CN108057456A - With the method for RuCu/N-CNTs catalysts synthesis 9- ethyl tetrahydro carbazoles - Google Patents
With the method for RuCu/N-CNTs catalysts synthesis 9- ethyl tetrahydro carbazoles Download PDFInfo
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- CN108057456A CN108057456A CN201711364110.6A CN201711364110A CN108057456A CN 108057456 A CN108057456 A CN 108057456A CN 201711364110 A CN201711364110 A CN 201711364110A CN 108057456 A CN108057456 A CN 108057456A
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- 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
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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Abstract
The invention discloses the methods that 9 ethyl tetrahydro carbazoles are synthesized with RuCu/N CNTs catalysts, belong to technical field of chemistry and chemical engineering.The RuCu/N CNTs catalyst prepared and 9 ethyl carbazoles are placed in autoclave by the present invention, and reaction kettle is risen to certain temperature, hydrogen is passed through in reaction kettle, are stirred to react certain time and 9 ethyl tetrahydro carbazoles are made.The RuCu/N CNTs catalyst is to be configured using Ru, Cu and deionized water according to certain mol proportion, and carrier N CNTs are added in above-mentioned solution, and reducing agent is added into mixed liquor, is made after filtered, dry.Support type RuCu/N CNTs catalyst prepared by the present invention has higher activity and selectivity.9 ethyl carbazole hydrogenation synthesis, 9 ethyl tetrahydro carbazole is carried out using the catalyst to react, for high selectivity up to more than 86%, yield is more than 83%.
Description
Technical field
The invention belongs to technical field of chemistry and chemical engineering, and in particular to a kind of to use RuCu/N-CNTs catalyst 9- ethyls
The method that carbazole synthesizes 9- ethyl tetrahydro carbazoles.
Background technology
9- ethyl tetrahydro carbazoles are a kind of important intermediates for synthesizing Anthraquinones organic pigment, in optical electro-chemistry, medicine, dye
The fields such as material, coating are with a wide range of applications, and have anticancer, sterilization, antimycotic and inhibition mosquito and other effects.At present, 9-
The rare report of synthetic method of ethyl tetrahydro carbazole.
Using phenylhydrazine, cyclohexanone as starting material during Li Ming etc., through acetic acid Cyclization tetrahydro carbazole, yield up to 70.5%,
9- ethyl tetrahydro carbazoles are made through alkylated reaction with bromoethane again.It is investigated through experiment of single factor, determines synthesis 9- ethyl tetrahydrochysenes
The optimal conditions of carbazole is:N (tetrahydro carbazole): n (bromoethane): n (sodium hydroxide)=1: 4: 1.5, m (tetrahydro carbazole): m (iodine
Change potassium)=1: 0.01, c (tetrahydro carbazole)=0.50mol/L, c (cetyl trimethylammonium bromide)=2.5 × 10-3Mol/L,
Acetonitrile is solvent, back flow reaction 9h, yield 86.0%.The route and traditional handicraft (cyclohexanone first through chlorination again with N- ethyls
Aniline condensation) compare, chlorinated secondary product can be avoided to generate, reaction is easy to control, but the process route is complicated, be related to reaction raw materials compared with
It is more, be not suitable for fine chemicals production.
The selective hydrogenation of 9- ethyl carbazoles has received widespread attention as the important process of synthesis 9- ethyl tetrahydro carbazoles.
The technique has many advantages, such as that process route is simple, easy to control, develops complete 9- ethyl carbazoles selective hydrogenation synthesis 9- ethyls
Tetrahydro carbazole is of great significance for the production of industrial 9- ethyls tetrahydro carbazole.The key of the wherein technique large-scale application exists
In developing efficient selective hydrocatalyst.
The content of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, provide and a kind of be catalyzed with RuCu/N-CNTs
The method of agent catalysis 9- ethyl carbazole synthesis 9- ethyl tetrahydro carbazoles, has good urge to the RuCu/N-CNTs catalyst
Change activity and selectivity.
The technical solution adopted by the present invention to solve the technical problems is as follows.
The RuCu/N-CNTs catalyst prepared and 9- ethyl carbazoles are placed in autoclave, reaction kettle is risen to
Certain temperature is passed through hydrogen in reaction kettle, is stirred to react certain time and 9- ethyl tetrahydro carbazoles are made.
The reaction temperature is 75~110 DEG C；The Hydrogen Vapor Pressure is 3.0~6.1MPa；The speed of agitator
For 400~520rpm；The reaction time is 1.5~4h；
The RuCu/N-CNTs catalyst includes Ru, Cu, N-CNTs, wherein：The molar ratio of Ru and Cu is 1：0.8~6；
The molar ratio of Ru and N-CNTs is 1：170~600；Ru derives from ruthenic chloride, and Cu derives from copper chloride；N-CNTs is by melamine
With CNTs in mass ratio 1：8 baking mixed obtain；
The RuCu/N-CNTs nanocatalysts are through the following steps that prepared：
(1) matched according to above-mentioned catalytic component, Ru salt, Cu salt and deionized water are configured in container, are sufficiently stirred
N-CNTs is added in above-mentioned mixed solution again afterwards；
(2) above-mentioned mixed solution is placed in 0 DEG C of water-bath, is added dropwise dropwise with the sodium borohydride of 0.1~0.4mol/L, and
Stir reductase 12 h；
(3) will step (2) solution filter after dry to get to RuCu/N-CNTs catalyst.
Further, in the preparation process (1) of the RuCu/N-CNTs catalyst：The molar ratio of Ru and Cu is 1：1.2~
The molar ratio of 3, Ru and N-CNTs is 1:200~400.
Further, the drying in the preparation process (3) of the RuCu/N-CNTs catalyst carries out in an oven, dry
Temperature is 75~110 DEG C, and drying time is 9~14h.
Compared with prior art, the beneficial effects of the invention are as follows：
The present invention uses RuCl using immersion reduction method, catalyst preparation3And CuCl2For presoma, support type is prepared
RuCu/N-CNTs catalyst, the catalyst have higher activity and selectivity.9- ethyl carbazoles are carried out using the catalyst to add
Hydrogen synthesis 9- ethyls tetrahydro carbazole reaction, for high selectivity up to more than 86%, yield is more than 83%.
Specific implementation method
The present invention is described in further details below by embodiment.But the example does not form the limit to the present invention
System.
Embodiment 1
Prepare catalyst process
By 0.02mmol RuCl3With 0.024mmol CuCl2In being dissolved in 10mL distilled water, one section is stirred in 0 DEG C of ice bath
Time, then 8mmol N-CNTs are added in above-mentioned solution, after being sufficiently stirred, the reduction of 0.1mol/L sodium borohydride solutions is added dropwise
2h, dry 14h, catalyst are denoted as RuCu in 75 DEG C of drying box after filtering1.2/ 400N-CNTs, closed preservation.
Hydrogenation process
The above-mentioned catalyst of 100mg and 10g 9- ethyl carbazoles are placed in autoclave, reaction kettle is risen to 110 DEG C,
Hydrogen is passed through in reaction kettle, makes its pressure for 6.1Mpa, 4h is stirred to react for 520rpm in rotating speed, analysis after reaction can obtain
The selectivity of 9- ethyl tetrahydro carbazoles is that the yield of 95%, 9- ethyl tetrahydro carbazoles is 92%.
Embodiment 2
By 0.02mmol RuCl3With 0.06mmol CuCl2In being dissolved in 10mL distilled water, when one section is stirred in 0 DEG C of ice bath
Between, then 4mmol N-CNTs are added in above-mentioned solution, after being sufficiently stirred, the reduction of 0.4mol/L sodium borohydride solutions is added dropwise
2h, dry 9h, catalyst are denoted as RuCu in 110 DEG C of drying box after filtering3/ 200N-CNTs, closed preservation.
Hydrogenation process
The above-mentioned catalyst of 100mg and 10g 9- ethyl carbazoles are placed in autoclave, reaction kettle is risen to 75 DEG C, instead
It answers and hydrogen is passed through in kettle, make its pressure for 3.0Mpa, 1.5h is stirred to react for 400rpm in rotating speed, analysis after reaction can obtain
The selectivity of 9- ethyl tetrahydro carbazoles is that the yield of 87.3%, 9- ethyl tetrahydro carbazoles is 83.5%.
Embodiment 3
By 0.02mmol RuCl3With 0.04mmol CuCl2In being dissolved in 10mL distilled water, when one section is stirred in 0 DEG C of ice bath
Between, then 7mmol N-CNTs are added in above-mentioned solution, after being sufficiently stirred, the reduction of 0.3mol/L sodium borohydride solutions is added dropwise
2h, dry 12h, catalyst are denoted as RuCu in 95 DEG C of drying box after filtering2/ 350N-CNTs, closed preservation.
Hydrogenation process
The above-mentioned catalyst of 100mg and 10g 9- ethyl carbazoles are placed in autoclave, reaction kettle is risen to 105 DEG C,
Hydrogen is passed through in reaction kettle, makes its pressure for 3.8Mpa, is stirred to react 3.5h in rotating speed for 450rpm, analysis can after reaction
The selectivity for obtaining 9- ethyl tetrahydro carbazoles is that the yield of 87.2%, 9- ethyl tetrahydro carbazoles is 85.4%.
Embodiment 4
By 0.02mmol RuCl3With 0.03mmol CuCl2In being dissolved in 10mL distilled water, when one section is stirred in 0 DEG C of ice bath
Between, then 6mmol N-CNTs are added in above-mentioned solution, after being sufficiently stirred, the reduction of 0.2mol/L sodium borohydride solutions is added dropwise
2h, dry 13h, catalyst are denoted as RuCu in 105 DEG C of drying box after filtering1.5/ 300N-CNTs, closed preservation.
Hydrogenation process
The above-mentioned catalyst of 100mg and 10g 9- ethyl carbazoles are placed in autoclave, reaction kettle is risen to 90 DEG C, instead
It answers and hydrogen is passed through in kettle, make its pressure for 4.4Mpa, 2.5h is stirred to react for 430rpm in rotating speed, analysis after reaction can obtain
The selectivity of 9- ethyl tetrahydro carbazoles is that the yield of 88.6%, 9- ethyl tetrahydro carbazoles is 85.7%.
Embodiment 5
By 0.02mmol RuCl3With 0.036mmol CuCl2In being dissolved in 10mL distilled water, one section is stirred in 0 DEG C of ice bath
Time, then 5.6mmol N-CNTs are added in above-mentioned solution, after being sufficiently stirred, 0.2mol/L sodium borohydride solutions are added dropwise also
Former 2h, dry 12h, catalyst are denoted as RuCu in 90 DEG C of drying box after filtering1.8/ 280N-CNTs, closed preservation.
Hydrogenation process
The above-mentioned catalyst of 100mg and 10g 9- ethyl carbazoles are placed in autoclave, reaction kettle is risen to 100 DEG C,
Hydrogen is passed through in reaction kettle, makes its pressure for 5.3Mpa, is stirred to react 3.2h in rotating speed for 480rpm, analysis can after reaction
The selectivity for obtaining 9- ethyl tetrahydro carbazoles is that the yield of 89.2%, 9- ethyl tetrahydro carbazoles is 86.9%.
Embodiment 6
By 0.02mmol RuCl3With 0.052mmol CuCl2In being dissolved in 10mL distilled water, one section is stirred in 0 DEG C of ice bath
Time, then 6.6mmol N-CNTs are added in above-mentioned solution, after being sufficiently stirred, 0.25mol/L sodium borohydride solutions are added dropwise
Reductase 12 h, dry 11.5h, catalyst are denoted as RuCu in 85 DEG C of drying box after filtering2.6/ 330N-CNTs, closed preservation.
Hydrogenation process
The above-mentioned catalyst of 100mg and 10g 9- ethyl carbazoles are placed in autoclave, reaction kettle is risen to 92 DEG C, instead
It answers and hydrogen is passed through in kettle, make its pressure for 5.0Mpa, 3.6h is stirred to react for 510rpm in rotating speed, analysis after reaction can obtain
The selectivity of 9- ethyl tetrahydro carbazoles is that the yield of 88.2%, 9- ethyl tetrahydro carbazoles is 84.3%.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, it is impossible to assert
The specific embodiment of the present invention is only limitted to this, for those of ordinary skill in the art to which the present invention belongs, is not taking off
On the premise of from present inventive concept, several simple deductions and replacement can also be made, should all be considered as belonging to the present invention by institute
Claims of submission determine the protection domain of patent.
Claims (3)
1. with the method for RuCu/N-CNTs catalysts synthesis 9- ethyl tetrahydro carbazoles, which is characterized in that by what is prepared
RuCu/N-CNTs catalyst and 9- ethyl carbazoles are placed in autoclave, and reaction kettle is risen to certain temperature, is led in reaction kettle
Enter hydrogen, be stirred to react certain time and 9- ethyl tetrahydro carbazoles are made；
The reaction temperature is 75~110 DEG C；The Hydrogen Vapor Pressure is 3.0~6.1MPa；The speed of agitator is 400
~520rpm；The reaction time is 1.5~4h；
The RuCu/N-CNTs catalyst includes Ru, Cu, N-CNTs, wherein：The molar ratio of Ru and Cu is 1：0.8~6；Ru with
The molar ratio of N-CNTs is 1：170~600；Ru derives from ruthenic chloride, and Cu derives from copper chloride；N-CNTs by melamine with
CNTs in mass ratio 1：8 baking mixed obtain；
The RuCu/N-CNTs nanocatalysts are through the following steps that prepared：
(1) match, Ru salt, Cu salt and deionized water are configured in container, after being sufficiently stirred again according to above-mentioned catalytic component
N-CNTs is added in above-mentioned mixed solution；
(2) above-mentioned mixed solution is placed in 0 DEG C of water-bath, is added dropwise dropwise with the sodium borohydride of 0.1mol/L~0.4mol/L,
And stir reductase 12 h；
(3) will step (2) solution filter after dry to get to RuCu/N-CNTs catalyst.
2. as described in claim 1 with the method for RuCu/N-CNTs catalysts synthesis 9- ethyl tetrahydro carbazoles, feature
It is, in the preparation process (1) of the RuCu/N-CNTs catalyst：The molar ratio of Ru and Cu is 1：1.2~3, Ru and N-CNTs
Molar ratio be 1:200~400.
3. as described in claim 1 with the method for RuCu/N-CNTs catalysts synthesis 9- ethyl tetrahydro carbazoles, feature
It is, the drying in the preparation process (3) of the RuCu/N-CNTs catalyst carries out in an oven, and drying temperature is 75~110
DEG C, drying time is 9~14h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232382A (en) * | 2013-04-19 | 2013-08-07 | 西安交通大学 | Hydrogenation method of ethylcarbazole and dehydrogenation method of product thereof |
| CN105217568A (en) * | 2015-10-16 | 2016-01-06 | 安徽工业大学 | A kind of loading type Ag-Pd/C 3n 4the method of nanocatalyst catalysis formate dehydrogenase |
-
2017
- 2017-12-18 CN CN201711364110.6A patent/CN108057456A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232382A (en) * | 2013-04-19 | 2013-08-07 | 西安交通大学 | Hydrogenation method of ethylcarbazole and dehydrogenation method of product thereof |
| CN105217568A (en) * | 2015-10-16 | 2016-01-06 | 安徽工业大学 | A kind of loading type Ag-Pd/C 3n 4the method of nanocatalyst catalysis formate dehydrogenase |
Non-Patent Citations (2)
| Title |
|---|
| E. ASEDEGBEGA-NIETO, ET.AL.: "Modification of catalytic properties over carbon supported Ru–Cu and Ni–Cu bimetallics II. Paracetamol hydrogenation and n-hexane conversion", 《APPLIED CATALYSIS A: GENERAL 》 * |
| 万超等: "乙基咔唑在Ru/C催化剂下催化加氢性能研究", 《太阳能学报》 * |
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Application publication date: 20180522 |