CN103709105A - Method for preparing 5-aminobenzimidazole derivative by using amorphous state Ni-B - Google Patents

Method for preparing 5-aminobenzimidazole derivative by using amorphous state Ni-B Download PDF

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CN103709105A
CN103709105A CN201410006283.0A CN201410006283A CN103709105A CN 103709105 A CN103709105 A CN 103709105A CN 201410006283 A CN201410006283 A CN 201410006283A CN 103709105 A CN103709105 A CN 103709105A
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benzimidazolinone
product
solution
amino
analog derivative
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孟舒献
马洪庆
冯亚青
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Tianjin University
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    • C—CHEMISTRY; METALLURGY
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention discloses a method for preparing a 5-aminobenzimidazole derivative by using an amorphous state Ni-B, belonging to the technical field of 5-aminobenzimidazole derivatives. The method comprises the steps of: dropwise adding a hydroboron solution in a nickel-containing compound solution to prepare an amorphous Ni-B catalyst; and performing hydrogenation reduction on the prepared Ni-B catalyst and a 5- nitrobenzimidazole derivative in a high-pressure kettle to prepare the a 5-aminobenzimidazole derivative. The method has the advantages that the Ni-B catalyst adopted in the process is easily stored and high in catalysis efficiency; and the process for preparing the 5-aminobenzimidazole derivative by using the catalyst is simple, and is low in preparation cost, the yield of the 5-aminobenzimidazole derivative reaches 90-93 percent, the purity is 99-99.7 percent, less three wastes are generated, and the pollution to the environment is hardly caused.

Description

Non-crystalline state Ni-B prepares the method for 5-Amino-2-benzimidazolinone analog derivative
Technical field
The present invention relates to a kind of method that non-crystalline state Ni-B prepares 5-Amino-2-benzimidazolinone analog derivative, belong to the technical field of 5-Amino-2-benzimidazolinone analog derivative.
Background technology
5-Amino-2-benzimidazolinone analog derivative is a kind of important Pigment Intermediates, for the preparation of high-grade pigment dyestuff, is.5-Amino-2-benzimidazolinone analog derivative is normally prepared through the reduction of 5-Nitro-2-benzimidazolinone analog derivative, and main method of reducing has iron powder reducing, hydrazine hydrate reduction and catalytic hydrogenating reduction.Current industrial main employing iron powder reducing method, technical maturity, facility investment is few, and iron powder is cheap, easy and simple to handle, but in this process, produces a large amount of ferric oxide mud, and aftertreatment more complicated, causes serious pollution to environment; Hydrazine hydrate reduction method, facility investment is little, and reaction conditions is gentle, and reduction effect is good, can carry out partial reduction, does not produce waste gas waste residue, but is only applicable to the synthetic of short run, short-term arylamine, and is not suitable for large-scale industrial production; Catalytic hydrogenating reduction method, react completely, side reaction is few, and the quality of product and yield are all very high, few to the pollution of environment, Okujima etc. [Koho.JP0259572[9059.572] .1990.2], adopt Pd/C to prepare 5-Amino-2-benzimidazolinone as catalyst reduction 5-Nitro-2-benzimidazolinone, yield is about 95%, but this catalyzer is expensive, difficulty is reclaimed in circulation, is difficult to suitability for industrialized production.Feng Yaqing etc. [200610130490.2], adopt skeleton nickel to prepare 5-Amino-2-benzimidazolinone as catalyst reduction 5-Nitro-2-benzimidazolinone, and yield is 89%～94%.
Summary of the invention
The object of the present invention is to provide a kind of non-crystalline state Ni-B to prepare the method for 5-Amino-2-benzimidazolinone analog derivative, adopt the prepared 5-Amino-2-benzimidazolinone analog derivative of this method, yield is higher, and quality is good, is easy to realize industrialization.
The present invention is realized by following technical proposals, and a kind of non-crystalline state Ni-B prepares the method for 5-Amino-2-benzimidazolinone analog derivative, and described 5-Amino-2-benzimidazolinone analog derivative structure is shown in formula 1
Figure 2014100062830100002DEST_PATH_IMAGE002
Formula 1
In formula: R is H or C 1～C 6straight or branched alkyl, is characterized in that comprising following process:
(1) preparation of non-crystalline state Ni-B catalyzer
By Ni(AC) 24H 2o, NiCl 26H 2o or NiNO 36H 2o is made into the solution A that concentration is 0.05～5mol/L, is heated to 30～100 ℃, by KBH 4or NaBH 4join pH and be 8～13 the NaOH aqueous solution and be mixed with the solution B that concentration is 0.05～5mol/L, by the Ni in A solution and B solution 2+: BH 4 -mol ratio is 1:(1～10), B solution is added drop-wise in A solution, at 30～100 ℃ of reaction 0.5～4h of temperature, the product obtaining is removed supernatant liquor, then with deionized water wash throw out wash to washings pH be 7, then with absolute ethanol washing to anhydrous, deposit in dehydrated alcohol standby;
(2) liquid phase catalytic hydrogenation reduction preparation 5-Amino-2-benzimidazolinone analog derivative
In autoclave, 5-Nitro-2-benzimidazolinone analog derivative is dissolved into in dehydrated alcohol, to be made into mass concentration be 6%～60% stock liquid, by 2%～20% of the quality of the 5-Nitro-2-benzimidazolinone analog derivative in this stock liquid, to the Ni-B catalyzer that adds step (1) to make in stock liquid, pass into again hydrogen, in temperature, be that 60～200 ℃ and pressure are under 1.0～6.0MPa condition, reaction 4～16h obtains product a, the filter cake that product a obtains is after filtration at 40～100 ℃ of hot water recrystallizations, remove by filter catalyzer, obtain 5-Amino-2-benzimidazolinone analog derivative xln product, the filtrate that product a obtains is after filtration concentrated through underpressure distillation, and suction filtration, obtains 5-Amino-2-benzimidazolinone analog derivative filter cake product, and crystallized product and the vacuum-drying of filter cake product are obtained to 5-Amino-2-benzimidazolinone analog derivative.
The invention has the advantages that, the Ni-B catalyzer adopting in this technological process, this catalyzer is easy to store, catalytic efficiency is high, adopt this catalyzer to prepare 5-Amino-2-benzimidazolinone analog derivative technique simple, preparation cost is low, product yield reaches 90%～93%, purity is 99% to 99.7%, and " three wastes " of generation are few, little to the pollution of environment.
Embodiment
Embodiment 1
By 4.58gNi(NO 3) 26H 2o is dissolved in 200ml deionized water, is warmed up to 40 ℃, obtains Ni(NO 3) 2solution.Claim that 0.3gNaOH is dissolved in 100ml deionized water, being made into pH is 8, by 3.24gKBH 4be dissolved in above-mentioned NaOH solution and obtain KBH 4solution.This solution is dropwise added drop-wise to Ni(NO 3) 2in solution, holding temperature is 40 ℃, produces a large amount of gas, and follows black precipitate to produce, time for adding is 2h, react again 2.5h, standing to room temperature, then extremely neutral with deionized water washing sediment, use again dehydrated alcohol diafiltration 3 times, obtain non-crystalline state Ni-B catalyzer, the dehydrated alcohol fluid-tight of this catalyzer, is labeled as F-2-3-1 type.
In autoclave, add 5-Nitro-2-benzimidazolinone 17.9g, dehydrated alcohol 100ml, F-2-3-1 type non-crystalline state Ni-B1.6g, pass into the hydrogen that pressure is 1.0MPa, be warming up to 60 ℃, reaction 8h, product filters through Büchner funnel the filter cake obtaining and removes by filter catalyzer at 50 ℃ of hot water recrystallizations, obtain 5-Amino-2-benzimidazolinone xln product, the filtrate of filtering through Büchner funnel is concentrated through underpressure distillation, suction filtration, obtain 5-Amino-2-benzimidazolinone filter cake product, xln product and the vacuum-drying of filter cake product are obtained to 5-Amino-2-benzimidazolinone 13.43g, product yield is 90.1%, purity is 99.4%, melting range is 249～250 ℃.
Embodiment 2
By 4.76gNiCl 26H 2o is dissolved in 100ml deionized water, is warmed up to 50 ℃, obtains NiCl 2solution.Claim that 0.8gNaOH is dissolved in 200ml deionized water, furnishing pH is 12, by 3.24gKBH 4be dissolved in above-mentioned NaOH solution and obtain KBH 4solution, is dropwise added drop-wise to NiCl by this solution 2in solution, holding temperature is 50 ℃, produces a large amount of gas, and follows black precipitate to produce, time for adding is 3h, react again 2.5h, standing to room temperature, then extremely neutral with deionized water washing sediment, use again dehydrated alcohol diafiltration 3 times, obtain non-crystalline state Ni-B catalyzer, the dehydrated alcohol fluid-tight of this catalyzer, is labeled as F-2-3-2 type.
In autoclave, add 5-Nitro-2-benzimidazolinone 17.9g, dehydrated alcohol 120ml, F-2-3-2 type non-crystalline state Ni-B1.8g, pass into the hydrogen that pressure is 1.2MPa, be warming up to 90 ℃, reaction 6h, product filters through Büchner funnel the filter cake obtaining and removes by filter catalyzer at 70 ℃ of hot water recrystallizations, obtain 5-Amino-2-benzimidazolinone xln product, the filtrate of filtering through Büchner funnel is concentrated through underpressure distillation, suction filtration, obtain 5-Amino-2-benzimidazolinone filter cake product, xln product and the vacuum-drying of filter cake product are obtained to 5-Amino-2-benzimidazolinone 13.59g, product yield is 91.2%, purity is 99.1%, melting range is 249～251 ℃.
Embodiment 3
By 4.98gNi(CH 3cOO) 24H 2o is dissolved in 300ml deionized water, is warmed up to 60 ℃, obtains Ni(CH 3cOO) 2solution.Claim that 0.9gNaOH is dissolved in 100ml deionized water, furnishing pH is 13, by 3.24gKBH 4be dissolved in above-mentioned NaOH solution and obtain KBH 4solution, is dropwise added drop-wise to Ni(CH by this solution 3cOO) 2in solution, holding temperature is 60 ℃, produces a large amount of gas, and follows black precipitate to produce, time for adding is 0.5h, react again 3h, standing to room temperature, then extremely neutral with deionized water washing sediment, use again dehydrated alcohol diafiltration 3 times, obtain non-crystalline state Ni-B catalyzer, the dehydrated alcohol fluid-tight of this catalyzer, is labeled as F-2-3-3 type.
In autoclave, add 5-Nitro-2-benzimidazolinone 17.9g, dehydrated alcohol 140ml, F-2-3-3 type non-crystalline state Ni-B1.2g, pass into the hydrogen that pressure is 1.4MPa, be warming up to 120 ℃, reaction 7h, product filters through Büchner funnel the filter cake obtaining and removes by filter catalyzer at 70 ℃ of hot water recrystallizations, obtain 5-Amino-2-benzimidazolinone xln product, the filtrate of filtering through Büchner funnel is concentrated through underpressure distillation, suction filtration, obtain 5-Amino-2-benzimidazolinone filter cake product, xln product and the vacuum-drying of filter cake product are obtained to 5-Amino-2-benzimidazolinone 13.8g, product yield is 92.6%, purity is 99.5%, melting range is 249～250 ℃.
Embodiment 4
By 4.98gNi(CH 3cOO) 24H 2o is dissolved in 100ml deionized water, is warmed up to 70 ℃, obtains Ni(CH 3cOO) 2solution.Claim that 1.2gNaOH is dissolved in 300ml deionized water, furnishing pH is 11, by 5.4gKBH 4be dissolved in above-mentioned NaOH solution and obtain KBH 4solution, is dropwise added drop-wise to Ni(CH by this solution 3cOO) 2in solution, holding temperature is 70 ℃, produces a large amount of gas, and follows black precipitate to produce, time for adding is 3h, react again 3.5h, standing to room temperature, then extremely neutral with deionized water washing sediment, use again dehydrated alcohol diafiltration 3 times, obtain non-crystalline state Ni-B catalyzer, the dehydrated alcohol fluid-tight of this catalyzer, is labeled as F-2-5-3 type.
In autoclave, add 5-Nitro-2-benzimidazolinone 17.9g, dehydrated alcohol 80ml, F-2-5-3 type non-crystalline state Ni-B1.5g, pass into the hydrogen that pressure is 1.6MPa, be warming up to 110 ℃, reaction 8h, product filters through Büchner funnel the filter cake obtaining and removes by filter catalyzer at 80 ℃ of hot water recrystallizations, obtain 5-Amino-2-benzimidazolinone xln product, the filtrate of filtering through Büchner funnel is concentrated through underpressure distillation, suction filtration, obtain 5-Amino-2-benzimidazolinone filter cake product, xln product and the vacuum-drying of filter cake product are obtained to 5-Amino-2-benzimidazolinone 13.91g, product yield is 93.3%, purity is 99.7%, melting range is 249～250 ℃.
Embodiment 5
By 9.96gNi(CH 3cOO) 24H 2o is dissolved in 100ml deionized water, is warmed up to 80 ℃, obtains Ni(CH 3cOO) 2solution.Claim that 0.7gNaOH is dissolved in 200ml deionized water, furnishing pH is 9, by 8.64gKBH 4be dissolved in above-mentioned NaOH solution and obtain KBH 4solution, is dropwise added drop-wise to Ni(CH by this solution 3cOO) 2in solution, holding temperature is 80 ℃, produces a large amount of gas, and follows black precipitate to produce, time for adding is 2h, dropwise reaction 0.5h, standing to room temperature, then extremely neutral with deionized water washing sediment, use again dehydrated alcohol diafiltration 3 times, obtain non-crystalline state Ni-B catalyzer, the dehydrated alcohol fluid-tight of this catalyzer, is labeled as F-4-3-3-type.
In autoclave, add 5-Nitro-2-benzimidazolinone 17.9g, dehydrated alcohol 60ml, F-4-3-3 type non-crystalline state Ni-B1.6g, pass into the hydrogen that pressure is 2.0MPa, be warming up to 140 ℃, reaction 4h, product filters through Büchner funnel the filter cake obtaining and removes by filter catalyzer at 70 ℃ of hot water recrystallizations, obtain 5-Amino-2-benzimidazolinone xln product, the filtrate of filtering through Büchner funnel is concentrated through underpressure distillation, suction filtration, obtain 5-Amino-2-benzimidazolinone filter cake product, xln product and the vacuum-drying of filter cake product are obtained to 5-Amino-2-benzimidazolinone 13.75g, product yield is 92.3%, purity is 99.5%, melting range is 249～251 ℃.
Embodiment 6
By 4.98gNi(CH3COO) 24H 2o is dissolved in 100ml deionized water, is warmed up to 100 ℃, claims that 0.9gNaOH is dissolved in 100ml deionized water, and furnishing pH is 13, by 5.4gKBH 4be dissolved in above-mentioned NaOH solution and obtain KBH 4solution, is dropwise added drop-wise to Ni(CH3COO by this solution) 2in solution, holding temperature is 100 ℃, produces a large amount of gas, and follows black precipitate to produce, time for adding is 1.5h, dropwise reaction 2h, standing to room temperature, then extremely neutral with deionized water washing sediment, use again dehydrated alcohol diafiltration 3 times, obtain non-crystalline state Ni-B catalyzer, the dehydrated alcohol fluid-tight of this catalyzer, is labeled as F-2-5-3-1 type.
In autoclave, add 5-nitro-6-methyl benzimidazolone 19.3g, dehydrated alcohol 100ml, F-2-5-3-1 type non-crystalline state Ni-B1.1g, pass into the hydrogen that pressure is 2.4MPa, be warming up to 160 ℃, reaction 4h, product filters through Büchner funnel the filter cake obtaining and removes by filter catalyzer at 80 ℃ of hot water recrystallizations, obtain 5-amino-6 methyl benzimidazolone xln product, the filtrate of filtering through Büchner funnel is concentrated through underpressure distillation, suction filtration, obtain the amino 6-methyl benzimidazolone of 5-filter cake product, xln product and the vacuum-drying of filter cake product are obtained to 5-amino-6 methyl benzimidazolone 14.71g, product yield is 90.3%, purity is 99.4%.

Claims (1)

1. non-crystalline state Ni-B prepares a method for 5-Amino-2-benzimidazolinone analog derivative, and described 5-Amino-2-benzimidazolinone analog derivative structure is shown in formula 1,
Figure 2014100062830100001DEST_PATH_IMAGE002
Formula 1
In formula: R is H or C 1～C 6straight or branched alkyl, is characterized in that comprising following process:
(1) preparation of non-crystalline state Ni-B catalyzer
By Ni(AC) 24H 2o, NiCl 26H 2o or NiNO 36H 2o is made into the solution A that concentration is 0.05～5mol/L, is heated to 30～100 ℃, by KBH 4or NaBH 4join pH and be 8～13 the NaOH aqueous solution and be mixed with the solution B that concentration is 0.05～5mol/L, by the Ni in A solution and B solution 2+: BH 4 -mol ratio is 1:(1～10), B solution is added drop-wise in A solution, at 30～100 ℃ of reaction 0.5～4h of temperature, the product obtaining is removed supernatant liquor, then with deionized water wash throw out wash to washings pH be 7, then with absolute ethanol washing to anhydrous, deposit in dehydrated alcohol standby;
(2) liquid phase catalytic hydrogenation reduction preparation 5-Amino-2-benzimidazolinone analog derivative
In autoclave, 5-Nitro-2-benzimidazolinone analog derivative is dissolved into in dehydrated alcohol, to be made into mass concentration be 6%～60% stock liquid, by 2%～20% of the quality of the 5-Nitro-2-benzimidazolinone analog derivative in this stock liquid, to the Ni-B catalyzer that adds step (1) to make in stock liquid, pass into again hydrogen, in temperature, be that 60～200 ℃ and pressure are under 1.0～6.0MPa condition, reaction 4～16h obtains product a, the filter cake that product a obtains is after filtration at 40～100 ℃ of hot water recrystallizations, remove by filter catalyzer, obtain 5-Amino-2-benzimidazolinone analog derivative xln product, the filtrate that product a obtains is after filtration concentrated through underpressure distillation, and suction filtration, obtains 5-Amino-2-benzimidazolinone analog derivative filter cake product, and crystallized product and the vacuum-drying of filter cake product are obtained to 5-Amino-2-benzimidazolinone analog derivative.
CN201410006283.0A 2014-01-07 2014-01-07 Method for preparing 5-aminobenzimidazole derivative by using amorphous state Ni-B Pending CN103709105A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN106397331A (en) * 2016-08-30 2017-02-15 山东汇海医药化工有限公司 Preparation method of 5-aminobenzimidazolone
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

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN106397331A (en) * 2016-08-30 2017-02-15 山东汇海医药化工有限公司 Preparation method of 5-aminobenzimidazolone
CN106397331B (en) * 2016-08-30 2019-03-19 山东汇海医药化工有限公司 A kind of preparation 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

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Application publication date: 20140409