CN103193714B - 5-amino-benzimidazolone synthetic method - Google Patents
5-amino-benzimidazolone synthetic method Download PDFInfo
- Publication number
- CN103193714B CN103193714B CN201310156518.XA CN201310156518A CN103193714B CN 103193714 B CN103193714 B CN 103193714B CN 201310156518 A CN201310156518 A CN 201310156518A CN 103193714 B CN103193714 B CN 103193714B
- Authority
- CN
- China
- Prior art keywords
- nitro
- benzimidazolinone
- reaction
- amino
- solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a 5-amino-benzimidazolone synthetic method. The 5-amino-benzimidazolone synthetic method comprises the following steps of: (1) rapidly adding phthalimide to a mixed liquor of fuming nitric acid and concentrated sulfuric acid in ice-water bath, and reacting to obtain 4-nitro-phthalimide; (2) adding the 4-nitro-phthalimide to a methanol solvent, feeding ammonia gas at low temperature, and reacting to generate 4-nitro-phthalic diamide; (3) dropwise adding a NaBrO solution to the mixed liquor of the 4-nitro-phthalic diamide and sodium hydroxide below 0 DEG C, and reacting to obtain 4-nitro-o-phenylenediamine; (4) synthesizing the solid 4-nitro-o-phenylenediamine and urea solid phase or liquid phase into 5-nitro-benzimidazolinone; and (5) carrying out catalytic hydrogenation on the 5-nitro-benzimidazolinone to obtain 5-amino-benzimidazolone. The 5-amino-benzimidazolone synthetic method has the advantages that the high-purity target product can be obtained, the generation of binitro products can be effectively avoided, the raw materials are cheap, and the reaction operation is easy.
Description
Technical field
The present invention relates to a kind of synthetic method of benzoglyoxaline ketone Pigment Intermediates, be specifically related to the synthetic method of 5-Amino-2-benzimidazolinone.
Background technology
Benzoglyoxaline ketone pigment is that one has high performance pigment dyestuff, has bright in color light, tinctorial strength high.Due in molecule containing imino-(-HN-) and carbonyl (-CO-), can easily form intermolecular and intramolecular hydrogen bond, by the effect of this reactive force, impart the performances such as fast light, heat-resisting, the weather of such pigment excellence, resistance to migration and solvent resistant.
5-Amino-2-benzimidazolinone is the important intermediate being widely used in synthesizing benzimidazole ketone pigment.Benzimidazolone can be prepared by the catalyzed reaction of the condensation of O-Phenylene Diamine and urea (or phosgene, triphosgene, methylcarbonate etc.), orthodichlorobenzene and ammonia and o-Nitraniline and the number of ways such as sulphur, formate reaction at high temperature.Synthetic route is as follows.
Above process is simple, easy to operate, but in nitrifying process, benzimidazolone easily generates dinitride, and dinitride not easily removes, when a nitro compounds is reduced, dinitrobenzene benzimidazolone is also reduced simultaneously, diamino benzimidazolone in product is very easily oxidized and generate the oxidation products of black, thus affects the quality of the finished product.
The method of another kind of synthesis 5-Amino-2-benzimidazolinone is with the reactant of two nitros for starting raw material, and this synthetic route is as follows.
This synthetic method has reduced the impact of the dinitrobenzene product that this step nitrated is brought, and owing to not having the generation of diamino benzimidazolone, products obtained therefrom quality is better, but technological process is more complicated, and synthesis cost is higher, and price is in a disadvantageous position.
Summary of the invention
Goal of the invention: the object of the present invention is to provide that a kind of reaction process is simple, the synthetic method of the 5-Amino-2-benzimidazolinone of good product quality.
Technical scheme: the synthetic method of 5-Amino-2-benzimidazolinone of the present invention, comprises the steps:
(1) phthalic imidine is joined fast in nitrosonitric acid and vitriol oil mixed solution under ice-water bath, react to obtain 4-nitrophthalimide;
(2) add in methanol solvate by 4-nitrophthalimide, pass into ammonia under low temperature, reaction generates 4-nitro phthalic diamide;
(3) below 0 DEG C, in 4-nitro phthalic diamide and sodium hydroxide mixed solution, NaBrO solution is dripped, the obtained NPD of reaction;
(4) solid NPD and urea solid phase or liquid phase reaction are generated 5-Nitro-2-benzimidazolinone;
(5) 5-Nitro-2-benzimidazolinone shortening obtains 5-Amino-2-benzimidazolinone target product.
The inventive method synthetic route is as follows:
In step (1), the preparation method of nitrosonitric acid and vitriol oil mixed solution is: be slowly added dropwise to by 98% vitriol oil under ice-water bath in the nitrosonitric acid constantly stirred, control temperature, at 0 ~ 15 DEG C, obtains nitrosonitric acid and vitriol oil mixed solution; Wherein, the mol ratio of nitric acid and the vitriol oil is preferably 1:3.
Further, in step (1), phthalic imidine joins after in nitrosonitric acid and vitriol oil mixed solution fast, naturally rise to room temperature, stir more than 10h, TLC and detect, react complete, yellow being generated liquid slowly pours in trash ice water, filters and frozen water washing precipitation, obtains light yellow solid 4-nitrophthalimide (a) after recrystallization.Preferably, dry after filter cake washing 2 ~ 3 times, recrystallization is by ethanol or methyl alcohol.
In step (2), logical ammonia while stirring at-5 DEG C ~ 0 DEG C, filters after reaction 3 ~ 5h, and filter cake washing 2 ~ 3 times, until washings be neutral, dryly obtains white solid 4-nitro phthalic diamide (b).
In step (3), NaBrO solution is added drop-wise in NaOH solution by bromine below 0 DEG C, obtains after stirring reaction 30min.
Below 0 DEG C, bromine is added drop-wise in NaOH solution, after stirring reaction 30min, this drop is added to and fills in 4-nitro phthalic diamide and another reactor of sodium hydroxide solution, drip off rear room temperature reaction 0.5 ~ 1h, be warming up to 50 ~ 100 DEG C, reaction solution is cooled after reaction 1 ~ 2h, dichloromethane extraction, activated carbon decolorizing, is spin-dried for solvent, solid is washed, dry garnet needle-like crystal NPD (c).Preferably, two cover reactor pipelines are connected.Wherein warming temperature is preferably 60 ~ 75 DEG C.
In step (4), solid state reaction step: solid NPD and urea are fully mixed in reactor, is heated to 160 ~ 180 DEG C, reaction 1 ~ 2h, be warming up to 200 ~ 220 DEG C of insulation reaction 2h, be cooled to 130 ~ 150 DEG C and add distilled water, stir after 30min, then be cooled to 98 ~ 105 DEG C and add a certain amount of dehydrated alcohol, be chilled to room temperature, filter, filter cake is washed, dry dark green solid 5-Nitro-2-benzimidazolinone (d).Preferably, in reactor, be filled with protection of inert gas, as nitrogen, argon gas.
In step (4), liquid phase reaction step: solid NPD and urea are fully mixed to join and fill in the reactor of orthodichlorobenzene, be heated to 180 ~ 200 DEG C, reaction 3 ~ 6h, be down to room temperature, filter, filter cake through ethanol in proper amount and water washing, dry dark green solid 5-Nitro-2-benzimidazolinone.
In step (5), 5-Nitro-2-benzimidazolinone and catalyzer join in hydrogenation reaction kettle, 1 ~ 1.5MPa hydrogen pressure and 60 ~ 100 DEG C, react 3 ~ 5h, obtain White snowflake shape solid 5-Amino-2-benzimidazolinone (e) in alcohol solvent; Wherein, described catalyzer is Pd-C or Raney Ni.Preferably, before described hydrogenation reaction kettle is filled with hydrogen reaction, is filled with the inert gas replacement such as argon gas or nitrogen and removes air.Wherein temperature of reaction is preferably 80 ~ 95 DEG C.
Compared with prior art, its beneficial effect is in the present invention: the present invention adopts phthalic imidine cyclization after elder generation is nitrated to prepare 5-Nitro-2-benzimidazolinone, the nitro compounds after purification is carried out hydro-reduction again and obtains high purity target product.Can not only efficiently avoid the generation of dinitrobenzene product like this, and raw material is cheap, reacts easy to operate.
Accompanying drawing explanation
Fig. 1 phthalic imidine raw material high-efficient liquid phase chromatogram.
The high-efficient liquid phase chromatogram of Fig. 2 embodiment 1 intermediate 4-nitrophthalimide.
The high-efficient liquid phase chromatogram of the 4-nitro phthalic diamide of the 2-in-1 one-tenth of Fig. 3 embodiment.
The high-efficient liquid phase chromatogram of Fig. 4 embodiment 4 intermediate NPD.
The high-efficient liquid phase chromatogram of Fig. 5 embodiment 5 intermediate NPD.
The high-efficient liquid phase chromatogram of Fig. 6 embodiment 6 intermediate NPD.
The high-efficient liquid phase chromatogram of Fig. 7 embodiment 8 intermediate NPD.
The high-efficient liquid phase chromatogram of Fig. 8 embodiment 9 intermediate 5-Nitro-2-benzimidazolinone.
The high-efficient liquid phase chromatogram of Fig. 9 embodiment 10 intermediate 5-Nitro-2-benzimidazolinone.
The high-efficient liquid phase chromatogram of Figure 10 embodiment 11 intermediate 5-Amino-2-benzimidazolinone.
The high-efficient liquid phase chromatogram of Figure 11 embodiment 12 intermediate 5-Amino-2-benzimidazolinone.
Embodiment
Below technical solution of the present invention is described in detail, but protection scope of the present invention is not limited to described embodiment.
The synthesis of embodiment 1:4-nitrophthalimide (a): the 100mL98% vitriol oil is slowly instilled in the 25mL98% nitrosonitric acid of the ice-water bath cooling of constantly stirring, control temperature is below 15 DEG C, drip and finish, add disposable for 60g phthalic imidine fast, stirring reaction, it is allowed naturally to rise to room temperature, reaction 10h, TLC detects, react complete, slowly yellow being generated liquid pours in 350g frozen water, light-yellow precipitate is had to separate out, filter and use frozen water washing leaching cake 2 ~ 3 times, light yellow solid 4-nitrophthalimide (a) 69.8g is obtained after ethyl alcohol recrystallization, productive rate: 89%, purity (HPLC detection) 99.4%, detected result is shown in Fig. 2.
The synthesis of embodiment 2:4-nitro phthalic diamide (b): the 4-nitrophthalimide of 60g is added in methanol solvate, ammonia is led to while stirring at-5 DEG C ~ 0 DEG C, filter after reaction 4h, filter cake washing 2 ~ 3 times is until washings is neutral, dry white 4-nitro phthalic diamide (b) 63.7g, productive rate 97.6%, purity (HPLC detection) 98.9%, detected result is shown in Fig. 3.
The configuration of embodiment 3:NaBrO solution: in 1L reactor, is added drop-wise in 350mL12%NaOH solution by 20mL bromine under cryosel bath, after stirring reaction 30min, is mixed with NaBrO solution, stand-by.
The synthesis (c) of embodiment 4:4-nitro-o-phenylenediamine: 20.9g4-nitro phthalic diamide (b) is joined in 250mL12% sodium hydroxide solution, under ice-water bath, the NaBrO solution newly prepared (embodiment 3 is made) is slowly instilled wherein, along with NaBrO solution constantly instills, white solid dissolves gradually, drip off and naturally rise to room temperature afterwards, after reaction 30min, be warming up to 50 DEG C, reaction solution is cooled after reacting 1h again, dichloromethane extraction, activated carbon decolorizing, be spin-dried for solvent, crude product underpressure distillation, obtain NPD garnet needle-like crystal (c) 13g, productive rate 85%, purity (HPLC detection) 98.7%, detected result is shown in Fig. 4.
The synthesis (c) of embodiment 5:4-nitro-o-phenylenediamine: 20.9g4-nitro phthalic diamide (b) is joined in 250mL12% sodium hydroxide solution, under ice-water bath, the NaBrO solution newly prepared (embodiment 3 is made) is slowly instilled wherein, along with NaBrO solution constantly instills, white solid dissolves gradually, drip off and naturally rise to room temperature afterwards, after reaction 30min, be warming up to 70 DEG C, reaction solution is cooled after reacting 1h again, dichloromethane extraction, activated carbon decolorizing, be spin-dried for solvent, crude product underpressure distillation, obtain NPD garnet needle-like crystal (c) 14.1g, productive rate 92%, purity (HPLC detection) 99.9%, detected result is shown in Fig. 5.
The synthesis (c) of embodiment 6:4-nitro-o-phenylenediamine: 20.9g4-nitro phthalic diamide (b) is joined in 250mL12% sodium hydroxide solution, under ice-water bath, the NaBrO solution newly prepared (embodiment 3 is made) is slowly instilled wherein, along with NaBrO solution constantly instills, white solid dissolves gradually, drip off and naturally rise to room temperature afterwards, after reaction 30min, be warming up to 90 DEG C, reaction solution is cooled after reacting 1h again, dichloromethane extraction, activated carbon decolorizing, be spin-dried for solvent, crude product underpressure distillation, obtain NPD garnet needle-like crystal (c) 13.6g, productive rate 89%, purity (HPLC detection) 97.7%, detected result is shown in Fig. 6.
The configuration of embodiment 7:NaBrO solution: in a reactor, is added drop-wise in 168mL25%NaOH solution by 20mL bromine under cryosel bath, after stirring reaction 30min, is mixed with NaBrO solution, stand-by.
The synthesis (c) of embodiment 8:4-nitro-o-phenylenediamine: 20.9g4-nitro phthalic diamide (b) is joined in 150mL25% sodium hydroxide solution, under ice-water bath, the NaBrO solution newly prepared (embodiment 7 is made) is slowly instilled wherein, along with NaBrO solution constantly instills, white solid dissolves gradually, drip off and naturally rise to room temperature afterwards, after reaction 30min, be warming up to 65 DEG C, reaction solution is cooled after reaction 1h, dichloromethane extraction, activated carbon decolorizing, be spin-dried for solvent, crude product underpressure distillation, obtain NPD garnet needle-like crystal (c) 13.3g, productive rate 87%, purity (HPLC detection) 99.6%, detected result is shown in Fig. 7.
The synthesis (d) of embodiment 9:5-nitrobenzimidazole ketone: add reactor after fully being mixed in glass mortar with 150g urea by 30.6g solid NPD, be heated to 180 DEG C, reaction 2h, be warming up to 200 DEG C of insulation reaction 1h, be cooled to 140 DEG C again and add 200mL distilled water, after stirring 30min, be cooled to 100 DEG C again and add 50mL industrial spirit, be chilled to room temperature, filter, filter cake is washed, dry blackish green 5-Nitro-2-benzimidazolinone (d) 26.5g, productive rate 74%, purity (HPLC detection) 97.3%, detected result is shown in Fig. 8.
The synthesis (d) of embodiment 10:5-nitrobenzimidazole ketone: 30.6g solid NPD and 150g urea are joined in 300mL orthodichlorobenzene solvent, be heated to 160 DEG C, reaction 4h, be chilled to room temperature, evaporated under reduced pressure solvent, solid a small amount of washing with alcohol after washing 3 ~ 5 times, dry blackish green 5-Nitro-2-benzimidazolinone (d) 33.9g, productive rate 95%, purity (HPLC detection) 99.0%, detected result is shown in Fig. 9.
The synthesis (e) of embodiment 11:5-aminobenzimidazole ketone: add 35.8g5-nitrobenzimidazole ketone and 1.5g Pd-C catalyzer and 100mL alcohol solvent in hydrogenation reaction kettle, N
2replace 3 times, H
2after replacing 2 times, fill H
2be 1.0MPa to pressure, raised temperature to 95 DEG C, reaction 5h, hydrogen is added 3 ~ 5 times, till 1h internal pressure no longer reduces in midway.Take out while hot, filter, solvent evaporated, hot water recrystallization, obtains White snowflake shape solid 5-Amino-2-benzimidazolinone (e) 27.7g, productive rate 93%, and purity (HPLC detection) 98.8%, detected result is shown in Figure 10.
The synthesis (e) of embodiment 12:5-aminobenzimidazole ketone: add 35.8g5-nitrobenzimidazole ketone and 1.8g nickel catalyzator and 100mL alcohol solvent in hydrogenation reaction kettle, N
2replace 3 times, H
2after replacing 2 times, fill H
2be 1.0MPa to pressure, raised temperature to 95 DEG C, supplies hydrogen to 2MPa, and reaction 5h, hydrogen is added 3 ~ 5 times, till 1h internal pressure no longer reduces in midway.Take out while hot, filter, solvent evaporated, hot water recrystallization, obtains White snowflake shape solid 5-Amino-2-benzimidazolinone (e) 27.0g, productive rate 90%, and purity (HPLC detection) 99.7%, detected result is shown in Figure 11.
As mentioned above, although represented with reference to specific preferred embodiment and described the present invention, it shall not be construed as the restriction to the present invention self.Under the spirit and scope of the present invention prerequisite not departing from claims definition, various change can be made in the form and details to it.
Claims (7)
1. a synthetic method for 5-Amino-2-benzimidazolinone, is characterized in that comprising the steps:
(1) phthalic imidine is joined fast in nitrosonitric acid and vitriol oil mixed solution under ice-water bath, react to obtain 4-nitrophthalimide;
(2) add in methanol solvate by 4-nitrophthalimide, pass into ammonia under low temperature, reaction generates 4-nitro phthalic diamide;
(3) below 0 DEG C, in 4-nitro phthalic diamide and sodium hydroxide mixed solution, NaBrO solution is dripped, room temperature reaction 0.5 ~ 1h, be warming up to 50 ~ 100 DEG C, reaction solution is cooled after reaction 1 ~ 2h, dichloromethane extraction, activated carbon decolorizing, is spin-dried for solvent, solid is washed, dry garnet needle-like crystal NPD;
Wherein, NaBrO solution is added drop-wise in NaOH solution by bromine below 0 DEG C, obtains after stirring reaction 30min;
(4) solid NPD and urea are generated 5-Nitro-2-benzimidazolinone by solid phase or liquid phase reaction:
A solid state reaction step: solid NPD and urea are fully mixed in reactor, be heated to 160 ~ 180 DEG C, reaction 1 ~ 2h, is warming up to 200 ~ 220 DEG C of insulation reaction 2h, is cooled to 130 ~ 150 DEG C and adds distilled water, after stirring 30min, be cooled to about 98 ~ 105 DEG C again and add dehydrated alcohol, be chilled to room temperature, filter, filter cake is washed, dry dark green solid 5-Nitro-2-benzimidazolinone;
B liquid phase reaction step: solid NPD and urea are fully mixed to join and fill in the reactor of orthodichlorobenzene, are heated to 180 ~ 200 DEG C, reaction 3 ~ 6h, be down to room temperature, filter, filter cake through ethanol in proper amount and water washing, dry dark green solid 5-Nitro-2-benzimidazolinone;
(5) 5-Nitro-2-benzimidazolinone shortening obtains 5-Amino-2-benzimidazolinone target product.
2. the synthetic method of 5-Amino-2-benzimidazolinone according to claim 1, it is characterized in that: in step (1), the preparation method of nitrosonitric acid and vitriol oil mixed solution is: be slowly added dropwise to by 98% vitriol oil in the nitrosonitric acid constantly stirred under ice-water bath, control temperature, at 0 ~ 15 DEG C, obtains nitrosonitric acid and vitriol oil mixed solution; Wherein, the mol ratio of nitric acid and the vitriol oil is 1:3.
3. the synthetic method of 5-Amino-2-benzimidazolinone according to claim 1 and 2, it is characterized in that: in step (1), phthalic imidine joins after in nitrosonitric acid and vitriol oil mixed solution fast, naturally rise to room temperature, stir more than 10h, TLC and detect, react complete, yellow being generated liquid slowly pours in trash ice water, filters and frozen water washing precipitation, obtains light yellow solid 4-nitrophthalimide after recrystallization.
4. the synthetic method of 5-Amino-2-benzimidazolinone according to claim 1, it is characterized in that: in step (2), ammonia is led to while stirring at-5 DEG C ~ 0 DEG C, filter after reaction 3 ~ 5h, filter cake washing 2 ~ 3 times until washings be neutral, dry must white solid 4-nitro phthalic diamide.
5. the synthetic method of 5-Amino-2-benzimidazolinone according to claim 1, is characterized in that: in step (4), be filled with protection of inert gas in reactor.
6. the synthetic method of 5-Amino-2-benzimidazolinone according to claim 1, it is characterized in that: in step (5), 5-Nitro-2-benzimidazolinone and catalyzer join in hydrogenation reaction kettle, 1 ~ 1.5MPa hydrogen pressure and 60 ~ 100 DEG C, react 3 ~ 5h in alcohol solvent, obtain White snowflake shape solid 5-Amino-2-benzimidazolinone; Wherein, described catalyzer is Pd-C or Raney Ni.
7. the synthetic method of 5-Amino-2-benzimidazolinone according to claim 1, is characterized in that: before described hydrogenation reaction kettle is filled with hydrogen reaction, is filled with inert gas replacement and removes air.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310156518.XA CN103193714B (en) | 2013-04-28 | 2013-04-28 | 5-amino-benzimidazolone synthetic method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310156518.XA CN103193714B (en) | 2013-04-28 | 2013-04-28 | 5-amino-benzimidazolone synthetic method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103193714A CN103193714A (en) | 2013-07-10 |
| CN103193714B true CN103193714B (en) | 2015-03-04 |
Family
ID=48716550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310156518.XA Active CN103193714B (en) | 2013-04-28 | 2013-04-28 | 5-amino-benzimidazolone synthetic method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103193714B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106348296B (en) * | 2016-08-30 | 2019-03-05 | 山东汇海医药化工有限公司 | A kind of processing method of AABI waste active carbon |
| CN107739348B (en) * | 2017-09-26 | 2021-07-09 | 四川航天川南火工技术有限公司 | Synthesis method of 5-nitrotetrazole copper |
| CN108101850B (en) * | 2017-12-21 | 2021-12-07 | 山东汇海医药化工有限公司 | Method for improving quality of 5-acetoacetylaminobenzimidazolone |
| CN108558888A (en) * | 2018-05-31 | 2018-09-21 | 兰州大学 | A kind of synthetic method of azophenlyene and imidazolone |
| CN110256435A (en) * | 2019-07-04 | 2019-09-20 | 绍兴市精益生物化工有限公司 | One-step synthesis method of 1, 3-dimethyl uric acid |
| CN111116486A (en) * | 2020-01-15 | 2020-05-08 | 山东汇海医药化工有限公司 | Synthesis method of 5-nitrobenzimidazole ketone |
| CN113441153B (en) * | 2020-03-24 | 2023-05-09 | 东营市天正化工有限公司 | Magnetic catalyst and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992017442A1 (en) * | 1991-04-01 | 1992-10-15 | Olin Corporation | Process for the preparation of isocyanates and carbamates using a silver salt promoted hofmann rearrangement |
| CN101987814A (en) * | 2009-08-05 | 2011-03-23 | 昆明制药集团股份有限公司 | Method for preparing 3,4,5-trimethoxyphenol |
| CN103012162A (en) * | 2012-12-25 | 2013-04-03 | 大连奇凯医药科技有限公司 | Preparation method of pentafluoroaniline |
-
2013
- 2013-04-28 CN CN201310156518.XA patent/CN103193714B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992017442A1 (en) * | 1991-04-01 | 1992-10-15 | Olin Corporation | Process for the preparation of isocyanates and carbamates using a silver salt promoted hofmann rearrangement |
| CN101987814A (en) * | 2009-08-05 | 2011-03-23 | 昆明制药集团股份有限公司 | Method for preparing 3,4,5-trimethoxyphenol |
| CN103012162A (en) * | 2012-12-25 | 2013-04-03 | 大连奇凯医药科技有限公司 | Preparation method of pentafluoroaniline |
Non-Patent Citations (3)
| Title |
|---|
| 5-氨基苯并咪唑酮及苯并咪唑类化合物的合成;邵广伟;《大连理工大学硕士学位论文》;20080901;第18、24-28页 * |
| 尹彦冰,等.金属酞菁的合成及其激光解吸质谱研究.《分子科学学报》.2009,第25卷(第5期),第365-367页. * |
| 崔天放,等."对苯二胺新型合成工艺研究进展".《精 细 化 工 中 间 体》.2007,第37卷(第4期),第5-8页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103193714A (en) | 2013-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103193714B (en) | 5-amino-benzimidazolone synthetic method | |
| CN105130926B (en) | A kind of preparation method of methylene blue | |
| CN103087550A (en) | Permanent violet product synthesis and production process | |
| CN106243105A (en) | Methylene-bridged 1,8 naphthyridines part and copper (I) coordination compound, preparation method and application | |
| CN103601668A (en) | Preparation method of N-phenyl-3-bromocarbazole | |
| CN101130499B (en) | Method for synthesizing nitryl arylamine compounds | |
| CN103232397B (en) | The synthetic method of 5-amino-N-substituted benzimidazole ketone | |
| CN104557598A (en) | Synthesis process of 2-methoxy-5-acetamino aniline | |
| Chen et al. | Highly selective reduction of nitrobenzenes to azoxybenzenes with a copper catalyst | |
| CN101402595A (en) | 9,9-dialkyl-2,7-disulfhydryl-3,6-diamino-fluorene hydrochlorate and method of preparing the same | |
| CN103819345B (en) | A kind of preparation method of 2-aminobiphenyl derivate | |
| CN103709045A (en) | Preparation method of 4-chlorine-3-trifluoromethyl aniline hydrochloride | |
| CN104974173B (en) | A kind of gulf embedding pentatomic sulphur heterocycle in position and hexa-atomic oxa- ring 3,4:The preparation method of 9,10 perylene tetracarboxylic acid N-butyls | |
| CN107698651B (en) | A kind of production technology of high-purity dutasteride | |
| CN102516133A (en) | Preparation method of methanesulfonic acid derivative | |
| CN108863900A (en) | A kind of preparation method of 5- fluoro indole -2- ketone | |
| CN104559309A (en) | Method for preparing blue reactive dyes | |
| CN103333204A (en) | Synthesis method of 9,9'-spirobifluorene derivative | |
| CN107903203B (en) | Synthetic method of 3, 4-dinitrophthalimide | |
| CN101514161A (en) | Method for preparing 2-bromo-7-nitrofluorenone | |
| CN102603622B (en) | Synthetic method of 2-amino-4-bromopyridine | |
| CN101525297A (en) | 9,9-dialkyl-2,7-dihydroxy-3,6-diamino TI-4,fluorene hydrochloride and preparation method thereof | |
| CN109438349A (en) | 6- (alpha-cyano imines) base phenanthridines class compound and its synthetic method | |
| CN102584713A (en) | Preparation method for 5,6-diamino benzimidazolone-2 | |
| CN105732510A (en) | Preparation method for 5,6-diaminobenzimidazolone-2 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 225722 Jiangsu city of Taizhou province Xinghua city people Zhangguo Town Road No. 2 Patentee after: SUNLOUR PIGMENT CO.,LTD. Address before: 225722 Jiangsu city of Taizhou province Xinghua city people Zhangguo Town Road No. 2 Patentee before: Jiangsu double ball pigment Limited by Share Ltd. Address after: 225722 Jiangsu city of Taizhou province Xinghua city people Zhangguo Town Road No. 2 Patentee after: Jiangsu double ball pigment Limited by Share Ltd. Address before: 225722 Jiangsu city of Taizhou province Xinghua city people Zhangguo Town Road No. 2 Patentee before: Jiangsu Shuangle Chemical Pigment Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |