CN1974559A - Skeleton nickel catalyzed 5-nitrobenzimidazole ketone reducing process for preparing 5-aminobenzimidazole ketone - Google Patents
Skeleton nickel catalyzed 5-nitrobenzimidazole ketone reducing process for preparing 5-aminobenzimidazole ketone Download PDFInfo
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Abstract
The present invention discloses skeleton nickel catalyzed 5-nitrobenzimidazole ketone reducing process for preparing 5-aminobenzimidazole ketone, and belongs to the field of 5-aminobenzimidazole ketone preparing technology. The process includes: adding Ni-Al alloy into NaOH solution at certain temperature and in certain concentration to react for certain time and washing with water and anhydrous alcohol for several times to obtain skeleton nickel maintained in anhydrous alcohol; setting skeleton nickel, 5-nitrobenzimidazole ketone and anhydrous alcohol in certain weight proportion into high pressure kettle to react at 80-120 deg.c and 1.0-6.0 MPa for 4-15 hr; filtering to eliminate catalyst, vacuum distilling, suction filtering, and vacuum drying the filter cake to obtain 5-aminobenzimidazole ketone. The present invention has the advantages of simple technological process, easy operation, low cost, product yield of 89.0-94.0 % and purity 97.0-99.8 %, and environment friendship.
Description
Technical field
The present invention relates to the method that a kind of skeleton nickel catalyzed reduction 5-nitrobenzimidazole ketone prepares the amino benzimidazolone of 5-, belong to the amino benzimidazolone technology of preparing of 5-.
Background technology
The amino benzimidazolone of 5-is a kind of important Pigment Intermediates, is used to prepare high-grade pigment dyestuff and is.The amino benzimidazolone of 5-normally prepares through the reduction of 5-nitrobenzimidazole ketone, and main method of reducing has iron powder reducing, hydrazine hydrate reduction and catalytic hydrogenating reduction.Present industrial main employing iron powder reducing method, technical maturity, facility investment is few, and iron powder is cheap, and is easy and simple to handle, but produces a large amount of ferric oxide mud in this process, and the aftertreatment more complicated causes serious pollution to environment; The hydrazine hydrate reduction method, facility investment is little, the reaction conditions gentleness, reduction effect is good, can carry out partial reduction, does not produce the waste gas waste residue, but only is suitable for synthetic with short run, short-term arylamine, and is not suitable for large-scale industrial production; The catalytic hydrogenating reduction method, react completely, side reaction is few, and the quality of product and yield are all very high, and be few to the pollution of environment, Okujima etc. [Koho.JP0259572[9059.572] .1990.2], adopt Pd/C to prepare the amino benzimidazolone of 5-as catalyst reduction 5-nitrobenzimidazole ketone, yield is about 95%, but this catalyzer costs an arm and a leg, relatively difficulty is reclaimed in circulation, is difficult to suitability for industrialized production.
Summary of the invention
The object of the present invention is to provide a kind of skeleton nickel catalyzed reduction 5-nitrobenzimidazole ketone to prepare the method for the amino benzimidazolone of 5-, adopt the amino benzimidazolone of the prepared 5-of this method, the yield height, quality is good, is easy to realize industrialization.
The present invention is achieved through the following technical solutions, and a kind of skeleton nickel catalyzed reduction 5-nitrobenzimidazole ketone prepares the method for the amino benzimidazolone of 5-, it is characterized in that comprising following process:
1, the preparation of skeletal nickel catalyst: with the alumel is raw material, and described alumel comprises: binary alloy, and wherein the massfraction of nickel is 47%, the massfraction of aluminium is 53%; Ternary alloy, wherein the massfraction of nickel is 46%, and the massfraction of titanium is 1～3%, and all the other are aluminium; Quad alloy, the massfraction of nickel are 46%, and the massfraction of chromium is 1%, and the massfraction of iron is 1～3%, and all the other are aluminium.It is 20～90 ℃ that alumel is joined temperature, and mass concentration is that the reaction times is 1～15 hour in 10～30% the NaOH solution, and being washed till with deionized water does not then have NaAlO in the washings
2Till, remove for several times with the dehydrated alcohol diafiltration again and anhydrate, after deposit in the ethanol solution standby.
2, liquid phase catalytic hydrogenation reductive process: the 5-nitrobenzimidazole ketone with 1g is benchmark, is solvent with the dehydrated alcohol, and consumption is 5～10ml; The skeleton nickel consumption be 5-nitrobenzimidazole ketone quality 3～10%, join in the autoclave, feed hydrogen, temperature of reaction is 80～120 ℃, and reaction pressure is 1.0～6.0MPa, reaction times is 4～15 hours, reaction solution is taken out, remove catalyzer after, the filtrate decompression distillation concentrates, suction filtration obtains the amino benzimidazolone of 5-with filter cake vacuum-drying.
Advantage of the present invention is that technology is simple, operation is easy, and cost is low, product yield is 89.0%～94.0%, purity is 97.0%～99.8%, and " three wastes " of generation are few, and are little to the pollution of environment.
Embodiment
Example 1 is with alumel (binary) 30g, join mass concentration and be 19%, volume is the NaOH solution of 200ml, stir, charge temperature is 10～15 ℃, and the reinforced time is 2 hours, is warming up to 20～25 ℃ afterwards, reacted 9 hours, use deionized water, dehydrated alcohol diafiltration for several times then, the skeleton nickel that makes is deposited in the dehydrated alcohol standby, be labeled as W-1-(two) type.
Get 5-nitrobenzimidazole ketone 18g, dehydrated alcohol 80ml, W-1-(two) type skeleton nickel 1.8g joins autoclave, feed hydrogen pressure to 2MPa, be warming up to 85 ℃, reacted 6 hours, the reaction solution filtration catalizer, filtrate concentrates, and suction filtration is dry in vacuum with filter cake, obtain the amino benzimidazolone 14.0g of 5-, yield is 93.2%, and purity is 97.2%, and fusing point is 248～251 ℃.
Example 2 is with nickel Al alloy (binary) 40g, join concentration and be 10%, volume is the NaOH solution of 600ml, stir, charge temperature is 85～90 ℃, and the reinforced time is 1.5 hours, is warming up to 90～95 ℃, reacted 1 hour, use deionized water, dehydrated alcohol diafiltration for several times then, the skeleton nickel that makes is deposited in the dehydrated alcohol standby, be labeled as T-1-(two) type.
Get 5-nitrobenzimidazole ketone 18g, dehydrated alcohol 100ml, T-1-(two) type skeleton nickel 1.8g joins autoclave, feed hydrogen pressure to 3MPa, be warming up to 85 ℃, reacted 5 hours, the reaction solution filtration catalizer, filtrate concentrates, and suction filtration is dry in vacuum with filter cake, obtain the amino benzimidazolone 14.0g of 5-, yield is 93.1%, and purity is 98.8%, and fusing point is 248～251 ℃.
Example 3 is with alumel (ternary) 30g, join concentration and be 19%, volume is the NaOH solution of 200ml, stir, charge temperature is 10～15 ℃, and the reinforced time is 2 hours, is warming up to 20～25 ℃, reacted 9 hours, use deionized water, dehydrated alcohol diafiltration for several times then, the skeleton nickel that makes is deposited in the dehydrated alcohol standby, be labeled as W-1-(three) type.
Get 5-nitrobenzimidazole ketone 18g, dehydrated alcohol 120ml, W-1-(three) type skeleton nickel 1.5g joins autoclave, feed hydrogen pressure to 4MPa, be warming up to 85 ℃, reacted 7 hours, the reaction solution filtration catalizer, filtrate concentrates, and suction filtration is dry in vacuum with filter cake, obtain the amino benzimidazolone 13.9g of 5-, yield is 92.5%, and purity is 98.8%, and fusing point is 249～251 ℃.
Example 4 is with alumel (ternary) 40g, join concentration and be 10%, volume is the NaOH solution of 600ml, stir, charge temperature is 85～90 ℃, and the reinforced time is 1.5 hours, is warming up to 90～95 ℃, reacted 1 hour, use deionized water, dehydrated alcohol diafiltration for several times then, the skeleton nickel that makes is deposited in the dehydrated alcohol standby, be labeled as T-1-(three) type.
Get 5-nitrobenzimidazole ketone 18g, dehydrated alcohol 120ml, T-1-(three) type skeleton nickel 0.9g joins autoclave, feed hydrogen pressure to 2MPa, be warming up to 90 ℃, reacted 10 hours, reaction solution is removed catalyzer, filtrate concentrates, and suction filtration is dry in vacuum with filter cake, obtain the amino benzimidazolone 13.7g of 5-, yield is 91.6%, and purity is 99.1%, and fusing point is 249～251 ℃.
Get 5-nitrobenzimidazole ketone 25g, dehydrated alcohol 200ml, T-1-(three) type skeleton nickel 1.0g joins autoclave, feed hydrogen pressure to 3MPa, be warming up to 90 ℃, reacted 10 hours, the reaction solution filtration catalizer, filtrate concentrates, and suction filtration is dry in vacuum with filter cake, obtain the amino benzimidazolone 19.4g of 5-, yield is 93.3%, and purity is 99.0%, and fusing point is 250～253 ℃.
Example 5 is with alumel (quaternary) 30g, joining concentration is 19%, volume is the NaOH solution of 200ml, stirs, and charge temperature is 10～15 ℃, the reinforced time is 2 hours, be warming up to 20～25 ℃, reacted 9 hours, use deionized water, dehydrated alcohol diafiltration then for several times, the skeleton nickel that makes is deposited in the dehydrated alcohol standby, be labeled as W-1-(four) type.
Get 5-nitrobenzimidazole ketone 18g, dehydrated alcohol 120ml, W-1-(four) type skeleton nickel 0.9g joins autoclave, feed hydrogen pressure to 2MPa, be warming up to 90 ℃, reacted 7 hours, the reaction solution filtration catalizer, filtrate concentrates, and suction filtration is dry in vacuum with filter cake, obtain the amino benzimidazolone 13.5g of 5-, yield is 90.1%, and purity is 98.7%, and fusing point is 248～251 ℃.
Example 6 is with alumel (quaternary) 40g, joining concentration is 10%, volume is the NaOH solution of 600ml, stirs, and charge temperature is 85～90 ℃, the reinforced time is 1.5 hours, be warming up to 90～95 ℃, reacted 1 hour, use deionized water, dehydrated alcohol diafiltration then for several times, the skeleton nickel that makes is deposited in the dehydrated alcohol standby, be labeled as T-1-(four) type.
Get 5-nitrobenzimidazole ketone 18g, dehydrated alcohol 120ml, T-1-(four) skeleton nickel 0.7g joins autoclave, feed hydrogen pressure to 3MPa, be warming up to 90 ℃, reacted 12 hours, the reaction solution filtration catalizer, filtrate concentrates, and suction filtration is dry in vacuum with filter cake, obtain the amino benzimidazolone 13.7g of 5-, yield is 91.3%, and purity is 99.3%, and fusing point is 250～253 ℃.
Get 5-nitrobenzimidazole ketone 25g, dehydrated alcohol 200ml, T-1-(four) skeleton nickel 1.0g joins autoclave, feed hydrogen pressure to 2MPa, be warming up to 90 ℃, reacted 14 hours, reaction solution is removed catalyzer, filtrate concentrates, and suction filtration is dry in vacuum with filter cake, obtain the amino benzimidazolone 19.3g of 5-, yield is 92.8%, and purity is 99.0%, and fusing point is 250～253 ℃.
Get 5-nitrobenzimidazole ketone 30g, dehydrated alcohol 250ml, T-1-(four) skeleton nickel 0.9g joins autoclave, feed hydrogen pressure to 2MPa, be warming up to 95 ℃, reacted 13 hours, the reaction solution filtration catalizer, filtrate concentrates, and suction filtration is dry in vacuum with filter cake, obtain the amino benzimidazolone 23.4g of 5-, yield is 93.5%, and purity is 99.4%, and fusing point is 249～252 ℃.
Claims (1)
1. a skeleton nickel catalyzed reduction 5-nitrobenzimidazole ketone prepares the method for the amino benzimidazolone of 5-, it is characterized in that comprising following process:
(1) preparation of skeletal nickel catalyst: with the alumel is raw material, and described alumel comprises: binary alloy, and wherein the massfraction of nickel is 47%, the massfraction of aluminium is 53%; Ternary alloy, wherein the massfraction of nickel is 46%, and the massfraction of titanium is 1～3%, and all the other are aluminium; Quad alloy, the massfraction of nickel is 46%, the massfraction of chromium is 1%, the massfraction of iron is 1～3%, all the other are aluminium, and it is 20～90 ℃ that alumel is joined temperature, and mass concentration is in 10～30% the NaOH solution, reaction times is 1～15 hour, and being washed till with deionized water does not then have NaAlO in the washings
2Till, remove for several times with the dehydrated alcohol diafiltration again and anhydrate, after deposit in the ethanol solution standby;
(2) liquid phase catalytic hydrogenation reductive process: the 5-nitrobenzimidazole ketone with 1g is benchmark, with the dehydrated alcohol is solvent, consumption is 5～10ml, the skeleton nickel consumption be 5-nitrobenzimidazole ketone quality 3～10%, they are joined in the autoclave, feed hydrogen, temperature of reaction is 80～120 ℃, reaction pressure is 1.0～6.0MPa, and the reaction times is 4～15 hours, and reaction solution is taken out, after removing catalyzer, the filtrate decompression distillation concentrates, and suction filtration obtains the amino benzimidazolone of 5-with filter cake vacuum-drying.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527393A (en) * | 2011-12-23 | 2012-07-04 | 中国石油化工股份有限公司 | Modification method for raney nickel catalyst for p-chloronitrobenzene hydrogenation |
| CN102796031A (en) * | 2012-08-22 | 2012-11-28 | 江西仁明医药化工有限公司 | Preparation method of 2-aminodiphenyl sulfide |
| CN102924385A (en) * | 2012-10-22 | 2013-02-13 | 江苏康恒化工有限公司 | Method for preparing 5-amino benzimidazolone with high purity by catalytic hydrogenation |
| CN104130194A (en) * | 2014-08-12 | 2014-11-05 | 南通醋酸化工股份有限公司 | Synthesis method of 5-amino benzimidazolone |
| CN104557727A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing 5-aminobenzimidazole ketone |
| CN109225255A (en) * | 2018-09-19 | 2019-01-18 | 东营市天正化工有限公司 | A kind of novel load Raney nickel and its method for preparing 5-Amino-2-benzimidazolinone |
| CN113149911A (en) * | 2021-04-13 | 2021-07-23 | 东营市天正化工有限公司 | Preparation method of high-purity 5-aminobenzimidazole ketone |
-
2006
- 2006-12-21 CN CN 200610130490 patent/CN1974559A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527393A (en) * | 2011-12-23 | 2012-07-04 | 中国石油化工股份有限公司 | Modification method for raney nickel catalyst for p-chloronitrobenzene hydrogenation |
| CN102796031A (en) * | 2012-08-22 | 2012-11-28 | 江西仁明医药化工有限公司 | Preparation method of 2-aminodiphenyl sulfide |
| CN102924385A (en) * | 2012-10-22 | 2013-02-13 | 江苏康恒化工有限公司 | Method for preparing 5-amino benzimidazolone with high purity by catalytic hydrogenation |
| CN104557727A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing 5-aminobenzimidazole ketone |
| CN104557727B (en) * | 2013-10-28 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of method for preparing 5 aminobenzimidazole ketone |
| CN104130194A (en) * | 2014-08-12 | 2014-11-05 | 南通醋酸化工股份有限公司 | Synthesis method of 5-amino benzimidazolone |
| CN104130194B (en) * | 2014-08-12 | 2016-08-31 | 南通醋酸化工股份有限公司 | A kind of synthetic method of 5-Amino-2-benzimidazolinone |
| CN109225255A (en) * | 2018-09-19 | 2019-01-18 | 东营市天正化工有限公司 | A kind of novel load Raney nickel and its method for preparing 5-Amino-2-benzimidazolinone |
| CN113149911A (en) * | 2021-04-13 | 2021-07-23 | 东营市天正化工有限公司 | Preparation method of high-purity 5-aminobenzimidazole ketone |
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