CN107880089A - A kind of trimethyl silicone hydride method of saccharide compound - Google Patents
A kind of trimethyl silicone hydride method of saccharide compound Download PDFInfo
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- CN107880089A CN107880089A CN201711225469.5A CN201711225469A CN107880089A CN 107880089 A CN107880089 A CN 107880089A CN 201711225469 A CN201711225469 A CN 201711225469A CN 107880089 A CN107880089 A CN 107880089A
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- saccharide compound
- silicone hydride
- trimethyl silicone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H23/00—Compounds containing boron, silicon, or a metal, e.g. chelates, vitamin B12
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
Abstract
The invention discloses a kind of method of saccharide compound trimethyl silicone hydride, the present invention is activated HMDS by solid-carried catalyst, saccharide compound can be converted into corresponding trimethyl silicone hydride product, particularly suitable saccharide compound is monose, oligosaccharides, sugar alcohol, glucoside compound；Compared with existing saccharide compound Silicane Method, this method can be realized under condition of no solvent, gently, efficiently prepare saccharide compound Silylation thing, course of reaction and post-processing operation are simple；Meanwhile this method avoids the harmful nitrogen-containing solvent of use environment and the alkali of stoichiometry, and catalyst reusable edible, there is higher Atom economy and environment friendly, thus meet green chemical concept.
Description
Technical field
The present invention relates to a kind of method of saccharide compound trimethyl silicone hydride；By the present invention in that with solid-carried catalyst pair
HMDS is activated, so as to realize the trimethyl silicone hydride that saccharide compound is realized under condition of no solvent.
Background technology
Silicon ethers protection group is a kind of common hydroxyl protecting group, and silicon ether protection group is easier to remove, removing bar used
Part does not have an impact typically to other protection groups, and is easier to realize selective protection, is a kind of preferably interim protection group.Sugar
The silanization of class compound tends to significantly change its physics and chemical property, such as the monose such as common glucose, galactolipin
It is solid under usual conditions, but its full trimethylsilylated derivative is the liquid with certain fluidity, Silylation thing
Volatility greatly improve, this property cause trimethyl silicone hydride protect carbohydrate be widely used in saccharide compound point
Analysis identification.The saccharide compound of silanization is also important organic synthesis precursor simultaneously, and sugar is can not only be used in carbohydrate chemistry synthesis
The donor of base, but also as glycosylated acceptor, and they have be different from other types protection group such as esters, benzyl oxide class
The electronics and three-dimensional effect of protection group, therefore embody the reactive and selective of uniqueness in synthesis chemistry.
Although the trimethyl silicone hydride of saccharide compound has important application in carbohydrate chemistry synthesis and analytical chemistry, with leading to
Normal single hydroxy compounds silanization is compared, and due to there is multiple hydroxyls on saccharide compound, and these hydroxyls are usually tight
Solid matter arranges, therefore very big to the persilylated difficulty of saccharide compound, and its silanization condition is more harsh.It is relatively conventional
Silylating reagent be trim,ethylchlorosilane, this kind of Silicane Method generally requires substantial amounts of alkali such as triethylamine, pyridine, imidazoles etc.
As acid binding agent, this causes there is substantial amounts of salt in silanization process（Quality is often more than the several times of substrate）Given birth to as accessory substance
Into.This kind of method needs aprotic solvent such as formamide, N,N-dimethylformamide, pyridine etc. for using big polarity nitrogenous simultaneously
Solvent increases the solubility of saccharide compound.Corrosion of the use of chloro-containing reagent to production equipment is very big, and a large amount of by-products
The generation of thing and the use of nitrogen-containing solvent not only increase the complexity of operation, add the cost of post processing, while
So that reaction of atomic economy substantially reduces, and it is unfavorable for environmental protection.Substantial amounts of solvent is used additionally, due to existing process, makes unit
The fertile product volume of reaction unit of volume declines, and is unfavorable for the extensive preparation of carbohydrate hydrosilylation product.
HMDS is applied to saccharide compound very early as a kind of silylating reagent cheap and easy to get
Trimethyl silicone hydride, its silanization process avoids a large amount of accessory substance generations, but its shortcoming is that reactivity is relatively low, is generally required
Catalyst is activated.There is partially catalyzed system to be used to activate hexamethyldisilane to carry out the silicon of common hydroxyl at present
Alkylation reaction, and the example for being applied to carbohydrate silanization is fewer, more important is the carbohydrate silanization that these have been reported
Reaction all needs also exist for substantial amounts of organic nitrogen-containing class or toxic solvent containing halogen.Have been reported that using trim,ethylchlorosilane and be used as catalysis
Agent, hexamethyldisilane are silylating reagent, to the trimethyl silicone hydride of carbohydrate in pyridine solvent（J. Am. Chem.
Soc., 1963, 85, 2497）.In recent years, find that trimethylsilyl trifluoromethanesulfonate (TMSOTf) can be used as pregnancy again
The activating reagent of base disilane, in dichloromethane solvent, it is possible to achieve the trimethyl silylation method of saccharide compound（Eur.
J. Org. Chem., 2012, 4, 744-753）.Used in report above is all liquid catalyst, it is necessary to anti-
Handled and decomposed with buck after should terminating, therefore operated more complicated.And because catalyst has been decomposed, therefore can not repeat to make
With.There is researcher that the blade drying and sintering of zinc Cd hyperaccumulator Thlaspi caerulescens is prepared into a kind of solid catalyst, in second
Reacted in nitrile solvent, the silanization of carbohydrate can be catalyzed.But the catalyst that this method is obtained by sintering plant leaf
The factors such as the place of production, plucking time where by Thlaspi caerulescens are influenceed very big, it is difficult to realize repeatability（Environ. Sci.
Pollut. Res., 2015, 22, 5686-5698）.Additionally while these methods realize the purpose of catalysis, but still will
Using the disagreeableness solvent of the environment such as pyridine, dichloromethane, acetonitrile, the solvent-free silane for preparing saccharide compound can not be realized
Change.
Green Chemistry is as one of Main way of new century chemical developer, in industries such as chemical industry, pharmacy, all increasingly
The environment for paying attention to bringing in production process influences and environmental benefit.Cleaning, environment-friendly synthetic method also turn into organic chemistry
One of the study hotspot in field, solvent-free reaction are exactly a kind of chemical reaction for meeting green chemical concept.Exploitation one kind is without molten
The Silicane Method of agent, will can significantly reduce the volume of Silanization reaction system, greatly simplify course of reaction, post processing,
The operations such as product separation, while also it is avoided that harmful nitrogenous, the halogen solvent of use environment and the alkali of stoichiometry.And it is being catalyzed
Silicane Method in, if the reusable edible of catalyst can be realized, will further improve the Atom economy and ring of reaction
Border friendly, green chemical concept is not only conformed with, also beneficial to the extensive preparation of Silylation thing.And in existing document report
In road, the I of only useful iodine2In/HMDS catalyst system and catalyzings, the silanization of carbohydrate under condition of no solvent may be implemented in.
But triiodide nitrogen can be produced during this simultaneously（NI3）, this is a kind of extremely unstable, dangerously explosive compound, in reality
Very big danger in operation be present, therefore this method has significant limitation, it is difficult to promoted the use of
（Tetrahedron,. 2012, 68, 3861-3867）.
The content of the invention
For the weak point of existing saccharide compound Silicane Method, it is an object of the invention to provide a kind of carbohydrate
Compound Silicane Method；This method uses solid-carried catalyst, it is possible to achieve easy under condition of no solvent, leniently reaction generation
Saccharide compound hydrosilylation product, while Posterior circle use can be recovered by filtration in the solid-carried catalyst.
The above-mentioned purpose of the present invention is realized by following technical schemes：Under inert gas atmosphere, six
Solid-carried catalyst is added in methyl disilazane, saccharide compound is added after mixing, stirring reaction is to having reacted at 0-125 DEG C
Entirely, reactant filters, and filtrate produces trimethyl silicone hydride saccharide compound, filter residue recycling after drying.
Mole addition of the HMDS is the 0.5-1.5 of free hydroxyl group integral molar quantity in saccharide compound
Times.
The solid-carried catalyst addition is the 2%-40% of saccharide compound quality.
For catalyst, routinely polishing or solvent impregnation are combined and are made the solid-carried catalyst with solid carrier,
Wherein catalyst is alkali metal perchlorate, the halide of alkaline-earth metal, the perchlorate of alkaline-earth metal, the trifluoro of alkaline-earth metal
Mesylate, the halide of transition metal, the perchlorate of transition metal, transition metal fluoroform sulphonate in one kind or
It is several；Solid carrier is silica gel, alundum (Al2O3), titanium dioxide, diatomite, kaolin, vermiculite, saponite, molecular sieve or activity
Charcoal.
The polishing that above-mentioned solid-carried catalyst uses in preparing is reference literature Applied Catalysis A:
Method in General 340 (2008) 42-51；Solvent impregnation is reference literature Applied Catalysis A:
Method in General 199 (2000) 239-244, but preparation technology is not limited only to the above method.
Content of the catalyst in solid-carried catalyst is 5-40wt%.
The saccharide compound is monose, oligosaccharides, sugar alcohol, glucoside compound.
Advantage of the present invention and technique effect：
Compared with existing saccharide compound Silicane Method, the inventive method can be being realized under condition of no solvent, gentle,
Saccharide compound Silylation thing is efficiently prepared, course of reaction and post-processing operation are simple；Meanwhile this method avoids using
The alkali of the harmful nitrogen-containing solvent of environment and stoichiometry, and catalyst reusable edible, there is higher Atom economy and environment
Friendly, thus meet green chemical concept.
Embodiment
The essentiality content of the present invention is further illustrated below by embodiment, but the present invention is not limited with this,
Method is conventional method unless otherwise specified in embodiment, and agents useful for same is conventional reagent or routinely unless otherwise specified
Reagent prepared by method.
Embodiment 1：In a nitrogen atmosphere, by 0.9 gram of sodium perchlorate-silica gel（Polishing is made, reference literature Applied
Catalysis A:Method in General 340 (2008) 42-51）It is suspended in 36.5 milliliters of HMDS
（0.7 times of free hydroxyl group integral molar quantity in glucose）In, by 9 grams of glucose (C6H12O6) above-mentioned suspension is added in batches
In, react at room temperature 12 hours；Reaction is filtered after terminating, and the oily liquids that filtrate obtains after being spin-dried for is full trimethyl silicon substrate protection
Glucose, yield 96%, filter residue recycling.
Embodiment 2：In a nitrogen atmosphere, by 3.6 grams of magnesium chloride-silica gel（Solvent impregnation is made, reference literature
Applied Catalysis A:Method in General 199 (2000) 239-244）It is suspended in 31.3 milliliters of pregnancy
Base disilazane（0.6 times of free hydroxyl group integral molar quantity in galactolipin）In, by 9 grams of galactolipin (C6H12O6) add in batches
State in suspension, 80 DEG C are reacted 24 hours；Reaction is filtered after terminating, and the oily liquids that filtrate obtains after being spin-dried for is full trimethyl
The galactolipin of silicon substrate protection, yield 91%.
Embodiment 3：In a nitrogen atmosphere, by 1.35 grams of barium perchlorate-silica gel（Polishing is made）It is suspended in 46.8 milliliters
HMDS (in sorbose 0.75 times of free hydroxyl group integral molar quantity) in, by 9 grams of sorbose (C6H12O6) in batches
Secondary to add in above-mentioned suspension, 50 DEG C are reacted 18 hours；Reaction is filtered after terminating, and the oily liquids that filtrate obtains after being spin-dried for is
The sorbose of full trimethyl silicon substrate protection, yield 93%.
Embodiment 4：In a nitrogen atmosphere, by 2.3 grams of copper bromide-silica gel（Polishing is made）It is suspended in 50 milliliters of pregnancy
(in mannose 0.8 times of free hydroxyl group integral molar quantity), 9 grams of mannose (C in base disilazane6H12O6) add in batches it is above-mentioned
In suspension, 60 DEG C are reacted 36 hours；Reaction is filtered after terminating, and the oily liquids that filtrate obtains after being spin-dried for is full trimethyl silicane
The mannose of base protection, yield 96%.
Embodiment 5：In a nitrogen atmosphere, by 1.8 grams of ferric perchlorate-silica gel（Solvent impregnation is made）It is suspended in 31.3 millis
In the HMDS (in fructose 0.6 times of free hydroxyl group integral molar quantity) risen, by 9 grams of fructose (C6H12O6) add in batches
Enter in above-mentioned suspension, react at room temperature 20 hours；Reaction is filtered after terminating, and the oily liquids that filtrate obtains after being spin-dried for is complete three
The fructose of methylsilyl protection, yield 94%.
Embodiment 6：In a nitrogen atmosphere, by 0.15 gram of trifluoromethanesulfonic acid scandium-silica gel（（Solvent impregnation is made）It is suspended in
In 29.2 milliliters of HMDS (in xylose 0.7 times of free hydroxyl group integral molar quantity), by 7.5 grams of xylose (C5H10O5)
Add in above-mentioned suspension, react at room temperature 48 hours in batches；Reaction is filtered after terminating, the oily liquids that filtrate obtains after being spin-dried for
The xylose of as full trimethyl silicon substrate protection, yield 97%.
Embodiment 7：In a nitrogen atmosphere, by 1.5 grams of lithium perchlorate-aluminum oxide（Solvent impregnation is made）Float on 31.3 millis
In the HMDS (in arabinose 0.75 times of free hydroxyl group integral molar quantity) risen, by 7.5 grams of arabinoses
(C5H10O5) add in batches in above-mentioned suspension, react at room temperature 24 hours；Reaction is filtered after terminating, what filtrate obtained after being spin-dried for
Oily liquids is the arabinose of full trimethyl silicon substrate protection, yield 92%.
Embodiment 8：In a nitrogen atmosphere, by 2.3 grams of magnesium bromide-aluminum oxide（Solvent impregnation is made）It is suspended in 33.3 millis
In the HMDS (in ribose 0.8 times of free hydroxyl group integral molar quantity) risen, by 7.5 grams of ribose (C5H10O5) in batches
Add in above-mentioned suspension, 50 DEG C are reacted 12 hours；Reaction is filtered after terminating, and the oily liquids that filtrate obtains after being spin-dried for is as complete
The ribose of trimethyl silicon substrate protection, yield 93%.
Embodiment 9：In a nitrogen atmosphere, by 1.6 grams of Calcium perchlorate-aluminum oxide（Polishing is made）It is suspended in 25 milliliters
In HMDS (in rhamnose 0.6 times of free hydroxyl group integral molar quantity), by 8.2 grams of rhamnose (C6H12O5) in batches
Add in above-mentioned suspension, react at room temperature 36 hours；Reaction is filtered after terminating, and the oily liquids that filtrate obtains after being spin-dried for is as complete
The rhamnose of trimethyl silicon substrate protection, yield 93%.
Embodiment 10：In a nitrogen atmosphere, by 0.45 gram of zirconium chloride-aluminum oxide（Polishing is made）It is suspended in 29.2 millis
In the HMDS (in glucose 0.7 times of free hydroxyl group integral molar quantity) risen, by 9 grams of Glucosamines
(C6H12O5N) add in batches in above-mentioned suspension, 0 DEG C is reacted 48 hours；Reaction is filtered after terminating, what filtrate obtained after being spin-dried for
Oily liquids is the Glucosamine of full trimethyl silicon substrate protection, yield 90%.
Embodiment 11：In a nitrogen atmosphere, by 1.7 grams of zinc perchlorate-aluminum oxide（Polishing is made）It is suspended in 83 milliliters
HMDS (in sucrose 1.0 times of free hydroxyl group integral molar quantity) in, by 17 grams of sucrose (C12H22O11) add in batches
Enter in above-mentioned suspension, react at room temperature 48 hours.Reaction is filtered after terminating, and the oily liquids that filtrate obtains after being spin-dried for is complete three
The sucrose of methylsilyl protection, yield 91%.
Embodiment 12：In a nitrogen atmosphere, by 0.85 gram of trifluoromethanesulfonic acid yttrium-aluminum oxide（Solvent impregnation is made）Suspend
In 83 milliliters of HMDSs (in lactose 1.0 times of free hydroxyl group integral molar quantity), by 17 grams of lactose (C12H22O11)
Add in batches in above-mentioned suspension, 10 DEG C are reacted 48 hours；Reaction is filtered after terminating, the oily liquids that filtrate obtains after being spin-dried for
The lactose of as full trimethyl silicon substrate protection, yield 93%.
Embodiment 13：In a nitrogen atmosphere, by 2.6 grams of cesium perchlorate-titanium dioxide（Solvent impregnation is made）It is suspended in
In 83 milliliters of HMDS (in trehalose 1.0 times of free hydroxyl group integral molar quantity), by 17 grams of trehaloses
(C12H22O11) add in batches in above-mentioned suspension, 50 DEG C are reacted 16 hours；Reaction is filtered after terminating, and filtrate obtains after being spin-dried for
Oily liquids be the protection of full trimethyl silicon substrate trehalose, yield 95%.
Embodiment 14：In a nitrogen atmosphere, by 5 grams of strontium bromide-titanium dioxide（Solvent impregnation is made）It is suspended in 80 millis
In the HMDS (in gossypose 0.7 times of free hydroxyl group integral molar quantity) risen, by 25 grams of gossypose (C18H32O16) plus
Enter in above-mentioned suspension, 80 DEG C are reacted 24 hours；Reaction is filtered after terminating, and the oily liquids that filtrate obtains after being spin-dried for is complete three
The gossypose of methylsilyl protection, yield 92%.
Embodiment 15：In a nitrogen atmosphere, by 2 grams of magnesium perchlorate-titanium dioxide（Polishing is made）It is suspended in 73 milliliters
HMDS (in melezitose monohydrate 0.7 times of free hydroxyl group integral molar quantity) in, by 20 grams of water of melezitose one
Compound (C18H34O17) add in above-mentioned suspension, 90 DEG C are reacted 8 hours；Reaction is filtered after terminating, the oil that filtrate obtains after being spin-dried for
Shape liquid is the melezitose of full trimethyl silicon substrate protection, yield 90%.
Embodiment 16：In a nitrogen atmosphere, by 0.4 gram of zinc chloride-titanium dioxide（Polishing is made）It is suspended in 4.4 milliliters
HMDS（1 times of free hydroxyl group integral molar quantity in stachyose）In, by 1 gram of stachyose (C24H42O21) in addition
State in suspension, 100 DEG C are reacted 4 hours；Reaction is filtered after terminating, and the oily liquids that filtrate obtains after being spin-dried for is full trimethyl
The stachyose of silicon substrate protection, yield 94%.
Embodiment 17：In a nitrogen atmosphere, by 5 grams of Manganese perchlorate-titanium dioxide（Polishing is made）Suspend 77 milliliters
HMDS（1.2 times of free hydroxyl group integral molar quantity in alpha-cyclodextrin）In, by 25 grams of alpha-cyclodextrin (C36H60O30) point
Batch is added in above-mentioned suspension, and 120 DEG C are reacted 8 hours；Reaction is filtered after terminating, and the oily liquids that filtrate obtains after being spin-dried for is i.e.
The alpha-cyclodextrin for the trimethyl silicon substrate protection protected for single part, yield 88%.
Embodiment 18：In a nitrogen atmosphere, by 2.5 grams of copper trifluoromethanesulfcomposite-titanium dioxide（Solvent impregnation is made）It is outstanding
Float on 96 milliliters of HMDS（1.5 times of free hydroxyl group integral molar quantity in beta-schardinger dextrin）In, 25 grams of β-ring is pasted
Essence (C42H70O35) add in batches in above-mentioned suspension, 125 DEG C are reacted 10 hours；Reaction centrifuges after terminating, and supernatant liquor simultaneously revolves
The oily liquids obtained after dry is the beta-schardinger dextrin of the trimethyl silicon substrate protection of single part protection, yield 89%.
Embodiment 19：In a nitrogen atmosphere, 1.2 grams of potassium hyperchlorate-diatomite are suspended in 21 milliliters of the silicon of hexamethyl two
Amine alkane（0.5 times of free hydroxyl group integral molar quantity in erythritol）In, by 6.1 grams of erythritol (C4H10O4) add in batches
State in suspension, react at room temperature 12 hours；Reaction is filtered after terminating, and the oily liquids that filtrate obtains after being spin-dried for is full trimethyl
The erythritol of silicon substrate protection, yield 96%.
Embodiment 20：In a nitrogen atmosphere, 0.8 gram of strontium bromide-montmorillonite is suspended in 28.6 milliliters of the silicon of hexamethyl two
Amine alkane（0.55 times of free hydroxyl group integral molar quantity in xylitol）In, by 7.6 grams of xylitol (C5H12O5) add in batches it is above-mentioned
In suspension, 50 DEG C are reacted 12 hours, and reaction is filtered after terminating, and the oily liquids that filtrate is spin-dried for obtaining is full trimethyl silicon substrate
The xylitol of protection, yield 96%.
Embodiment 21：In a nitrogen atmosphere, 1.5 grams of perchloric acid strontium-kaolin are suspended in 28.6 milliliters of hexamethyl two
Silicon amine alkane（0.55 times of equivalent of each free hydroxyl group integral molar quantity）In, by 7.6 grams of arabite (C5H12O5) add in batches
Enter in above-mentioned suspension, 50 DEG C are reacted 12 hours.Reaction is filtered after terminating, and the oily liquids that filtrate is spin-dried for obtaining is full front three
The arabite of base silicon substrate protection, yield 95%.
Embodiment 22：In a nitrogen atmosphere, 0.5 gram of yttrium trichloride-molecular sieve is suspended in 37.5 milliliters of hexamethyl two
Silicon amine alkane（0.6 times of free hydroxyl group integral molar quantity in mannitol）In, by 9.1 grams of mannitol (C6H14O6) add in batches it is above-mentioned
In suspension, react at room temperature 24 hours；Reaction is filtered after terminating, and the oily liquids that filtrate is spin-dried for obtaining is full trimethyl silicon substrate
The mannitol of protection, yield 96%.
Embodiment 23：In a nitrogen atmosphere, 0.9 gram of silver perchlorate-saponite is suspended in 37.5 milliliters of the silicon of hexamethyl two
Amine alkane（0.6 times of free hydroxyl group integral molar quantity in D-sorbite）In, by 9.1 grams sorbitol (C6H14O6) add in batches
State in suspension, react at room temperature 24 hours, reaction is filtered after terminating, and the oily liquids that filtrate is spin-dried for obtaining is full trimethyl silicane
The D-sorbite of base protection, yield 92%.
Embodiment 24：In a nitrogen atmosphere, 0.9 gram of trifluoromethanesulfonic acid zinc-vermiculite is suspended in 37.5 milliliters of hexamethyl
Disilazane（0.9 times of free hydroxyl group integral molar quantity in maltitol）In, by 9.1 grams of maltitol (C6H14O6) add in batches
Enter in above-mentioned suspension, react at room temperature 24 hours；Reaction is filtered after terminating, and the oily liquids that filtrate is spin-dried for obtaining is full front three
The maltitol of base silicon substrate protection, yield 94%.
Embodiment 25：In a nitrogen atmosphere, 0.25 gram of lithium perchlorate-zinc chloride-activated-carbon catalyst is suspended in 1.55
The HMDS of milliliter（0.6 times of free hydroxyl group integral molar quantity in 3- indyl-β-D- glucopyranosides）In, will
1 gram of 3- indyl-β-D- glucopyranosides (C14H17NO6) add in above-mentioned suspension, 10 DEG C are reacted 6 hours, and reaction terminates
After centrifuge, collect the 3- indyl-β-D- pyrroles that obtained oily liquids after supernatant liquor is spin-dried for is full trimethyl silicon substrate protection
Glucopyranoside glycosides, yield 91%.
Embodiment 26：In a nitrogen atmosphere, 0.8 gram of magnesium bromide-copper trifluoromethanesulfcomposite-silica gel is suspended in 9.6 milliliters
HMDS（0.8 times of free hydroxyl group integral molar quantity in Puerarin）In, by 4 grams of Puerarin (C21H20O9) add it is above-mentioned
In suspension, react at room temperature 48 hours；Reaction is filtered after terminating, and the oily liquids that filtrate is spin-dried for obtaining is full trimethyl silicon substrate
The Puerarin of protection, yield 94%.
Embodiment 27：In a nitrogen atmosphere, 0.8 gram of barium perchlorate-silver trifluoromethanesulfonate-aluminum oxide is suspended in 11.6 millis
The HMDS risen（0.8 times of free hydroxyl group integral molar quantity in aloin）In, by 4 grams of aloin (C21H22O9) add
In above-mentioned suspension, react at room temperature 24 hours, reaction is filtered after terminating, and the oily liquids that filtrate is spin-dried for obtaining is full trimethyl
The aloin of silicon substrate protection, yield 92%.
Embodiment 28：In a nitrogen atmosphere, by 0.4 gram of ferric bromide-cupric perchlorate-titanium dioxide suspending in 3.16 milliliters
HMDS（1.0 times of free hydroxyl group integral molar quantity in lamp-dish flower acetic）In, by 1 gram of lamp-dish flower acetic
(C21H18O12) add in batches in above-mentioned suspension, 80 DEG C are reacted 12 hours, and reaction centrifuges after terminating, and collects the oily on upper strata
Liquid produces the lamp-dish flower acetic of full trimethyl silicon substrate protection, yield 93% after being spin-dried for.
Embodiment 29：In a nitrogen atmosphere, 1 gram of manganous chloride-trifluoromethanesulfonic acid scandium-diatomite is suspended in 15 milliliters
HMDS（0.7 times of free hydroxyl group integral molar quantity in L-Ascorbic acid glucoside）In, by 5 grams of ascorbic acid grapes
Glucosides (C12H18O11) add in batches in above-mentioned suspension, react at room temperature 36 hours, reaction is filtered after terminating, and filtrate is spin-dried for
To oily liquids be the protection of full trimethyl silicon substrate ascorbic acid glucoside, yield 90%.
Embodiment 30：In a nitrogen atmosphere, 1 gram of potassium hyperchlorate-trifluoromethanesulfonic acid zinc-montmorillonite is suspended in 11.2 milliliters
HMDS（0.7 times of free hydroxyl group integral molar quantity in amarogentin）In, by 5 grams of amarogentin (C20H27NO11)
Add in above-mentioned suspension, react at room temperature 48 hours in batches, reaction centrifuges after terminating, and filters, and filtrate is spin-dried for obtained oily
Liquid is the amarogentin of full trimethyl silicon substrate protection, yield 92%.
Embodiment 31：In a nitrogen atmosphere, will be suspended in using the 0.20 gram of trifluoromethanesulfonic acid scandium-silica gel once reclaimed afterwards
In 29.2 milliliters of HMDS (in xylose 0.7 times of free hydroxyl group integral molar quantity), by 7.5 grams of xylose (C5H10O5)
Add in above-mentioned suspension, react at room temperature 48 hours in batches, reaction is filtered after terminating, the oily liquids that filtrate obtains after being spin-dried for
The xylose of as full trimethyl silicon substrate protection, yield 94%.
Embodiment 32：In a nitrogen atmosphere, will be suspended using the 1.00 grams of trifluoromethanesulfonic acid yttriums once reclaimed afterwards-aluminum oxide
In 83 milliliters of HMDSs (in lactose 1.0 times of free hydroxyl group integral molar quantity), by 17 grams of lactose (C12H22O11)
Add in batches in above-mentioned suspension, 10 DEG C are reacted 48 hours, and reaction is filtered after terminating, the oily liquids that filtrate obtains after being spin-dried for
The lactose of as full trimethyl silicon substrate protection, yield 92%.
Claims (5)
1. a kind of trimethyl silicone hydride method of saccharide compound, it is characterised in that：Under inert gas atmosphere, in hexamethyl two
Solid-carried catalyst is added in silicon amine alkane, saccharide compound is added after mixing, stirring reaction is to reacting complete at 0-125 DEG C, instead
Thing is answered to filter, filtrate produces trimethyl silicone hydride saccharide compound, filter residue recycling after drying.
2. the trimethyl silicone hydride method of saccharide compound according to claim 1, it is characterised in that：Hmds
Mole addition of alkane is 0.5-1.5 times of free hydroxyl group integral molar quantity in saccharide compound.
3. the trimethyl silicone hydride method of saccharide compound according to claim 1, it is characterised in that：Solid-carried catalyst adds
Dosage is the 2%-40% of saccharide compound quality.
4. the trimethyl silicone hydride method of saccharide compound according to claim 1, it is characterised in that：Solid-carried catalyst is
Catalyst is combined by polishing or solvent impregnation and is made with solid carrier, wherein catalyst be alkali metal perchlorate,
The halide of alkaline-earth metal, the perchlorate of alkaline-earth metal, the fluoroform sulphonate of alkaline-earth metal, transition metal halide,
One or more in the perchlorate of transition metal, the fluoroform sulphonate of transition metal；Solid carrier is silica gel, three oxidations
Two aluminium, titanium dioxide, diatomite, kaolin, vermiculite, saponite, molecular sieve or activated carbon.
5. the trimethyl silicone hydride method of saccharide compound according to claim 3, it is characterised in that：Saccharide compound is
Monose, oligosaccharides, sugar alcohol or glucoside compound.
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| CN114524839A (en) * | 2022-01-12 | 2022-05-24 | 湖北江瀚新材料股份有限公司 | Preparation method of stearyloxy trimethylsilane |
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