CN1600774A - Method for synthesizing 1-amino naphthalenes - Google Patents
Method for synthesizing 1-amino naphthalenes Download PDFInfo
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- CN1600774A CN1600774A CN 03160125 CN03160125A CN1600774A CN 1600774 A CN1600774 A CN 1600774A CN 03160125 CN03160125 CN 03160125 CN 03160125 A CN03160125 A CN 03160125A CN 1600774 A CN1600774 A CN 1600774A
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Abstract
A process for synthesizing amino naphthalene by nitro naphthalene with carbon monoxide and water, selenium as catalyst, organic alkali and inorganic alkali as assistant catalyst in organic solvent, the molar ratio of nitro naphthalene and water is 1:1 to 1:1000, the molar amount of selenium is 0.1-100% of the molar amount of nitro naphthalene; the molar amount of organic alkali and inorganic alkali is 1-36 hours; reaction temperature is 20-120 deg.C.
Description
Technical field
The present invention relates to the synthetic of 1-amino naphthalenes, relate in particular to a kind of method of utilizing carbon monoxide and water to synthesize the 1-amino naphthalenes by the selenium catalytic reduction.
Background technology
The 1-amino naphthalenes is widely used in fields such as medicine, agricultural chemicals, dyestuff, auxiliary agent as a kind of important organic synthesis intermediate and raw material.At present, the 1-amino naphthalenes all is to make via 1-nitro-naphthalene reduction, and relevant quantity of document is huge, integrates to be used for industrialized nitro-compound method of reducing and to mainly contain following several: iron reduction, sodium sulfide reducing, electrolytic reduction and catalytic hydrogenating reduction.Though it is wide that iron filings method and sulfuration alkaline process adapt to, technology is simple, and Technological Economy is more reasonable, and environmental pollution is serious, has begun to be eliminated gradually; Electrolytic process productive rate height, easy and simple to handle, environmental friendliness, but energy consumption is big, existing synthetic and half suitability for industrialized production in laboratory that is used for more; Shortening method output is big, and the quality product height has significant superiority to solving problem of environmental pollution, therefore, and the industrial main flow that become of this method, but this method need be used more expensive catalyzer and hydrogen, the cost height, and operation is complicated.In addition, also have under catalyst action with reduction methods such as the reduction method of hydrazine and metal hydrides, but they only are applicable to special aromatic nitro compound reduction, and cost is higher, does not have ubiquity.
Summary of the invention
The object of the present invention is to provide the method for the synthetic 1-amino naphthalenes of a kind of catalytic reduction that reaction conditions gentleness, cost are low under normal pressure.
For achieving the above object, the technical solution used in the present invention is as follows: in the presence of carbon monoxide and water, with the 1-nitro-naphthalene is raw material, selenium is catalyzer, organic bases or mineral alkali are promotor, or do not add any promotor, and in organic solvent, under normal pressure, react, be that amino prepares the 1-amino naphthalenes with nitroreduction; Reaction formula is as follows:
Wherein:
The molar ratio of material of 1-nitro-naphthalene and water is 1: 1 to 1: 1000; The mole dosage of selenium is 0.1～100% of a reactant aromatic nitro compound; The mole dosage of organic bases or mineral alkali is 0～200% of a reactant aromatic nitro compound; Reaction times is 1～36 hour; Temperature of reaction is 20～120 ℃.Described mineral alkali is one or more mixtures in sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium acetate and the potassium acetate; Describedly do not add any promotor and be meant and only make catalyzer and need not add other material can react as promotor with selenium; Described carbon monoxide can use the industrial carbon monoxide tail gas that contains air, nitrogen, carbonic acid gas, water vapour, and wherein the content sum of nitrogen, carbonic acid gas, water vapour is smaller or equal to 95% of cumulative volume, and air content is smaller or equal to 30% of cumulative volume; Described organic solvent is one or more polarity, nonpolar inert solvent, described polar solvent is tetrahydrofuran (THF) (THF), N, dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), glycol ether, N-formyl piperidine (FP), ethylene glycol diethyl ether, dioxane, crown ether or acetone; Non-polar solvent is toluene, normal hexane, dimethylbenzene or benzene.
The present invention has following advantage:
1. the present invention is a synthesis under normal pressure, and facility investment is few, and is easy to operate and safe.
2. cost is low.Raw material is simple, be easy to get, and only uses the lower nonmetal selenium of price to be catalyzer.
3. environmentally friendly.It is green reaction that the present invention does not have the three wastes substantially, has reached the requirement of cleaner production, helps large-scale industrial production.
4. the reaction process difficulty is low.The present invention is easy and simple to handle, and product separates with the postorder of catalyzer easily.
5. good economy performance.Reaction preference height of the present invention, to adopt nonmetal selenium be catalyzer can reach more than 99% the reduction selectivity of nitro.
6. has phase transfer function.In catalyzed reaction of the present invention, solid selenium powder catalyzer is insoluble in the reaction system before the reaction beginning, the selenium of solid phase changes the active specy that is dissolved in reaction system into and carries out the homogeneous catalyzed reaction in reaction process, after reaction ends, catalyzer is separated out with the solid phase selenium powder again, very easily separates with product.Therefore, the present invention combines the advantage of homogeneous catalysis and heterogeneous catalyst.
Embodiment
The following examples are to detailed description of the present invention, rather than limitation of the present invention.
Embodiment 1
Having prolong and stirring adding 1-nitro-naphthalene (10mmol), Se (0.4mmol), H in the there-necked flask at 100ml
2O (0.1mol), triethylamine (5mmol) and solvent DMF (40ml), continue logical people's carbon monoxide, then be heated to 88 ℃ of stirring reactions 4 hours, be cooled to room temperature, carbon monoxide is switched to oxygen or after pneumatic blending 0.5-1 hour, filters out selenium powder, will filter after gained filtrate concentrates, carry out assay with gas-chromatography, getting 1-amino naphthalenes chromatogram yield is 100% (in the 1-nitro-naphthalene).Assay adopts the HP-4890D gas chromatography system, comprises fid detector, SE-54 capillary column (30m * 0.32mm * 1.5 μ m), and temperature of vaporization chamber is 280 ℃, column temperature: 250 ℃, external standard method is quantitative.
Embodiment 2
Solvent is a formyl piperidine, and the reaction times is 10 hours, and other experimental technique and condition are with embodiment 1, and it is 50% (in the 1-nitro-naphthalene) that gas Chromatographic Determination gets 1-amino naphthalenes yield.
Embodiment 3: solvent is DMSO, and the reaction times is 3 hours, and other experimental technique and condition are with embodiment 1, and it is 100% (in the 1-nitro-naphthalene) that gas Chromatographic Determination gets 1-amino naphthalenes yield.
Embodiment 4: solvent is DMF, 50 ℃ of temperature of reaction, and the reaction times is 7 hours, and other experimental technique and condition are with embodiment 1, and it is 100% (in the 1-nitro-naphthalene) that gas Chromatographic Determination gets 1-amino naphthalenes yield.
Embodiment 5: promotor is that 35 ℃ of reaction times of NaOH (5mmol) temperature of reaction are 34 hours, and other experimental technique and condition are with embodiment 1, and it is 100% (in the 1-nitro-naphthalene) that gas Chromatographic Determination gets 1-amino naphthalenes yield.
Embodiment 6: no promotor, and 95 ℃ of temperature of reaction, the reaction times is 4 hours, and other experimental technique and condition are with embodiment 1, and it is 33% (in the 1-nitro-naphthalene) that gas Chromatographic Determination gets 1-amino naphthalenes yield.
Claims (6)
1, a kind of method of synthetic 1-amino naphthalenes, its reaction formula is as follows:
With the 1-nitro-naphthalene is raw material, and selenium is catalyzer, continues to feed carbon monoxide in the organic solvent, in the presence of water, 20～120 ℃ were reacted 1～36 hour, and were cooled to room temperature, carbon monoxide is switched to oxygen or pneumatic blending 0.2-5 hour, filter out the catalyzer selenium powder;
Wherein:
The molar ratio of material of 1-nitro-naphthalene and water is 1: 1 to 1: 1000
The mole dosage of selenium is 0.1～100% of a 1-nitro-naphthalene.
2, in accordance with the method for claim 1, it is characterized in that, is promotor with organic bases or mineral alkali in the reaction, and its mole dosage is 0～200% of a 1-nitro-naphthalene.
3, in accordance with the method for claim 2, it is characterized in that described mineral alkali is one or more the mixture in sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium acetate and the potassium acetate; Described organic bases is triethylamine, aniline, pyridine, triphenylphosphine, 1,5-diaza-bicyclo [5.4.0]-5-undecylene (DBU), 1,5-diaza-bicyclo [5.3.0]-5-nonene (DBN), N-crassitude and 1, the mixture of one or more in 4-diaza-bicyclo [2.2.2] octane (DABCO).
4, in accordance with the method for claim 1, it is characterized in that, wherein said carbon monoxide can use the industrial carbon monoxide tail gas that contains air, nitrogen, carbonic acid gas, water vapour, wherein the content sum of nitrogen, carbonic acid gas, water vapour is smaller or equal to 95% of cumulative volume, and air content is less than 30%.
5, in accordance with the method for claim 1, it is characterized in that wherein said organic solvent is one or more polarity, nonpolar inert solvent.
6, in accordance with the method for claim 5; it is characterized in that; described polar solvent is tetrahydrofuran (THF), N; dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), glycol ether, ethylene glycol diethyl ether, N-formyl piperidine (FP), dioxane, crown ether or acetone, non-polar solvent is toluene, dimethylbenzene, normal hexane or benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03160125 CN1600774A (en) | 2003-09-26 | 2003-09-26 | Method for synthesizing 1-amino naphthalenes |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03160125 CN1600774A (en) | 2003-09-26 | 2003-09-26 | Method for synthesizing 1-amino naphthalenes |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173999A (en) * | 2011-02-28 | 2011-09-07 | 盐城工学院 | Method for synthesizing 2-amino-N,N-dimethylbenzamide |
| CN102675162A (en) * | 2012-05-09 | 2012-09-19 | 辽宁大学 | Method for synthesizing CLT acid |
| CN104262171A (en) * | 2014-09-24 | 2015-01-07 | 哈尔滨工业大学 | Method for preparing 1,4,5,8-tetraaminonaphthalene tin chloride hydrochloride |
| CN110437111A (en) * | 2019-08-26 | 2019-11-12 | 辽宁大学 | A method of synthesis C acid |
| CN110437110A (en) * | 2019-08-26 | 2019-11-12 | 辽宁大学 | A method of synthesis M acid |
-
2003
- 2003-09-26 CN CN 03160125 patent/CN1600774A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173999A (en) * | 2011-02-28 | 2011-09-07 | 盐城工学院 | Method for synthesizing 2-amino-N,N-dimethylbenzamide |
| CN102675162A (en) * | 2012-05-09 | 2012-09-19 | 辽宁大学 | Method for synthesizing CLT acid |
| CN102675162B (en) * | 2012-05-09 | 2014-03-26 | 辽宁大学 | Method for synthesizing CLT acid |
| CN104262171A (en) * | 2014-09-24 | 2015-01-07 | 哈尔滨工业大学 | Method for preparing 1,4,5,8-tetraaminonaphthalene tin chloride hydrochloride |
| CN104262171B (en) * | 2014-09-24 | 2016-08-24 | 哈尔滨工业大学 | A kind of preparation method of 1,4,5,8-tetramino naphthalene stannic chloride hydrochlorate |
| CN110437111A (en) * | 2019-08-26 | 2019-11-12 | 辽宁大学 | A method of synthesis C acid |
| CN110437110A (en) * | 2019-08-26 | 2019-11-12 | 辽宁大学 | A method of synthesis M acid |
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