CN1749239A - Method for synthesizing hydrogenated azo compounds - Google Patents
Method for synthesizing hydrogenated azo compounds Download PDFInfo
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- CN1749239A CN1749239A CN 200510047119 CN200510047119A CN1749239A CN 1749239 A CN1749239 A CN 1749239A CN 200510047119 CN200510047119 CN 200510047119 CN 200510047119 A CN200510047119 A CN 200510047119A CN 1749239 A CN1749239 A CN 1749239A
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- hydrodiazo
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Abstract
The present invention is the synthesis process of hydrogenating aromatic azo compound into hydrogenated azo compounds at normal pressure inside organic solvent in the presence of CO and water as well as Se as catalyst with or without organic or inorganic alkali as co-catalyst. Where, the aromatic azo compound may have substituted radical, and the reaction has molar ratio between aromatic azo compound and water of 1 to 1-20, molar ratio between aromatic azo compound and CO of 1 to 1.1-3, molar amount of Se in 0.1-8 % of aromatic azo compound, reaction time of 0.5-3 hr, and reaction time of 30-100 deg c. The synthesis process is simple and safe, and has easy to obtain material, no pollution, high selectivity, no influence on the sensitive radicals on the aromatic ring, high yield and reusability of the catalyst.
Description
Technical field
The present invention relates to the synthetic method of azobenzene compound, relate in particular to a kind of method of utilizing catalyzing carbon monoxide reduction synthesizing hydrodiazo benzene-like compounds.
Background technology
Hydrazobenzene is applied to fields such as medicine, agricultural chemicals as important organic synthesis intermediate and the raw material of a big class.The hydrodiazo kind compound preparation is a raw material with azobenzene compound and azoxybenzene compound mainly, the method that present reduction-oxidation azo aromatic compound prepares the hydrodiazo aromatic compound mainly contains: the metallic reducing method, catalysis hydrazine reduction method and sodium sulfide reducing method, though aforesaid method technology is ripe, but byproduct of reaction is the product that environment is polluted, in reduction process, belong to superseded method, its cost of catalysis hydrazine reduction method is higher, the catalyzing carbon monoxide method of reducing, at the existing report of reduction nitro, azoxy is carried out the reductive report but have not yet to see.
Summary of the invention
The object of the present invention is to provide a kind of method of the catalytic reduction that reaction conditions gentleness, cost are low under normal pressure fragrance azoxy compound synthesizing hydrodiazo kind compound.
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 fragrant azoxy compound 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, azoxy is reduced to hydrodiazo.Reaction formula is as follows:
Wherein: X or Y be-H ,-R ,-OH ,-NH
2,-R-NH
2, RO-,-Cl ,-F ,-Br ,-CHF
3,-CHO
The molar ratio of material of above-mentioned fragrant azoxy compound and water is 1: 1～20, and the water yield is with suitable excessive being advisable; The mol ratio of reactant aromatic azo-compound and CO is 1: 2.2～4, and the mole dosage of selenium is 0.5～8% of a reactant aromatic azo-compound; The mole dosage of promotor is 0～10% of a reactant fragrance azoxy compound; Temperature of reaction is 30～100 ℃, reaction times is 0.5-3 hour, different azoxy compounds, and catalyst levels, promotor consumption reaction times difference, the prolongation reaction times can make the reactant Restore All, reaction late phase reaction speed is slower, proceed to conventional liquid chromatography for measuring productive rate variation below 1% in reaction, stop to feed carbon monoxide, after the cooling, switch aerating oxygen or air to catalyzer and separate out, filter, distill, wash aftertreatment then according to a conventional method.
Described promotor is: mineral alkali be sodium hydroxide and/or potassium hydroxide and/or yellow soda ash and/salt of wormwood and/or sodium acetate and/or potassium acetate; Described organic bases is triethylamine and/or aniline and/or pyridine and/or triphenylphosphine and/or 1,5-diaza-bicyclo [5.4.0]-5-undecylene (DBU) and/or 1,5-diaza-bicyclo [5.3.0]-5-nonene (DBN) and/or N-crassitude and/or 1,4-diaza-bicyclo [2.2.2] octane (DABCO).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 and/or water vapour except that using technical pure CO, wherein the content sum of nitrogen, carbonic acid gas and/or water vapour is smaller or equal to 95% of cumulative volume, air content is smaller or equal to 30% of cumulative volume, the carbon monoxide consumption is measured consumption in molar ratio, feed carbon monoxide and can adopt continuously excessively for shortening the reaction times, the carbon monoxide of effusion recycles; Wherein said organic solvent is one or more polarity and/or nonpolar inert solvent; Described polar solvent is tetrahydrofuran (THF), N, dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), glycol ether, ethylene glycol diethyl ether, dioxane, crown ether or acetone, and non-polar solvent is normal hexane, toluene or benzene.Selecting for use of solvent is to select the big solvent of solubleness according to the solubleness of aromatic azo-compound in solvent, and its consumption is being advisable by the solubilizing reaction material.
Wherein, be alkyl, amino, alkylamino, alkoxyl group etc. to electron substituent group in the described reactant fragrance azoxy compound, electron-withdrawing substituent is the chlorine that directly links to each other with aromatic ring, fluorine, bromine, trifluoromethyl, alkyloyl etc.
Reaction preference height of the present invention, to adopt nonmetal selenium be catalyzer can reach more than 99% the reduction selectivity of azoxy, and sensitive group such as halogen, alkyloyl is unaffected on the aromatic ring, and productive rate is therefrom waited until height; The present invention has the efficient of atomic economy reaction.Simultaneously, method of the present invention can be to the azo-group on azo aromatic compound reduction, thereby is that raw material need not the separating aromatic azo-compound with the azoxy aromatics.
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 substance 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 under oxygen or air effect, very easily separates with product.Therefore, the present invention combines the advantage of homogeneous catalysis and heterogeneous catalyst.
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.
Raw material simple, be easy to get, only use the lower nonmetal selenium of price to be catalyzer, cost is low.
3. the present invention is environmentally friendly, and not having the three wastes substantially is green reaction, has reached the requirement of cleaner production, helps large-scale industrial production.
4. reaction process difficulty of the present invention is low.Easy and simple to handle, product separates with the postorder of catalyzer easily.
5. good economy performance.This method reduction selectivity can reach 99%, the productive rate height.
Embodiment
Below by embodiment in detail the present invention is described in detail; Yet, the invention is not restricted to following embodiment.
Embodiment 1
Having prolong and stirring adding zinin 9.8g (50mmol), Se 0.08 (1mmol), H in the there-necked flask at 500ml
2O 9g (0.5mol), triethylamine 0.5g (5mmol) and solvent DMF 200mL continue logical people's carbon monoxide, and were heated to 88 ℃ of stirring reactions 0.5 hour, are cooled to room temperature, and carbon monoxide is switched to oxygen or after pneumatic blending 0.5-1 hour, filters out selenium powder.Underpressure distillation (5kPa is following) steams solvent, and productive rate 95% is filtered in washing.
Embodiment 2
The temperature of reaction water yield, carbon monoxide, catalytic amount are as follows, and experimental technique and condition are with embodiment 1.
| Temperature (℃) | H 2O(mol) | CO(mol) | Se(mmol) | Time (min) | Productive rate (%) |
| 30 | 0.2 | 0.16 | 0.25 | 180 | 90 |
| 100 | 1 | 0.20 | 0.80 | 60 | 95 |
| 50 | 0.5 | 0.12 | 3.0 | 60 | 90 |
| 80 | 0.1 | 0.10 | 4.0 | 30 | 90 |
Embodiment 3
Solvent and alkali are as shown in the table, and experimental technique and charging capacity and condition are with embodiment 1.
| Solvent | Alkali | Temperature of reaction (℃) | Reaction times (min) | Productive rate (%) |
| DMSO | —— | 90 | 30 | 95 |
| Tetrahydrofuran (THF) | DBU | 50 | 150 | 80 |
| Toluene | Triethylamine | 80 | 180 | 48 |
| Acetone | Pyridine | 70 | 100 | 50 |
| Dioxane | Aniline | 90 | 140 | 76 |
| One diethyl two that contracts | Yellow soda ash | 80 | 130 | 68 |
| Alcohol | ||||
| Ethylene glycol diethyl ether | Sodium hydroxide | 80 | 150 | 83 |
Embodiment 4:
Different promotor combinations, experimental technique and condition are with embodiment 1
| Solvent | Consumption (ml) | The promotor combination | Consumption g (5mmol) | Reaction times mm | Productive rate (%) |
| The DMSO tetrahydrofuran (THF) | 100 100 | The sodium hydroxide sodium acetate | 0.1 0.2 | 30 | 96 |
| Toluene benzene | 100 100 | The sodium acetate triethylamine | 0.2 0.25 | 30 | 70 |
| Dioxane DMSO | 100 100 | Pyridine triethylamine sodium acetate | 0.1 0.15 0.15 | 40 | 90 |
| Glycol ether acetone | 100 100 | DBN DABCO | 0.35 0.25 | 50 | 80 |
| DMSO DMF | 100 100 | Sodium hydroxide DBU | 0.1 0.4 | 60 | 95 |
| Normal hexane toluene | 100 100 | Sodium acetate DBN | 0.2 0.35 | 80 | 86 |
Embodiment 5:
Reduce with industrial carbon monoxide tail gas, its experimental technique and condition are with embodiment 1.
| CO forms | Volume content % | Reaction times min | Productive rate % |
| Air water CO | 10 5 85 | 60 | 96 |
| N 2 CO 2 CO | 50 45 5 | 150 | 95 |
| N 2 | 20 | 100 | 95 |
| Water vapour CO 2 CO | 10 20 50 |
Embodiment 6:
Different material is as follows, and other experimental technique and condition are with embodiment 1.
| Raw material | Reaction times (min) | Productive rate (%) | |
| X | Y | ||
| Right-NH 2 | H | 30 | 90 |
| Right-NH 2 | To N, the N-dimethylamino | 50 | 97 |
| To methyl | To chlorine | 30 | 95 |
| To chlorine | To trifluoromethyl | 40 | 95 |
| Between hydroxyl | To amino | 60 | 90 |
| To fluorine | Adjacent aldehyde radical | 50 | 95 |
Claims (6)
1. the method for a synthesizing hydrodiazo kind compound, it is characterized in that: in the presence of carbon monoxide and water, with fragrant azoxy compound is raw material, selenium is catalyzer, organic bases or mineral alkali are promotor, or do not add any promotor, in organic solvent under normal pressure, temperature of reaction is 30～100 ℃, proceed to conventional liquid chromatography for measuring in reaction, productive rate changes below 1%, stops to feed carbon monoxide, switch aerating oxygen or air, filter, distill, wash aftertreatment then;
Azoxy is reduced to hydrodiazo, and reaction formula is as follows:
Wherein: X or Y be-H ,-R ,-OH ,-NH
2,-R-NH
2,-Cl-F-CHF
3-COH.
2, the method for synthesizing hydrodiazo kind compound according to claim 1 is characterized in that: the molar ratio of material of described fragrant azoxy compound and water is 1: 1～20; The mol ratio of reactant aromatic azo-compound and CO is 1: 2.2～4, and the mole dosage of selenium is 0.5～8% of a reactant aromatic azo-compound; The mole dosage of promotor is 0～10% of a reactant aromatic azo-compound.
3. according to the method for the described synthesizing hydrodiazo kind compound of claim 1, it is characterized in that: described promotor mineral alkali be sodium hydroxide and/or potassium hydroxide and/or yellow soda ash and/salt of wormwood and/or sodium acetate and/or potassium acetate; Described organic bases is triethylamine and/or aniline and/or pyridine and/or triphenylphosphine and/or 1,5-diaza-bicyclo [5.4.0]-5-undecylene (DBU) and/or 1,5-diaza-bicyclo [5.3.0]-5-nonene (DBN) and/or N-crassitude and/or 1,4-diaza-bicyclo [2.2.2] octane (DABCO).
4. according to the method for the described synthesizing hydrodiazo kind compound of 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 and/or water vapour, wherein the content sum of nitrogen, carbonic acid gas and/or water vapour is smaller or equal to 95% of cumulative volume, and air content is less than 30%.
5. according to the method for the described synthesizing hydrodiazo kind compound of claim 1, it is characterized in that: wherein said organic solvent is one or both polarity and/or nonpolar inert solvent.
6. according to the method for the described synthesizing hydrodiazo kind compound of 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, dioxane, crown ether or acetone, non-polar solvent is normal hexane, toluene or benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100471195A CN1295208C (en) | 2005-09-01 | 2005-09-01 | Method for synthesizing hydrogenated azo compounds |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100471195A CN1295208C (en) | 2005-09-01 | 2005-09-01 | Method for synthesizing hydrogenated azo compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1749239A true CN1749239A (en) | 2006-03-22 |
| CN1295208C CN1295208C (en) | 2007-01-17 |
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|---|---|---|---|
| CNB2005100471195A Expired - Fee Related CN1295208C (en) | 2005-09-01 | 2005-09-01 | Method for synthesizing hydrogenated azo compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1210255C (en) * | 2002-11-23 | 2005-07-13 | 宋伟 | Method for preparing2,2'-dichlorohydrazobenzene |
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