CN103288608A - Novel method for catalyzing selective oxidization of alcohol substance by using nanometer nickel oxide - Google Patents
Novel method for catalyzing selective oxidization of alcohol substance by using nanometer nickel oxide Download PDFInfo
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- CN103288608A CN103288608A CN2013102164590A CN201310216459A CN103288608A CN 103288608 A CN103288608 A CN 103288608A CN 2013102164590 A CN2013102164590 A CN 2013102164590A CN 201310216459 A CN201310216459 A CN 201310216459A CN 103288608 A CN103288608 A CN 103288608A
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Abstract
The invention relates to a novel method for catalyzing selective oxidization of an alcohol substance by using nanometer nickel oxide. The method disclosed by the invention comprises the steps of: with nanometer nickel oxide as a catalyst, a nitro-compound as an oxidizing agent and KOH as a synergist, catalyzing and oxidizing an alcohol compound so as to prepare aldehyde or ketone at a gage pressure of 0-1 MPa and at a reaction temperature of 50-150 DEG C, and a corresponding nitro-compound is reduced into amine. According to the method disclosed by the invention, the defects that a catalyst is expensive, unsafe and not environment-friendly, and has high requirements on equipment, etc are overcome. The method disclosed by the invention can be used for simultaneously catalyzing selective oxidization of the alcohol compound and selective reduction of the nitro-compound; a preparation process of the needed catalyst is simple; the catalyst is cheap; the novel method can be operated at low temperature and normal pressure when being applied to the reaction and are mild in condition, high in selectivity and moderate in yield.
Description
Technical field
The present invention relates to a kind of new purposes of nano-nickel oxide, be specifically related to the novel method of nano-nickel oxide catalyzing alcohols matter selective oxidation.
Background technology
Aldehyde and ketone are the important organic compound of a class, and it synthesizes and occupy important status in organic synthesis.The production of aldehydes or ketones industrially mainly prepares aldehydes or ketones by the alcohol compound selective oxidation except extracting from natural product.Alcohols selective oxidation method has a wide range of applications in extensive chemical industry production, also is the important content of fine chemistry industry research.But the catalytic oxidation of alcohol compound is easy to take place deep oxidation, and for example the catalyzed oxidation of primary alconol also very easily generates corresponding acid, CO except generating purpose product aldehyde compound
2The product of even depth oxidation, this just makes the purpose selectivity of product reduce.People slowly turn to research emphasis exploitation highly selective, environmentally friendly catalyzer and cheap oxygenant for this reason.With nitric acid as oxygenant, oxidation in acetic acid aqueous solution prepares the O-phthalic aldehyde reaction and studies to phthalyl alcohol, discovery is in 80 ℃ of temperature of reaction, n (oxygenant): n (alcohol)=2.5: 1, reaction times when being 1h, yield can reach 76.0%, selectivity is up to 99.5%, but the theory of " Green Chemistry " has been run counter in the use of a large amount of acid solutions.Chinese patent CN 102826979A has reported that be the method for phenyl aldehyde and methyl benzoate compounds with C5H6Br2N2O2 with benzylalcohol compounds selective oxidation, its invention uses C5H6Br2N2O2 as oxygenant, with alcohol as solvent, the mol ratio of control C5H6Br2N2O2 and benzylalcohol is 4-2: 1, and can be corresponding methyl benzoate with the benzylalcohol selective oxidation; And with halogenated alkane as solvent, the mol ratio of control C5H6Br2N2O2 and benzylalcohol is 1.5-0.5: 1, the benzylalcohol selective oxidation can be become corresponding phenyl aldehyde.Chinese patent CN 101564692A provides a kind of preparation method and application of benzyl alcohol selective oxidation catalyst, and catalyzer is by carrier magnesium-aluminium spinel MgAl
2O
4One or more metal oxides among supported V, Mo, W, Ag, Cu, Zn, Co, Ni, Fe or the Sn are formed, this catalyzer is applied in the reaction of benzyl alcohol selective preparing benzaldehyde by oxidizing, with oxygen, air or hydrogen peroxide as oxidant, has higher catalytic performance.Chinese patent CN 102719844A adopts ionic liquid as supporting electrolyte, and acetonitrile is as cosolvent, at temperature of reaction 25-70 ℃ supercritical CO
2Utilize the autoclave that has electrode to carry out electrochemical electrolysis in the environment, benzyl alcohol selective is oxidized to phenyl aldehyde.Under optimal conditions, phenyl aldehyde yield and selectivity all can reach more than 99.8%.These alcohols selective oxidations prepare the method for aldehyde and ketone, though overcome the problem of " Green Chemistry ", the catalyst preparation process of higher reaction pressure, complexity and the Application and Development that more expensive unfavourable condition such as oxygenant have limited this class technology.
Arylamine is the important organic synthesis intermediate of a class and raw material, for the synthesis of multiple fine chemicals such as agricultural chemicals, medicine, rubber ingredients, dyestuff and pigment, sensitive materials etc.Arylamine can be obtained by corresponding reducing aromatic nitro compound, and industrial method of going back original aromatic nitro compound is varied, and wherein, the catalytic hydrogenating reduction method is advocated energetically owing to have advantage such as environmental friendliness, throughput height, constant product quality.Being usually used in the catalyzer of catalytic hydrogenating reduction nitro thing, is the low price of the non-precious metal catalyst of representative with nickel, has obtained widespread use industrial.But the leading catalyzer Raney-Ni of industry is owing to existing a large amount of impurity and caustic alkali to handle the micropore that the back exists in preparation process, influenced its selectivity, make the content of by product zinin and nitrogen benzide increase, and the thermotolerance of this catalyzer is also relatively poor, easily form local superheating, limited throughput and catalyst life.In addition, the industrial hydrogen that generally all adopts directly reduces the halogenated aromatic nitro-compound as reducing gas, and this is not only to equipment and safety requirements strictness, and the dehalogenation side reaction is more serious.Chinese patent CN 1219598C is raw material with the aromatic nitro compound, ammonia synthesis gas or hydrogen are sources of hydrogen, make catalyzer with the alloy after-treatment products that nickel powder, aluminium powder, silicon compound fusion are made, the synthesis technique for preparing aromatic amine through shortening, though obtain good yield, because reaction is to carry out in autoclave, and directly use ammonia synthesis gas or hydrogen to be sources of hydrogen, feasible reaction is under high pressure (greater than the 1MPa) environment, and is strict to equipment and safety requirements.Therefore, prepare a kind of highly selective and low-cost catalyzer and simultaneously seem particularly important in conjunction with the reactive mode of safety and environmental protection, and to utilize the oxidisability of nitro in the reduction nitro be a desirable operational path with the aldehydes or ketones that alcohol is oxidized into the height using value.
Summary of the invention
Purpose of the present invention just is to overcome above-mentioned defective, the new purposes of development nano-nickel oxide.
Technical scheme of the present invention is:
The novel method of nano-nickel oxide catalyzing alcohols matter selective oxidation, its major technique is characterised in that with nano-nickel oxide makes catalyzer, under gauge pressure 0-1MPa, temperature of reaction 50-150 ℃, be oxygenant with the nitro-compound, KOH is synergistic agent, compounds with catalytic oxidation of alcohol prepares aldehydes or ketones, and corresponding nitro-compound is reduced into amine.
Described nano-nickel oxide prepares by solid phase or liquid phase ordinary method.
Described alcohols is primary alconol or secondary alcohol.
Described nitro-compound is aromatic nitro compound or aliphatic nitro compound.
The present invention's selective oxidation of catalyzing alcohols compound and selective reduction of nitro-compound simultaneously, the catalyst preparation process that reacts required is simple, low price; When being applied to this reaction, can under the low-temperature atmosphere-pressure condition, operate, mild condition, and selectivity is higher, and yield is suitable.
Embodiment
Technical thought of the present invention is catalysis nitro-compound selective reduction when comprising under the condition of normal pressure with the oxidation of nano-nickel oxide catalyzing alcohols compound selective, obtains good yield.
Nano-nickel oxide prepares by solid phase or liquid phase ordinary method, and alcohols is primary alconol or secondary alcohol.
Embodiment 1:
P-Nitrophenyl chloride oxidation Virahol
1.1g potassium hydroxide, 0.16g nickel oxide nano powder and 20mL Virahol are added in the 100ml there-necked flask successively, and again to wherein adding the 3.2g parachloronitrobenzene, wherein catalyst levels is 3% of reactant parachloronitrobenzene quality, reacts 4h down in 83 ℃.Reaction product is filtered with the dissolving of 1,2-ethylene dichloride, and gas-chromatography detects analysis.Product acetone yield is 50%, and the p-Chlorobenzoic acid amide yield is 65%.
Embodiment 2:
O-Nitrochlorobenzene oxidation Virahol
With 1.1g potassium hydroxide, 0.1g nickel oxide nano powder and 20mL Virahol add in the 100ml there-necked flask successively, and again to wherein adding the 3.2g o-chloronitrobenzene, wherein catalyst levels is 3% of reactant o-chloronitrobenzene quality, react 4h down in 83 ℃.Reaction product is filtered with the dissolving of 1,2-ethylene dichloride, and gas-chromatography detects analysis.Product acetone yield is 56%, and the Ortho-Chloro aniline yield is 77%.
Embodiment 3:
The nitrobenzene oxidation Virahol
With 1.1g potassium hydroxide, 0.16g nickel oxide nano powder and 20mL Virahol add in the 100ml there-necked flask successively, and again to wherein adding 2.1g oil of mirbane, wherein catalyst levels is 5% of reactant oil of mirbane quality, react 4h down in 97 ℃.Reaction product 1, gas-chromatography detects analysis behind the 2-ethylene dichloride dissolution filter.Product acetone yield is 56%, and aniline yield rate is 68%
Embodiment 4:
P-Nitrophenyl chloride oxidation n-propyl alcohol
With 1.1g potassium hydroxide, 0.16g nickel oxide nano powder and 20mL n-propyl alcohol add in the 100ml there-necked flask successively, and again to wherein adding the 3.2g parachloronitrobenzene, wherein catalyst levels is 5% of reactant parachloronitrobenzene quality, react 4h down in 97 ℃.Reaction product 1, gas-chromatography detects analysis behind the 2-ethylene dichloride dissolution filter.Product propionic aldehyde yield is 52%, and the p-Chlorobenzoic acid amide yield is 68%.
Embodiment 5:
O-Nitrochlorobenzene oxidation n-propyl alcohol
With 1.1g potassium hydroxide, 0.16g nickel oxide nano powder and 20mL n-propyl alcohol add in the 100ml there-necked flask successively, and again to wherein adding the 3.2g o-chloronitrobenzene, wherein catalyst levels is 5% of reactant o-chloronitrobenzene quality, react 4h down in 97 ℃.Reaction product 1, gas-chromatography detects analysis behind the 2-ethylene dichloride dissolution filter.Product propionic aldehyde yield is 54%, and the Ortho-Chloro aniline yield is 70%.
Embodiment 6:
The nitrobenzene oxidation n-propyl alcohol
With 1.1g potassium hydroxide, 0.16g nickel oxide nano powder and 20mL n-propyl alcohol add in the 100ml there-necked flask successively, and again to wherein adding 2.1g oil of mirbane, wherein catalyst levels is 5% of reactant oil of mirbane quality, react 4h down in 97 ℃.Reaction product 1, gas-chromatography detects analysis behind the 2-ethylene dichloride dissolution filter.Product propionic aldehyde yield is 58%, and aniline yield rate is 64%
Embodiment 7:
O-Nitrochlorobenzene oxidation n-Octanol
With 3g potassium hydroxide, 0.2gNiO nano powder and 50mL n-Octanol add in the 100ml there-necked flask successively, to wherein adding the 6.4g o-Nitrochlorobenzene, react 5h down in 80 ℃ again.Reaction product is filtered the back gas-chromatography and is detected analysis.Product n-octaldehyde yield is 79%, and the Ortho-Chloro aniline yield is 70%.
Embodiment 8:
The nitrobenzene oxidation n-Octanol
3g potassium hydroxide, 0.2gNiO nano powder and 50mL n-Octanol are added in the 100ml there-necked flask successively, to wherein adding 4.3g oil of mirbane, react 5h down in 80 ℃ again.Reaction product is filtered the back gas-chromatography and is detected analysis.Product n-octaldehyde yield is 88%, and aniline yield rate is 73%.
Claims (4)
1. the novel method of nano-nickel oxide catalyzing alcohols matter selective oxidation, it is characterized in that making catalyzer with nano-nickel oxide, under gauge pressure 0-1MPa, temperature of reaction 50-150 ℃, be oxygenant with the nitro-compound, KOH is synergistic agent, compounds with catalytic oxidation of alcohol prepares aldehydes or ketones, and corresponding nitro-compound is reduced into amine.
2. according to the novel method of the described nano-nickel oxide catalyzing alcohols of claim 1 matter selective oxidation, it is characterized in that nano-nickel oxide prepares by solid phase or liquid phase ordinary method.
3. according to the novel method of the described nano-nickel oxide catalyzing alcohols of claim 1 matter selective oxidation, it is characterized in that described alcohols is primary alconol or secondary alcohol.
4. according to the novel method of the described nano-nickel oxide catalyzing alcohols of claim 1 matter selective oxidation, it is characterized in that described nitro-compound is aromatic nitro compound or aliphatic nitro compound.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112705205A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst for preparing arylamine and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62123162A (en) * | 1985-11-25 | 1987-06-04 | Nippon Kayaku Co Ltd | Production of cyano-substituted aniline compound |
| CN1055922A (en) * | 1990-04-21 | 1991-11-06 | 浙江工学院 | 2,4-xylidine and 2, the preparation method of 6-xylidine |
| CN1349433A (en) * | 1999-03-03 | 2002-05-15 | 洛伊纳-威尔克股份公司 | Nickel catalyst for hydrogenating functional groups and method for producing same |
| CN1493526A (en) * | 2003-09-16 | 2004-05-05 | 上海大学 | Collosol gel production method of nano NiO material |
| CN1686831A (en) * | 2005-04-07 | 2005-10-26 | 华南理工大学 | Microwave method for synthesizing nano nickel oxide |
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2013
- 2013-05-29 CN CN201310216459.0A patent/CN103288608B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62123162A (en) * | 1985-11-25 | 1987-06-04 | Nippon Kayaku Co Ltd | Production of cyano-substituted aniline compound |
| CN1055922A (en) * | 1990-04-21 | 1991-11-06 | 浙江工学院 | 2,4-xylidine and 2, the preparation method of 6-xylidine |
| CN1349433A (en) * | 1999-03-03 | 2002-05-15 | 洛伊纳-威尔克股份公司 | Nickel catalyst for hydrogenating functional groups and method for producing same |
| CN1493526A (en) * | 2003-09-16 | 2004-05-05 | 上海大学 | Collosol gel production method of nano NiO material |
| CN1686831A (en) * | 2005-04-07 | 2005-10-26 | 华南理工大学 | Microwave method for synthesizing nano nickel oxide |
Non-Patent Citations (1)
| Title |
|---|
| J.MICHAEL ROBINSON等: "Benzoin Enediol Dianion and Hydroxide Ion in DMSO: A Single Electron Transfer Reduction System Driven by the Irreversible Benzilic Acid Rearrangement", 《J.ORG.CHEM.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112705205A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst for preparing arylamine and preparation method and application thereof |
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