CN115197185B - Preparation method of transition metal catalyzed pyranoside derivative - Google Patents

Preparation method of transition metal catalyzed pyranoside derivative Download PDF

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CN115197185B
CN115197185B CN202110388197.0A CN202110388197A CN115197185B CN 115197185 B CN115197185 B CN 115197185B CN 202110388197 A CN202110388197 A CN 202110388197A CN 115197185 B CN115197185 B CN 115197185B
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transition metal
deionized water
isopropanol
metal catalyst
carbohydrate
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CN115197185A (en
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路芳
卢锐
司晓勤
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D309/10—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/26—Acyclic or carbocyclic radicals, substituted by hetero rings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Organic Chemistry (AREA)
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Abstract

The invention discloses a preparation method of a transition metal catalyzed pyranoside derivative. In particular to a method for preparing a pyranoside derivative by taking carbohydrate and the like as raw materials and carrying out dehydration coupling reaction with isopropanol in a mixed solvent system of deionized water and dipolar aprotic solvent under the action of a transition metal catalyst. The method has the advantages of short route, mild condition, high atom economy and good application prospect.

Description

Preparation method of transition metal catalyzed pyranoside derivative
Technical Field
The invention relates to the fields of organic synthesis, fine chemical engineering, medicine, daily cosmetics and the like, relates to a preparation method of a transition metal catalyzed pyranoside derivative, and in particular relates to a method for obtaining the pyranoside derivative by taking carbohydrate and isopropanol as raw materials and performing dehydration coupling reaction under the action of a transition metal catalyst.
Background
The glycoside compounds have important bioactivity and are widely applied to the industries of medicines and cosmetics. C-glycoside is an O-glycoside analogue with an oxygen atom on the glycosidic bond replaced by a methylene, and the C-glycoside molecule has good stability to acid and enzyme catalytic hydrolysis due to the replacement of the glycosidic oxygen atom by the methylene. Currently, only limited methods of C-glycoside synthesis are disclosed and most require a hydrogenation step to obtain the final target product. CN202010629023.4 discloses a method for preparing C-pyranoside, i.e. vitriol, by using a biological enzyme one-pot method, specifically xylose and isopropanol are used as substrates, and corresponding C-pyranoside is produced under the catalytic action of isopropanol dehydrogenase, vitriol synthase, carbonyl reductase and coenzyme nicotinamide adenine dinucleotide. However, the process requires the synergistic action of a plurality of enzyme catalysts, and has the advantages of long flow, low efficiency and high cost, and is difficult to realize large-scale production. Therefore, the development of a simple, efficient and low-cost preparation method of the C-glycoside derivative is very important for the application of the C-glycoside derivative in the fields of medicines, cosmetics and the like.
Disclosure of Invention
The invention aims to provide a method for obtaining a pyranoside derivative by taking carbohydrate and isopropanol as raw materials and performing dehydration coupling reaction under the action of a transition metal catalyst.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the specific process method comprises the following steps: the molar ratio was set to 1: 10-10: 1 (the mass ratio of the carbohydrate and the dipolar aprotic solvent is 1:100-2:1; the volume ratio of the deionized water and the dipolar aprotic solvent is 1:10-10:1), adding a transition metal catalyst (the molar ratio of the dosage of the transition metal catalyst to the carbohydrate and the carbohydrate is 1:1000-1:10) into a stainless steel reaction kettle, controlling the reaction temperature to be 30-200 ℃ for 0.5-24 hours, collecting the reaction solution after the reaction is stopped, decompressing and distilling to remove the mixed solvent and the excessive isopropanol, adding deionized water to dissolve and filter to remove the catalyst, extracting with ethyl acetate for three times, removing residual byproducts, collecting the water phase, decompressing and distilling, and vacuum-drying for 0.5-24 hours at 25-100 ℃ to obtain the target product C-glucopyranoside derivative; the embodiment of the invention performs performance evaluation and process condition test in a stainless steel reaction kettle, but is not limited to the stainless steel reaction kettle.
The saccharide carbohydrate is selected from one of glucose, mannose, galactose, xylose, arabinose, lactose, maltose and cellobiose;
the transition metal catalyst is selected from at least one of ferric acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, vanadyl acetylacetonate, molybdenum acetylacetonate, ruthenium acetylacetonate, vanadyl sulfate, ammonium metavanadate, ammonium molybdate, rhenium methyltrioxide, rhenium heptaoxide, ammonium perrhenate, molybdenum hexacarbonyl, tungsten hexacarbonyl, ferrocene, cobaltocene, nickel dicyclopentadienyl and triphenylphosphine ruthenium chloride;
the dipolar aprotic solvent is at least one selected from acetonitrile, acetone, N, N-dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide and hexamethylphosphoramide.
Optionally, the lower molar ratio of the saccharide carbohydrate feedstock to isopropanol is selected from the group consisting of 1:10, 1:5, 2:5, 3:5, 1:1; the upper limit is selected from 10:1, 5:1, 5:2, 5:3, 1:1;
optionally, the lower limit of the volume ratio of deionized water to dipolar aprotic solvent in the mixed solvent system is selected from 1:100, 1:50, 1:25, 1:20, 1:3, 1:1; the upper limit is selected from 2:1, 3:2, 1:1;
optionally, the lower limit of the molar ratio of the amount of the transition metal catalyst to the carbohydrate raw material is selected from 1:1000, 1:500, 1:250 and 1:200; the upper limit is selected from 1:10, 1:50, 1:100, 1:200;
alternatively, the reaction temperature is 120 ℃.
Compared with the prior art, the method has the following characteristics:
the invention provides a method for obtaining a pyranoside derivative by taking carbohydrate and isopropanol as raw materials and carrying out dehydration coupling reaction under the action of a transition metal catalyst, wherein the process only removes one molecule of water while the carbon chain grows, and has no generation of carbon-containing byproducts and higher atom economy. The method has the advantages of simple process, strong operability, wide sources of raw materials, recoverable catalyst and considerable scale prospect.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
The starting materials and catalysts in the examples of the present application were purchased commercially, unless otherwise specified.
Sugar such as glucose and maltose is available from Shanghai Ala Biochemical technology Co.Ltd.
The transition metal complex catalysts cobalt acetylacetonate, vanadyl acetylacetonate, molybdenum hexacarbonyl and the like are purchased from national drug group chemical reagent company, ltd.
Dipolar aprotic solvents acetonitrile, N-dimethyl sulfoxide, N-dimethylformamide, and the like are purchased from national pharmaceutical group chemical reagent company, inc.
The yield of the product pyranoside derivative is calculated according to the following formula:
example 1
1.80kg of glucose is completely dissolved in 6.00L of mixed solvent of deionized water and acetonitrile (the volume ratio of the deionized water to the acetonitrile is 1:1), transferred into a 20L stainless steel reaction kettle, and 0.90kg of isopropanol is pumped into the reaction kettle by a peristaltic pump while stirring, and uniformly mixed. Then adding 0.24kg of transition metal catalyst vanadyl acetylacetonate, sealing the reaction kettle, stirring, heating to 120 ℃, stopping reacting for 12 hours, collecting reaction liquid, distilling under reduced pressure to remove solvent and excessive isopropanol, adding 1L of deionized water to dissolve and filter to remove the catalyst, extracting with ethyl acetate three times (each time with the dosage of 0.25L), removing residual byproducts, collecting water phase, distilling under reduced pressure, and vacuum drying at 40 ℃ for 12 hours to obtain the target product C-glucopyranoside derivative with the yield of 36.5 percent, wherein 0.81kg is obtained.
Example 2
1.80kg of glucose is completely dissolved in 6.00L of mixed solvent of deionized water and acetonitrile (the volume ratio of the deionized water to the acetonitrile is 1:1), transferred into a 20L stainless steel reaction kettle, and 0.90kg of isopropanol is pumped into the reaction kettle by a peristaltic pump while stirring, and uniformly mixed. Then adding 0.18kg of transition metal catalyst ammonium molybdate, sealing the reaction kettle, stirring, heating to 120 ℃, stopping reacting for 12 hours, collecting reaction liquid, distilling under reduced pressure to remove solvent and excessive isopropanol, adding 1L of deionized water to dissolve and filter to remove the catalyst, extracting with ethyl acetate three times (each time with the dosage of 0.25L), removing residual byproducts, collecting water phase, distilling under reduced pressure, and vacuum drying at 40 ℃ for 12 hours to obtain the target product C-glucopyranoside derivative with the yield of 23.9 percent.
Example 3
1.80kg of glucose is completely dissolved in 6.00L of mixed solvent of deionized water and acetonitrile (the volume ratio of the deionized water to the acetonitrile is 1:1), transferred into a 20L stainless steel reaction kettle, and 0.90kg of isopropanol is pumped into the reaction kettle by a peristaltic pump while stirring, and uniformly mixed. Then 0.23kg of transition metal catalyst methyl rhenium trioxide is added, the reaction kettle is closed, the stirring is carried out, the temperature is raised to 120 ℃, the reaction is stopped after 12 hours, the reaction liquid is collected, the solvent and the excessive isopropanol are removed by reduced pressure distillation, 1L of deionized water is added for dissolving and filtering to remove the catalyst, the catalyst is extracted three times (each time with the dosage of 0.25L), the residual byproducts are removed, the water phase is collected, the reduced pressure distillation is carried out, and the vacuum drying is carried out at 40 ℃ for 12 hours, thus obtaining the target product C-glucopyranoside derivative with the yield of 0.91kg and 41.0 percent.
Example 4
1.80kg of glucose is completely dissolved in 6.00L of mixed solvent of deionized water and acetonitrile (the volume ratio of the deionized water to the acetonitrile is 1:1), transferred into a 20L stainless steel reaction kettle, and 0.90kg of isopropanol is pumped into the reaction kettle by a peristaltic pump while stirring, and uniformly mixed. Then adding 0.08kg of transition metal catalyst triphenylphosphine ruthenium chloride, sealing the reaction kettle, stirring, heating to 120 ℃, stopping reacting for 12 hours, collecting the reaction liquid, distilling under reduced pressure to remove the solvent and excessive isopropanol, adding 1L of deionized water to dissolve and filter out the catalyst, extracting with ethyl acetate three times (each time with the dosage of 0.25L), removing residual byproducts, collecting water phase, distilling under reduced pressure, and vacuum drying at 40 ℃ for 12 hours to obtain 1.21kg of target product C-glucopyranoside derivative with the yield of 54.5%.
Example 5
1.80kg of glucose is completely dissolved in 6.00L of mixed solvent of deionized water and acetonitrile (the volume ratio of the deionized water to the acetonitrile is 1:1), transferred into a 20L stainless steel reaction kettle, and 0.90kg of isopropanol is pumped into the reaction kettle by a peristaltic pump while stirring, and uniformly mixed. Then adding 0.30kg of transition metal catalyst molybdenum acetylacetonate, sealing the reaction kettle, stirring, heating to 120 ℃, stopping reacting for 12 hours, collecting reaction liquid, distilling under reduced pressure to remove solvent and excessive isopropanol, adding 1L of deionized water to dissolve and filter to remove the catalyst, extracting with ethyl acetate three times (each time with the dosage of 0.25L), removing residual byproducts, collecting water phase, distilling under reduced pressure, and vacuum drying at 40 ℃ for 12 hours to obtain the target product C-glucopyranoside derivative with the yield of 68.9%.
Example 6
1.80kg of glucose is completely dissolved in 6.00L of mixed solvent of deionized water and N, N-dimethylformamide (the volume ratio of the deionized water to the N, N-dimethylformamide is 1:1), and the mixture is transferred into a 20L stainless steel reaction kettle, and 0.90kg of isopropanol is pumped into the reaction kettle by a peristaltic pump while stirring, and the mixture is uniformly mixed. Then adding 0.30kg of transition metal catalyst molybdenum acetylacetonate, sealing the reaction kettle, stirring, heating to 120 ℃, stopping reacting for 12 hours, collecting reaction liquid, distilling under reduced pressure to remove solvent and excessive isopropanol, adding 1L of deionized water to dissolve and filter to remove the catalyst, extracting with ethyl acetate three times (each time with the dosage of 0.25L), removing residual byproducts, collecting water phase, distilling under reduced pressure, and vacuum drying at 40 ℃ for 12 hours to obtain 1.05kg of target product C-glucopyranoside derivative with the yield of 47.3%.
Example 7
1.80kg of glucose is completely dissolved in 6.00L of deionized water and acetone mixed solvent (the volume ratio of deionized water to acetone is 1:1), transferred into a 20L stainless steel reaction kettle, and 0.90kg of isopropanol is pumped into the reaction kettle by a peristaltic pump while stirring, and uniformly mixed. Then adding 0.30kg of transition metal catalyst molybdenum acetylacetonate, sealing the reaction kettle, stirring, heating to 120 ℃, stopping reacting for 12 hours, collecting reaction liquid, distilling under reduced pressure to remove solvent and excessive isopropanol, adding 1L of deionized water to dissolve and filter to remove the catalyst, extracting with ethyl acetate three times (each time with the dosage of 0.25L), removing residual byproducts, collecting water phase, distilling under reduced pressure, and vacuum drying at 40 ℃ for 12 hours to obtain 1.15kg of target product C-glucopyranoside derivative with the yield of 51.8%.
Example 8
1.80kg of glucose is completely dissolved in 6.00L of deionized water and acetonitrile (the volume ratio of deionized water to acetonitrile is 1:3), transferred into a 20L stainless steel reaction kettle, and 0.90kg of isopropanol is pumped into the reaction kettle by a peristaltic pump while stirring, and uniformly mixed. Then adding 0.30kg of transition metal catalyst molybdenum acetylacetonate, sealing the reaction kettle, stirring, heating to 120 ℃, stopping reacting for 12 hours, collecting reaction liquid, distilling under reduced pressure to remove solvent and excessive isopropanol, adding 1L of deionized water to dissolve and filter to remove the catalyst, extracting with ethyl acetate three times (each time with the dosage of 0.25L), removing residual byproducts, collecting water phase, distilling under reduced pressure, and vacuum drying at 40 ℃ for 12 hours to obtain 2.00kg of target product C-glucopyranoside derivative with the yield of 90.1%.
Example 9
3.42kg of maltose is completely dissolved in 6.00L of deionized water and acetonitrile (the volume ratio of deionized water to acetonitrile is 1:3), transferred into a 20L stainless steel reaction kettle, and 0.90kg of isopropanol is pumped into the reaction kettle by a peristaltic pump while stirring, and uniformly mixed. Then adding 0.30kg of transition metal catalyst molybdenum acetylacetonate, sealing the reaction kettle, stirring, heating to 120 ℃, stopping reacting for 12 hours, collecting reaction liquid, distilling under reduced pressure to remove solvent and excessive isopropanol, adding 1L of deionized water to dissolve and filter to remove the catalyst, extracting with ethyl acetate three times (each time with the dosage of 0.25L), removing residual byproducts, collecting water phase, distilling under reduced pressure, and vacuum drying at 40 ℃ for 12 hours to obtain 3.21kg of target product C-pyran maltoside derivative with the yield of 83.6%.
In summary, the present application provides a method for preparing a pyranoside derivative, which uses carbohydrate and isopropanol as raw materials to further react with a transition metal catalyst to obtain the pyranoside derivative, and has high atom economy. The source of raw materials is wide, and the catalyst can be recovered. Simple process, mild condition, strong operability and large-scale prospect.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.

Claims (8)

1. A preparation method of a transition metal catalyzed pyranoside derivative is characterized in that,
at least comprises the following steps: carrying out dehydration coupling reaction on a raw material containing carbohydrate and isopropanol in a mixed solvent system of deionized water and a dipolar aprotic solvent under the action of a transition metal catalyst to obtain a pyranoside derivative in one step;
the saccharide carbohydrate is selected from one of glucose, mannose, galactose, xylose and arabinose;
the transition metal catalyst is at least one selected from vanadyl acetylacetonate, molybdenum acetylacetonate, ammonium molybdate, methyl rhenium trioxide and triphenylphosphine ruthenium chloride;
the dipolar aprotic solvent is at least one selected from acetonitrile, acetone, N, N-dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide and hexamethylphosphoramide.
2. The method according to claim 1, wherein,
at least comprises the following steps: dissolving carbohydrate in a mixed solvent system of deionized water and a dipolar aprotic solvent, sequentially adding isopropanol and a transition metal catalyst, performing reduced pressure distillation, filtering, extracting with ethyl acetate, collecting a water phase, performing reduced pressure distillation again, and performing vacuum drying to obtain the pyranoside derivative.
3. The method according to claim 1, wherein,
the molar ratio of the carbohydrate raw material to the isopropanol is 1: 10-10: 1.
4. the method according to claim 1, wherein,
the volume ratio of deionized water to dipolar aprotic solvent in the mixed solvent system is 1: 10-10: 1.
5. the method according to claim 1, wherein,
the molar ratio of the dosage of the transition metal catalyst to the carbohydrate raw material of the saccharide is 1: 1000-1: 10.
6. the method according to claim 1, wherein,
the reaction temperature is 30-200 ℃.
7. The method according to claim 1, wherein,
the reaction temperature was 120 ℃.
8. The method according to claim 1, wherein,
the reaction time is 0.5-12 hours.
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WO1998008854A2 (en) * 1996-08-26 1998-03-05 Novartis Ag Sugar derivatives as sialyl lewis x mimetics
WO2002051828A2 (en) * 2000-12-22 2002-07-04 L'oreal Novel c-glycoside derivatives and use thereof
CN108883122A (en) * 2016-03-11 2018-11-23 菲姆布里昂医疗公司 There are the C- glycoside compounds for treating disease
CN111559998A (en) * 2020-05-20 2020-08-21 铭颜生物科技(广州)有限公司 Synthesis method of hydroxypropyl tetrahydropyrane triol
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