CN103275006B - Method for synthesizing iminostilbene intermediate of carbamazepine - Google Patents
Method for synthesizing iminostilbene intermediate of carbamazepine Download PDFInfo
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- CN103275006B CN103275006B CN201310205428.5A CN201310205428A CN103275006B CN 103275006 B CN103275006 B CN 103275006B CN 201310205428 A CN201310205428 A CN 201310205428A CN 103275006 B CN103275006 B CN 103275006B
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- LCGTWRLJTMHIQZ-UHFFFAOYSA-N 5H-dibenzo[b,f]azepine Chemical compound C1=CC2=CC=CC=C2NC2=CC=CC=C21 LCGTWRLJTMHIQZ-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 18
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 title abstract 2
- 229960000623 carbamazepine Drugs 0.000 title abstract 2
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000000463 material Substances 0.000 claims abstract description 25
- ZSMRRZONCYIFNB-UHFFFAOYSA-N 6,11-dihydro-5h-benzo[b][1]benzazepine Chemical group C1CC2=CC=CC=C2NC2=CC=CC=C12 ZSMRRZONCYIFNB-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 11
- 238000001953 recrystallisation Methods 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 229910001220 stainless steel Inorganic materials 0.000 abstract 1
- 239000010935 stainless steel Substances 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 206010034759 Petit mal epilepsy Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- IEEQFKQCBYZYKE-UHFFFAOYSA-N [Fe].[Yb] Chemical compound [Fe].[Yb] IEEQFKQCBYZYKE-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 208000028683 bipolar I disease Diseases 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000007269 dehydrobromination reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 206010015037 epilepsy Diseases 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- ZSOJHTHUCUGDHS-UHFFFAOYSA-N gadolinium iron Chemical compound [Fe].[Gd] ZSOJHTHUCUGDHS-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 206010044652 trigeminal neuralgia Diseases 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing an iminostilbene intermediate of carbamazepine. The method is characterized by comprising the following steps of: coating a catalyst on the inner wall of a reaction tube, externally heating the reaction tube through infrared ray to increase the temperature of the reaction tube to 300-380 DEG C; introducing an iminodibenzyl material which is molten by preheating and shown in a formula (I) into the reaction tube through hot air, wherein the temperature of the hot air is 110-150 DEG C, the pressure of the hot air is controlled to be 0.05-0.15MPa, air velocity is controlled to be 22-30L/h, and the addition amount of the iminodibenzyl is 7kg/h; introducing the material from the reaction tube to a cooling tower; spraying the material by cold water, thereby obtaining a solid which is not soluble in water; separating the solid and recrystallizing the separated solid to obtain the iminostilbene represented by a formula (II). In the formula (I) and the formula (II), the catalyst is NiO, the total amount of NiO is 1000-2000g, and the reaction tube is made from a stainless steel material.
Description
Technical field
A kind of method that the present invention relates to synthetic Carbamzepine intermediate iminostilbene, belongs to field of medicaments.
Background technology
Iminostilbene is the main intermediate of synthetic Carbamzepine, and Carbamzepine acts on all types epilepsy for the treatment of except petit mal, treatment trigeminal neuralgia and prevention manic depressive illness etc.In the chemical synthesis process of prior art iminostilbene, a kind of technique is the method preparation that adopts bromination, dehydrobromination; Another kind of technique is the technology that adopts catalytic dehydrogenation, for example Chinese patent 101307021, on fixed catalytic bed, fill enough catalyzer, electrically heated makes catalytic bed temperature be increased to 400～600 ℃, by the iminodibenzyl that is preheated to melting by high-pressure water vapor bring into fixed catalytic bed in, material, by after fixed catalytic bed, enters in the receiving trap that water coolant is housed, the mixed solution evaporating water post crystallization obtaining, obtains described iminostilbene crude product; Described catalyst activity composition is the mixture of following 4 kinds of component arbitrary proportions: 1. CaO, 2. SiO
2, 3. ZnO, the 4. alloy of rare earth metal and iron (as gadolinium-iron alloy, ytterbium iron alloy etc.); Described support of the catalyst is potter's clay, and activeconstituents charge capacity is 40～70% (in activeconstituents total masses).Methylene dichloride, ethylene dichloride, chloroform, acetone, benzene,toluene,xylene, the crystallization of chlorobenzene organic solvent for crude reaction.
In these techniques, the first technique is traditional technology, contains bromine impurity, causes last medicine side reaction very large, and processing step is long, produces the three wastes, big for environment pollution.The second technique, makes mixed catalyst trouble, and crystallization organic solvent toxicity used is larger, all belongs to a class, two class organic solvents, and environmental pollution is larger, and temperature of reaction is high, and receiving liquid needs evaporate to dryness, and energy consumption is large.
Summary of the invention
The object of the invention is the shortcoming existing in order to overcome prior art, a kind of simple process is provided, reaction yield is moderate, production cost is low, energy consumption is low, in technological design without waste water, exhaust gas emission, the method for a kind of synthetic Carbamzepine intermediate iminostilbene of low-carbon (LC), environmental protection.
The technical scheme of the method for a kind of synthetic Carbamzepine intermediate iminostilbene of the present invention is: it is characterized in that: catalyzer is coated with to stain in reaction tube, with infrared rays to reaction tubes external heat, make reaction tube temperature be increased to 300 ~ 380 ℃, by being preheated to the iminodibenzyl material shown in the formula I of melting, by warm air, bring in reaction tubes, 110 ~ 150 ℃ of hot air temperatures, control heat air pressure 0.05 ~ 0.15MPa, control air velocity 22～30L/h, iminodibenzyl add-on is 7kg/h, material enters in cooling tower after by reaction tubes, with cold water, spray, obtain and water-insoluble solids, recrystallization after separated, obtain the iminostilbene shown in formula II,
（Ⅰ） （Ⅱ）
Described catalyzer is NiO, and the total amount of NiO is 1000 ~ 2000g, and described reaction tubes material is that stainless material is made.
The invention discloses a kind of method of synthetic Carbamzepine intermediate iminostilbene, during production, select the reaction tubes of sufficient length, in reaction tube, scribble catalyst NiO, use again infrared heating, at reaction tubes outer wall, wrap the electrothermal tube of infrared rays silicon carbide, make reaction tube temperature be increased to 300～380 ℃, again the material iminodibenzyl (shown in I) that is preheated to melting is brought in reaction tubes by heat of compression air, controlling air velocity 22～30L/h (calculates with iminodibenzyl liquid volume, flow velocity is 0.2 times of air velocity) iminodibenzyl add-on is 7kg/h, material is by after reaction tubes, enter in cooling tower, with cold water, spray, obtain solids, use again anhydrous 99% ethyl alcohol recrystallization of solvent separated, obtain product iminostilbene, isolated water can reenter Sprayer Circulation and use, raw materials recovery is applied mechanically, and described catalyzer is NiO, and the total amount of NiO is 1000 ~ 2000g, and described reaction tubes material is that stainless material is made, and tube inner diameter is 5cm, and length is 6 ~ 10m.
Compared with the prior art, its advantage is this programme: primary first-order equation yield can reach 65%, and recovery raw material is again applied mechanically yield and can be reached 93%, and catalyzer does not need to load, and is coated in reaction tube, and production cost is low; Operational path is advanced, easy to operate, and solvent for use is dehydrated alcohol, and toxicity is little, without waste water, environment is not produced to pollution, recrystallization solvent recovery.
Embodiment
The present invention relates to a kind of method of synthetic Carbamzepine intermediate iminostilbene, its technical characteristics is: catalyzer is coated with to stain in reaction tube, with infrared rays to reaction tubes external heat, make reaction tube temperature be increased to 300 ~ 380 ℃, by being preheated to the iminodibenzyl material shown in the formula I of melting, by warm air, bring in reaction tubes, 110 ~ 130 ℃ of hot air temperatures, control heat air pressure 0.05 ~ 0.15MPa, control air velocity 22～30L/h, iminodibenzyl add-on is 7kg/h, material enters in cooling tower after by reaction tubes, with cold water, spray, obtain and water-insoluble solids, recrystallization after separated, obtain the iminostilbene shown in formula II,
（Ⅰ） （Ⅱ）
Described catalyzer is NiO, and the total amount of NiO is 1000 ~ 2000g, and described reaction tubes material is that stainless material is made.
During production, select the reaction tubes of sufficient length, in reaction tube, scribble catalyst NiO, use again infrared heating, at reaction tubes outer wall, wrap the electrothermal tube of infrared rays silicon carbide, make reaction tube temperature be increased to 300～380 ℃, again the material iminodibenzyl (shown in I) that is preheated to melting is brought in reaction tubes by heat of compression air, controlling air velocity 22～30L/h (calculates with iminodibenzyl liquid volume, flow velocity is 0.2 times of air velocity) iminodibenzyl add-on is 7kg/h, material is by after reaction tubes, enter in cooling tower, with cold water, spray, obtain solids, use again anhydrous 99% ethyl alcohol recrystallization of solvent separated, obtain product iminostilbene, isolated water can reenter Sprayer Circulation and use, raw materials recovery is applied mechanically, and described catalyzer is NiO, and the total amount of NiO is 1000 ~ 2000g, and described reaction tubes material is that stainless material is made, and tube inner diameter is 5cm, and length is 6 ~ 10m.
Embodiment 1, control heat air pressure are 0.05 ~ 0.15MPa, control air velocity 22 ~ 30 l/h, and the iminodibenzyl that is preheated to melting is brought in reaction tubes by warm air, iminodibenzyl add-on is 7kg/h, reaction tube temperature is 350 ℃, and tube length of reaction tube is 6 meters, and catalyzer total amount is 1000g, primary first-order equation yield 63%, use again ethyl alcohol recrystallization, reclaim raw material 34%, after raw material is applied mechanically, total yield of products 90%, purity 98.6%.
Embodiment 2, control heat air pressure are 0.05 ~ 0.15MPa, control air velocity 22 ~ 30 l/h, and the iminodibenzyl that is preheated to melting is brought in reaction tubes by warm air, iminodibenzyl add-on is 7kg/h, reaction tube temperature is 350 ℃, and tube length of reaction tube is 8 meters, and catalyzer total amount is 1500g, primary first-order equation yield 66%, use again ethyl alcohol recrystallization, reclaim raw material 33%, after raw material is applied mechanically, total yield of products 94%, purity 98.8%.
Embodiment 3, control heat air pressure are 0.05 ~ 0.15MPa, control air velocity 22 ~ 30 l/h, and the iminodibenzyl that is preheated to melting is brought in reaction tubes by warm air, iminodibenzyl add-on is 7kg/h, reaction tube temperature is 350 ℃, and tube length of reaction tube is 10 meters, and catalyzer total amount is 2000g, primary first-order equation yield 66%, use again ethyl alcohol recrystallization, reclaim raw material 32%, after raw material is applied mechanically, total yield of products 93.2%, purity 99%.
Compared with the prior art, its advantage is this programme: primary first-order equation yield can reach 65%, and recovery raw material is again applied mechanically yield and can be reached 93%, and catalyzer does not need to load, and is coated in reaction tube, and production cost is low; Operational path is advanced, easy to operate, and solvent for use is dehydrated alcohol, and toxicity is little, without waste water, environment is not produced to pollution, recrystallization solvent recovery.
Claims (2)
1. the method for a synthetic Carbamzepine intermediate iminostilbene, it is characterized in that: catalyzer is coated with to stain in reaction tube, at reaction tubes outer wall, wrap the electrothermal tube of infrared rays silicon carbide, with infrared rays to reaction tubes external heat, reaction tube temperature is 350 ℃, by being preheated to the iminodibenzyl material shown in the formula I of melting, by warm air, bring in reaction tubes, 110 ~ 150 ℃ of hot air temperatures, control heat air pressure 0.05 ~ 0.15MPa, control air velocity 22～30L/h, iminodibenzyl add-on is 7kg/h, material enters in cooling tower after by reaction tubes, with cold water, spray, obtain and water-insoluble solids, use again anhydrous 99% ethyl alcohol recrystallization of solvent separated, isolated water reenters Sprayer Circulation and uses, raw materials recovery is applied mechanically, recrystallization after separated, obtain the iminostilbene shown in formula II,
Described catalyzer is NiO, and the total amount of NiO is 1000 ~ 2000g, and described reaction tubes material is that stainless material is made.
2. the method for a kind of synthetic Carbamzepine intermediate iminostilbene as claimed in claim 1, is characterized in that: described tube inner diameter is 5cm, and length is 6 ~ 10m.
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108863933A (en) * | 2018-06-25 | 2018-11-23 | 江苏鹏鹞药业有限公司 | The method for synthesizing carbamazepine |
| CN111217751B (en) * | 2020-03-16 | 2021-06-08 | 浙江华洲药业有限公司 | Synthesis method of iminostilbene |
| CN115057817B (en) * | 2022-06-15 | 2023-09-08 | 浙江华洋药业有限公司 | Production process of iminostilbene |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3531466A (en) * | 1965-05-14 | 1970-09-29 | Helmut Beschke | Process for the production of iminostilbene |
| EP0237952B1 (en) * | 1986-03-14 | 1991-10-30 | Orion-Yhtymä Oy Fermion | Process for the preparation of 5h-dibenzo-(b, f)-azepine |
| CN1754623A (en) * | 2004-09-30 | 2006-04-05 | 友联有机合成化学有限公司 | Catalyst and its preparation method and use of the said catalyst in 5h-dibenzanthracene-(b,f)-aza |
| CN101307021A (en) * | 2008-07-04 | 2008-11-19 | 浙江工业大学 | Chemical synthesis process for iminostilbene |
| 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 |
-
2013
- 2013-05-29 CN CN201310205428.5A patent/CN103275006B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3531466A (en) * | 1965-05-14 | 1970-09-29 | Helmut Beschke | Process for the production of iminostilbene |
| EP0237952B1 (en) * | 1986-03-14 | 1991-10-30 | Orion-Yhtymä Oy Fermion | Process for the preparation of 5h-dibenzo-(b, f)-azepine |
| CN1754623A (en) * | 2004-09-30 | 2006-04-05 | 友联有机合成化学有限公司 | Catalyst and its preparation method and use of the said catalyst in 5h-dibenzanthracene-(b,f)-aza |
| CN101307021A (en) * | 2008-07-04 | 2008-11-19 | 浙江工业大学 | Chemical synthesis process for iminostilbene |
| 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 |
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| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20231208 Granted publication date: 20141203 Pledgee: Shandong juancheng Rural Commercial Bank Co.,Ltd. Pledgor: Juancheng Yaoshun Textile Co.,Ltd. Registration number: Y2022980001813 |
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| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A method for synthesizing the intermediate of carbamazepine, aminostilbene Effective date of registration: 20231211 Granted publication date: 20141203 Pledgee: Shandong juancheng Rural Commercial Bank Co.,Ltd. Pledgor: Juancheng Yaoshun Textile Co.,Ltd. Registration number: Y2023980070932 |