CN106588829B - Tetrahydrofuran C-H heterogeneous oxidation method - Google Patents
Tetrahydrofuran C-H heterogeneous oxidation method Download PDFInfo
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- CN106588829B CN106588829B CN201610954980.8A CN201610954980A CN106588829B CN 106588829 B CN106588829 B CN 106588829B CN 201610954980 A CN201610954980 A CN 201610954980A CN 106588829 B CN106588829 B CN 106588829B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-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
- C07D307/18—Heterocyclic compounds containing five-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
- C07D307/20—Oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
Abstract
The present invention relates to a kind of tetrahydrofuran C-H heterogeneous oxidation methods, 4 are embedded in organic silicon nano pipe, 4 '-[4- (trimethoxy silane) butyl] -2,2 '-bipyridyls and be coordinated dichloro (pentamethylcyclopentadiene base) close iridium dimer obtain iridium base bipyridyl-organic silicon nano pipe heterogeneous catalyst.The catalyst is mixed with tetrahydrofuran, using sodium metaperiodate as oxidant, heavy water is that solvent react under room temperature.The catalyst has clearly cellular structure, bigger serface, and uniform active sites have fine catalytic effect to tetrahydrofuran C-H oxidation, have higher stability because of it and easily recycle feature, so having good actual application prospect in the industry.
Description
Technical field
The present invention relates to a kind of tetrahydrofuran C-H heterogeneous system oxidation technologies, belong to the application of organic matter conversion aspect.
Background technique
Tetrahydrofuran (THF) also known as Isosorbide-5-Nitrae-epoxy butane, an oxygen five rings etc. are a kind of five-membered ring ether.Because it α position hydrogen compared with
Vivaciously, so being easily oxidized.Tetrahydrofuran oxidation product mainly has gamma-butyrolacton, 2- hydroxyl tetrahydrofuran, 1,4- fourth two
Acid, 4 hydroxybutyric acid etc..Wherein gamma-butyrolacton purposes is the most extensive, is important fine chemistry industry and medicine intermediate, main to use
In pyrrolidones series of products α-acetyl group, the synthesis of gamma-butyrolacton and medicine intermediate cyclopropylamine etc. is also applied to chemurgy
The fields such as, petrochemistry.Country's gamma-butyrolacton annual consumption is about 1.8 ten thousand tons at present, and wherein pyrrolones product consumption accounts for
50% or more (including N- methyl alpha-pyrrolidone, alpha-pyrrolidone, n-vinyl pyrrolidone and polyvinylpyrrolidone),
Cyclopropylamine accounts for 20%, α-vinyl gamma-butyrolacton and accounts for 20%, other account for 4% or so.With China's expanding economy, γ-Ding Nei
The application field of ester can more extensively, and the demand to gamma-butyrolacton will be increased with annual 10% or so speed.In addition, Isosorbide-5-Nitrae-
Succinic acid is also widely used for the industries such as medicine, pesticide, dyestuff, fragrance, paint, food, plastics, can also be used to synthesis one
A little important chemical products.Therefore the catalysis oxidation of research tetrahydrofuran has certain meaning.
Currently, the catalyst for aoxidizing tetrahydrofuran has transient metal complex, bromine and acid etc., wherein with transition metal
Complex is in the majority.But mostly based on homogeneous molecular catalyst, catalyst is very unstable in the reaction in this way, is oxidized easily
And lose activity, it is difficult to separate from reaction system again after reaction, so that catalyst cannot be recycled, so that largely
Catalyst wastes.And if homogeneous molecular catalyst is immobilized to (i.e. heterogeneous catalyst) on suitable carrier
Catalyst is solved to be difficult to recycle and the problems such as stability difference.Therefore, realize that homogeneous molecular catalyst heterogeneouss are used for tetrahydrofuran
C-H oxidation be current urgent problem to be solved.
Summary of the invention
The object of the present invention is to provide a kind of tetrahydrofuran C-H heterogeneous system oxidation technology, experimental provision needed for this method
Simply, easy to operate, obtained molecule heterogeneous catalyst large specific surface area, aperture is uniform, and active sites are evenly distributed, to tetrahydro
The C-H selective oxidation of furans has good catalytic effect.Because it has good stability and is easy from reaction system
It separates and is recycled, so having biggish actual application prospect in the industry.
The present invention is to be realized by the following technical programs, a kind of tetrahydrofuran C-H heterogeneous system oxidation technology,
It is characterized in that including following procedure:
(1) by potassium chloride, template, organosilane precursors 1,4- bis- (three ethoxy silicon substrates) benzene, 4,4 '-[4- (trimethoxies
Base silane) butyl] -2,2 '-bipyridyls sequentially add the mixture stirred to get in hydrochloric acid solution；
(2) obtained mixture is placed in 70-110 DEG C of insulating box and stands 20-30h；After to be filtered, dry, it will obtain
Solid product carry out reflux extraction under the conditions of being not less than 60 DEG C of temperature in ethyl alcohol and hydrochloric acid mixed solution, the time is no less than
6h is filtered, washed again later, is dried to obtain solid product bipyridyl-organic silicon nano pipe；
(3) under 60-80 DEG C of nitrogen atmosphere, by obtained bipyridyl-organic silicon nano pipe and dichloro (pentamethyl ring penta 2
Alkenyl) close iridium dimer flow back in ethanol；Solid product filters later, is sufficiently washed with water and n,N-Dimethylformamide,
Air drying obtains final iridium base bipyridyl-organic silicon nano pipe multiphase molecular catalyst；
(4) iridium base bipyridyl obtained-organic silicon nano pipe multiphase molecular catalyst and tetrahydrofuran are mixed, with high iodine
Sour sodium is oxidant, and reaction 12-24h is carried out at 20-40 DEG C by solvent of heavy water.
In the step 1), the substance withdrawl syndrome of potassium chloride is 0.098-0.39mol/L；The concentration of hydrochloric acid is 1.5-
2.5mol/L；The mass ratio of the material value range of organosilane precursors and template be 13:1-66:1, organosilane precursors with
The mass ratio of the material example range of 4,4 '-[4- (trimethoxy silane) butyl] -2,2 '-bipyridyls is 7/3:1-9:1.
Whipping temp is 30 DEG C -40 DEG C in the step 1), mixing time 12-24h.
In the step 2), drying temperature is 20 DEG C -100 DEG C.
Bipyridyl-organic silicon nano pipe and dichloro (pentamethylcyclopentadiene base) close the matter of iridium dimer in the step 3)
Amount is than being 10:1-20:1.
Reflux is no less than 12h in ethanol in the step 3).
The ratio between amount of substance of catalyst and tetrahydrofuran is between 1/200-1/50 in the step 4), the high iodine of oxidant
The amount of the substance of sour sodium is 2-8 times of tetrahydrofuran used；Heavy water volume is 100-300 times of tetrahydrofuran volume.
On the basis of meeting theoretical common sense, above-mentioned each condition can be recombinated arbitrarily, obtain preferable the method for the present invention.
It is an advantage of the current invention that heterogeneous catalyst is simple and easy in preparation process, tetrahydrofuran aoxidizes reaction condition temperature
With, it is important that we repeatedly can efficiently be recycled at catalyst obtained, and energy highly selective (being greater than 95%)
More tetrahydrofurans are oxidized to widely used gamma-butyrolacton and 1,2- succinic acid.Turn for the selectivity of more organic matters
Change and provides a kind of new possible ways.
Detailed description of the invention
Fig. 1 is 1 step 1 of embodiment, bipyridyl prepared by 2,3-organic silicon nano pipe heterogeneous catalyst electron microscopic picture.
Fig. 2 is bipyridyl-organic silicon nano pipe heterogeneous catalyst structure chart prepared by embodiment 1,2,3.
Fig. 3 is that tetrahydrofuran aoxidizes process in 1,2,3 step 4 of embodiment.
Fig. 4 is heterogeneous catalyst prepared by embodiment 1,2,3 and homogeneous catalyst stability test figure.
Fig. 5 is that tetrahydrofuran aoxidizes selectivity of product figure in 1,2,3 step 4 of embodiment.
Specific embodiment
Feature of the invention is further described below by example, but the invention is not limited to following examples.
(1) by potassium chloride, template (triblock copolymer surfactant polyoxyethylene-polyoxypropylene polyoxyethylene,
P123), organosilane precursors 1,4- bis- (three ethoxy silicon substrates) benzene, 4,4 '-[4- (trimethoxy silane) butyl] -2,2 '-connection
Pyridine sequentially adds in hydrochloric acid solution and stirs 12-24h at 30 DEG C -40 DEG C；
(2) mixture for obtaining step 1 is placed in 70-110 DEG C of insulating box and stands 20-30h；It, will after to be filtered, dry
Obtained solid product carries out reflux extraction under the conditions of being not less than 60 DEG C of temperature in ethyl alcohol and hydrochloric acid mixed solution, and the time is many
In 6h, it is filtered, washed again later, is dried to obtain solid product bipyridyl-organic silicon nano pipe；
(3) under 60-80 DEG C of nitrogen atmosphere, by obtained bipyridyl-organic silicon nano pipe and dichloro (pentamethyl ring penta 2
Alkenyl) close iridium dimer [Cp*IrCl (μ-Cl)]2Reflux is no less than 12h in ethanol；Solid product filters later, with water and
N,N-Dimethylformamide is sufficiently washed, and air drying obtains final iridium base bipyridyl-organic silicon nano pipe multiphase Journal of Molecular Catalysis
Agent.
(4) three mouthfuls of burnings are added in iridium base bipyridyl obtained-organic silicon nano pipe multiphase molecular catalyst and tetrahydrofuran
In bottle, using sodium metaperiodate as oxidant, reaction 12-24h is carried out at 20-40 DEG C by solvent of heavy water.
In step 1, the substance withdrawl syndrome of potassium chloride is 0.098-0.39mol/L；The concentration of hydrochloric acid is 1.5-
2.5mol/L, preferably 1.8-2.2mol/L；The mass ratio of the material value range of organosilane precursors and template is 13:1-66:
1, organosilane precursors and 4,4 '-[4- (trimethoxy silane) butyl] -2, the mass ratio of the material example range of 2 '-bipyridyls is
7/3:1-9:1。
In step 2, drying temperature is 20 DEG C -100 DEG C, preferably 50 DEG C -70 DEG C.
Bipyridyl-organic silicon nano pipe and dichloro (pentamethylcyclopentadiene base) close the mass ratio of iridium dimer in step 3
For 10:1-20:1.
The ratio between amount of substance of catalyst and tetrahydrofuran is between 1/200-1/50 in step 4, oxidizing agent sodium periodate
The amount of substance be 2-8 times, preferably 4-6 times of tetrahydrofuran used.Solvent volume is 100-300 times of tetrahydrofuran volume.
Embodiment 1
Step 1: 0.875g KCl and 0.275g triblock copolymer surfactant polyoxyethylene-polyoxypropylene-is poly-
Ethylene oxide EO20-PO70-EO20 (P123) is dissolved in 120mL 1.8M hydrochloric acid solution, and quickly stirring forms it into homogeneous transparent
Solution is added bis- (the three ethoxy silicon substrates) benzene of 3.15mmol organosilane precursors Isosorbide-5-Nitrae-and continues strong stirring, reduces stirring rate
Continue to stir, then bipyridyl presoma 4,4 '-[4- (Trimethoxysilanyl) butyl] -2,2 '-is added in 0.35mmol
Bipyridine is stirred for 24 hours at 30 DEG C.
Step 2: obtained white emulsion being added in 100ml polytetrafluoroethylliner liner and is placed in 70 DEG C of thermostatic drying chambers
In, it after standing 30h, is filtered using sand core funnel, is repeatedly washed with deionized water and guarantee that there is no bubble generations in filtrate.
After obtained product is dried and dehydrated at 20 DEG C, (extractant is extracted under the conditions of carrying out 60 DEG C using ethyl alcohol and concentrated hydrochloric acid
For dehydrated alcohol and concentrated hydrochloric acid mixed solution, the two volume ratio is the 10h that 100/1) flows back.It is again that it is dry at 20 DEG C later,
Obtain solid product bipyridyl-organic silicon nano pipe.
Step 3: under 60 DEG C of nitrogen atmospheres, bipyridyl-organic silicon nano pipe and 0.1g [Cp*IrCl (μ-that 1g is obtained
Cl)]2It flows back in ethanol for 24 hours, solid product filters later, is sufficiently washed with water and n,N-Dimethylformamide, air drying
Obtain final bipyridyl-organic silicon nano pipe multiphase molecular catalyst.
Step 4: under 20 DEG C of nitrogen atmosphere environment, the 0.003mmol heterogeneous catalyst prepared being added to equipped with 10mL
In the three-necked flask of heavy water, the reactant tetrahydrofuran of 0.6mmol is then added, 1.2mmol sodium periodate oxidation is added later
The trimethylsilyl sodium propionate internal standard compound of agent and correct amount is reacted for 24 hours.Finally utilize liquid core magnetic test oxidation product
Amount.
Embodiment 2
Step 1: by 1.75g KCl and 0.55g triblock copolymer surfactant polyoxyethylene-polyoxypropylene-polyoxy
Ethylene EO20-PO70-EO20 (P123) is dissolved in 120mL 2M hydrochloric acid solution, and quickly it is molten to form it into homogeneous transparent for stirring
Liquid is added bis- (triethoxy silicon substrate) benzene of 2.8mmol organosilane precursors Isosorbide-5-Nitrae-and continues strong stirring, reduce stirring rate after
Continuous stirring, is then added 0.7mmol bipyridyl presoma 4,4 '-[4- (Trimethoxysilanyl) butyl] -2,2 ' -
Bipyridine stirs 18h at 35 DEG C.
Step 2: obtained white emulsion being added in 100ml polytetrafluoroethylliner liner and is placed in 90 DEG C of thermostatic drying chambers
In, it after standing 25h, is filtered using sand core funnel, is repeatedly washed with deionized water and guarantee that there is no bubble generations in filtrate.
After obtained product is dried and dehydrated at 50 DEG C, extract return method 8h under the conditions of carrying out 70 DEG C using ethyl alcohol and concentrated hydrochloric acid.
It is again that it is dry at 50 DEG C later, obtain solid product bipyridyl-organic silicon nano pipe.
Step 3: under 70 DEG C of nitrogen atmospheres, bipyridyl-organic silicon nano pipe and 0.1g [Cp*IrCl that 1.5g is obtained
(μ-Cl)]2Flow back 18h in ethanol, and solid product filters later, is sufficiently washed with water and n,N-Dimethylformamide, room temperature
Drying can equally obtain final bipyridyl-organic silicon nano pipe multiphase molecular catalyst.
Step 4: under 30 DEG C of nitrogen atmosphere environment, the 0.006mmol heterogeneous catalyst prepared being added to equipped with 5mL weight
In the three-necked flask of water, the reactant tetrahydrofuran of 0.6mmol is then added, the agent of 2.4mmol sodium periodate oxidation is added later
Reaction 18h is carried out with the trimethylsilyl sodium propionate internal standard compound of correct amount.Finally utilize liquid core magnetic test oxidation product
Amount.
Embodiment 3
Step 1: by 3.5KCl and 1.1g triblock copolymer surfactant polyoxyethylene-polyoxypropylene polyoxyethylene
EO20-PO70-EO20 (P123) is dissolved in the hydrochloric acid solution of 120mL 2.2M, and quickly it is molten to form it into homogeneous transparent for stirring
Liquid is added bis- (triethoxy silicon substrate) benzene of 2.45mmol organosilane precursors Isosorbide-5-Nitrae-and continues strong stirring, reduces stirring rate
Continue to stir, 1.05mmol bipyridyl presoma 4,4 '-[4- (Trimethoxysilanyl) butyl] -2,2 '-is then added
Bipyridine stirs 12h at 40 DEG C.
Step 2: obtained white emulsion being added in 100ml polytetrafluoroethylliner liner and is placed in 110 DEG C of thermostatic drying chambers
In, 20h is stood, is filtered using sand core funnel, is repeatedly washed with deionized water and guarantees that there is no bubble generations in filtrate.?
After obtained product is dried and dehydrated at 60 DEG C, extract return method is carried out under the conditions of carrying out 80 DEG C using ethyl alcohol and concentrated hydrochloric acid
6h.It is again that it is dry at 60 DEG C later, obtain solid product bipyridyl-organic silicon nano pipe.
Step 3: under 80 DEG C of nitrogen atmospheres, bipyridyl-organic silicon nano pipe and 0.1g [Cp*IrCl (μ-that 2g is obtained
Cl)]2Flow back 12h in ethanol, and solid product filters later, is sufficiently washed with water and n,N-Dimethylformamide, air drying
It equally can also obtain final bipyridyl-organic silicon nano pipe multiphase molecular catalyst.
Step 4: under 40 DEG C of nitrogen atmosphere environment, the 0.012mmol heterogeneous catalyst prepared being added to equipped with 15mL
In the three-necked flask of heavy water, the reactant tetrahydrofuran of 0.6mmol is then added, 3.6mmol sodium periodate oxidation is added later
The trimethylsilyl sodium propionate internal standard compound of agent and correct amount carries out reaction 12h.Finally utilize liquid core magnetic test oxidation product
Amount.
Embodiment 4
Step 1: by 3.5KCl and 1.1g triblock copolymer surfactant polyoxyethylene-polyoxypropylene polyoxyethylene
EO20-PO70-EO20 (P123) is dissolved in the hydrochloric acid solution of 120mL 1.5M, and quickly it is molten to form it into homogeneous transparent for stirring
Liquid is added bis- (triethoxy silicon substrate) benzene of 2.45mmol organosilane precursors Isosorbide-5-Nitrae-and continues strong stirring, reduces stirring rate
Continue to stir, 1.05mmol bipyridyl presoma 4,4 '-[4- (Trimethoxysilanyl) butyl] -2,2 '-is then added
Bipyridine stirs 12h at 40 DEG C.
Step 2: obtained white emulsion being added in 100ml polytetrafluoroethylliner liner and is placed in 110 DEG C of thermostatic drying chambers
In, 20h is stood, is filtered using sand core funnel, is repeatedly washed with deionized water and guarantees that there is no bubble generations in filtrate.?
After obtained product is dried and dehydrated at 70 DEG C, extract return method is carried out under the conditions of carrying out 80 DEG C using ethyl alcohol and concentrated hydrochloric acid
6h.It is again that it is dry at 70 DEG C later, obtain solid product bipyridyl-organic silicon nano pipe.
Step 3: under 80 DEG C of nitrogen atmospheres, bipyridyl-organic silicon nano pipe and 0.1g [Cp*IrCl (μ-that 2g is obtained
Cl)]2Flow back 12h in ethanol, and solid product filters later, is sufficiently washed with water and n,N-Dimethylformamide, air drying
It equally can also obtain final bipyridyl-organic silicon nano pipe multiphase molecular catalyst.
Step 4: under 40 DEG C of nitrogen atmosphere environment, the 0.012mmol heterogeneous catalyst prepared being added to equipped with 15mL
In the three-necked flask of heavy water, the reactant tetrahydrofuran of 0.6mmol is then added, 4.8mmol sodium periodate oxidation is added later
The trimethylsilyl sodium propionate internal standard compound of agent and correct amount carries out reaction 12h.Finally utilize liquid core magnetic test oxidation product
Amount.
Embodiment 5
Step 1: by 3.5KCl and 1.1g triblock copolymer surfactant polyoxyethylene-polyoxypropylene polyoxyethylene
EO20-PO70-EO20 (P123) is dissolved in the hydrochloric acid solution of 120mL 2.5M, and quickly it is molten to form it into homogeneous transparent for stirring
Liquid is added bis- (triethoxy silicon substrate) benzene of 2.45mmol organosilane precursors Isosorbide-5-Nitrae-and continues strong stirring, reduces stirring rate
Continue to stir, 1.05mmol bipyridyl presoma 4,4 '-[4- (Trimethoxysilanyl) butyl] -2,2 '-is then added
Bipyridine stirs 12h at 40 DEG C.
Step 2: obtained white emulsion being added in 100ml polytetrafluoroethylliner liner and is placed in 110 DEG C of thermostatic drying chambers
In, 20h is stood, is filtered using sand core funnel, is repeatedly washed with deionized water and guarantees that there is no bubble generations in filtrate.?
After obtained product is dried and dehydrated at 100 DEG C, extract return method is carried out under the conditions of carrying out 80 DEG C using ethyl alcohol and concentrated hydrochloric acid
6h.It is again that it is dry at 100 DEG C later, obtain solid product bipyridyl-organic silicon nano pipe.
Step 3: under 80 DEG C of nitrogen atmospheres, bipyridyl-organic silicon nano pipe and 0.1g [Cp*IrCl (μ-that 2g is obtained
Cl)]2Flow back 12h in ethanol, and solid product filters later, is sufficiently washed with water and n,N-Dimethylformamide, air drying
It equally can also obtain final bipyridyl-organic silicon nano pipe multiphase molecular catalyst.
Step 4: under 40 DEG C of nitrogen atmosphere environment, the 0.012mmol heterogeneous catalyst prepared being added to equipped with 15mL
In the three-necked flask of heavy water, the reactant tetrahydrofuran of 0.6mmol is then added, the agent of 3mmol sodium periodate oxidation is added later
Reaction 12h is carried out with the trimethylsilyl sodium propionate internal standard compound of correct amount.Finally utilize liquid core magnetic test oxidation product
Amount.
Using F20 transmission electron microscopes (TEM) of Dutch FEI Co. Tecnai G2 and Hitachi, Japan
Hitachi S-4800 scanning electron microscope (SEM) analyzes sample microscopic appearance, and Fig. 1 show heterogeneous catalyst
TEM and SEM picture, it can be seen that organic silicon nano pipe is about 6nm with clearly nano tubular structure, caliber, and thickness of pipe wall is about
For 3nm.Fig. 2 be multiphase molecular catalyst structure, can find out from structure chart we be homogeneous molecular complex it is immobilized to
On organic silicon nano pipe, to realize the purpose of molecular catalyst multiphase.
Fig. 3 be tetrahydrofuran aoxidize product, there are many oxidation product, but mainly with gamma-butyrolacton, 2- hydroxyl tetrahydrofuran,
Based on 1,4- succinic acid.Fig. 4 is heterogeneous catalyst and homogeneous catalyst stability test, it can be seen that heterogeneous catalyst can be high
Effect is recycled for multiple times, and has good stability.Fig. 5 is the selective figure of tetrahydrofuran difference oxidation product.From figure
It will be seen that heterogeneous catalyst can make being oxidized to for tetrahydrofuran selectivity apply more extensive gamma-butyrolacton and 1,
4- succinic acid.This is mainly due to the duct effect of interaction and organic silicon nano pipe between carrier and molecular catalyst
It answers.
The present invention, which discloses, proposes a kind of tetrahydrofuran C-H heterogeneous system oxidation technology.Although method and system of the invention
Standby technology is described by preferred embodiments, and related technical personnel can not depart from the content of present invention, in spirit and scope
Methods and techniques described herein is modified or is reconfigured, to realize final technology of preparing.In particular
It is that all similar replacements and change are apparent to those skilled in the art, they are considered as being included in
In spirit of that invention, range and content.
Claims (7)
1. a kind of tetrahydrofuran C-H heterogeneous oxidation method；It is characterized by comprising following procedure:
(1) by potassium chloride, template, organosilane precursors 1,4- bis- (three ethoxy silicon substrates) benzene, 4,4 '-[4- (trimethoxy silicon
Alkane) butyl] -2,2 '-bipyridyls sequentially add the mixture stirred to get in hydrochloric acid solution；
(2) obtained mixture is placed in 70-110 DEG C of insulating box and stands 20-30h；After to be filtered, dry, consolidate what is obtained
Body product carries out reflux extraction under the conditions of being not less than 60 DEG C of temperature in ethyl alcohol and hydrochloric acid mixed solution, and the time is no less than 6h, it
It is filtered, washed again afterwards, is dried to obtain solid product bipyridyl-organic silicon nano pipe；
(3) under 60-80 DEG C of nitrogen atmosphere, by obtained bipyridyl-organic silicon nano pipe and dichloro (pentamethylcyclopentadiene
Base) close iridium dimer flow back in ethanol；Solid product filters later, is sufficiently washed with water and n,N-Dimethylformamide,
Air drying obtains final iridium base bipyridyl-organic silicon nano pipe multiphase molecular catalyst；
(4) iridium base bipyridyl obtained-organic silicon nano pipe multiphase molecular catalyst and tetrahydrofuran are mixed, with sodium metaperiodate
For oxidant, reaction 12-24h is carried out at 20-40 DEG C by solvent of heavy water.
2. the method as described in claim 1, it is characterized in that the substance withdrawl syndrome of potassium chloride is 0.098- in the step 1)
0.39mol/L；The concentration of hydrochloric acid is 1.5-2.5mol/L；The mass ratio of the material value range of organosilane precursors and template
For 13:1-66:1, organosilane precursors and 4,4 '-[4- (trimethoxy silane) butyl] -2, the amount of the substance of 2 '-bipyridyls
Proportional region is 7:3-9:1.
3. the method as described in claim 1, it is characterized in that whipping temp is 30 DEG C -40 DEG C in the step 1), mixing time
For 12-24h.
4. the method as described in claim 1, it is characterized in that drying temperature is 20 DEG C -100 DEG C in the step 2).
5. the method as described in claim 1, it is characterized in that bipyridyl-organic silicon nano pipe and dichloro (five in the step 3)
Methyl cyclopentadienyl) mass ratio of iridium dimer is closed as 10-20:1.
6. the method as described in claim 1, it is characterized in that reflux is no less than 12h in ethanol in the step 3).
7. the method as described in claim 1, it is characterized in that in the step 4) substance of catalyst and tetrahydrofuran amount it
Than between 1/200-1/50, the amount of the substance of oxidizing agent sodium periodate is 2-8 times of tetrahydrofuran used；Solvent volume is four
100-300 times of hydrogen furans volume.
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