CN107474016A - A kind of synthetic method of 2 phenylbenzimidazol analog derivatives of amino substitution - Google Patents

A kind of synthetic method of 2 phenylbenzimidazol analog derivatives of amino substitution Download PDF

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Publication number
CN107474016A
CN107474016A CN201710533895.9A CN201710533895A CN107474016A CN 107474016 A CN107474016 A CN 107474016A CN 201710533895 A CN201710533895 A CN 201710533895A CN 107474016 A CN107474016 A CN 107474016A
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CN
China
Prior art keywords
synthetic method
phenylbenzimidazole
acid
amino substitution
analog derivative
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CN201710533895.9A
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Chinese (zh)
Inventor
林桂海
洪俊杰
董刘宏
范占成
张爱珠
张增礼
冯珍会
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Zhejiang Qing Xin Mstar Technology Ltd
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Zhejiang Qing Xin Mstar Technology Ltd
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Priority to CN201710533895.9A priority Critical patent/CN107474016A/en
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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
    • C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2

Abstract

The present invention relates to a kind of synthetic method of 2 phenylbenzimidazol analog derivatives of amino substitution.This method is condensed to yield amide compound, then catalytic hydrogenation using nitro-substituted benzoic acid compound and dinitroanilines cheap and easy to get as raw material, while cyclization obtains benzimidazoles derivative, reacts green high-efficient, and yield simple to operate is outstanding.

Description

A kind of synthetic method of the 2-Phenylbenzimidazole analog derivative of amino substitution
Technical field
The present invention relates to a kind of synthetic method of the 2-Phenylbenzimidazole analog derivative of amino substitution.
Background technology
The benzimidazoles compound of amino substitution, especially 2- (4- aminophenyls) -5- aminobenzimidazoles (APABI) it is, a kind of high molecular polymer monomer well, for synthesis of polyimides thin-film material, is widely used in high property In the equipment such as energy computer, work station, telecommunications industry and space flight；It can also be used to be used to synthesize polyamidoimide material, be applicable In motor, aviation machine, auto parts and resistance to exposed material etc.；It can also be used for synthesizing poly- (ether amide), available for preparing filter water The pellicle of solution and purified water；Simultaneously by APABI- polyimides thin polymer film with copper foil glue is compound can prepare flexibility Printed circuit board (PCB), APABI polymeric modification material are the preferred material of liquid crystal display (LCD) alignment films.It is new in a word The material modified unique properties of APABI, are widely used, and market prospects are increasing, and new synthetic technology and work are all being explored by each state Skill route.
But the synthesis of benzimidazole monomer still has the inferior position that pollution is larger, cost is higher, condition is harsh.It is French special Sharp FR2502151 is with 1- amino -2,4- dinitro benzene and 4- nitrobenzoyl chlorides for raw material, and by being condensed, being hydrogenated with, cyclization obtains 2- (4- aminophenyls) -5- aminobenzimidazoles, but a large amount of HCl sour gas can be produced by reacting in condensation course, to environment It is unfriendly；Need to add hydrochloric acid in Simultaneous hydrogenation process, cyclization process will then strengthen alkali neutralization, produce substantial amounts of high-salt wastewater. Chinese patent CN101397275A then passes through condensation, cyclization as raw material using 4- nitrobenzoyl chlorides and NPD, added Hydrogen synthetic product, although without high-salt wastewater, a large amount of HCl sour gas, and 4- nitre are still produced in condensation course Base o-phenylenediamine price is higher, and cost is not dominant.
The content of the invention
The problem of existing for prior art, it is an object of the invention to design to provide a kind of green high-efficient cheap amino The synthetic method of substituted 2-Phenylbenzimidazole analog derivative.
A kind of synthetic method of the 2-Phenylbenzimidazole analog derivative of described amino substitution, it is characterised in that：With honest and clean The nitro-substituted benzoic acid compound and dinitroanilines of valency are raw material, are heated to reflux taking off under acid catalyst effect Water, direct polycondensation obtain amide compound, then lower three nitros of catalytic hydrogenating reduction of metallic catalyst effect, while cyclization obtains It is as described below to product, its chemical equation：
。
The synthetic method of the 2-Phenylbenzimidazole analog derivative of described a kind of amino substitution, it is characterised in that described The benzoic acid compounds of nitro substitution are m-Nitrobenzoic Acid, o-nitrobenzoic acid, paranitrobenzoic acid, described dinitro benzene Aminated compounds is：2,3- dinitroanilines, 2,4- dinitroanilines, 2,5- dinitroanilines, 2,6- dinitroanilines.
The synthetic method of the 2-Phenylbenzimidazole analog derivative of described a kind of amino substitution, it is characterised in that described The acid catalyst of condensation reaction includes：Boric acid, metaboric acid, the boric acid catalyst of alumina load.
The synthetic method of the 2-Phenylbenzimidazole analog derivative of described a kind of amino substitution, it is characterised in that described The dosage of catalyst is 0.5 ~ 20%, preferably the 2 ~ 10% of benzoic acid derivative quality.
The synthetic method of the 2-Phenylbenzimidazole analog derivative of described a kind of amino substitution, it is characterised in that described The solvent of condensation reaction is toluene, meta-xylene, ortho-xylene or paraxylene.
A kind of synthetic method of the 2-Phenylbenzimidazole analog derivative of described amino substitution, it is characterised in that the contracting The time for closing reaction is 1 ~ 24 h, preferably 5 ~ 12 h.
The synthetic method of the 2-Phenylbenzimidazole analog derivative of described a kind of amino substitution, it is characterised in that described The metallic catalyst of catalytic hydrogenation reaction includes Pd/C, Pt/C, Raney Ni catalyst.
The synthetic method of the 2-Phenylbenzimidazole analog derivative of described a kind of amino substitution, it is characterised in that described The dosage of hydrogenation catalyst is 0.01 ~ 5%, preferably the 0.1 ~ 2% of acid amides quality.
The synthetic method of the 2-Phenylbenzimidazole analog derivative of described a kind of amino substitution, it is characterised in that described to urge Changing the solvent that hydrogenation reaction uses includes methanol, ethanol, tetrahydrofuran, ethyl acetate, isopropanol, ethyl propionate or acetic acid.
The synthetic method of the 2-Phenylbenzimidazole analog derivative of described a kind of amino substitution, it is characterised in that described to urge The temperature for changing hydrogenation reaction is 20 ~ 200oC, preferably 50 ~ 120oC, the pressure of catalytic hydrogenation reaction is 0.2 ~ 12 Mpa, Preferably 4 ~ 8 Mpa.
A kind of synthetic method of the 2-Phenylbenzimidazole analog derivative of above-mentioned amino substitution, it is reasonable in design, with cheap The nitro-substituted benzoic acid compound and dinitroanilines being easy to get are raw material, are condensed to yield amide compound, then Catalytic hydrogenation, while cyclization obtains benzimidazoles derivative, reacts green high-efficient, yield simple to operate is outstanding.
Embodiment
Further illustrate the present invention with reference to embodiments.
Embodiment 1
18.3 g paranitrobenzoic acids, 20.1 g 2,4- dinitroanilines, 200 mL first are added in 500 mL four-hole bottle Benzene and 1.0 g boric acid, are heated to seething with excitement, and moisture caused by reflux water-dividing removing, react 6 h, cool down, filtering, drying obtains 30.5 g N- (4- nitro benzoyls) -2,4- dinitroaniline solids, HPLC purity 93.5%, yield 78.3%.
Obtained acid amides, 200 mL absolute ethyl alcohols, the Pd/C of 0.15 g 5% are added in 500 mL autoclave, 80oC, H2The MPa of pressure 8, reacts 5 h, and cooling drives kettle, catalyst, N is recovered by filtration2Under atmosphere, filtrate air-distillation is removed 150 ML solvents, 100 mL purified waters are added, are cooled to 20oC, it is filtrated to get 20.1 g 2- (4- aminophenyls) -5- amino benzos Imidazoles, HPLC purity 95.7%, yield 93.5%.
Embodiment 2
Added in 500 mL four-hole bottle between 18.3 g m-Nitrobenzoic Acids, 22.5 g 2,4- dinitroanilines, 200 mL Dimethylbenzene and 0.5 g boric acid, are heated to seething with excitement, and moisture caused by reflux water-dividing removing, react 12 h, cool down, filtering, dry To 25.5 g N- (3- nitro benzoyls) -2,4- dinitroaniline solids, HPLC purity 91.0%, yield 63.8%.
Obtained acid amides, 200 mL acetic acid, the Pd/C of 0.20g 5% are added in 500 mL autoclave, 110oC, H2The MPa of pressure 6, reacts 4 h, and cooling drives kettle, catalyst, N is recovered by filtration2Under atmosphere, filtrate air-distillation is removed into 150 mL Solvent, 100 mL purified waters are added, are cooled to 20oC, it is filtrated to get 16.2 g 2- (3- aminophenyls) -5- amino benzo miaows Azoles, HPLC purity 96.2%, yield are 90.5 %.
Embodiment 3
Added in 500 mL four-hole bottle 20.0 g paranitrobenzoic acids, 20.1 g 2,3- dinitroanilines, 200 mL pairs Dimethylbenzene and 0.2 g metaboric acids, are heated to seething with excitement, and moisture caused by reflux water-dividing removing, react 24 h, cool down, filter, drying Obtain 21.0 g N- (4- nitro benzoyls) -2,3- dinitroaniline solids, HPLC purity 96.5%, yield 55.7%.
Obtained acid amides, 200 mL anhydrous tetrahydro furans, the Pd/C of 0.1 g 5% are added to 500 mL autoclave In, 80oC, H2The MPa of pressure 8, reacts 5 h, and cooling drives kettle, catalyst, N is recovered by filtration2Under atmosphere, filtrate air-distillation is removed 150 mL solvents are removed, 100 mL purified waters is added, is cooled to 20oC, it is filtrated to get 12.1 g 2- (4- aminophenyls) -4- ammonia Base benzimidazole, HPLC purity 94.7%, yield are 80.8 %.
Embodiment 4
It is adjacent that 18.3 g paranitrobenzoic acids, 20.1 g 2,5- dinitroanilines, 300 mL are added in 500 mL four-hole bottle Dimethylbenzene and 2.0 g boric acid, are heated to seething with excitement, and moisture caused by reflux water-dividing removing, react 8 h, cool down, filtering, dry To 31.3 g N- (4- nitro benzoyls) -2,4- dinitroaniline solids, HPLC purity 95.5%, yield 82.1%.
Obtained acid amides, 200 mL absolute ethyl alcohols, 1.0 g Raney Ni catalyst are added to 500 mL reaction under high pressure In kettle, 80oC, H2The MPa of pressure 8, reacts 12 h, and cooling drives kettle, catalyst, N is recovered by filtration2Under atmosphere, filtrate normal pressure is steamed 150 mL solvents are removed in distillation, add 100 mL purified waters, are cooled to 20oC, be filtrated to get 19.9 g 2- (4- aminophenyls)- 6- aminobenzimidazoles, HPLC purity 92.1%, yield 88.1%.
Embodiment 5
36.6 g o-nitrobenzoic acids, 42.5 g 2,4- dinitroanilines, 500 mL first are added in 1000 mL four-hole bottle The boric acid catalyst of benzene and 3.0 g alumina loads, is heated to seething with excitement, and moisture caused by reflux water-dividing removing, reacts 16 h, cold But, filter, dry and obtain 50.1 g N- (2- nitro benzoyls) -2,4- dinitroaniline solids, HPLC purity 91.5%, Yield is 63.0%.
Obtained acid amides, 400 mL isopropanols, the Pt/C catalyst of 0.2 g 1% are added to 500 mL autoclave In, 60oC, H2The MPa of pressure 2, reacts 4 h, and cooling drives kettle, catalyst, N is recovered by filtration2Under atmosphere, filtrate air-distillation is removed 350 mL solvents are removed, 200 mL purified waters is added, is cooled to 20oC, it is filtrated to get 30.6 g 2- (2- aminophenyls) -5- ammonia Base benzimidazole, HPLC purity 93.3%, yield 84.4%.

Claims (10)

  1. A kind of 1. synthetic method of the 2-Phenylbenzimidazole analog derivative of amino substitution, it is characterised in that：With cheap nitro Substituted benzoyl acid compound and dinitroanilines are raw material, are heated to reflux being dehydrated under acid catalyst effect, directly Amide compound is condensed to yield, then lower three nitros of catalytic hydrogenating reduction of metallic catalyst effect, while cyclization obtains product, Its chemical equation is as described below：
    。
  2. 2. a kind of synthetic method of the 2-Phenylbenzimidazole analog derivative of amino substitution according to claim 1, it is special The benzoic acid compounds for levying the nitro substitution described in being are m-Nitrobenzoic Acid, o-nitrobenzoic acid, paranitrobenzoic acid, institute The dinitroanilines stated are：2,3- dinitroanilines, 2,4- dinitroanilines, 2,5- dinitroanilines, 2,6- bis- Nitroaniline.
  3. 3. a kind of synthetic method of the 2-Phenylbenzimidazole analog derivative of amino substitution according to claim 1, it is special Sign is that the acid catalyst of described condensation reaction includes：Boric acid, metaboric acid, the boric acid catalyst of alumina load.
  4. 4. a kind of synthetic method of the 2-Phenylbenzimidazole analog derivative of amino substitution according to claim 1 or 3, its The dosage for being characterised by described acid catalyst is 0.5 ~ 20%, preferably the 2 ~ 10% of benzoic acid derivative quality.
  5. 5. a kind of synthetic method of the 2-Phenylbenzimidazole analog derivative of amino substitution according to claim 1, it is special Sign is that the solvent of described condensation reaction is toluene, meta-xylene, ortho-xylene or paraxylene.
  6. 6. a kind of synthetic method of the 2-Phenylbenzimidazole analog derivative of amino substitution according to claim 1, it is special Sign is that the time of the condensation reaction is 1 ~ 24 h, preferably 5 ~ 12 h.
  7. 7. a kind of synthetic method of the 2-Phenylbenzimidazole analog derivative of amino substitution according to claim 1, it is special Sign is that the metallic catalyst of described catalytic hydrogenation reaction includes Pd/C, Pt/C, Raney Ni catalyst.
  8. 8. a kind of synthetic method of the 2-Phenylbenzimidazole analog derivative of amino substitution according to claim 1 or 7, its The dosage for being characterised by described hydrogenation catalyst is 0.01 ~ 5%, preferably the 0.1 ~ 2% of acid amides quality.
  9. 9. a kind of synthetic method of the 2-Phenylbenzimidazole analog derivative of amino substitution according to claim 1, it is special Sign is that the solvent that the catalytic hydrogenation reaction uses includes methanol, ethanol, tetrahydrofuran, ethyl acetate, isopropanol, propionic acid second Ester or acetic acid.
  10. 10. a kind of synthetic method of the 2-Phenylbenzimidazole analog derivative of amino substitution according to claim 1, it is special Sign is that the temperature of the catalytic hydrogenation reaction is 20 ~ 200oC, preferably 50 ~ 120oC, the pressure of catalytic hydrogenation reaction are 0.2 ~ 12 Mpa, preferably 4 ~ 8 Mpa.
CN201710533895.9A 2017-07-03 2017-07-03 A kind of synthetic method of 2 phenylbenzimidazol analog derivatives of amino substitution Pending CN107474016A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2125791A (en) * 1982-08-24 1984-03-14 Ici Plc Manufacture of substituted phenylaminobenzimidazoles
EP1598353A1 (en) * 2004-05-17 2005-11-23 Boehringer Ingelheim International GmbH Pyrrolobenzimidazolones and their use as antiproliferative agents
CN105693610A (en) * 2014-11-28 2016-06-22 四川省宜宾五粮液集团宜宾制药有限责任公司 A preparing method of (R,S)-8-chloro-1-methyl-2,3,4,5-tetrahydro-1H-3-benzazepine, a lorcaserin intermediate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2125791A (en) * 1982-08-24 1984-03-14 Ici Plc Manufacture of substituted phenylaminobenzimidazoles
EP1598353A1 (en) * 2004-05-17 2005-11-23 Boehringer Ingelheim International GmbH Pyrrolobenzimidazolones and their use as antiproliferative agents
CN105693610A (en) * 2014-11-28 2016-06-22 四川省宜宾五粮液集团宜宾制药有限责任公司 A preparing method of (R,S)-8-chloro-1-methyl-2,3,4,5-tetrahydro-1H-3-benzazepine, a lorcaserin intermediate

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
TATIANA FONSECA，ET AL.: "A short synthesis of phenanthro[2,3-d]imidazoles from dehydroabietic acid. Application of the methodology as a convenient route to benzimidazoles", 《TETRAHEDRON》 *
金宁人等: "高纯度2-(4-氨基苯基)-1H-苯并咪唑-5-胺的合成", 《化工进展》 *

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Application publication date: 20171215