CN110327964A - A kind of vanadium catalyst and preparation method thereof for thioether selective oxidation - Google Patents
A kind of vanadium catalyst and preparation method thereof for thioether selective oxidation Download PDFInfo
- Publication number
- CN110327964A CN110327964A CN201910709661.4A CN201910709661A CN110327964A CN 110327964 A CN110327964 A CN 110327964A CN 201910709661 A CN201910709661 A CN 201910709661A CN 110327964 A CN110327964 A CN 110327964A
- Authority
- CN
- China
- Prior art keywords
- vanadium
- catalyst
- thioether
- dicyandiamide
- chitosan
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 27
- 150000003568 thioethers Chemical class 0.000 title claims abstract description 27
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 25
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 229920001661 Chitosan Polymers 0.000 claims abstract description 22
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000003462 sulfoxides Chemical class 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims description 43
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 18
- 238000001291 vacuum drying Methods 0.000 claims description 18
- 235000015110 jellies Nutrition 0.000 claims description 17
- 239000008274 jelly Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- YWOQNRUBCZGGTI-UHFFFAOYSA-N phenylsulfanylmethanamine Chemical compound NCSC1=CC=CC=C1 YWOQNRUBCZGGTI-UHFFFAOYSA-N 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- 238000011010 flushing procedure Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- -1 cyanogen Amine Chemical class 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 239000000376 reactant Substances 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- JXTGICXCHWMCPM-UHFFFAOYSA-N (methylsulfinyl)benzene Chemical compound CS(=O)C1=CC=CC=C1 JXTGICXCHWMCPM-UHFFFAOYSA-N 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- PNKHPQMATQQYFZ-UHFFFAOYSA-N propan-2-one;vanadium Chemical compound [V].CC(C)=O PNKHPQMATQQYFZ-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000001772 anti-angiogenic effect Effects 0.000 description 1
- 230000000767 anti-ulcer Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003177 cardiotonic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/394—
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
Abstract
A kind of vanadium catalyst and preparation method thereof for thioether selective oxidation, using chitosan as carbon source and nitrogen source, using dicyandiamide as auxiliary carbon source and nitrogen source, using vanadium acetylacetonate as vanadium source, utilize the coordination of amino or hydroxyl and metal formation complex compound in chitosan and dicyandiamide molecular structure, vanadium species are dispersed in the structure of chitosan and dicyandiamide, then in N2Above-mentioned raw materials are heat-treated at 550~950 DEG C under atmosphere, prepare N doping porous carbon load catalytic component based on vanadium, in the catalyst, the weight percent of metal V is that 5~10%, N weight percent is 3~8%.The catalyst shows high activity, highly selective and high stability catalytic property in the reaction of thioether selective oxidation sulfoxide.
Description
Technical field
It is the present invention relates to a kind of heterogeneous catalyst and preparation method thereof, in particular to a kind of for thioether selective oxidation
Vanadium catalyst and preparation method thereof.
Background technique
Sulfoxides are important sulfur-containing compound, and sulphur atom therein is tetrahedral structure, there is a pair of of lone pair electrons,
Similar to sp3The carbon atom of hydridization.In addition, sulfoxide compound can be used for antiulcer as a kind of important organic intermediate
In the medical products such as drug, cardiotonic and anti-angiogenic expansion, and also have extensively in fine chemistry industry, pesticide and organic synthesis industry
Using.
Thioether selective oxidation is the most succinct method for synthesizing sulfoxide, but sulfide oxidation generates corresponding sulfone class production because existing
The possibility of object, so the highly selective sulfoxide type product that obtains proposes high requirement to the oxidation reaction of thioether.Traditional life
Production method mostly uses metal oxide and organic peroxide is oxidant, directly progress oxidation reaction.For example, Palmieri etc.
People is aoxidized (Synthetic communications, 1984,14,1111- using concentrated nitric acid and tetrabutyl chlorauride ammonium salt
1117)；Asady et al. aoxidized using acid iodide and silica (Synthetic communications, 2005,35,
775-784)；Beller et al. aoxidized using hydrogen peroxide (Advanced Synthesis&Catalysis, 2007,
349,2425-2430), but these methods or poisonous and harmful expensive reagent is used, or the not high substrate of selectivity is suitable
It is wideless with property, or be easy substrate peroxidating generating sulfone.A large amount of generations of especially waste affect greatly environment, no
Meet the requirement of Modern Green chemical industry.Therefore, the high-performance heterogeneous catalyst for developing a kind of preparation method simplicity carrys out selective oxygen
Changing thioether becomes urgent problem to be solved to sulfoxide.
Summary of the invention
The catalyst activity that sulfoxide is generated for existing thioether selective oxidation is not high and is easy to run off there are active component
Problem, the technical problem to be solved in the present invention is to provide what a kind of high activity, highly selective, easy recycling were reused to be used for thioether
Vanadium catalyst of selective oxidation and preparation method thereof.
To solve this technical problem, the technical solution adopted by the present invention are as follows:
A kind of vanadium catalyst for thioether selective oxidation, it is characterised in that: using chitosan as carbon source and nitrogen source, with double
Cyanamide be auxiliary carbon source and nitrogen source, using vanadium acetylacetonate as vanadium source, using in chitosan and dicyandiamide molecular structure amino or
Hydroxyl and metal form the coordination of complex compound, vanadium species are dispersed in the structure of chitosan and dicyandiamide, then in N2
Above-mentioned raw materials are heat-treated at 550~950 DEG C under atmosphere, directly prepare N doping porous carbon load catalytic component based on vanadium,
In the catalyst, the weight percent of metal V is that 5~10%, N weight percent is 3~8%.
The preparation method of the catalyst the following steps are included:
(1) chitosan and dicyandiamide are placed in the round-bottomed flask of 250mL by weight the ratio for 1:1~5, then plus
Enter the acetum 120mL that concentration is 2%, above-mentioned solution is placed in 60~90 DEG C of stirred in water bath 12h；
(2) vanadium acetylacetonate is added in the ratio that dicyandiamide molar ratio in vanadium acetylacetonate and step (1) is 1:10~20
Enter into the solution of step (1), and heating stirring 8h forms jelly in 60~80 DEG C of water-bath, is then placed in jelly
In vacuum drying oven dry 10 at 80~120 DEG C~sample is obtained for 24 hours；
(3) by sample obtained by step (2) in N2Under atmosphere, with 2.3 DEG C of min-1Heating rate, temperature is risen to 550
~950 DEG C, it is heat-treated 3~10h, is cooled to room temperature, obtains black solid；
(4) black solid that step (3) obtains is immersed in 1~5M aqueous sulfuric acid, is heated to 60~90 DEG C of processing
Collect solid afterwards for 24 hours, and it to solution is neutral with distilled water flushing.Obtained solid is finally placed in 120 DEG C of vacuum drying ovens
Middle dry 12h, obtained black solid catalyst i.e. of the present invention.
Application of the above-mentioned catalyst in thioether selective oxidation sulfoxide, it is characterised in that: the catalyst is used for thioether
The reaction of selective oxidation sulfoxide, by corresponding substrate (aminomethyl phenyl thioether), solvent (acetonitrile), oxidant (tert-butyl mistake
Hydrogen oxide) and catalyst reaction, reaction temperature is 40 DEG C.
Porous carbon materials are because its source is wide, acid and alkali-resistance, has the characteristics that bigger serface is industrially widely used.It grinds
Study carefully the reactivity worth for showing that the incorporation of nitrogen-atoms helps to improve load type metal catalyst.The present invention prepares this N in design
When adulterating porous carbon load high degree of dispersion catalytic component based on vanadium, amino or hydroxyl abundant in chitosan and dicyandiamide molecular structure are utilized
Base and metal form the huge ability of complex compound, vanadium species are highly dispersed in chitosan and dicyandiamide structure, then in N2
Above-mentioned raw materials are heat-treated under atmospheric condition, directly prepare the catalytic component based on vanadium with high degree of dispersion.Due to inertia height
Strong interaction may occur between the lone pair electrons of N species and the d track of V species in warm treatment process, so that obtained N
Adulterating porous carbon load catalytic component based on vanadium has high stability.So the final catalyst that we prepare is in thioether selectivity oxygen
Change in the reaction of sulfoxide processed and shows high activity, highly selective and high stability catalytic property.Further, since the metal being added
The dosage in vanadium source is far smaller than the total amount of nitrogen in system so that the metal V of the overwhelming majority is finally expected to prepare with N coordination
The catalytic component based on vanadium of high degree of dispersion out.So far, using chitosan and dicyandiamide prepared as carbon source and nitrogen source N adulterate it is more
The carbon material supported high degree of dispersion catalytic component based on vanadium in hole, and the research for being applied to thioether selective oxidation reaction not yet appears in the newspapers
Road.
Specific embodiment
The present invention is further illustrated below by embodiment, but the present invention is not limited thereto.
Embodiment 1
The dicyandiamide of the chitosan of 1.0g and 1.0g is placed in the round-bottomed flask of 250mL by weight for the ratio of 1:1,
Then the acetum 120mL that concentration is 2% is added, above-mentioned solution is placed in 60 DEG C of water-bath and is stirred 12h；By acetyl
Dicyandiamide molar ratio is the ratio of 1:10 in acetone vanadium and above-mentioned solution, and 1.6g vanadium acetylacetonate is added in solution, and 60
DEG C water-bath in heating stirring 8h form jelly, jelly is then placed in vacuum drying oven at 80 DEG C dry 10h；By gained
Sample is in N2Under atmosphere, with 2.3 DEG C of min-1Heating rate, temperature is risen to 550 DEG C, 5h is heat-treated, is cooled to room temperature, obtains
To black solid；Obtained black solid is immersed in 1M aqueous sulfuric acid, 60 DEG C of processing is heated to and collects solid afterwards for 24 hours,
And it to solution is neutral with distilled water flushing.Obtained solid is finally placed in 120 DEG C of vacuum drying ovens dry 12h, is obtained
Black solid be catalyst of the present invention.It is 8% that the weight percent of metal V, which is 5%, N weight percent, in the catalyst.
Take reaction of the 40mg catalyst for thioether selective oxidation sulfoxide, reactant aminomethyl phenyl thioether
0.120mL, oxidant tert-butyl hydroperoxide 0.20mL, solvent acetonitrile 3.0mL, reacts by 40 DEG C of reaction temperature, reaction time 8h
As a result: methyl phenyl sulfoxide yield is 90%.
Embodiment 2
The dicyandiamide of the chitosan of 1.0g and 5.0g is placed in the round-bottomed flask of 250mL by weight for the ratio of 1:5,
Then the acetum 120mL that concentration is 2% is added, above-mentioned solution is placed in 80 DEG C of water-bath and is stirred 12h；By acetyl
Dicyandiamide molar ratio is the ratio of 1:20 in acetone vanadium and above-mentioned solution, and 4.1g vanadium acetylacetonate is added in solution, and
Heating stirring 8h forms jelly in 90 DEG C of water-bath, and jelly is then placed in vacuum drying oven at 120 DEG C dry 12h；It will
Gained sample is in N2Under atmosphere, with 2.3 DEG C of min-1Heating rate, temperature is risen to 950 DEG C, 3h is heat-treated, is cooled to room
Temperature obtains black solid；Obtained black solid is immersed in 5M aqueous sulfuric acid, 90 DEG C of processing is heated to and collects afterwards for 24 hours
Solid, and it to solution is neutral with distilled water flushing.Obtained solid is finally placed in 120 DEG C of vacuum drying ovens dry 12h,
Obtained black solid is catalyst of the present invention.The weight percent of metal V is 10%, N weight percent in the catalyst
It is 3%.
Take reaction of the 40mg catalyst for thioether selective oxidation sulfoxide, reactant aminomethyl phenyl thioether
0.120mL, oxidant tert-butyl hydroperoxide 0.20mL, solvent acetonitrile 3.0mL, reacts by 40 DEG C of reaction temperature, reaction time 8h
As a result: methyl phenyl sulfoxide yield is 92%.
Embodiment 3
The dicyandiamide of the chitosan of 1.0g and 3.0g is placed in the round-bottomed flask of 250mL by weight for the ratio of 1:3,
Then the acetum 120mL that concentration is 2% is added, above-mentioned solution is placed in 70 DEG C of water-bath and is stirred 12h；By acetyl
Dicyandiamide molar ratio is the ratio of 1:15 in acetone vanadium and above-mentioned solution, and 3.3g vanadium acetylacetonate is added in solution, and
Heating stirring 8h forms jelly in 70 DEG C of water-bath, and jelly is then placed in vacuum drying oven at 100 DEG C dry 12h；It will
Gained sample is in N2Under atmosphere, with 2.3 DEG C of min-1Heating rate, temperature is risen to 750 DEG C, 6h is heat-treated, is cooled to room
Temperature obtains black solid；Obtained black solid is immersed in 2M aqueous sulfuric acid, 70 DEG C of processing is heated to and collects afterwards for 24 hours
Solid, and it to solution is neutral with distilled water flushing.Obtained solid is finally placed in 120 DEG C of vacuum drying ovens dry 12h,
Obtained black solid is catalyst of the present invention.The weight percent of metal V is that 8%, N weight percent is in the catalyst
4%.
Take reaction of the 40mg catalyst for thioether selective oxidation sulfoxide, reactant aminomethyl phenyl thioether
0.120mL, oxidant tert-butyl hydroperoxide 0.20mL, solvent acetonitrile 3.0mL, reacts by 40 DEG C of reaction temperature, reaction time 8h
As a result: methyl phenyl sulfoxide yield is 97%.
Embodiment 4
The dicyandiamide of the chitosan of 1.0g and 2.5g is placed in the round-bottomed flask of 250mL by weight the ratio for 1:2.5
In, the acetum 120mL that concentration is 2% is then added, above-mentioned solution is placed in 80 DEG C of water-bath and is stirred 12h；It presses
Dicyandiamide molar ratio is the ratio of 1:12 in vanadium acetylacetonate and above-mentioned solution, and 3.5g vanadium acetylacetonate is added in solution,
And heating stirring 8h forms jelly in 85 DEG C of water-bath, and jelly is then placed in vacuum drying oven at 90 DEG C dry 18h；
By gained sample in N2Under atmosphere, with 2.3 DEG C of min-1Heating rate, temperature is risen to 850 DEG C, 8h is heat-treated, is cooled to
Room temperature obtains black solid；Obtained black solid is immersed in 3.5M aqueous sulfuric acid, after being heated to 80 DEG C of processing for 24 hours
Collect solid, and it to solution is neutral with distilled water flushing.Finally obtained solid is placed in 120 DEG C of vacuum drying ovens dry
12h, obtained black solid are catalyst of the present invention.The weight percent of metal V is 7%, N weight percent in the catalyst
Number is 5%.
Take reaction of the 40mg catalyst for thioether selective oxidation sulfoxide, reactant aminomethyl phenyl thioether
0.120mL, oxidant tert-butyl hydroperoxide 0.20mL, solvent acetonitrile 3.0mL, reacts by 40 DEG C of reaction temperature, reaction time 8h
As a result: methyl phenyl sulfoxide yield is 92%.
Embodiment 5
The dicyandiamide of the chitosan of 1.0g and 4.0g is placed in the round-bottomed flask of 250mL by weight for the ratio of 1:4,
Then the acetum 120mL that concentration is 2% is added, above-mentioned solution is placed in 80 DEG C of water-bath and is stirred 12h；By acetyl
Dicyandiamide molar ratio is the ratio of 1:18 in acetone vanadium and above-mentioned solution, and 3.7g vanadium acetylacetonate is added in solution, and
Heating stirring 8h forms jelly in 65 DEG C of water-bath, and then jelly is placed in vacuum drying oven at 95 DEG C and is dried for 24 hours；By institute
Sample is obtained in N2Under atmosphere, with 2.3 DEG C of min-1Heating rate, temperature is risen to 650 DEG C, 10h is heat-treated, is cooled to room
Temperature obtains black solid；Obtained black solid is immersed in 2.5M aqueous sulfuric acid, 65 DEG C of processing is heated to and receives afterwards for 24 hours
Collect solid, and it to solution is neutral with distilled water flushing.Finally obtained solid is placed in 120 DEG C of vacuum drying ovens dry
12h, obtained black solid are catalyst of the present invention.The weight percent of metal V is 5%, N weight percent in the catalyst
Number is 7%.
Take reaction of the 40mg catalyst for thioether selective oxidation sulfoxide, reactant aminomethyl phenyl thioether
0.120mL, oxidant tert-butyl hydroperoxide 0.20mL, solvent acetonitrile 3.0mL, reacts by 40 DEG C of reaction temperature, reaction time 8h
As a result: methyl phenyl sulfoxide yield is 89%.
Application examples 1
The reaction for being applied to thioether selective oxidation sulfoxide according to catalytic component based on vanadium 40.0mg prepared by embodiment 1 is taken,
Reactant aminomethyl phenyl thioether 0.120mL, oxidant tert-butyl hydroperoxide 0.20mL, solvent acetonitrile 3.0mL, reaction temperature 40
DEG C, reaction time 8h.Catalyst is reused 10 times, and the yield of sulfoxide is held in 95%.
Comparative example 1
The dicyandiamide of the chitosan of 1.0g and 1.0g is placed in the round-bottomed flask of 250mL by weight for the ratio of 1:1,
Then the acetum 120mL that concentration is 2% is added, above-mentioned solution is placed in 60 DEG C of water and is stirred to form jelly
Stop heating afterwards, then will obtain sample and be placed in vacuum drying oven at 100 DEG C dry 12h；By gained sample in N2Under atmosphere, with
2.3℃·min-1Heating rate, temperature is risen to 550 DEG C, 5h is heat-treated, is cooled to room temperature, obtains black solid；It will obtain
Black solid be immersed in 1M aqueous sulfuric acid, be heated to 60 DEG C of processing and collect solid afterwards for 24 hours, and with distilled water flushing its extremely
Solution is neutrality.Obtained solid is finally placed in 120 DEG C of vacuum drying ovens dry 12h, obtained black solid is N doping
Porous carbon support material.
40mg N doping porous carbon support is taken to be used for the reaction of thioether selective oxidation sulfoxide, reactant aminomethyl phenyl sulphur
Ether 0.120mL, oxidant tert-butyl hydroperoxide 0.20mL, solvent acetonitrile 3.0mL, 40 DEG C of reaction temperature, reaction time 8h, instead
Answer result: methyl phenyl sulfoxide yield is 3%.
Comparative example 2
The chitosan of 1.0g is placed in the round-bottomed flask of 250mL, the acetum 120mL that concentration is 2% is then added,
Above-mentioned solution is placed in 60 DEG C of water-bath and is stirred 12h；It is by vanadium acetylacetonate and chitosan molar ratio in above-mentioned solution
0.4g vanadium acetylacetonate is added in solution by the ratio of 1:10, and heating stirring 8h forms jelly in 60 DEG C of water-bath,
Then sample will be obtained and be placed in vacuum drying oven at 80 DEG C dry 10h；Above-mentioned solution is placed in 60 DEG C of water be stirred with
Stop heating after forming jelly, then will obtain sample and be placed in vacuum drying oven at 100 DEG C dry 12h；Gained sample is existed
N2Under atmosphere, with 2.3 DEG C of min-1Heating rate, temperature is risen to 550 DEG C, 5h is heat-treated, is cooled to room temperature, obtains black
Solid；Obtained black solid is immersed in 1M aqueous sulfuric acid, 60 DEG C of processing is heated to and collects solid afterwards for 24 hours, and with steaming
It is neutral that distilled water, which rinses it to solution,.Obtained solid is finally placed in 120 DEG C of vacuum drying ovens dry 12h, obtained black
Solid is catalyst of the present invention.
Take reaction of the 40mg catalyst for thioether selective oxidation sulfoxide, reactant aminomethyl phenyl thioether
0.120mL, oxidant tert-butyl hydroperoxide 0.20mL, solvent acetonitrile 3.0mL, reacts by 40 DEG C of reaction temperature, reaction time 8h
As a result: methyl phenyl sulfoxide yield is 15%.
Claims (4)
1. a kind of vanadium catalyst for thioether selective oxidation, it is characterised in that: using chitosan as carbon source and nitrogen source, with double cyanogen
Amine utilizes the amino or hydroxyl in chitosan and dicyandiamide molecular structure using vanadium acetylacetonate as vanadium source for auxiliary carbon source and nitrogen source
Base and metal form the coordination of complex compound, vanadium species are dispersed in the structure of chitosan and dicyandiamide, then in N2Gas
Above-mentioned raw materials are heat-treated at 550~950 DEG C under atmosphere, prepare N doping porous carbon load catalytic component based on vanadium, the catalysis
In agent, the weight percent of metal V is that 5~10%, N weight percent is 3~8%.
2. a kind of preparation method of the vanadium catalyst for thioether selective oxidation, it is characterised in that the following steps are included:
(1) chitosan and dicyandiamide are placed in the round-bottomed flask of 250mL by weight the ratio for 1:1~5, are then added dense
Above-mentioned solution, is placed in 60~90 DEG C of stirred in water bath 12h by the acetum 120mL that degree is 2%；
(2) vanadium acetylacetonate is added in the ratio that dicyandiamide molar ratio in vanadium acetylacetonate and step (1) is 1:10~20
In the solution of step (1), and heating stirring 8h forms jelly in 60~80 DEG C of water-bath, and jelly is then placed in vacuum
In baking oven dry 10 at 80~120 DEG C~sample is obtained for 24 hours；
(3) by sample obtained by step (2) in N2Under atmosphere, with 2.3 DEG C of min-1Heating rate, temperature is risen to 550~950
DEG C, it is heat-treated 3~10h, is cooled to room temperature, obtains black solid；
(4) black solid that step (3) obtains is immersed in 1~5M aqueous sulfuric acid, after being heated to 60~90 DEG C of processing for 24 hours
Collect solid, and with distilled water flushing its to solution be it is neutral, finally obtained solid is placed in 120 DEG C of vacuum drying ovens dry
12h obtains catalyst.
3. application of the catalyst described in claim 1 in thioether selective oxidation sulfoxide.
4. application of the catalyst described in claim 1 in thioether selective oxidation sulfoxide, it is characterised in that: by aminomethyl phenyl
Thioether, acetonitrile, tert-butyl hydroperoxide and catalyst reaction, reaction temperature are 40 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910709661.4A CN110327964A (en) | 2019-08-02 | 2019-08-02 | A kind of vanadium catalyst and preparation method thereof for thioether selective oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910709661.4A CN110327964A (en) | 2019-08-02 | 2019-08-02 | A kind of vanadium catalyst and preparation method thereof for thioether selective oxidation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110327964A true CN110327964A (en) | 2019-10-15 |
Family
ID=68148438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910709661.4A Withdrawn CN110327964A (en) | 2019-08-02 | 2019-08-02 | A kind of vanadium catalyst and preparation method thereof for thioether selective oxidation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110327964A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111617747A (en) * | 2020-05-11 | 2020-09-04 | 贵州大学 | Chitosan/nano-metal composite hydrogel and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249959A (en) * | 2011-05-19 | 2011-11-23 | 浙江工业大学 | Method for preparing sulfoxide through catalytic oxidation |
| CN102951636A (en) * | 2012-11-19 | 2013-03-06 | 大连理工大学 | Nitrogen-doped chitosan-based activated carbon and preparation method thereof |
| CN105293483A (en) * | 2015-12-08 | 2016-02-03 | 武汉理工大学 | In-situ preparation method of transition metal doped porous graphene |
| CN105642243A (en) * | 2016-01-20 | 2016-06-08 | 南京中医药大学 | Preparation method of chitosan-based activated carbon containing transition metal ions |
| CN108273536A (en) * | 2018-01-25 | 2018-07-13 | 太原理工大学 | A kind of preparation method of N doping three-dimensional porous nano ferrum-based catalyst |
| CN108586297A (en) * | 2017-12-13 | 2018-09-28 | 广东省石油与精细化工研究院 | A kind of method that thioether aqueous phase oxidation prepares sulfoxide and sulfone |
-
2019
- 2019-08-02 CN CN201910709661.4A patent/CN110327964A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249959A (en) * | 2011-05-19 | 2011-11-23 | 浙江工业大学 | Method for preparing sulfoxide through catalytic oxidation |
| CN102951636A (en) * | 2012-11-19 | 2013-03-06 | 大连理工大学 | Nitrogen-doped chitosan-based activated carbon and preparation method thereof |
| CN105293483A (en) * | 2015-12-08 | 2016-02-03 | 武汉理工大学 | In-situ preparation method of transition metal doped porous graphene |
| CN105642243A (en) * | 2016-01-20 | 2016-06-08 | 南京中医药大学 | Preparation method of chitosan-based activated carbon containing transition metal ions |
| CN108586297A (en) * | 2017-12-13 | 2018-09-28 | 广东省石油与精细化工研究院 | A kind of method that thioether aqueous phase oxidation prepares sulfoxide and sulfone |
| CN108273536A (en) * | 2018-01-25 | 2018-07-13 | 太原理工大学 | A kind of preparation method of N doping three-dimensional porous nano ferrum-based catalyst |
Non-Patent Citations (2)
| Title |
|---|
| HÉLÈNE PELLISSIER: "Recent advances in enantioselective vanadium-catalyzed transformations", 《COORDINATION CHEMISTRY REVIEWS》 * |
| 王勇等: "氮掺杂的多孔炭材料及其在多相催化中的应用研究", 《中国化学会第28届学术年会第1分会场摘要集》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111617747A (en) * | 2020-05-11 | 2020-09-04 | 贵州大学 | Chitosan/nano-metal composite hydrogel and preparation method and application thereof |
| CN111617747B (en) * | 2020-05-11 | 2022-05-31 | 贵州大学 | Chitosan/nano-metal composite hydrogel and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108586297B (en) | Method for preparing sulfoxide and sulfone by oxidizing thioether in water phase | |
| CN110372483B (en) | Process method for preparing glutaraldehyde by catalytic oxidation of cyclopentene | |
| CN107652170B (en) | Method for preparing glutaraldehyde by catalyzing cyclopentene to oxidize through organic-inorganic heteropolyacid salt | |
| CN110327964A (en) | A kind of vanadium catalyst and preparation method thereof for thioether selective oxidation | |
| Dias et al. | A recyclable hybrid manganese (III) porphyrin magnetic catalyst for selective olefin epoxidation using molecular oxygen | |
| CN111686730B (en) | Preparation method and application of catalyst for synthesizing 2-phenylimidazole by Debus method | |
| MX2009010709A (en) | Improved mixed metal oxide catalysts and process for (amm) oxidation of lower alkane hydrocarbons. | |
| CN106669737B (en) | A kind of carbon/palladium-cobalt heterogeneous catalyst preparation method of magnetic core-shell structure | |
| CN107082892A (en) | A kind of preparation method of bimetallic organic framework material and its application in cyclohexylhydroperoxdecomposition decomposition reaction | |
| CN1175934C (en) | Molecular sieve catalyst containing pores in tungsten media utilized for synthesizing glutaraldehyde and its preparation method | |
| CN104383965A (en) | Metal-organic framework immobilized tungsten oxide catalyst for synthesizing glutaraldehyde and production method of metal-organic framework immobilized tungsten oxide catalyst | |
| CN111450818B (en) | Niobium pentoxide @ reduced graphene oxide catalyst and preparation method and application thereof | |
| CN101157677B (en) | Method for catalytic preparation of delta-valerolactone by using supported nano-gold catalyst | |
| CN108295899B (en) | Two-dimensional copper-based nanosheet catalyst, and preparation method and application thereof | |
| CN110152706A (en) | A method of with eutectic precursor preparation richness carbon carbonitride visible light catalyst | |
| CN113845500B (en) | Method for preparing 5-formyl-2-furancarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural | |
| CN1184003C (en) | Supported tungstic acid catalyst for synthesizing glutaraldehyde and its producing method | |
| CN113198492B (en) | Catalyst for preparing pyruvate by photocatalytic oxidation of lactate and method thereof | |
| CN112206796B (en) | Phosphoric acid modified molybdenum vanadium niobium composite metal oxide catalyst and method for synthesizing lactide | |
| CN114308134A (en) | Method for preparing metal oxide microreactor by using halloysite nanotubes and application of method | |
| CN110038636B (en) | AgI/Ag-Ce-2MI composite photocatalyst and preparation and application thereof | |
| CN113801044A (en) | Method for synthesizing sulfone compound by oxidizing sulfoxide compound | |
| CN112023984A (en) | Chromium-based inorganic catalytic material and application thereof in benzene-containing waste liquid | |
| CN112661730A (en) | Method for preparing 2, 5-furan dicarbaldehyde from 5-hydroxymethylfurfural | |
| CN112830871B (en) | Method for preparing cyclopentanone by catalytic conversion of furan derivative |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20191015 |