244A CN 105330704 B CN105330704 B CN 105330704B
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deoxy
glucose
preparation
chloride
anhydride
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CN105330704A (en
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袁文蛟
王立晖
刘雅莉
王静
刘美玲
齐菲
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Tianjin Modern Vocational Technology College
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
    • C07H3/08—Deoxysugars; Unsaturated sugars; Osones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives

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Abstract

The present invention provides a kind of preparation methods of 2-deoxy-D-glucose; the following steps are included: (1) promotor, sulfoxide and water are added into chemical compounds I; after fully reacting; reaction solution is filtered, is concentrated, recrystallize after obtain compound ii; wherein, substituent R is formoxyl, acetyl group, propiono, benzoyl, benzyl or dimethyl tertiary butyl silicon substrate；(2) after being deprotected compound ii, 2-deoxy-D-glucose is obtained after recrystallization.The preparation method of 2-deoxy-D-glucose of the present invention is using the glucose malt sugar protected as starting material, and by catalyzing hydrolysis, deprotection, only 2 Walk react, and 2-deoxy-D-glucose can be made.In preparation process, reaction condition is mild, and reaction reagent is easy to get, and reaction yield is high, and purification of intermediate method is simple and easy, and final products purity is high has wide commercial application prospect.

Description

The preparation method of 2-deoxy-D-glucose
Technical field
The invention belongs to drug production fields, more particularly, to a kind of preparation method of 2-deoxy-D-glucose.
Background technique
Desoxysugar has important biological function, and the 2-deoxyribosyl skeleton composition part important as DNA loses biology The complete and transmitting of communication breath has important biological function.Other aspects, desoxysugar frequently appear in cardiac glycoside, antibiotic and resist Research is found to have in the compound of obvious biological activity among cancer drug, the kinetic property of sugar chain portion regulating medicine, It plays an important role in the identification of the transhipment of drug, drug and action target spot.Wherein, 2-deoxy-D-glucose is not only many The composition segment of bioactive substance, itself also has multiple biological activities, is widely applied to drug, food and agricultural Field.2-deoxy-D-glucose is studied to be found to have the effect for resisting a variety of viruses；Meanwhile 2-deoxy-D-glucose is also demonstrate,proved It is bright to have the function of inhibiting Several Kinds of Malignancy；2-deoxy-D-glucose can be used as food additives use；The Portugal 2- deoxidation-D- Grape sugar be also widely applied to agricultural production such as it can inhibit the corruption of fruits and vegetables, improve and produce the conversion of meat poultry The effects of rate.
Since 2-deoxy-D-glucose is less in nature, mainly obtained by synthetic method.Primary synthetic methods have It is several below: using D-Glucose alkene as starting material, to make promotor catalyzing hydrolysis using minerals acid and obtain 2- deoxidation-D- grape Sugar；It is synthesized using glucosan derivative as starting material through Multi-step conversion；It is anti-with nitromethane by starting material of D-arabinose Ying Hou, through acetylation, reduction, hydrolysis and etc. finally obtain 2-deoxy-D-glucose.Above method reaction step is long, reaction Total recovery is lower, purification difficult, it is difficult to be commercialized.
Summary of the invention
In view of this, the present invention is directed to propose a kind of preparation method of 2-deoxy-D-glucose, method mild condition are received Rate is high, and purification process is simple, is easy to large scale preparation.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A kind of preparation method of 2-deoxy-D-glucose, comprising the following steps:
(1) promotor, sulfoxide and water are added into chemical compounds I, after fully reacting, reaction solution is filtered, is concentrated, again Compound ii is obtained after crystallization, wherein chemical compounds I, the general formula of compound ii are as follows:
Wherein, substituent R is in formoxyl, acetyl group, propiono, benzoyl, benzyl or dimethyl tertiary butyl silicon substrate One kind；
(2) after being deprotected compound 2,2-deoxy-D-glucose is obtained after recrystallization.
Further, promotor is acid anhydrides or chloride in the step (1)；Preferably, acid anhydrides be formic anhydride, acetic anhydride, Propionic andydride, butyric anhydride, trifluoroacetic anhydride, the one or more of methanesulfonic acid acid anhydride or trifluoromethanesulfanhydride anhydride；Preferably, chloride For thionyl chloride, phosphorus oxychloride, phosphorus trichloride, chloroacetic chloride, oxalyl chloride, chlorobenzoyl chloride, p-methyl benzene sulfonic chloride, Cyanuric Chloride or The one or more of chlorosuccinimide.
Further, sulfoxide is one in alkyl sulfoxide, alkenyl sulfoxide, alkynyl sulfoxide or phenylsulfone in the step (1) Kind.
Preferably, sulfoxide is dimethyl sulfoxide.
Further, the reaction temperature of the step (1) is -20 DEG C -180 DEG C, and the reaction time is 1-72 hours；Preferably, Reaction temperature is 10 DEG C -40 DEG C, and the reaction time is 1-5 hours.
Further, the concentration of chemical compounds I is 0.01-3mol/L in the step (1)；Preferably, the concentration of chemical compounds I is 0.1-0.5mol/L；Preferably, the concentration of compound 1 is 0.25mol/L.
Further, the solvent that re-crystallization step uses in the step (1) is methanol, ethyl alcohol, normal propyl alcohol, isopropanol, just Butanol, the tert-butyl alcohol, N,N-dimethylformamide, dimethyl sulfoxide, toluene, methylene chloride, chloroform, acetonitrile, dioxane, tetrahydro Furans, ether or methyl tertiary butyl ether(MTBE) are one or more kinds of.
Further, in the step (1) chemical compounds I preparation method: D-Glucose alkene is protected, compound is obtained Ⅰ。
Further, chemical compounds I in the step (1), promotor, sulfoxide, water molar ratio be 1:(0.01-3): (0.03- 9):(1-50)；Preferably, chemical compounds I, promotor, sulfoxide, water molar ratio be 1:(0.1-0.5): (0.5-0.8): (1-5).
Further, the solvent that re-crystallization step uses in the step (2) is methanol, ethyl alcohol, normal propyl alcohol, isopropanol, just Butanol, the tert-butyl alcohol, N,N-dimethylformamide, dimethyl sulfoxide, toluene, methylene chloride, chloroform, acetonitrile, dioxane, tetrahydro The one or more of furans, ether or methyl tertiary butyl ether(MTBE).
Compared with the existing technology, the preparation method of 2-deoxy-D-glucose of the present invention has the advantage that
The preparation method of 2-deoxy-D-glucose of the present invention is using the glucose malt sugar protected as starting material, warp Catalyzing hydrolysis, deprotection are crossed, only 2 Walk react, and 2-deoxy-D-glucose can be made.In preparation process, reaction condition is mild, Reaction reagent is easy to get, and reaction yield is high, and purification of intermediate method is simple and easy, and final products purity is high has wide business Application prospect.
Specific embodiment
In order to enable the public to fully understand technical spirit and invention advantage of the invention, applicant will be below to the present invention Specific embodiment detailed description, but applicant is to the limitation that the description of embodiment is not to technical solution, it is any according to Inventive concept, which changes in the form rather than substance, all should be considered as protection scope of the present invention.
Embodiment 1
A kind of preparation method of 2-deoxy-D-glucose, comprising the following steps:
(1) at room temperature, Cyanuric Chloride is added into acetonitrile (4L) solution of compound III (272.3g, 1.0mol) (36.9g, 0.2mol), dimethyl sulfoxide (46.8g, 0.6mol) and water (54g, 3mol).It, will be anti-after being stirred at room temperature 3.5 hours Liquid is answered to filter, filtrate decompression concentration.Crude product is recrystallized to give compounds Ⅳ (267.6g, white solid) using ether (500mL) Yield 92%.Hydrogen nuclear magnetic resonance spectrum: (600MHz, CDCl3)δ5.54–5.35(m,8H),5.08–4.95(m,6H),4.37– 4.19 (m, 10H), 4.13 (t, J=13.3Hz, 5H), 3.69 (d, J=6.9Hz, 1H), 3.49 (s, 1H), 3.04 (s, 4H), 2.42 (dd, J=11.9,4.1Hz, 1H), 2.32-2.27 (m, 4H), 2.14-2.00 (m, 45H), 1.88-1.73 (m, 5H).
(2) compounds Ⅳ (200g, 0.69mol) is dissolved in anhydrous methanol (1.38L), freshly prepd sodium methoxide is added 6h is stirred at room temperature after (3.7g, 0.069mol), is added acid-exchange resin Dowex-50 (20g).After 1h is stirred at room temperature, mistake Filter, filtrate decompression concentration.Crude product positive definite alcohol, methanol mixture (the molar ratio 1:1 of positive definite alcohol, methanol) be recrystallized to give 2- Deoxidation-D-Glucose 100g, yield 88%.Hydrogen nuclear magnetic resonance spectrum: (400MHz, CD3OD) δ 5.26 (d, J=2.6,1H), 3.90 (m, 1H), 3.80 (m, 1H), 3.68 (m, 1H), 3.64 (m, 1H), 3.26 (m, 1H), 2.05 (dd, J=5.0,12.8,1H), 1.62 (dt, J=2.6,12.8,1H).
Chemical equation is as follows:
Embodiment 2
A kind of preparation method of 2-deoxy-D-glucose, comprising the following steps:
(1) at room temperature, Cyanuric Chloride is sequentially added into acetonitrile (4L) solution of compound V (416.5g, 1.0mol) (36.9g, 0.2mol), dimethyl sulfoxide (46.8g, 0.6mol) and water (54g, 3mol).It, will be anti-after being stirred at room temperature 3.5 hours Liquid is answered to filter, filtrate decompression concentration.Crude product is recrystallized to give compound VI (412.8g, white solid) with ether (500mL), is received Rate 95%.Hydrogen nuclear magnetic resonance spectrum: (600MHz, CDCl3) δ 7.36-7.24 (m, 65H), 7.17 (d, J=6.0Hz, 10H), 5.38 (s, 4H), 4.88 (t, J=11.0Hz, 5H), 4.70-4.60 (m, 10H), 4.57 (dd, J=12.1,6.5Hz, 6H), 4.51 (dd, J=12.1,4.6Hz, 10H), 4.04 (dt, J=7.7,7.0Hz, 9H), 3.76-3.61 (m, 10H), 3.61-3.54 (m, 1H), 3.46-3.41 (m, 4H), 3.43 (dd, J=14.9,9.0Hz, 2H)), 3.28 (s, 4H), 2.28 (dd, J=12.9, 4.4Hz, 5H), 1.67 (t, J=12.1Hz, 4H), 1.55 (dd, J=21.9,11.8Hz, 1H).
(2) compound VI (300g, 0.69mol) is dissolved in anhydrous methanol (1.38L), 5% Pd/C (15g) is added and exists Under 100psi pressure, 12h is stirred at room temperature.Then it filters, filtrate decompression concentration.Mixture (the positive definite of crude product positive definite alcohol, methanol The molar ratio 1:1 of alcohol, methanol) it is recrystallized to give 2-DG 113g, yield 91%.Hydrogen nuclear magnetic resonance spectrum: (400MHz,CD3OD) δ 5.26 (d, J=2.6,1H), 3.90 (m, 1H), 3.80 (m, 1H), 3.68 (m, 1H), 3.64 (m, 1H), 3.26 (m, 1H), 2.05 (dd, J=5.0,12.8,1H), 1.62 (dt, J=2.6,12.8,1H).
Chemical equation is as follows:
Embodiment 3
A kind of preparation method of 2-deoxy-D-glucose, comprising the following steps:
(1) at room temperature, Cyanuric Chloride is sequentially added into acetonitrile (4L) solution of compound VII (458.4g, 1.0mol) (36.9g, 0.2mol), dimethyl sulfoxide (46.8g, 0.6mol) and water (54g, 3mol).It, will be anti-after being stirred at room temperature 3.5 hours Liquid is answered to filter, filtrate decompression concentration.Crude product is recrystallized to give compound VIII (395.5g, white solid) with ether (500mL), is received Rate 83%.Hydrogen nuclear magnetic resonance spectrum: (600MHz, CDCl3) δ 8.04 (t, J=9.7Hz, 46H), 7.96 (dt, J=13.7, 6.9Hz, 92H), 7.57-7.47 (m, 69H), 7.38 (ddd, J=13.0,11.4,6.7Hz, 138H), 5.85-5.77 (m, 20H), 5.64 (t, J=9.7Hz, 20H), 5.59 (t, J=9.7Hz, 3H), 5.54 (s, 20H), 5.47-5.39 (m, 3H), 5.17-5.12 (m, 3H), 4.62 (ddd, J=10.8,9.9,2.7Hz, 43H), 4.44 (ddd, J=15.9,11.9,4.5Hz, 23H), 4.08-4.02 (m, 3H), 3.56-3.37 (m, 23H), 2.67 (dd, J=11.9,4.4Hz, 3H), 2.55 (dd, J= 12.8,5.1Hz, 20H), 2.00 (t, J=11.9Hz, 20H), 1.93 (t, J=10.8Hz, 3H).
(2) compound VIII (328.8g, 0.69mol) is dissolved in anhydrous methanol (1.38L), freshly prepd sodium methoxide is added 6h is stirred at room temperature after (3.7g, 0.069mol), is added acid-exchange resin Dowex-50 (20g).After 1h is stirred at room temperature, mistake Filter, filtrate decompression concentration.Crude product positive definite alcohol, methanol mixture (the molar ratio 1:1 of positive definite alcohol, methanol) be recrystallized to give 2- Deoxidation-D-Glucose 92.2g, yield 81%.Hydrogen nuclear magnetic resonance spectrum: (400MHz, CD3OD) δ 5.26 (d, J=2.6,1H), 3.90 (m, 1H), 3.80 (m, 1H), 3.68 (m, 1H), 3.64 (m, 1H), 3.26 (m, 1H), 2.05 (dd, J=5.0,12.8, 1H), 1.62 (dt, J=2.6,12.8,1H).
Chemical equation is as follows:
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (9)

1. a kind of preparation method of 2-deoxy-D-glucose, it is characterised in that: the following steps are included:
(1) promotor, dimethyl sulfoxide and water are added into chemical compounds I, after fully reacting, reaction solution is filtered, is concentrated, Compound ii is obtained after recrystallization, wherein chemical compounds I, the general formula of compound ii are as follows:
Wherein, substituent R is one in formoxyl, acetyl group, propiono, benzoyl, benzyl or dimethyl tertiary butyl silicon substrate Kind；
(2) after being deprotected compound 2,2-deoxy-D-glucose is obtained after recrystallization；
Promotor is acid anhydrides or chloride in the step (1)；
Acid anhydrides is formic anhydride, acetic anhydride, propionic andydride, butyric anhydride, trifluoroacetic anhydride, methanesulfonic acid acid anhydride or trifluoro in the step (1) The one or more of methanesulfonic acid acid anhydride；
In the step (1) chloride be thionyl chloride, it is phosphorus oxychloride, phosphorus trichloride, chloroacetic chloride, oxalyl chloride, chlorobenzoyl chloride, right The one or more of toluene sulfonyl chloride, Cyanuric Chloride or chlorosuccinimide.
2. the preparation method of 2-deoxy-D-glucose according to claim 1, it is characterised in that: the step (1) it is anti- Answering temperature is 10 DEG C -40 DEG C, and the reaction time is 1-5 hours.
3. the preparation method of 2-deoxy-D-glucose according to claim 1, it is characterised in that: step (1) middleization The concentration for closing object I is 0.01-3mol/L.
4. the preparation method of 2-deoxy-D-glucose according to claim 3, it is characterised in that: step (1) middleization The concentration for closing object I is 0.1-0.5mol/L.
5. the preparation method of 2-deoxy-D-glucose according to claim 4, it is characterised in that: step (1) middleization The concentration for closing object 1 is 0.25mol/L.
6. the preparation method of 2-deoxy-D-glucose according to claim 1, it is characterised in that: weight in the step (1) The solvent that crystallisation step uses is methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol, N,N-dimethylformamide, two Methyl sulfoxide, toluene, methylene chloride, chloroform, acetonitrile, dioxane, tetrahydrofuran, ether or methyl tertiary butyl ether(MTBE) one kind or two Kind or more.
7. the preparation method of 2-deoxy-D-glucose according to claim 1, it is characterised in that: step (1) middleization It closes the preparation method of object I: D-Glucose alkene being protected, chemical compounds I is obtained.
8. the preparation method of 2-deoxy-D-glucose described in any one of -7 according to claim 1, it is characterised in that: described Chemical compounds I in step (1), promotor, dimethyl sulfoxide, water molar ratio be 1:(0.01-3): (0.03-9): (1-50).
9. the preparation method of 2-deoxy-D-glucose according to claim 8, it is characterised in that: weight in the step (2) The solvent that crystallisation step uses is methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol, N,N-dimethylformamide, two Methyl sulfoxide, toluene, methylene chloride, chloroform, acetonitrile, dioxane, tetrahydrofuran, ether or methyl tertiary butyl ether(MTBE) one kind or It is two or more.
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CN102924540A (en) * 2012-10-22 2013-02-13 山东鲁抗舍里乐药业有限公司 Preparation method of 2-deoxy-D-glucose
CN103910767A (en) * 2013-01-06 2014-07-09 路梦洋 Preparation method of 2-deoxy-D-glucose
CN103951714A (en) * 2014-04-03 2014-07-30 马玉 Preparation method of 2-deoxy-D-glucose

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Publication number Priority date Publication date Assignee Title
CN1800193A (en) * 2005-12-07 2006-07-12 江苏汉发贸易发展有限公司 2-deoxidized glucose preparation method
WO2008069440A1 (en) * 2006-12-06 2008-06-12 Samchully Pharm. Co., Ltd. The preparation method of 2-de0xy-l-rib0se
CN102924540A (en) * 2012-10-22 2013-02-13 山东鲁抗舍里乐药业有限公司 Preparation method of 2-deoxy-D-glucose
CN103910767A (en) * 2013-01-06 2014-07-09 路梦洋 Preparation method of 2-deoxy-D-glucose
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