CN106238087A - The preparation method of the azepine material with carbon element that a kind of cyclodextrin is constructed - Google Patents
The preparation method of the azepine material with carbon element that a kind of cyclodextrin is constructed Download PDFInfo
- Publication number
- CN106238087A CN106238087A CN201610618641.2A CN201610618641A CN106238087A CN 106238087 A CN106238087 A CN 106238087A CN 201610618641 A CN201610618641 A CN 201610618641A CN 106238087 A CN106238087 A CN 106238087A
- Authority
- CN
- China
- Prior art keywords
- azepine
- carbon element
- preparation
- cyclodextrin
- black solid
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 46
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 title claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229920000858 Cyclodextrin Polymers 0.000 title claims abstract description 23
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- 239000012065 filter cake Substances 0.000 claims abstract description 7
- 239000002210 silicon-based material Substances 0.000 claims abstract description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- RESTWAHJFMZUIZ-UHFFFAOYSA-N 1-ethyl-4-nitrobenzene Chemical compound CCC1=CC=C([N+]([O-])=O)C=C1 RESTWAHJFMZUIZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 3
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- -1 aromatic amine compound Chemical class 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 6
- 239000007858 starting material Substances 0.000 abstract description 2
- 239000001116 FEMA 4028 Substances 0.000 abstract 2
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 abstract 2
- 235000011175 beta-cyclodextrine Nutrition 0.000 abstract 2
- 229960004853 betadex Drugs 0.000 abstract 2
- 238000006722 reduction reaction Methods 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QXDYIBHUQHUJJI-UHFFFAOYSA-N nitrobenzene phenol Chemical compound OC1=CC=CC=C1.[O-][N+](=O)C1=CC=CC=C1 QXDYIBHUQHUJJI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The preparation method of the azepine material with carbon element that a kind of cyclodextrin is constructed, step is as follows: 1) beta cyclodextrin and tripolycyanamide is added in sulfuric acid solution, obtains mixed liquor；2) in mixed liquor, add orderly mesoporous silicon material SBA 15, after temperature reaction, obtain black solid a；3) beta cyclodextrin and tripolycyanamide are added in sulfuric acid solution, add above-mentioned black solid a, after temperature reaction, obtain black solid b；4) by black solid b roasting in nitrogen atmosphere, claying into power after being cooled to room temperature, add back flow reaction in NaOH solution, filter cake is washed with water to the aobvious neutrality of filtrate, dried prepared azepine material with carbon element；The azepine material with carbon element that the cyclodextrin of preparation is constructed is for the reduction of nitro-aromatic.The invention have the advantage that this preparation method technique is simple, cheaper starting materials is easy to get, the material specific surface area obtained is big, aperture is reasonable and selectivity is good, and product yield is the highest, and the preparation for aromatic amine compound provides a green, efficient technique.
Description
Technical field
The present invention is subordinate to without metal catalytic field, relates to the preparation method of the azepine material with carbon element that a kind of cyclodextrin is constructed.
Technical background
Aromatic amine compounds is widely used in medicine, pigment, pesticide, auxiliary agent and dyestuff as a kind of important chemical intermediate
In field, its synthetic method receives much concern, and sees 1) Li Y.；Zhou Y.-X.；Ma X.；Jiang H.-L,；
Chem.Commun.,2016,52,4199-4202；2)Abdullsev M.-G.；Gebekova Z.-G.；Petrol.Chem.,
2016,56(2):146-150.At present, people are often through nitro-aromatic reduction synthesis aromatic amine compounds, and method of reducing has three
Kind: metal deoxidization, electrolytic reduction and catalytic hydrogenating reduction method, see 1) P é lisson C.-H.；Audrey D.-N.；
Roucoux A.；ACS Sustainable Chem.Eng.,2016,4,1834-1839；2)Mondal J.；Kundu S.-
K.；Hung Ng W.-K.；Singuru R.；Borah P.；Hirao H.；Zhao Y.-L.；Bhaumik A.；
Chem.Eur.J.,2015,21,19016-19027；3)Srivastava S.；Dagur M.-S.；Ali A.；Gupta R.；
Dalton Trans.,2015,44,17453-17461.Wherein, metal deoxidization is by metallic reducing agent and proton donor
Realize.Iron powder is a kind of modal reducing agent, and iron powder reducing is simple to operate, low for equipment requirements, and has good choosing
Selecting property, but can produce a large amount of containing amine waste water and iron cement in producing, therefore and nonideal reducing process pollute environment, see
1) sing heartily, Dalian University of Technology Ph.D. Dissertation, 2010.Electroreduction uses copper or alloy to be electrode, in the electrolyte also
Former nitro-aromatic prepares arylamine, and this technique production cost is the highest, and so far there are no, and industry is reported, sees 2) beam national flag, Donghua University
Master thesis, 2014.Catalytic hydrogenating reduction method is with hydrogen cheap and easy to get as hydrogen source, realizes nitre under catalyst action
The reduction of base aromatic hydrocarbons.The use of hydrogen reduces production cost, has significant superiority to solving problem of environmental pollution.So
And, the metal load type catalyst such as this technique many employings palladium, platinum, nickel, the use of these metals adds life to a certain extent
Produce cost, simultaneously result in metal residual in product, see 1) Wang J.-Q.；Ge D.-H.；Cao X.-Q.；Tang M.-
H.；Pan Y.；Gu H.-W.；Chem.Commun.,2015,51,9216-9219；2)Li L.-Y.；Zhou C.-S.；Zhao
H.-X.；Wang R.-H.；Nano Res.,2015,8(3):709-721；3)Liu W.-J.；Tian K.；Jiang H.；
Green Chem,2015,17,821-826.Additionally, this technique is reduced for polysubstituted Nitro-aromatic Compounds in Different, can produce a large amount of
Side reaction, affect the selectivity of product, see Feng W.-H.；Dong H.-X.；Niu L.-B.；Wen X.；Huo L.；
Bai G.-Y.；J.Mater.Chem.A,2015,3,19807-19814.As can be seen here, construct non-metal catalyst, improve and produce
Product selectivity is two large problems the most urgently to be resolved hurrily.
Material with carbon element is always emphasis of concern as a kind of non-metal catalyst, and its research and development also achieves one
Fixed progress.Such as, graphene oxide is used for hydrocarbon priming reaction and has constructed biphenol compound by Ma et al., sees 1) Gao
Y.-J.；Tang P.；Zhou H.；Zhang W.；Yang H.-J.；Yan N.；Hu G.；Mei G.-H.；Wang J.-G.；
Ma d.；Angew.Chem.Int.Ed.,2015,54,1-6；Arai et al. is prepared for azepine material with carbon element, and for the selection of alcohol
Property oxidation reaction, sees 2) Watanabe H.；Asano S.；Fujita S.-I.；Yoshida H.；Arai M.；ACS
Catal.,2015,5,2886-2894.Bao et al. azepine material with carbon element replacement for mercury catalyst has catalyzed and synthesized chloroethene effectively
Alkene, sees 3) Li X.-Y.；Pan X.-L.；Yu L.；Ren P.-J.；Wu X.；Sun L.-T.；Jiao F.；Bao X.-
H.；Nat.Commun.,2014,1-7.In this project, it is order mesoporous that we have constructed azepine with beta-schardinger dextrin-and tripolycyanamide
Material with carbon element, this material can effectively be catalyzed nitro-aromatic reduction and generate aromatic amine compounds, and the preparation for aromatic amine compound carries
A green, efficient technique are supplied.The reduction of 4-ethyl-nitrobenzene generates the chemical equation of 4-MEA and is shown below:
Summary of the invention
It is an object of the invention to for above-mentioned two large problems the most urgently to be resolved hurrily, it is provided that the azepine that a kind of cyclodextrin is constructed
The preparation method of material with carbon element, this preparation method utilizes cyclodextrin to construct a kind of azepine meso-porous carbon material, and preparation technology is simple, former
Expect cheap and easy to get, the big (818.65m of the material specific surface area obtained2/ g), aperture rationally (about 3.56nm) and selectivity are good, can make
Achieve the reduction of nitro-aromatic for non-metal catalyst, product yield is the highest, and the preparation for aromatic amine compound provides one
Technique green, efficient.
Technical scheme:
The preparation method of the azepine material with carbon element that a kind of cyclodextrin is constructed, step is as follows:
1) beta-schardinger dextrin-and tripolycyanamide are separately added in 2.7wt% sulfuric acid solution, are stirred at room temperature uniformly, are mixed
Liquid, beta-schardinger dextrin-and tripolycyanamide mass ratio are 1.14:0.11, and beta-schardinger dextrin-with the mass ratio of 2.7wt% sulfuric acid solution is
1.14:5.14；
2) in above-mentioned mixed liquor, add orderly mesoporous silicon material SBA-15, after stirring, be warming up to 80-100 DEG C,
Keeping 6h, then heat to 150-160 DEG C, keep 6h, obtain black solid a, mixed liquor is 6.39 with the mass ratio of SBA-15:
1；
3) beta-schardinger dextrin-and tripolycyanamide are separately added in the sulfuric acid solution of 1.8wt%, beta-schardinger dextrin-and tripolycyanamide
Mass ratio is 0.73:0.07, and beta-schardinger dextrin-is 0.73:5.09 with the mass ratio of 1.8wt% sulfuric acid solution, after stirring, adds
Enter above-mentioned black solid a, be warming up to 80-100 DEG C, keep 6h, then heat to 150-160 DEG C, keep 6h, obtain black solid
b；
4) by above-mentioned black solid b roasting in nitrogen atmosphere, roasting process, for be warming up to 600 DEG C with 1 DEG C/min, keeps
3h, then rise to 900 DEG C with 5 DEG C/min, keep 4h, be cooled to room temperature, then clay into power, add NaOH, the mixing of second alcohol and water
Solution, in mixed solution, ethanol and the concentration that water volume ratio is 1:1, NaOH are 1mol/L, and 2h is to remove SBA-15 in backflow, filters
After filter cake again add the 2h that refluxes in the NaOH solution of 1mol/L, after filtration, filter cake is washed with water to the aobvious neutrality of filtrate, in
70 DEG C of dry 24h, prepare azepine material with carbon element.
The application of the azepine material with carbon element that a kind of prepared cyclodextrin is constructed, for the reduction of nitro-aromatic, method is as follows:
It is that 6mmol:1mmol:4mL adds in airtight reactor tube by hydrazine hydrate, nitro-aromatic and ethanol by amount ratio, is subsequently adding azepine
Material with carbon element, nitro-aromatic is 100:6.6-8.1 with the mass ratio of azepine material with carbon element, reacts 2-12h, after filtration at 80-120 DEG C
Collect filtrate to be analyzed by gas chromatogram.
Described nitro-aromatic is 4-ethyl-nitrobenzene, Nitrobenzol, 4-methyl Nitrobenzol, 4-nitrophenol or 4-ethyl nitro
Benzene.
The invention have the advantage that
This preparation method utilizes cyclodextrin to construct a kind of azepine meso-porous carbon material, and preparation technology is simple, cheaper starting materials is easy
, the big (818.65m of the material specific surface area obtained2/ g), aperture rationally (about 3.56nm) and selectivity are good, can be as without metal
Catalyst achieves the reduction of nitro-aromatic, and product yield is the highest, provides a green, efficiently for the preparation of aromatic amine compound
Technique.
Accompanying drawing explanation
Fig. 1 is the TEM figure that azepine material with carbon element constructed by cyclodextrin.
Fig. 2 is the XRD figure that azepine material with carbon element constructed by cyclodextrin.
Fig. 3 is the BET figure that azepine material with carbon element constructed by cyclodextrin.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, following example be illustrative rather than
Determinate, it is impossible to limit protection scope of the present invention with this.
Embodiment 1:
The preparation method of the azepine material with carbon element that a kind of cyclodextrin is constructed, step is as follows:
1) 1.14g beta-schardinger dextrin-and 0.11g tripolycyanamide are separately added in 5.14g, 2.7wt% sulfuric acid solution, room temperature
Stir, obtain mixed liquor；
2) in above-mentioned mixed liquor, add the orderly mesoporous silicon material SBA-15 of 1g, after stirring, be warming up to 100 DEG C,
Keep 6h, then heat to 160 DEG C, keep 6h, obtain black solid a；
3) 0.73g beta-schardinger dextrin-and 0.07g tripolycyanamide are separately added in the sulfuric acid solution of 5.09g, 1.8wt%, stir
After mixing uniformly, add above-mentioned black solid a, be warming up to 100 DEG C, keep 6h, then heat to 160 DEG C, keep 6h, obtain black
Solid b；
4) black solid b rises to 600 DEG C with 1 DEG C/min in being placed in the tube furnace of nitrogen protection, keeps after 3h, with 5 DEG C/
Min rises to 900 DEG C, keeps 4h, is cooled to room temperature, then clays into power, and adds 10mL NaOH, the mixed solution of second alcohol and water, mixed
Closing ethanol and the concentration that water volume ratio is 1:1, NaOH in solution is 1mol/L, and 2h is to remove SBA-15 in backflow, will after filtration again
Filter cake adds the 2h that refluxes in the NaOH solution that 10mL, concentration are 1mol/L, filters, by gained filter cake with substantial amounts of after being cooled to room temperature
Water washing, to the aobvious neutrality of filtrate, then in 70 DEG C of dry 24h, prepares azepine mesoporous carbon.
Fig. 1 is the TEM figure of the azepine material with carbon element of preparation.Showing in figure, this material has orderly pore passage structure.
Fig. 2 is the XRD figure of the azepine material with carbon element of preparation.Showing in figure, this material has diffraction maximum in (100) face, has and has
The pore passage structure of sequence.
Fig. 3 is the BET figure of the azepine material with carbon element of preparation.Showing in figure, the BET curve of this material has back stagnant ring, belongs to
Mesoporous material.
Azepine material with carbon element by preparation is used for the reduction reaction of 4-ethyl-nitrobenzene, and method is:
By 0.076g (0.5mmol) 4-ethyl-nitrobenzene, 0.15g (3mmol) hydrazine hydrate, 5mg azepine material with carbon element and 2mL second
Alcohol adds in the reaction tube that 5mL is airtight, and reactant liquor stirs 12h in 100 DEG C, filters, and filtrate is analyzed obtaining by gas chromatogram
The conversion ratio of 4-ethyl-nitrobenzene is more than 99%, and the selectivity of 4-MEA is more than 99%.
Embodiment 2:
The preparation method of the azepine material with carbon element that a kind of cyclodextrin is constructed, same as in Example 1；Azepine material with carbon element by preparation
For the reduction reaction of nitro-aromatic, method is substantially the same manner as Example 1, and difference is: nitro-aromatic is Nitrobenzol, filter
Liquid gas chromatogram is analyzed obtaining the conversion ratio of Nitrobenzol and is more than 99%, and the selectivity of aniline is more than 99%.
Embodiment 3:
The preparation method of the azepine material with carbon element that a kind of cyclodextrin is constructed, same as in Example 1；Azepine material with carbon element by preparation
For the reduction reaction of nitro-aromatic, method is substantially the same manner as Example 1, and difference is: nitro-aromatic is 4-methyl nitre
Base benzene, the conversion ratio that filtrate is analyzed obtaining 4-methyl Nitrobenzol by gas chromatogram is more than 99%, the selection of 4-monomethylaniline.
Property more than 99%.
Embodiment 4:
The preparation method of the azepine material with carbon element that a kind of cyclodextrin is constructed, same as in Example 1；Azepine material with carbon element by preparation
For the reduction reaction of nitro-aromatic, method is substantially the same manner as Example 1, and difference is: nitro-aromatic is 4-Nitrobenzol
Phenol, the conversion ratio that filtrate is analyzed obtaining 4-nitrophenol by gas chromatogram is more than 99%, and the selectivity of PAP is
97%.
Embodiment 5:
The preparation method of the azepine material with carbon element that a kind of cyclodextrin is constructed, same as in Example 1；Azepine material with carbon element by preparation
For the reduction reaction of nitro-aromatic, method is substantially the same manner as Example 1, and difference is: nitro-aromatic is 4-ethyl nitre
Base benzene, it is 48% that filtrate gas chromatogram is analyzed obtaining the conversion ratio of 4-ethyl-nitrobenzene, the selectivity of 4-MEA
More than 99%.
Claims (3)
1. the preparation method of the azepine material with carbon element that a cyclodextrin is constructed, it is characterised in that step is as follows:
1) beta-schardinger dextrin-and tripolycyanamide are separately added in 2.7wt% sulfuric acid solution, are stirred at room temperature uniformly, obtain mixed liquor,
Beta-schardinger dextrin-and tripolycyanamide mass ratio are 1.14:0.11, and beta-schardinger dextrin-is 1.14 with the mass ratio of 2.7wt% sulfuric acid solution:
5.14；
2) in above-mentioned mixed liquor, add orderly mesoporous silicon material SBA-15, after stirring, be warming up to 80-100 DEG C, keep
6h, then heats to 150-160 DEG C, keeps 6h, obtains black solid a, and mixed liquor is 6.39:1 with the mass ratio of SBA-15；
3) beta-schardinger dextrin-and tripolycyanamide are separately added in the sulfuric acid solution of 1.8wt%, beta-schardinger dextrin-and tripolycyanamide quality
It is 0.73:5.09 than the mass ratio for 0.73:0.07, beta-schardinger dextrin-and 1.8wt% sulfuric acid solution, after stirring, in addition
State black solid a, be warming up to 80-100 DEG C, keep 6h, then heat to 150-160 DEG C, keep 6h, obtain black solid b；
4) by above-mentioned black solid b roasting in nitrogen atmosphere, roasting process, for be warming up to 600 DEG C with 1 DEG C/min, keeps 3h,
Rise to 900 DEG C with 5 DEG C/min again, keep 4h, be cooled to room temperature, then clay into power, add NaOH, second alcohol and water mixing molten
Liquid, in mixed solution, ethanol and the concentration that water volume ratio is 1:1, NaOH are 1mol/L, and 2h is to remove SBA-15, after filtration in backflow
Filter cake again add the 2h that refluxes in the NaOH solution of 1mol/L, after filtration, filter cake is washed with water to the aobvious neutrality of filtrate, in 70
DEG C dry 24h, prepares azepine material with carbon element.
2. the application of the azepine material with carbon element that the cyclodextrin prepared by a claim 1 is constructed, it is characterised in that: for nitro virtue
The reduction of hydrocarbon, method is as follows: by hydrazine hydrate, nitro-aromatic and ethanol by amount ratio be 6mmol:1mmol:4mL add airtight instead
Ying Guanzhong, is subsequently adding azepine material with carbon element, and nitro-aromatic is 100:6.6-8.1 with the mass ratio of azepine material with carbon element, in 80-120
Reacting 2-12h at DEG C, filtering and collecting filter liquid gas chromatogram is analyzed.
3. the application of the azepine material with carbon element constructed according to the cyclodextrin prepared by claim 2, it is characterised in that: described nitro virtue
Hydrocarbon is 4-ethyl-nitrobenzene, Nitrobenzol, 4-methyl Nitrobenzol, 4-nitrophenol or 4-ethyl-nitrobenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610618641.2A CN106238087A (en) | 2016-07-27 | 2016-07-27 | The preparation method of the azepine material with carbon element that a kind of cyclodextrin is constructed |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610618641.2A CN106238087A (en) | 2016-07-27 | 2016-07-27 | The preparation method of the azepine material with carbon element that a kind of cyclodextrin is constructed |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106238087A true CN106238087A (en) | 2016-12-21 |
Family
ID=57606136
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610618641.2A Pending CN106238087A (en) | 2016-07-27 | 2016-07-27 | The preparation method of the azepine material with carbon element that a kind of cyclodextrin is constructed |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106238087A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112138698A (en) * | 2020-09-16 | 2020-12-29 | 吉林化工学院 | Preparation method of nitrogen-doped carbon nano material and application of nitrogen-doped carbon nano material in nitrobenzene hydrogenation reaction |
| CN113198432A (en) * | 2021-06-18 | 2021-08-03 | 江苏乾汇和环保再生有限公司 | Preparation method of biomass activated carbon |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003181301A (en) * | 2003-01-14 | 2003-07-02 | Ibiden Co Ltd | Method for manufacturing catalyst carrier |
| CN104174421A (en) * | 2014-08-08 | 2014-12-03 | 浙江大学 | Heterogeneous catalyst for selective hydrogenation reaction of aryl nitro-compound and application of heterogeneous catalyst |
| CN104743540A (en) * | 2013-12-31 | 2015-07-01 | 西北大学 | Preparation method for nitrogen-doped carbon material |
| CN105669464A (en) * | 2016-04-01 | 2016-06-15 | 湘潭大学 | Application of metal-free hydrogenation catalyst in catalyzing hydrogenation reaction of nitrobenzene and derivatives thereof |
-
2016
- 2016-07-27 CN CN201610618641.2A patent/CN106238087A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003181301A (en) * | 2003-01-14 | 2003-07-02 | Ibiden Co Ltd | Method for manufacturing catalyst carrier |
| CN104743540A (en) * | 2013-12-31 | 2015-07-01 | 西北大学 | Preparation method for nitrogen-doped carbon material |
| CN104174421A (en) * | 2014-08-08 | 2014-12-03 | 浙江大学 | Heterogeneous catalyst for selective hydrogenation reaction of aryl nitro-compound and application of heterogeneous catalyst |
| CN105669464A (en) * | 2016-04-01 | 2016-06-15 | 湘潭大学 | Application of metal-free hydrogenation catalyst in catalyzing hydrogenation reaction of nitrobenzene and derivatives thereof |
Non-Patent Citations (2)
| Title |
|---|
| JUNKAI HU ET AL.,: "Capacitance behavior of ordered mesoporous carbon/Fe2O3 composites: Comparison between 1D cylindrical, 2D hexagonal, and 3D bicontinuous mesostructures", 《CARBON》 * |
| SHIN-ICHIRO FUJITA ET AL.,: "Nitrogen and oxygen-doped metal-free carbon catalysts for chemoselective transfer hydrogenation of nitrobenzene,styrene, and 3-nitrostyrene with hydrazine", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112138698A (en) * | 2020-09-16 | 2020-12-29 | 吉林化工学院 | Preparation method of nitrogen-doped carbon nano material and application of nitrogen-doped carbon nano material in nitrobenzene hydrogenation reaction |
| CN113198432A (en) * | 2021-06-18 | 2021-08-03 | 江苏乾汇和环保再生有限公司 | Preparation method of biomass activated carbon |
| CN113198432B (en) * | 2021-06-18 | 2023-07-21 | 江苏乾汇和环保再生有限公司 | Preparation method of biomass activated carbon |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cheng et al. | NiCo 2 O 4 nanosheets as a novel oxygen-evolution-reaction cocatalyst in situ bonded on the gC 3 N 4 photocatalyst for excellent overall water splitting | |
| CN110270348B (en) | Noble metal monatomic catalyst and preparation and application thereof | |
| Zhang et al. | In situ mosaic strategy generated Co-based N-doped mesoporous carbon for highly selective hydrogenation of nitroaromatics | |
| Wang et al. | A robust titanium isophthalate metal-organic framework for visible-light photocatalytic CO2 methanation | |
| Cui et al. | Au/Ag–Mo nano-rods catalyzed reductive coupling of nitrobenzenes and alcohols using glycerol as the hydrogen source | |
| Liu et al. | Mild, selective and switchable transfer reduction of nitroarenes catalyzed by supported gold nanoparticles | |
| Yu et al. | Enhanced visible light photocatalytic non-oxygen coupling of amines to imines integrated with hydrogen production over Ni/CdS nanoparticles | |
| Dong et al. | A highly stable all-in-one photocatalyst for aryl etherification: the Ni II embedded covalent organic framework | |
| Xu et al. | Photocatalytic activity of transition-metal-ion-doped coordination polymer (CP): photoresponse region extension and quantum yields enhancement via doping of transition metal ions into the framework of CPs | |
| Shi et al. | A microporous mixed-metal (Na/Cu) mixed-ligand (flexible/rigid) metal–organic framework for photocatalytic H 2 generation | |
| CN105294447B (en) | A kind of method for being catalyzed hydrogenation of chloronitrobenzene and preparing aniline | |
| Zhang et al. | N-doped hierarchical porous carbon anchored tiny Pd NPs: A mild and efficient quinolines selective hydrogenation catalyst | |
| CN105859610B (en) | Using the synthetic method of 2,2 '-bipyridyls of load type double-metal nanocatalyst | |
| Azad et al. | Excellent photocatalytic reduction of nitroarenes to aminoarenes by BiVO4 nanoparticles grafted on reduced graphene oxide (rGO/BiVO4) | |
| Wang et al. | Facile synthesis of Rh anchored uniform spherical COF for one-pot tandem reductive amination of aldehydes to secondary Imines | |
| Chen et al. | Synergistic effect of bimetallic PdAu nanocrystals on oxidative alkyne homocoupling | |
| Yue et al. | Highly selective hydrogenation of halogenated nitroarenes over Ru/CN nanocomposites by in situ pyrolysis | |
| Wang et al. | A highly efficient Co-based catalyst fabricated by coordination-assisted impregnation strategy towards tandem catalytic functionalization of nitroarenes with various alcohols | |
| Zhuang et al. | Preparation and catalytic properties of Pd nanoparticles supported on micro-crystal DUT-67 MOFs | |
| CN106238087A (en) | The preparation method of the azepine material with carbon element that a kind of cyclodextrin is constructed | |
| Karim et al. | A dinuclear iron complex as an efficient electrocatalyst for homogeneous water oxidation reaction | |
| Jiang et al. | Controllable synthesis of ultrasmall Pd nanocatalysts templated by supramolecular coordination cages for highly efficient reductive dehalogenation | |
| Niakan et al. | Binuclear palladium complex immobilized on mesoporous SBA-16: efficient heterogeneous catalyst for the carbonylative Suzuki coupling reaction of aryl iodides and arylboronic acids using Cr (CO) 6 as carbonyl source | |
| CN105693490A (en) | Method for oxidizing preparation of TMBQ (2,3,5-trimethylbenzoquinone) | |
| Wang et al. | A facile synthesis of Pt@ Ir zigzag bimetallic nanocomplexes for hydrogenation reactions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20161221 |
|
| WD01 | Invention patent application deemed withdrawn after publication |