CN103193714A - 5-amino-benzimidazolone synthetic method - Google Patents
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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 a kind of high performance pigment dyestuff that has, and it is bright-coloured to have coloured light, characteristics such as tinctorial strength height.Because containing imino-in the molecule (HN-) (CO-), can easily form intermolecular and intramolecular hydrogen bond, by the effect of this reactive force, give performances such as fast light, heat-resisting, the weather of such pigment excellence, anti-migration and anti-solvent with carbonyl.
5-Amino-2-benzimidazolinone is the important intermediate that is widely used in synthesizing benzimidazole ketone pigment.Benzimidazolone can be by O-Phenylene Diamine and urea (or phosgene, triphosgene, methylcarbonate etc.) catalyzed reaction and the o-Nitraniline of condensation, orthodichlorobenzene and ammonia prepare with sulphur, formate number of ways such as reaction at high temperature.Synthetic route is as follows.
Above process is simple, easy to operate, but in nitrifying process, benzimidazolone generates the dinitrobenzene thing easily, and the dinitrobenzene thing is difficult for removing, and when a nitro thing was reduced, dinitrobenzene benzo imidazolone also was reduced simultaneously, diamino benzo imidazolone in the product is very easily oxidized and generate the oxidation products of black, thereby influences the quality of the finished product.
The method of another kind of synthetic 5-Amino-2-benzimidazolinone is that the reactant with two nitros is starting raw material, and this synthetic route is as follows.
This synthetic method has reduced the influence of the dinitrobenzene product that nitrated this step brings, owing to there is not the generation of diamino benzo imidazolone, the products obtained therefrom quality is better, but technological process is complicated, and synthetic 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) under the ice-water bath phthalic imidine is joined in nitrosonitric acid and the vitriol oil mixed solution fast, react 4-nitro phthalic imidine;
(2) 4-nitro phthalic imidine is added in the methanol solvate, feed ammonia under the low temperature, reaction generates 4-nitro phthalic diamide;
(3) dripping NaBrO solution below 0 ℃ in 4-nitro phthalic diamide and sodium hydroxide mixed solution, reaction makes 4-nitro O-Phenylene Diamine;
(4) with solid 4-nitro O-Phenylene Diamine and urea solid phase or liquid phase reaction generation 5-Nitro-2-benzimidazolinone;
(5) the 5-Nitro-2-benzimidazolinone shortening gets the 5-Amino-2-benzimidazolinone target product.
The inventive method synthetic route is as follows:
In the step (1), the preparation method of nitrosonitric acid and vitriol oil mixed solution is: under the ice-water bath 98% vitriol oil is slowly splashed in the nitrosonitric acid of continuous stirring, the control temperature obtains nitrosonitric acid and vitriol oil mixed solution at 0～15 ℃; Wherein, the mol ratio of nitric acid and the vitriol oil is preferably 1:3.
Further, in the step (1), after phthalic imidine joins in nitrosonitric acid and the vitriol oil mixed solution fast, naturally rise to room temperature, stir more than the 10h, TLC detects, react complete, yellow Generation Liquid is slowly poured in the trash ice water, filtered and the frozen water washing precipitation, get light yellow solid 4-nitro phthalic imidine (a) behind the recrystallization.Preferably, dry after the filter cake washing 2～3 times, recrystallization is by ethanol or methyl alcohol.
In the step (2), under-5 ℃～0 ℃, lead to ammonia while stirring, reaction 3～5h after-filtration, the filter cake washing is neutral until washings 2～3 times, the dry white solid 4-nitro phthalic diamide (b) that gets.
In the step (3), NaBrO solution is below 0 ℃ bromine to be added drop-wise in the NaOH solution, to obtain behind the stirring reaction 30min.
Below 0 ℃ bromine is being added drop-wise in the NaOH solution, behind the stirring reaction 30min, this drop is added to fills in 4-nitro phthalic diamide and another reactor of sodium hydroxide solution, drip off back room temperature reaction 0.5～1h, be warming up to 50～100 ℃, cool off reaction solution behind reaction 1～2h, dichloromethane extraction, activated carbon decolorizing is spin-dried for solvent, the solid washing, the dry garnet needle-like crystal 4-nitro O-Phenylene Diamine (c) that gets.Preferably, two cover reactors are connected with pipeline.The temperature that wherein heats up is preferably 60～75 ℃.
In the step (4), the solid state reaction step: solid 4-nitro O-Phenylene Diamine and urea fully are mixed in the reactor, are heated to 160～180 ℃, reaction 1～2h, be warming up to 200～220 ℃ of insulation reaction 2h, be cooled to 130～150 ℃ and add distilled water, behind the stirring 30min, be cooled to 98～105 ℃ again and add a certain amount of dehydrated alcohols, be chilled to room temperature, filter filter cake washing, the dry blackish green solid 5-Nitro-2-benzimidazolinone (d) that gets.Preferably, be filled with protection of inert gas in the reactor, as nitrogen, argon gas.
In the step (4), the liquid phase reaction step: solid 4-nitro O-Phenylene Diamine and urea fully are mixed to join in the reactor that fills orthodichlorobenzene, be heated to 180～200 ℃, reaction 3～6h, be down to room temperature, filter, filter cake is through an amount of ethanol and water washing, dry blackish green solid 5-Nitro-2-benzimidazolinone.
In the step (5), 5-Nitro-2-benzimidazolinone and catalyzer join in the hydrogenation reaction kettle, 1～1.5MPa hydrogen pressure and 60～100 ℃, react 3～5h in the alcohol solvent, get white flakes solid 5-Amino-2-benzimidazolinone (e); Wherein, described catalyzer is Pd-C or Raney Ni.Preferably, before described hydrogenation reaction kettle charges into hydrogen reaction, charge into inert gas replacements such as argon gas or nitrogen and remove air.Wherein temperature of reaction is preferably 80～95 ℃.
The present invention compared with prior art, its beneficial effect is: the present invention adopts phthalic imidine to prepare 5-Nitro-2-benzimidazolinone through nitrated back cyclization earlier, the nitro thing after purifying is carried out hydro-reduction again obtain the high purity target product.Not only can avoid the generation of dinitrobenzene product so effectively, and raw material is cheap, reacts easy to operate.
Description of drawings
Fig. 1 phthalic imidine raw material high-efficient liquid phase chromatogram.
The high-efficient liquid phase chromatogram of Fig. 2 embodiment 1 intermediate 4-nitro phthalic imidine.
The high-efficient liquid phase chromatogram of the 4-nitro phthalic diamide that Fig. 3 embodiment 2 synthesizes.
The high-efficient liquid phase chromatogram of Fig. 4 embodiment 4 intermediate 4-nitro O-Phenylene Diamines.
The high-efficient liquid phase chromatogram of Fig. 5 embodiment 5 intermediate 4-nitro O-Phenylene Diamines.
The high-efficient liquid phase chromatogram of Fig. 6 embodiment 6 intermediate 4-nitro O-Phenylene Diamines.
The high-efficient liquid phase chromatogram of Fig. 7 embodiment 8 intermediate 4-nitro O-Phenylene Diamines.
The high-efficient liquid phase chromatogram of Fig. 8 embodiment 9 intermediate 5-Nitro-2-benzimidazolinones.
The high-efficient liquid phase chromatogram of Fig. 9 embodiment 10 intermediate 5-Nitro-2-benzimidazolinones.
The high-efficient liquid phase chromatogram of Figure 10 embodiment 11 intermediate 5-Amino-2-benzimidazolinones.
The high-efficient liquid phase chromatogram of Figure 11 embodiment 12 intermediate 5-Amino-2-benzimidazolinones.
Embodiment
Below technical solution of the present invention is elaborated, but protection scope of the present invention is not limited to described embodiment.
Embodiment 1:4-nitro phthalic imidine (a) synthetic: the 100mL98% vitriol oil is slowly splashed in the 25mL98% nitrosonitric acid of ice-water bath cooling of continuous stirring, the control temperature is below 15 ℃, drip and finish, with the disposable quick adding of 60g phthalic imidine, stirring reaction, allow it rise to room temperature naturally, reaction 10h, TLC detects, react complete, slowly yellow Generation Liquid is poured in the 350g frozen water, had light-yellow precipitate to separate out, filter and with frozen water washing leaching cake 2～3 times, get light yellow solid 4-nitro phthalic imidine (a) 69.8g behind the ethyl alcohol recrystallization, productive rate: 89%, purity (HPLC detection) 99.4%, detected result is seen Fig. 2.
Synthesizing of embodiment 2:4-nitro phthalic diamide (b): the 4-nitro phthalic imidine of 60g is added in the methanol solvate, under-5 ℃～0 ℃, lead to ammonia while stirring, reaction 4h after-filtration, the filter cake washing is neutral until washings 2～3 times, dry white 4-nitro phthalic diamide (b) 63.7g that gets, productive rate 97.6%, purity (HPLC detection) 98.9%, detected result is seen Fig. 3.
The configuration of embodiment 3:NaBrO solution: in the 1L reactor, cryosel is bathed down the 20mL bromine is added drop-wise in the 350mL12%NaOH solution, behind the stirring reaction 30min, is mixed with NaBrO solution, and is stand-by.
Synthetic (c) of embodiment 4:4-nitro O-Phenylene Diamine: 20.9g4-nitro phthalic diamide (b) is joined in the 250mL12% sodium hydroxide solution, the NaBrO solution that to newly prepare under the ice-water bath (embodiment 3 is made) slowly splashes into wherein, along with NaBrO solution constantly splashes into, white solid dissolves gradually, drip off the back and rise to room temperature naturally, behind the reaction 30min, be warming up to 50 ℃, cool off reaction solution after reacting 1h again, dichloromethane extraction, activated carbon decolorizing is spin-dried for solvent, the crude product underpressure distillation, get 4-nitro O-Phenylene Diamine garnet needle-like crystal (c) 13g, productive rate 85%, purity (HPLC detection) 98.7%, detected result is seen Fig. 4.
Synthetic (c) of embodiment 5:4-nitro O-Phenylene Diamine: 20.9g4-nitro phthalic diamide (b) is joined in the 250mL12% sodium hydroxide solution, the NaBrO solution that to newly prepare under the ice-water bath (embodiment 3 is made) slowly splashes into wherein, along with NaBrO solution constantly splashes into, white solid dissolves gradually, drip off the back and rise to room temperature naturally, behind the reaction 30min, be warming up to 70 ℃, cool off reaction solution after reacting 1h again, dichloromethane extraction, activated carbon decolorizing is spin-dried for solvent, the crude product underpressure distillation, get 4-nitro O-Phenylene Diamine garnet needle-like crystal (c) 14.1g, productive rate 92%, purity (HPLC detection) 99.9%, detected result is seen Fig. 5.
Synthetic (c) of embodiment 6:4-nitro O-Phenylene Diamine: 20.9g4-nitro phthalic diamide (b) is joined in the 250mL12% sodium hydroxide solution, the NaBrO solution that to newly prepare under the ice-water bath (embodiment 3 is made) slowly splashes into wherein, along with NaBrO solution constantly splashes into, white solid dissolves gradually, drip off the back and rise to room temperature naturally, behind the reaction 30min, be warming up to 90 ℃, cool off reaction solution after reacting 1h again, dichloromethane extraction, activated carbon decolorizing is spin-dried for solvent, the crude product underpressure distillation, get 4-nitro O-Phenylene Diamine garnet needle-like crystal (c) 13.6g, productive rate 89%, purity (HPLC detection) 97.7%, detected result is seen Fig. 6.
The configuration of embodiment 7:NaBrO solution: in a reactor, cryosel is bathed down the 20mL bromine is added drop-wise in the 168mL25%NaOH solution, behind the stirring reaction 30min, is mixed with NaBrO solution, and is stand-by.
Synthetic (c) of embodiment 8:4-nitro O-Phenylene Diamine: 20.9g4-nitro phthalic diamide (b) is joined in the 150mL25% sodium hydroxide solution, the NaBrO solution that to newly prepare under the ice-water bath (embodiment 7 is made) slowly splashes into wherein, along with NaBrO solution constantly splashes into, white solid dissolves gradually, drip off the back and rise to room temperature naturally, behind the reaction 30min, be warming up to 65 ℃, cool off reaction solution behind the reaction 1h, dichloromethane extraction, activated carbon decolorizing is spin-dried for solvent, the crude product underpressure distillation, get 4-nitro O-Phenylene Diamine garnet needle-like crystal (c) 13.3g, productive rate 87%, purity (HPLC detection) 99.6%, detected result is seen Fig. 7.
Synthetic (d) of embodiment 9:5-nitrobenzimidazole ketone: 30.6g solid 4-nitro O-Phenylene Diamine and 150g urea are fully mixed the back add reactor in glass mortar, be heated to 180 ℃, reaction 2h, be warming up to 200 ℃ of insulation reaction 1h, be cooled to 140 ℃ again and add 200mL distilled water, after stirring 30min, be cooled to 100 ℃ again and add the 50mL industrial spirit, be chilled to room temperature, filter, the filter cake washing, dry blackish green 5-Nitro-2-benzimidazolinone (d) 26.5g that gets, productive rate 74%, purity (HPLC detection) 97.3%, detected result is seen Fig. 8.
Synthetic (d) of embodiment 10:5-nitrobenzimidazole ketone: 30.6g solid 4-nitro O-Phenylene Diamine and 150g urea are joined in the 300mL orthodichlorobenzene solvent, be heated to 160 ℃, reaction 4h, be chilled to room temperature, the evaporated under reduced pressure solvent, solid washs after washing 3～5 times with small amount of ethanol, dry blackish green 5-Nitro-2-benzimidazolinone (d) 33.9g that gets, productive rate 95%, purity (HPLC detection) 99.0%, detected result is seen Fig. 9.
Synthetic (e) of the amino benzimidazolone of embodiment 11:5-: in hydrogenation reaction kettle, add 35.8g5-nitrobenzimidazole ketone and 1.5g Pd-C catalyzer and 100mL alcohol solvent, N
2Replace 3 times, H
2After replacing 2 times, fill H
2To pressure be 1.0MPa, rising temperature to 95 ℃, reaction 5h adds hydrogen midway 3～5 times, till the 1h internal pressure no longer reduces.Take out while hot, filter, solvent evaporated, the hot water recrystallization gets white flakes solid 5-Amino-2-benzimidazolinone (e) 27.7g, productive rate 93%, purity (HPLC detection) 98.8%, detected result is seen Figure 10.
Synthetic (e) of the amino benzimidazolone of embodiment 12:5-: in hydrogenation reaction kettle, add 35.8g5-nitrobenzimidazole ketone and 1.8g nickel catalyzator and 100mL alcohol solvent, N
2Replace 3 times, H
2After replacing 2 times, fill H
2To pressure be 1.0MPa, rising temperature to 95 ℃ is supplied hydrogen to 2MPa, reaction 5h adds hydrogen midway 3～5 times, till the 1h internal pressure no longer reduces.Take out while hot, filter, solvent evaporated, the hot water recrystallization gets white flakes solid 5-Amino-2-benzimidazolinone (e) 27.0g, productive rate 90%, purity (HPLC detection) 99.7%, detected result is seen Figure 11.
As mentioned above, although represented and explained the present invention that with reference to specific preferred embodiment it shall not be construed as the restriction to the present invention self.Under the spirit and scope of the present invention prerequisite that does not break away from the claims definition, can make various variations in the form and details to it.
Claims (10)
1. the synthetic method of a 5-Amino-2-benzimidazolinone is characterized in that comprising the steps:
(1) under the ice-water bath phthalic imidine is joined in nitrosonitric acid and the vitriol oil mixed solution fast, react 4-nitro phthalic imidine;
(2) 4-nitro phthalic imidine is added in the methanol solvate, feed ammonia under the low temperature, reaction generates 4-nitro phthalic diamide;
(3) dripping NaBrO solution below 0 ℃ in 4-nitro phthalic diamide and sodium hydroxide mixed solution, reaction makes 4-nitro O-Phenylene Diamine;
(4) solid 4-nitro O-Phenylene Diamine and urea are generated 5-Nitro-2-benzimidazolinone by solid phase or liquid phase reaction;
(5) the 5-Nitro-2-benzimidazolinone shortening gets the 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 the step (1), the preparation method of nitrosonitric acid and vitriol oil mixed solution is: under the ice-water bath 98% vitriol oil is slowly splashed in the nitrosonitric acid of continuous stirring, the control temperature obtains nitrosonitric acid and vitriol oil mixed solution at 0 ~ 15 ℃; 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 the step (1), after phthalic imidine joins in nitrosonitric acid and the vitriol oil mixed solution fast, naturally rise to room temperature, stir more than the 10h, TLC detects, react complete, yellow Generation Liquid is slowly poured in the trash ice water, filtered and the frozen water washing precipitation, get light yellow solid 4-nitro phthalic imidine behind the recrystallization.
4. the synthetic method of 5-Amino-2-benzimidazolinone according to claim 1, it is characterized in that: in the step (2), under-5 ℃ ~ 0 ℃, lead to ammonia while stirring, reaction 3 ~ 5h after-filtration, the filter cake washing is neutral until washings 2 ~ 3 times, the dry white solid 4-nitro phthalic diamide that gets.
5. the synthetic method of 5-Amino-2-benzimidazolinone according to claim 1, it is characterized in that: in the step (3), NaBrO solution is below 0 ℃ bromine to be added drop-wise in the NaOH solution, to obtain behind the stirring reaction 30min.
6. the synthetic method of 5-Amino-2-benzimidazolinone according to claim 1 or 5, it is characterized in that: in the step (3), after dripping NaBrO solution in 4-nitro phthalic diamide and the sodium hydroxide mixed solution, room temperature reaction 0.5 ~ 1h is warming up to 50 ~ 100 ℃, cool off reaction solution behind reaction 1 ~ 2h, dichloromethane extraction, activated carbon decolorizing is spin-dried for solvent, the solid washing, the dry garnet needle-like crystal 4-nitro O-Phenylene Diamine that gets.
7. the synthetic method of 5-Amino-2-benzimidazolinone according to claim 1 is characterized in that: in the step (4),
A solid state reaction step: solid 4-nitro O-Phenylene Diamine and urea fully are mixed in the reactor, be heated to 160 ~ 180 ℃, reaction 1 ~ 2h is warming up to 200 ~ 220 ℃ of insulation reaction 2h, is cooled to 130 ~ 150 ℃ and adds distilled water, after stirring 30min, be cooled to again about 98～105 ℃ and add dehydrated alcohol, be chilled to room temperature, filter, filter cake washing, dry blackish green solid 5-Nitro-2-benzimidazolinone;
B liquid phase reaction step: solid 4-nitro O-Phenylene Diamine and urea fully are mixed to join in the reactor that fills orthodichlorobenzene, are heated to 180 ~ 200 ℃, reaction 3 ~ 6h, be down to room temperature, filter, filter cake is through an amount of ethanol and water washing, dry blackish green solid 5-Nitro-2-benzimidazolinone.
8. the synthetic method of 5-Amino-2-benzimidazolinone according to claim 7 is characterized in that: in the step (4), be filled with protection of inert gas in the reactor.
9. the synthetic method of 5-Amino-2-benzimidazolinone according to claim 1, it is characterized in that: in the step (5), 5-Nitro-2-benzimidazolinone and catalyzer join in the hydrogenation reaction kettle, 1 ~ 1.5MPa hydrogen pressure and 60 ~ 100 ℃, react 3 ~ 5h in the alcohol solvent, get white flakes solid 5-Amino-2-benzimidazolinone; Wherein, described catalyzer is Pd-C or Raney Ni.
10. the synthetic method of 5-Amino-2-benzimidazolinone according to claim 1 is characterized in that: before described hydrogenation reaction kettle charges into hydrogen reaction, charge into inert gas replacement and remove air.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106348296A (en) * | 2016-08-30 | 2017-01-25 | 山东汇海医药化工有限公司 | AABI waste active carbon treatment method |
| CN107739348A (en) * | 2017-09-26 | 2018-02-27 | 中国航天科技集团公司川南机械厂 | A kind of synthetic method of 5 nitro tetrazolium copper |
| CN108101850A (en) * | 2017-12-21 | 2018-06-01 | 山东汇海医药化工有限公司 | A kind of method for improving 5-acetoacetamido benzimidazolone quality |
| 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 |
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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 |
|---|
| 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》, vol. 25, no. 5, 31 October 2009 (2009-10-31), pages 365 - 367 * |
| 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》, vol. 37, no. 4, 31 August 2007 (2007-08-31), pages 5 - 8 * |
| 邵广伟: "5-氨基苯并咪唑酮及苯并咪唑类化合物的合成", 《大连理工大学硕士学位论文》, 1 September 2008 (2008-09-01) * |
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| CN107739348A (en) * | 2017-09-26 | 2018-02-27 | 中国航天科技集团公司川南机械厂 | A kind of synthetic method of 5 nitro tetrazolium copper |
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| 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 |
| CN113441153A (en) * | 2020-03-24 | 2021-09-28 | 东营市天正化工有限公司 | Magnetic catalyst and preparation method thereof |
| 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 |
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