CN104557727A - Method for preparing 5-aminobenzimidazole ketone - Google Patents
Method for preparing 5-aminobenzimidazole ketone Download PDFInfo
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- CN104557727A CN104557727A CN201310515919.XA CN201310515919A CN104557727A CN 104557727 A CN104557727 A CN 104557727A CN 201310515919 A CN201310515919 A CN 201310515919A CN 104557727 A CN104557727 A CN 104557727A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D235/26—Oxygen atoms
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Abstract
The invention provides a method for preparing 5-aminobenzimidazolone, wherein the method comprises: in the presence of a nickel-based amorphous alloy catalyst, contacting 5-nitrobenzimidazolone with a hydrogen-containing gas, and separating 5-aminobenzimidazolone from the contacted mixture. According to the method provided by the invention, the conversion rate of the 5-nitrobenzimidazolone is high, the selectivity of the 5-aminobenzimidazolone is high, the conversion rate of the 5-nitrobenzimidazolone is up to 99.5%, the selectivity of the 5-aminobenzimidazolone is higher than 98.0%, and the method is environment-friendly, thereby having a good industrial application prospect.
Description
Technical field
The present invention relates to the method preparing 5-Amino-2-benzimidazolinone, in particular to 5-Nitro-2-benzimidazolinone and hydrogen-containing gas for raw material, the method using nickel base amorphous alloy catalyzer to carry out hydrogenating reduction to prepare 5-Amino-2-benzimidazolinone.
Background technology
5-Amino-2-benzimidazolinone is the important intermediate of synthesizing benzimidazole ketone pigment, and benzimidazolone pigment is the high-grade pigment dyestuff of a kind of widely used azo-type.Molecular structure of chemistry as high-grade pigment dyestuff mostly is heterocyclic derivative, the agent structure of benzimidazolone is azo, there is good planes of molecules and molecular symmetry, intramolecular hydrogen bond can be formed, intermolecular hydrogen is good for, or form metal complex or increase relative molecular mass, to improve the performance of pigment.
Due to existence that is amino and carbonyl in 5-Amino-2-benzimidazolinone molecule, the intermolecular hydrogen of easy formation is good for, make this pigment have excellent fast light, fastness to weathering, heat-resistant stability, resistance to migration and solvent resistance, light fastness can reach 7-8 level, and thermotolerance is more than 250 DEG C.Owing to having various superior performance, benzimidazolone pigment is made to meet more special application requiring, as manufactured the original finish paint of car, retouching paint and metallic paint for painting industry; For the manufacture of building coating and emulsion paint; For polyethylene, polyvinyl chloride, polystyrene and other need the painted of the polymkeric substance at high temperature processed; For the painted of the fiber stostes such as polypropylene fibre, acrylic, viscose glue, modification viscose glue and for the manufacture of senior outdoor advertising printing ink.
Usually, 5-Amino-2-benzimidazolinone prepares through 5-Nitro-2-benzimidazolinone reduction, and method of reducing has iron powder reducing, hydrazine hydrate reduction and catalytic hydrogenating reduction.
Iron powder reducing method iron powder used is cheap, is the main method of current industrial employing, but but there is serious problem of environmental pollution, produce a large amount of waste water and " iron mud " in process of production, and labour intensity is large, operating environment inclement condition, is difficult to realize continuous prodution.
The facility investment of hydrazine hydrate reduction method is little, and reaction conditions is gentle, and reduction effect is good, does not produce waste gas waste residue, but is only applicable to short run, and be not suitable for large-scale industrial production, and hydrazine hydrate toxicity is very large, brings great injury to the health of operator.
Catalytic hydrogenating reduction method take hydrogen as reductive agent, and reaction orientation can be made to carry out, and because hydrogenation method does not produce harmful side product, waste gas and waste liquid discharge is few, and do not relate to strong acid, highly basic medium, have technique advanced person, yield is high, good product quality, advantages of environment protection.Be main for the catalyzer of 5-Amino-2-benzimidazolinone mainly with Raney Ni for 5-Nitro-2-benzimidazolinone Hydrogenation.
CN1974559A discloses a kind of method preparing 5-Amino-2-benzimidazolinone with skeleton nickel catalyzed 5-nitrobenzimidazole ketone reducing, comprise skeleton nickel and 5-Nitro-2-benzimidazolinone and dehydrated alcohol according to certain mass ratio, join in reactor, reaction conditions: temperature is 80-120 DEG C, pressure is 1.0-6.0MPa, the reaction times is 4-15 hour, takes out filtrate, after removing catalyzer, filtrate decompression distillation and concentration, suction filtration, obtains 5-Amino-2-benzimidazolinone by filter cake vacuum-drying.Advantage of the present invention is that technique is simple, and operation is easy, and cost is low, and product yield is 89.0-94.0%, purity is 97.0-99.8%, and " three wastes " of generation are few, little to the pollution of environment.
Fine chemistry industry (2007,24(8): 829 ~ 832) adopt skeleton nickel reduction 5-Nitro-2-benzimidazolinone synthesis 5-Amino-2-benzimidazolinone, catalyst levels is 1.3-1.4%, temperature of reaction is 90-95 DEG C, and reaction pressure is 2-3MPa, and the reaction times is 8-15h, the ethanolic soln of reaction soln to be concentration be 120mL/mol5-nitrobenzimidazole ketone, with this understanding, product yield is 90%, and mass fraction of product is more than 99%.
But traditional Raney Ni selectivity is poor, produces more by product, and easy inactivation, can not operate continuously; The existence of by product will affect the direct use of 5-Amino-2-benzimidazolinone, need increase multiple refining, sepn process to remove these impurity, therefore make industrial cost increase.How improving catalytic activity, the extending catalyst life-span, promote the industrial application of eco-friendly Catalytic Hydrogenation Techniques, is urgent problem.
Summary of the invention
The object of this invention is to provide a kind of cleaning, efficient, catalyst activity is high and long service life, the 5-Nitro-2-benzimidazolinone Hydrogenation that hydrogenation conversion is high, selectivity is high is for the method for 5-Amino-2-benzimidazolinone.
For realizing aforementioned object, the invention provides a kind of method preparing 5-Amino-2-benzimidazolinone, wherein, the method comprises: under nickel base amorphous alloy catalyzer exists, 5-Nitro-2-benzimidazolinone is contacted with hydrogen-containing gas, from the mixture after contact, isolates 5-Amino-2-benzimidazolinone.
Method of the present invention, 5-Nitro-2-benzimidazolinone transformation efficiency is high, 5-Amino-2-benzimidazolinone selectivity is high, the transformation efficiency of 5-Nitro-2-benzimidazolinone can reach more than 99.5%, the selectivity of 5-Amino-2-benzimidazolinone is more than 98.0%, and environmental friendliness, has good prospects for commercial application.
Compared with prior art, 5-Nitro-2-benzimidazolinone Hydrogenation of the present invention has clear superiority for the method for 5-Amino-2-benzimidazolinone: product is easily separated with catalyst system, good product purity, and target product selectivity is high.And catalyzer can be applied mechanically and reclaim use, product cost is reduced, and method of the present invention does not produce harmful side product, waste gas, discharging of waste liquid amount are few, environmental friendliness.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of method preparing 5-Amino-2-benzimidazolinone, wherein, the method comprises: under nickel base amorphous alloy catalyzer exists, by 5-Nitro-2-benzimidazolinone
contact with hydrogen-containing gas, from the mixture after contact, isolate 5-Amino-2-benzimidazolinone
According to the method preparing 5-Amino-2-benzimidazolinone of the present invention, preferred described nickel base amorphous alloy catalyzer is amorphous Ni-Al-M catalyzer, and M is other metallic elements.So can improve the transformation efficiency of 5-Nitro-2-benzimidazolinone and the selectivity of 5-Amino-2-benzimidazolinone further.
According to the method preparing 5-Amino-2-benzimidazolinone of the present invention, described hydrogen-containing gas can be the gas containing hydrogen or other hydrogeneous gas, and for the present invention, preferred described hydrogen-containing gas is hydrogen.
According to the method preparing 5-Amino-2-benzimidazolinone of the present invention, be preferably benchmark with total catalyst weight, the weight ratio between Ni, Al and M is 1-200:0.5-30:1, is preferably 5-60:1-10:1.
According to the method preparing 5-Amino-2-benzimidazolinone of the present invention, preferred described M be selected from VIII race's metal of I B race, II B race, III B race, IV B race, VI B race, VII B race and non-nickel one or more, described M is selected from one or more in titanium, cobalt, molybdenum, cerium, zirconium, chromium, manganese, iron, platinum, copper, ruthenium and palladium particularly.So can improve the transformation efficiency of 5-Nitro-2-benzimidazolinone and the selectivity of 5-Amino-2-benzimidazolinone further.
According to the method preparing 5-Amino-2-benzimidazolinone of the present invention, preferred described M is titanium.So can improve the transformation efficiency of 5-Nitro-2-benzimidazolinone and the selectivity of 5-Amino-2-benzimidazolinone further.
According to the method preparing 5-Amino-2-benzimidazolinone of the present invention, the preparation method of described nickel base amorphous alloy catalyzer can be the customary preparation methods of this area, can adopt any one existing method preparation preparing amorphous alloy catalyst.For the present invention, preferred described nickel base amorphous alloy catalyzer can be prepared as follows: alloy heating and melting nickel, aluminium and metal M and aluminium formed, with the rate of cooling of >=1000 DEG C/S, melts is solidified, afterwards, carry out extracting dealuminzation with the alloy of alkaline solution to solidification.Wherein, take catalyst weight as benchmark, the consumption of each component and described extracting make the weight ratio in final catalyzer between Ni, Al and M be 1-200:0.5-30:1, are preferably 5-60:1-10:1.Meanwhile, the usual requirement used according to amorphous alloy catalyst, after alkali density dealuminzation, also comprises the step of catalyzer distilled water wash, extremely neutral by the washings of described washing control discharge, also preserves in ethanol afterwards by washing with alcohol.
According to the method preparing 5-Amino-2-benzimidazolinone of the present invention, when described M is titanium, preferred described nickel base amorphous alloy catalyzer is prepared as follows: contacted with the solution of titanium-containing compound by Ni-Al amorphous alloy.So can improve the activity of catalyzer.
In the present invention, described Ni-Al amorphous alloy, by by Ni-Al alloy molten then chilling, then with the aluminium in alkali density Ni-Al amorphous alloy removing alloy, obtains the non-crystalline state Ni-Al alloy catalyst of chilling.
According to the method preparing 5-Amino-2-benzimidazolinone of the present invention, preferably the condition that Ni-Al amorphous alloy contacts with titanium-containing compound solution is comprised: temperature is 20-100 DEG C, be preferably 30-80 DEG C.So can improve the activity of catalyzer.
According to the method preparing 5-Amino-2-benzimidazolinone of the present invention, more preferably the condition that Ni-Al amorphous alloy contacts with titanium-containing compound solution is also comprised: the time of contact is 5-120min, preferred 20-100min.So can improve the activity of catalyzer.
According to the method preparing 5-Amino-2-benzimidazolinone of the present invention, more preferably the condition that Ni-Al amorphous alloy contacts with titanium-containing compound solution is also comprised: the weight ratio of titanium tetrachloride and Ni-Al amorphous alloy is 0.001-1:1, be preferably 0.002-2:1, be more preferably 0.01-0.5:1.So can improve the activity of catalyzer.
According to the method preparing 5-Amino-2-benzimidazolinone of the present invention, more preferably the condition that Ni-Al amorphous alloy contacts with the solution of titanium-containing compound is also comprised: in titanium-containing compound solution, the concentration of titanium-containing compound is 10-30 % by weight, be preferably 20 % by weight.So can improve the activity of the catalyzer prepared further.
According to the method preparing 5-Amino-2-benzimidazolinone of the present invention, more preferably the condition that Ni-Al amorphous alloy contacts with titanium-containing compound solution also comprised: the consumption of titanium-containing compound solution did not at least have described Ni-Al amorphous alloy, the volume ratio of preferred titanium-containing compound solution and described Ni-Al amorphous alloy is 1-10:1.
According to the method preparing 5-Amino-2-benzimidazolinone of the present invention, the range of choices of the kind of described titanium-containing compound is wider, inorganic titanium-containing compound or organic titanium-containing compound all may be used for the present invention, for the present invention, preferred described titanium-containing compound is one or more in titanium tetrachloride, titanium ethanolate and butyl (tetra) titanate.
According to the method preparing 5-Amino-2-benzimidazolinone of the present invention, solvent in preferred titanium-containing compound solution is water and/or alcohol, according to one of the present invention preferred embodiment, when titanium-containing compound is titanium tetrachloride, the solvent in the solution of titanium-containing compound is water; Titanium-containing compound be titanium ethanolate and/or butyl (tetra) titanate time, the solvent in the solution of titanium-containing compound is alcohol.
According to the method preparing 5-Amino-2-benzimidazolinone of the present invention, preferred described alcohol is the alcohol of C1-C10, is more preferably the alcohol of C1-C5, one or more more preferably in methyl alcohol, ethanol and Virahol, is particularly preferably ethanol and/or Virahol.So can improve the activity of catalyzer further.
According to the method preparing 5-Amino-2-benzimidazolinone of the present invention, the condition of preferred described contact comprises: temperature is 50-250 DEG C, is preferably 70-160 DEG C.
According to the method preparing 5-Amino-2-benzimidazolinone of the present invention, the condition of preferred described contact also comprises: the pressure of contact is 0.1-15MPa, is preferably 0.3-8.0MPa, most preferably is 2-5MPa.
According to the method preparing 5-Amino-2-benzimidazolinone of the present invention, the condition of preferred described contact also comprises: catalyst concn is 0.01-20 % by weight.
According to the method preparing 5-Amino-2-benzimidazolinone of the present invention, the condition of preferred described contact also comprises: the residence time is 1-500min, is preferably 60-300min.
According to the method preparing 5-Amino-2-benzimidazolinone of the present invention, preferred described contact is carried out in the presence of solvent, the degree of mixing in reaction system between each reactant can be improved so further, enhanced dispersion and more easily to reaction severe degree regulate.Under preferable case, described solvent be selected from the fatty alcohol with 1-2 carbon atom and have in the aliphatic hydrocarbon of 4-6 carbon atom one or more, preferably methyl alcohol and/or ethanol.
According to the method preparing 5-Amino-2-benzimidazolinone of the present invention, the consumption of described solvent is not particularly limited, and can be conventional selection.Usually, the mass ratio of described solvent and 5-Nitro-2-benzimidazolinone is 0.5-10:1, is preferably 1-6:1.
In the present invention, described contact can be carried out in existing various reactor, the form of the present invention to described reactor has no particular limits, wherein, the example of described reactor includes but not limited to: fixed-bed reactor, paste state bed reactor, tank reactor and fluidized-bed reactor, is preferably tank reactor or fluidized-bed reactor.Wherein, described fluidized-bed reactor can be plug flow reactor, bubbling style reactor or magnetically stabilized bed reactor etc.Described tank reactor can be batch tank reactor.
In the present invention, paste state bed reactor refers to the well known to those of ordinary skill in the art reaction vessel be suspended in by solid particle catalyst in reaction liquid material, as mechanical stirring kettle, gas stirring still and make solid catalyst be suspended in liquid phase suspension bed bioreactor in reaction vessel by liquid-flow, paste state bed reactor can be single reactor, also can be two to the reactor of multiple serial or parallel connection.
The invention will be further described for following examples, but therefore do not limit the scope of the invention.
In following examples and comparative example, if not otherwise specified, used reagent is commercially available reagent.
In following examples and comparative example, if not otherwise specified, pressure is gauge pressure.
In following examples and comparative example, the composition of the liquid phase mixture adopting liquid chromatography for measuring to be obtained by reacting, undertaken quantitatively by correcting normalization method, sample use liquid phase chromatography is analyzed:
HPLC chromatographic condition is as follows:
Chromatographic column: ODS-2C18(150mm × 4.6mm);
Moving phase: 10mmol ammonium acetate solution: methyl alcohol=60:40;
Column temperature: 35 DEG C
Wavelength: 240nm
Sample size: 5uL
Adopt the following transformation efficiency of formulae discovery 5-Nitro-2-benzimidazolinone and the selectivity of 5-Amino-2-benzimidazolinone.
Preparation embodiment 1
1.5kg nickel and 1.5kg aluminium are joined in plumbago crucible, it is heated to melting in high frequency furnace, then this fused solution is sprayed onto a rotating speed from crucible nozzle is on the copper roller of 600 revs/min, logical water coolant in copper roller, throw away along copper roller tangent line after aluminium alloy cools fast with the speed of cooling of 1000 DEG C/s, form flakey band, flakey band is less than 70 microns through being ground to particle diameter, obtains mother alloy.Slowly joined in the there-necked flask filling 500 grams of 20wt% aqueous sodium hydroxide solutions by 50g mother alloy, controlling its temperature is that 80 DEG C and constant temperature stir 1 hour.After stopping heating and stirring, elimination liquid is 10 by the distilled water washs of 100 DEG C to pH value;
At 50 DEG C, the 20.0g Ni-Al alloy of above-mentioned preparation being added to 30mL titanium tetrachloride concentration is 20%(weight) titanium tetrachloride aqueous solution in stir, reaction 60min after, being washed with distilled water to pH value is about 7, catalyzer composition in table 1.
Preparation embodiment 2
1.5kg nickel and 1.5kg aluminium are joined in plumbago crucible, it is heated to melting in high frequency furnace, then this fused solution is sprayed onto a rotating speed from crucible nozzle is on the copper roller of 1000 revs/min, logical water coolant in copper roller, throw away along copper roller tangent line after aluminium alloy cools fast with the speed of cooling of 1000 DEG C/s, form flakey band, flakey band is less than 70 microns through being ground to particle diameter, obtains mother alloy.Slowly joined in the there-necked flask filling 500 grams of 20wt% aqueous sodium hydroxide solutions by 50g mother alloy, controlling its temperature is that 80 DEG C and constant temperature stir 1 hour.After stopping heating and stirring, elimination liquid is 10 by the distilled water washs of 100 DEG C to pH value;
At 50 DEG C, under the state stirred, in the 20.0g Ni-Al alloy of above-mentioned preparation, add 25mL titanium tetrachloride concentration be 20%(weight) titanium tetrachloride aqueous solution in stir, after reaction 60min, being washed with distilled water to pH value is about 7.Catalyzer composition is in table 1.
Preparation embodiment 3
1.5kg nickel and 1.5kg aluminium are joined in plumbago crucible, it is heated to melting in high frequency furnace, then this fused solution is sprayed onto a rotating speed from crucible nozzle is on the copper roller of 800 revs/min, logical water coolant in copper roller, throw away along copper roller tangent line after aluminium alloy cools fast with the speed of cooling of 1000 DEG C/s, form flakey band, flakey band is less than 70 microns through being ground to particle diameter, obtains mother alloy.Slowly joined in the there-necked flask filling 500 grams of 20wt% aqueous sodium hydroxide solutions by 50g mother alloy, controlling its temperature is that 80 DEG C and constant temperature stir 1 hour.After stopping heating and stirring, elimination liquid is 10 by the distilled water washs of 100 DEG C to pH value;
At 50 DEG C, the 20.0g Ni-Al alloy of above-mentioned preparation being added to 60mL titanium tetrachloride concentration is 20%(weight) stir in the aqueous solution, after reaction 60min, being washed with distilled water to pH value is about 7.Catalyzer composition is in table 1.
Preparation embodiment 4
Join in plumbago crucible by 1.5kg nickel and 1.5kg aluminium, it is heated to melting in high frequency furnace, then pour fused solution in plumbago crucible naturally cooling, bulk alloy is less than 70 microns through being ground to particle diameter, obtains mother alloy.Slowly being joined by 50g mother alloy and filling 500 grams of concentration is in the there-necked flask of 20wt% aqueous sodium hydroxide solution, and controlling its temperature is that 80 DEG C and constant temperature stir 1 hour.After stopping heating and stirring, elimination liquid is 10 by the distilled water washs of 100 DEG C to pH value;
At normal temperatures the 20.0g Ni-Al alloy of above-mentioned preparation being added to 60mL titanium tetrachloride concentration is 20%(weight) stir in the aqueous solution of titanium tetrachloride, after reaction 60min, being washed with distilled water to pH value is about 7.Catalyzer composition is in table 1.
Preparation embodiment 5
By 1.5kg nickel, 1.0kg aluminium and 1kg Ti
10al
90alloy joins in plumbago crucible, it is heated to melting in high frequency furnace, then this fused solution is sprayed onto rotating speed from crucible nozzle is on the copper roller of 1000/ point, logical water coolant in copper roller, throw away along copper roller tangent line after aluminium alloy cools fast with the speed of cooling of 1000 DEG C/s, form flakey band, flakey band is less than 70 microns through being ground to particle diameter, obtains mother alloy.Slowly being joined by 50g mother alloy and filling 500 grams of concentration is in the there-necked flask of 20 % by weight aqueous sodium hydroxide solutions, and controlling its temperature is that 80 DEG C and constant temperature stir 1 hour.Stop heating and after stirring, elimination liquid, is 7 with the distilled water washs of 100 DEG C to pH value, obtains Ni-Al-Ti amorphous alloy, forms in table 1.
Preparation embodiment 6
1.5kg nickel, 1.0kg aluminium, 0.05kgFe and 0.1kg Cr are joined in plumbago crucible, it is heated to melting in high frequency furnace, then this fused solution is sprayed onto rotating speed from crucible nozzle is on the copper roller of 1000 revs/min, logical water coolant in copper roller, throw away along copper roller tangent line after aluminium alloy cools fast with the speed of cooling of 1000 DEG C/s, form flakey band, flakey band is less than 70 microns through being ground to particle diameter, obtains mother alloy.Slowly being joined by 50g mother alloy and filling 500 grams of concentration is in the there-necked flask of 20 % by weight aqueous sodium hydroxide solutions, and controlling its temperature is that 80 DEG C and constant temperature stir 1 hour.Stop heating and after stirring, elimination liquid, is 7 with the distilled water washs of 100 DEG C to pH value, obtains Ni-Al-Fe-Cr amorphous alloy, forms in table 1.
Preparation embodiment 7
By 1.5kg nickel, 1.0kg aluminium and 1kg Mo
10al
90alloy joins in plumbago crucible, it is heated to melting in high frequency furnace, then this fused solution is sprayed onto rotating speed from crucible nozzle is on the copper roller of 1000 revs/min, logical water coolant in copper roller, throw away along copper roller tangent line after aluminium alloy cools fast with the speed of cooling of 1000 DEG C/s, form flakey band, flakey band is less than 70 microns through being ground to particle diameter, obtains mother alloy.Slowly being joined by 50g mother alloy and filling 500 grams of concentration is in the there-necked flask of 20 % by weight aqueous sodium hydroxide solutions, and controlling its temperature is that 80 DEG C and constant temperature stir 1 hour.Stop heating and after stirring, elimination liquid, is 7 with the distilled water washs of 100 DEG C to pH value, obtains Ni-Al-Mo amorphous alloy, forms in table 1.
Preparation embodiment 8
1.5kg nickel, 1.0kg aluminium and 0.04kg iron are joined in plumbago crucible, it is heated to melting in high frequency furnace, then this fused solution is sprayed onto rotating speed from crucible nozzle is on the copper roller of 1000 revs/min, logical water coolant in copper roller, throw away along copper roller tangent line after aluminium alloy cools fast with the speed of cooling of 1000 DEG C/s, form flakey band, flakey band is less than 70 microns through being ground to particle diameter, obtains mother alloy.Slowly being joined by 50g mother alloy and filling 500 grams of concentration is in the there-necked flask of the aqueous sodium hydroxide solution of 20 % by weight, and controlling its temperature is that 80 DEG C and constant temperature stir 1 hour.Stop heating and after stirring, elimination liquid, is 7 with the distilled water washs of 100 DEG C to pH value, obtains Ni-Al-Fe amorphous alloy, forms in table 1.
Table 1
| Preparation embodiment | Catalyzer composition * |
| 1 | Ni 83.8Ti 6.2Al 10.0 |
| 2 | Ni 83.5Ti 6.5Al 10.0 |
| 3 | Ni 83.0Ti 6.3Al 10.7 |
| 4 | Ni 83.5Ti 5.7Al 10.8 |
| 5 | Ni 84Ti 5.7Al 10.3 |
| 6 | Ni 85Fe 1.0Cr 2.1Al 11.4 |
| 7 | Ni 84Mo 4.7Al 11.3 |
| 8 | Ni 87Fe 1.7Al 11.3 |
* subscript represents the weight percentage of metal.
Embodiment 1-8
In 500mL autoclave, add 60g5-nitrobenzimidazole ketone, 300mL dehydrated alcohol, 2g amorphous nickel alloy catalyst (deriving from the catalyzer of preparation embodiment 1-8), sealing autoclave, with 1MPa hydrogen exchange three times, is then filled with hydrogen and makes hydrogen pressure (hydrogen pressure) to 2.0Ma.Under 600rpm stirs, at 90 DEG C, react 4h, catalyzer is isolated in release, and adopt liquid chromatograph assay products, reaction result is in table 2.
Table 2
| Embodiment | Catalyst source | Transformation efficiency, % | Selectivity, % |
| 1 | Preparation embodiment 1 | 100 | 99.4 |
| 2 | Preparation embodiment 2 | 100 | 99.2 |
| 3 | Preparation embodiment 3 | 100 | 99.1 |
| 4 | Preparation embodiment 4 | 98.2 | 97.3 |
| 5 | Preparation embodiment 5 | 100 | 98.9 |
| 6 | Preparation embodiment 6 | 95.4 | 96.5 |
| 7 | Preparation embodiment 7 | 94.5 | 94.3 |
| 8 | Preparation embodiment 8 | 95.3 | 95.4 |
Embodiment 9
In 500mL autoclave, add 60g5-nitrobenzimidazole ketone, 300mL dehydrated alcohol, 2g amorphous nickel alloy catalyst, catalyzer consists of Ni
84ti
5.7al
10.3(the method preparation according to preparing embodiment 5), sealing autoclave, with 1MPa hydrogen exchange three times, is then filled with hydrogen and makes hydrogen pressure to 4.0Ma.Under 600rpm stirs, at 90 DEG C, react 3h, catalyzer is isolated in release, and adopt liquid chromatograph assay products, reaction result is in table 3.
Embodiment 10
In 500mL autoclave, add 60g5-nitrobenzimidazole ketone, 300mL dehydrated alcohol, 2g amorphous nickel alloy catalyst, catalyzer consists of Ni
84ti
5.7al
10.3(the method preparation according to preparing embodiment 5), sealing autoclave, with 1MPa hydrogen exchange three times, is then filled with hydrogen and makes hydrogen pressure to 2.0Ma.Under 600rpm stirs, at 110 DEG C, react 3h, catalyzer is isolated in release, and adopt liquid chromatograph assay products, reaction result is in table 3.
Embodiment 11
In 500mL autoclave, add 60g5-nitrobenzimidazole ketone, 300mL dehydrated alcohol, 2g amorphous nickel alloy catalyst, catalyzer consists of Ni
84ti
5.7al
10.3(the method preparation according to preparing embodiment 5) and sealing autoclave, with 1MPa hydrogen exchange three times, is then filled with hydrogen and makes hydrogen pressure to 2.0Ma.Under 600rpm stirs, at 160 DEG C, react 3h, catalyzer is isolated in release, and adopt liquid chromatograph assay products, reaction result is in table 3.
Embodiment 12
In 500mL autoclave, add 60g5-nitrobenzimidazole ketone, 300mL hexanaphthene, 2g amorphous nickel alloy catalyst, catalyzer consists of Ni
84ti
5.7al
10.3(the method preparation according to preparing embodiment 5) and sealing autoclave, with 1MPa hydrogen exchange three times, is then filled with hydrogen and makes hydrogen pressure to 2.0Ma.Under 600rpm stirs, at 160 DEG C, react 4h, catalyzer is isolated in release, and adopt liquid chromatograph assay products, reaction result is in table 3.
Table 3
| Embodiment | Transformation efficiency, % | Selectivity, % |
| 9 | 100 | 99.2 |
| 10 | 100 | 99.1 |
| 11 | 100 | 93.2 |
| 12 | 93.2 | 93.1 |
More than describe the preferred embodiment of the present invention in detail, but, the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention, can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to demetalization scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (9)
1. prepare the method for 5-Amino-2-benzimidazolinone for one kind, it is characterized in that, the method comprises: under nickel base amorphous alloy catalyzer exists, 5-Nitro-2-benzimidazolinone contacted with hydrogen-containing gas, from the mixture after contact, isolate 5-Amino-2-benzimidazolinone.
2. method according to claim 1, wherein, described nickel base amorphous alloy catalyzer is amorphous Ni-Al-M catalyzer, described M be selected from VIII race's metal of I B race, II B race, III B race, IV B race, VI B race, VII B race and non-nickel one or more.
3. method according to claim 2, wherein, be benchmark with total catalyst weight, the weight ratio between Ni, Al and M is 1-200:0.5-30:1.
4. method according to claim 2, wherein, described M is titanium, described nickel base amorphous alloy catalyzer is prepared as follows: contacted with titanium-containing compound solution by Ni-Al amorphous alloy, titanium-containing compound is one or more in titanium tetrachloride, titanium ethanolate and butyl (tetra) titanate, and the solvent in titanium-containing compound solution is alcohol and/or water.
5. method according to claim 4, wherein, the condition that Ni-Al amorphous alloy contacts with titanium-containing compound solution comprised: temperature is 20-100 DEG C, the time is 5-120min, and the weight ratio of titanium-containing compound and Ni-Al amorphous alloy is 0.001-1:1; The consumption of titanium-containing compound solution did not at least have described Ni-Al amorphous alloy, and in titanium-containing compound solution, the concentration of titanium-containing compound is 10-30 % by weight.
6. method according to claim 4, wherein, when titanium-containing compound is titanium tetrachloride, the solvent in the solution of titanium-containing compound is water; Titanium-containing compound be titanium ethanolate and/or butyl (tetra) titanate time, the solvent in the solution of titanium-containing compound be ethanol and/Virahol.
7. method according to claim 1, wherein, comprises the condition that 5-Nitro-2-benzimidazolinone contacts with hydrogen-containing gas: temperature is 50-250 DEG C, and hydrogen pressure is 0.1-15MPa, and catalyst concn is 0.01-20 % by weight, and the residence time is 1-500min.
8. method according to claim 1, wherein, described 5-Nitro-2-benzimidazolinone contact with hydrogen-containing gas is carried out in the presence of solvent, and the mass ratio of described solvent and 5-Nitro-2-benzimidazolinone is 0.5-10:1.
9. method according to claim 8, wherein, described solvent be selected from the fatty alcohol with 1-2 carbon atom and have in the aliphatic hydrocarbon of 4-6 carbon atom one or more.
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