CN105439954A - One-step synthesis method of iminostilbene - Google Patents
One-step synthesis method of iminostilbene Download PDFInfo
- Publication number
- CN105439954A CN105439954A CN201410496618.1A CN201410496618A CN105439954A CN 105439954 A CN105439954 A CN 105439954A CN 201410496618 A CN201410496618 A CN 201410496618A CN 105439954 A CN105439954 A CN 105439954A
- Authority
- CN
- China
- Prior art keywords
- iminostilbene
- synthetic method
- catalyst
- iminodibenzyl
- hydrogen acceptor
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention provides a one-step synthesis method of iminostilbene. The method includes that with iminodibenzyl as a raw material, under a condition of the presence of a hydrogen acceptor, a catalyst is used for one-step catalytic dehydrogenation preparation of iminostilbene in a liquid-phase system. The method comprises the following steps: adding iminodibenzyl, the catalyst and the hydrogen acceptor with a certain proportion into a reactor with heating stirring and refluxing devices, in a nitrogen protection atmosphere, electrically heating to a reflux state, maintaining stirring for a certain period of time, then cooling, adding a certain proportion of a suspending agent, next removing the catalyst, recrystallizing the crude product, and drying to obtain the iminostilbene finished product. Compared with a conventional production process, the liquid phase catalytic dehydrogenation one-step synthesis process has the advantages of simple route, not high reaction temperature, low equipment investment, simple operation, fewer by-products, high product purity, no bromine in the product, recoverable and reusable used solvents, and small influence on the environment.
Description
Technical field
The invention belongs to organic chemistry filed, relate to a kind of single step synthetic method of iminostilbene.Specifically, the present invention relates to iminodibenzyl is raw material, through the method for catalytic dehydrogenation one-step synthesis iminostilbene.
Background technology
Iminostilbene (IS), molecular formula: C
14h
11n is a kind of important medicine intermediate, is usually used in synthesizing Carbamzepine, oxcarbazepine, also can be used for prevention and therapy hepatitis C, as anti-hemolysis medicine, and synthesis rhodium catalyst part, and be also the important synthesis material of the aspect such as genetically engineered, materialogy.
The commercial run of current domestic production iminostilbene is mainly bromination method; take iminodibenzyl as raw material; through acidylate, bromination, dehydrobromination, acidylate four step is gone to synthesize iminostilbene; this method exists that low conversion rate, dopant species are many, the drawback such as waste time and energy, and quality product is not high, and uses bromine in the reaction; have greater environmental impacts; be not suitable for modern crafts, along with people are to the pay attention to day by day of environment protection, bromination method production technique will progressively by market.
CN102120729 discloses the industrial method that iminostilbene is produced in a kind of iminodibenzyl catalytic dehydrogenation, reaction mass enters dehydrogenation reactor after heating and melting mixes with high-temperature water vapor, carry out the absorption tower that enters after heat is reclaimed in heat exchange with interchanger, absorbing the solvent of reaction product through acquisition product iminostilbenes such as evaporation, crystallizations from reactor logistics out through an interchanger.CN101307021 discloses a kind of method that vapor catalytic dehydrogenation on a fixed bed prepares iminostilbene, and material is equipped with the receiving trap of water coolant by entering after fixed bed, and after the mixed solution evaporating water obtained, recrystallization obtains iminostilbene.Above-mentioned production technique is the method adopting vapor catalytic dehydrogenation technology to prepare iminostilbene, and temperature of reaction is generally at 400 ~ 600 DEG C, high to equipment requirements, and scale of investment is large, and product separation is difficult, and process energy consumption is higher.
Summary of the invention
For overcoming the shortcoming of prior art, the invention provides the chemical synthesis process of a kind of single step liquid-phase catalysis Oxidative Dehydrogenation for iminostilbene, operational path is simple, by product is few, and the iminostilbene product of preparation is not brominated, can be used for producing without bromine Carbamzepine, is one of iminostilbene industrial expansion trend.
The technical solution used in the present invention is: the single step synthetic method of iminostilbene, is characterized in that, take iminodibenzyl as raw material, through catalytic dehydrogenation one-step synthesis iminostilbene in liquid-phase system.Said method comprising the steps of:
(1) in the reactor with heated and stirred and reflux, add the iminodibenzyl of certain mol proportion, catalyzer and hydrogen acceptor, under nitrogen protection atmosphere, electrically heated is to reflux state, stirs maintenance 10 ~ 22 hours;
(2) be cooled to after below 40 DEG C, add a certain amount of suspension agent, to be heated to after reflux state Removal of catalyst while hot, filtrate distillation cools except after desolventizing, and the solvent after distillation can be recycled;
(3) in filtrate, add a certain amount of recrystallization solvent, be heated to all dissolve rear cooling, after crystallize out filtration drying, obtain iminostilbene finished product.
Described catalyzer is noble metal catalyst: as palladium, platinum etc.
Described support of the catalyst is gac.
The activity component load quantity of described catalyzer is 3 ~ 10%, preferably 10%.
Described hydrogen acceptor is Ortho Nitro Toluene, dimethyl maleate etc., and preferred Ortho Nitro Toluene is as hydrogen acceptor.
Described reaction is carried out under nitrogen atmosphere, and temperature of reaction is 200 ~ 240 DEG C, preferably 210 ~ 220 DEG C.
The mol ratio of described raw material iminodibenzyl, catalyzer and hydrogen acceptor is 1:0.5 ~ 3.0:0.05 ~ 0.2, preferred 1:0.5 ~ 1.0:0.08 ~ 0.16.
Described suspension agent is toluene, acetone, ethyl acetate, DMF etc., preferred toluene, acetone.
Described recrystallization solvent is methyl alcohol, ethanol, Virahol, toluene, benzene etc., preferred dehydrated alcohol, Virahol.
Beneficial effect of the present invention is mainly reflected in: compared with the two kinds of production technique introduced above, liquid-phase catalysis dehydrogenation single step synthesis route is simple, temperature of reaction is not high, facility investment is little, simple to operate, by product is few, and product purity is high and not brominated, the solvent used is all recyclable to be applied mechanically, little to environmental influence.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.It should be noted that, these embodiments are not for limiting the scope of the invention, and protection scope of the present invention is as the criterion with appending claims.
Embodiment 1: to heating, stir and reflux reactor in add 40g iminodibenzyl, 15ml Ortho Nitro Toluene, 2.5g5% palladium-carbon catalyst, at 210 ~ 240 DEG C reflux 10 ~ 24 hours.Slightly cool in backward reactor and add 150ml toluene as suspension agent, Removal of catalyst while hot, distillation carries out recrystallization except adding 200ml dehydrated alcohol after desolventizing, crystallize out is iminostilbene finished product, be weighed as 29.5g after drying, yield is 74.6%, and product purity is 99.42%(GC).
Embodiment 2: to heating, stir and reflux reactor in add 40g iminodibenzyl, 15ml Ortho Nitro Toluene, 3.0g5% palladium-carbon catalyst, at 210 ~ 240 DEG C reflux 10 ~ 24 hours.Slightly cool in backward reactor and add 150ml toluene as suspension agent, Removal of catalyst while hot, distillation carries out recrystallization except adding 200ml dehydrated alcohol after desolventizing, crystallize out is iminostilbene finished product, be weighed as 30.3g after drying, yield is 76.5%, and product purity is 99.48%(GC).
Embodiment 3: to heating, stir and reflux reactor in add 40g iminodibenzyl, 15ml Ortho Nitro Toluene, 2.5g10% palladium-carbon catalyst, at 210 ~ 240 DEG C reflux 10 ~ 24 hours.Slightly cool in backward reactor and add 150ml toluene as suspension agent, Removal of catalyst while hot, distillation carries out recrystallization except adding 200ml dehydrated alcohol after desolventizing, crystallize out is iminostilbene finished product, be weighed as 31.6g after drying, yield is 79.8%, and product purity is 99.88%.
Embodiment 4: to heating, stir and reflux reactor in add 40g iminodibenzyl, 15ml Ortho Nitro Toluene, 3.0g10% palladium-carbon catalyst, at 210 ~ 240 DEG C reflux 10 ~ 24 hours.Slightly cool in backward reactor and add 150ml toluene as suspension agent, Removal of catalyst while hot, distillation carries out recrystallization except adding 200ml dehydrated alcohol after desolventizing, crystallize out is iminostilbene finished product, be weighed as 31.7g after drying, yield is 80.1%, and product purity is 99.94%.
Embodiment 5: to heating, stir and reflux reactor in add 40g iminodibenzyl, 20ml Ortho Nitro Toluene, 2.5g10% palladium-carbon catalyst, at 210 ~ 240 DEG C reflux 10 ~ 24 hours.Slightly cool in backward reactor and add 150ml acetone as suspension agent, Removal of catalyst while hot, distillation carries out recrystallization except adding 200ml dehydrated alcohol after desolventizing, crystallize out is iminostilbene finished product, be weighed as 31.8g after drying, yield is 80.4%, and product purity is 99.68%(GC).
Embodiment 6: to heating, stir and reflux reactor in add 40g iminodibenzyl, 20ml Ortho Nitro Toluene, 3.0g10% palladium-carbon catalyst, at 210 ~ 240 DEG C reflux 10 ~ 24 hours.Slightly cool in backward reactor and add 150ml acetone as suspension agent, Removal of catalyst while hot, distillation carries out recrystallization except adding 200ml dehydrated alcohol after desolventizing, crystallize out is iminostilbene finished product, be weighed as 32.4g after drying, yield is 81.9%, and product purity is 99.72%(GC).
Claims (10)
1. a single step synthetic method for iminostilbene, is characterized in that, is raw material with iminodibenzyl, through catalytic dehydrogenation one-step synthesis iminostilbene in liquid-phase system, said method comprising the steps of:
(1) in the reactor with heated and stirred and reflux, add iminodibenzyl, catalyzer and hydrogen acceptor, under nitrogen protection atmosphere, electrically heated is to reflux state, stirs maintenance 10 ~ 22 hours;
(2) be cooled to after below 40 DEG C, add suspension agent, to be heated to after reflux state Removal of catalyst while hot, filtrate distillation cools except after desolventizing, and the solvent cycle after distillation uses;
(3) in filtrate, add recrystallization solvent, be heated to all dissolve rear cooling, after crystallize out filtration drying, obtain iminostilbene finished product.
2. the synthetic method according to claims 1, is characterized in that described catalyzer is noble metal catalyst, is selected from palladium, platinum catalyst.
3. the synthetic method according to claims 1 or 2, is characterized in that described support of the catalyst is gac.
4. the synthetic method according to claims 1 and 2, is characterized in that the activity component load quantity of described catalyzer is 3 ~ 10%.
5. the synthetic method according to claims 1, is characterized in that described hydrogen acceptor is Ortho Nitro Toluene, dimethyl maleate.
6. the synthetic method according to claims 1, it is characterized in that reaction is carried out under nitrogen atmosphere, temperature of reaction is 200 ~ 240 DEG C.
7. the synthetic method according to claims 1, is characterized in that the mol ratio of raw material iminodibenzyl, catalyzer and hydrogen acceptor is 1:0.5 ~ 3.0:0.05 ~ 0.2.
8. the synthetic method according to claims 1, is characterized in that the mol ratio of raw material iminodibenzyl, catalyzer and hydrogen acceptor is 1:0.5 ~ 1.0:0.08 ~ 0.16.
9. the synthetic method according to claims 1, is characterized in that described suspension agent is toluene, acetone, ethyl acetate, DMF.
10. the synthetic method according to claims 1, is characterized in that described recrystallization solvent is methyl alcohol, ethanol, Virahol, toluene, benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410496618.1A CN105439954A (en) | 2014-09-25 | 2014-09-25 | One-step synthesis method of iminostilbene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410496618.1A CN105439954A (en) | 2014-09-25 | 2014-09-25 | One-step synthesis method of iminostilbene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105439954A true CN105439954A (en) | 2016-03-30 |
Family
ID=55550653
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410496618.1A Pending CN105439954A (en) | 2014-09-25 | 2014-09-25 | One-step synthesis method of iminostilbene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105439954A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111217751A (en) * | 2020-03-16 | 2020-06-02 | 浙江华洲药业有限公司 | Synthesis method of iminostilbene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0237952A1 (en) * | 1986-03-14 | 1987-09-23 | Orion-Yhtymä Oy Fermion | Process for the preparation of 5H-Dibenzo-(b, f)-azepine |
| EP0396134A1 (en) * | 1989-05-04 | 1990-11-07 | Alkaloida Vegyeszeti Gyar | Process for the preparation of 5H-dibenz (b,f) azepines |
| CN102120729A (en) * | 2011-01-30 | 2011-07-13 | 华东理工大学 | Industrial method for producing iminostilbene through catalytic dehydrogenation of iminodibenzyl |
| CN102432538A (en) * | 2011-10-25 | 2012-05-02 | 华东理工大学 | Integrated industrial production method for producing iminostilbene by continuous catalytic deamination and catalytic dehydrogenation of 2,2'-diamino-bibenzyl |
-
2014
- 2014-09-25 CN CN201410496618.1A patent/CN105439954A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0237952A1 (en) * | 1986-03-14 | 1987-09-23 | Orion-Yhtymä Oy Fermion | Process for the preparation of 5H-Dibenzo-(b, f)-azepine |
| EP0396134A1 (en) * | 1989-05-04 | 1990-11-07 | Alkaloida Vegyeszeti Gyar | Process for the preparation of 5H-dibenz (b,f) azepines |
| CN102120729A (en) * | 2011-01-30 | 2011-07-13 | 华东理工大学 | Industrial method for producing iminostilbene through catalytic dehydrogenation of iminodibenzyl |
| CN102432538A (en) * | 2011-10-25 | 2012-05-02 | 华东理工大学 | Integrated industrial production method for producing iminostilbene by continuous catalytic deamination and catalytic dehydrogenation of 2,2'-diamino-bibenzyl |
Non-Patent Citations (1)
| Title |
|---|
| VILMOS GALAMB，等: "5H-Dibenz[b,f]azepines. Part 6. Kinetics of palladium-catalyzed transfer dehydrogenation of 10,11-dihydro-5H-dibenz[b,f]azepine", 《JOURNAL OF CHEMICAL RESEARCH, SYNOPSES》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111217751A (en) * | 2020-03-16 | 2020-06-02 | 浙江华洲药业有限公司 | Synthesis method of iminostilbene |
| CN111217751B (en) * | 2020-03-16 | 2021-06-08 | 浙江华洲药业有限公司 | Synthesis method of iminostilbene |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kantevari et al. | HClO4–SiO2 and PPA–SiO2 catalyzed efficient one-pot Knoevenagel condensation, Michael addition and cyclo-dehydration of dimedone and aldehydes in acetonitrile, aqueous and solvent free conditions: Scope and limitations | |
| Azizi et al. | Multicomponent domino reactions in deep eutectic solvent: An efficient strategy to synthesize multisubstituted cyclohexa-1, 3-dienamines | |
| ES2338664T3 (en) | NEW SYNTHESIS PROCEDURE OF (7-METOXI-1-NAFTIL) ACETONITRILE AND ITS APPLICATION TO THE SYNTHESIS OF AGOMELATIN. | |
| Wang et al. | A simple and clean procedure for the synthesis of polyhydroacridine and quinoline derivatives: Reaction of Schiff base with 1, 3-dicarbonyl compounds in aqueous medium | |
| CN108659041B (en) | Phosphine ligand compound based on tetramethyl spiroindane skeleton, intermediate thereof, preparation method and application | |
| Kanamathareddy et al. | Calixarenes: selective functionalization and bridge building | |
| Srivastava et al. | Direct sulfonylation of Baylis–Hillman alcohols and diarylmethanols with TosMIC in ionic liquid-[Hmim] HSO4: an unexpected reaction | |
| CN107235891B (en) | Preparation method of 4-bromocarbazole | |
| CN105439954A (en) | One-step synthesis method of iminostilbene | |
| CN115403577B (en) | Synthesis method of carboxyl azaindole | |
| CN105566223A (en) | Crude iminostilbene product recrystallization method | |
| Prasad et al. | Synthesis of functionalized carbamates and quinones via sequential oxidation of salicylaldehydes using TBHP as the oxidant | |
| CN113004233B (en) | Compound for preparing PRC2 inhibitor, preparation method and application thereof | |
| CN114644663A (en) | Chiral tridentate nitrogen phosphine ligand and application thereof in asymmetric hydrogenation reaction of ketone | |
| JPWO2007063974A1 (en) | Method for adding hydrogen to aromatic ring of aromatic ring compound | |
| WO2013153957A1 (en) | Method for producing hydrogenated biphenol | |
| WO2021242807A1 (en) | Methods for preparing methyl (s)-2-amino-3-(4-(2,3-dimethylpyridin-4-yl)phenyl)propionate and hydrochloric acid salts thereof | |
| CN102432486A (en) | Synthesis method of 1,3-propanediol-bis(4-nitrobenzoic acid)ester | |
| CN107954960B (en) | Synthetic method of 1,3-dihydroisobenzofuran compound | |
| CN104478779A (en) | Novel synthesis method of nootropic piracetam | |
| CN115477631B (en) | Synthesis method of compound containing dimethyl enol group | |
| Jiang et al. | Doebner condensation in ionic liquids [Bmim] BF4 and [Bpy] BF4 to synthesize α, β-unsaturated carboxylic acid | |
| CN103570606A (en) | Method for preparing carbazole and vinyl carbazole | |
| CN115093308B (en) | Synthesis method of 1-bromo-4-phenyl naphthalene | |
| EP2876108B1 (en) | Compounds of chiral aromatic spiroketal diphosphine ligands, preparation methods and uses thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160330 |
|
| RJ01 | Rejection of invention patent application after publication |