CN104177268A - 一种1-[2-氨基-1-(4-甲氧基苯基)乙基]环己醇的制备方法 - Google Patents
一种1-[2-氨基-1-(4-甲氧基苯基)乙基]环己醇的制备方法 Download PDFInfo
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- CN104177268A CN104177268A CN201410483328.3A CN201410483328A CN104177268A CN 104177268 A CN104177268 A CN 104177268A CN 201410483328 A CN201410483328 A CN 201410483328A CN 104177268 A CN104177268 A CN 104177268A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- SUQHIQRIIBKNOR-UHFFFAOYSA-N N,N-didesmethylvenlafaxine Chemical compound C1=CC(OC)=CC=C1C(CN)C1(O)CCCCC1 SUQHIQRIIBKNOR-UHFFFAOYSA-N 0.000 title abstract 2
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 9
- 229910000564 Raney nickel Inorganic materials 0.000 claims abstract description 8
- 230000002829 reductive effect Effects 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 16
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 13
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 4
- ASYJSBPNAIDUHX-UHFFFAOYSA-N 2-(1-hydroxycyclohexyl)-2-(4-methoxyphenyl)acetonitrile Chemical compound C1=CC(OC)=CC=C1C(C#N)C1(O)CCCCC1 ASYJSBPNAIDUHX-UHFFFAOYSA-N 0.000 abstract 1
- 239000007868 Raney catalyst Substances 0.000 abstract 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 239000011345 viscous material Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 7
- 229960004688 venlafaxine Drugs 0.000 description 7
- PNVNVHUZROJLTJ-UHFFFAOYSA-N venlafaxine Chemical compound C1=CC(OC)=CC=C1C(CN(C)C)C1(O)CCCCC1 PNVNVHUZROJLTJ-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000004845 hydriding Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- QZAYGJVTTNCVMB-UHFFFAOYSA-N serotonin Chemical compound C1=C(O)C=C2C(CCN)=CNC2=C1 QZAYGJVTTNCVMB-UHFFFAOYSA-N 0.000 description 2
- 229960002416 venlafaxine hydrochloride Drugs 0.000 description 2
- QYRYFNHXARDNFZ-UHFFFAOYSA-N venlafaxine hydrochloride Chemical compound [H+].[Cl-].C1=CC(OC)=CC=C1C(CN(C)C)C1(O)CCCCC1 QYRYFNHXARDNFZ-UHFFFAOYSA-N 0.000 description 2
- SFLSHLFXELFNJZ-QMMMGPOBSA-N (-)-norepinephrine Chemical compound NC[C@H](O)C1=CC=C(O)C(O)=C1 SFLSHLFXELFNJZ-QMMMGPOBSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical class NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 1
- 229940123445 Tricyclic antidepressant Drugs 0.000 description 1
- RBVIRFFQHJFBBX-UHFFFAOYSA-N aluminum rhodium Chemical compound [Al].[Rh] RBVIRFFQHJFBBX-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 229960002748 norepinephrine Drugs 0.000 description 1
- SFLSHLFXELFNJZ-UHFFFAOYSA-N norepinephrine Natural products NCC(O)C1=CC=C(O)C(O)=C1 SFLSHLFXELFNJZ-UHFFFAOYSA-N 0.000 description 1
- 150000007925 phenylethylamine derivatives Chemical class 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229940076279 serotonin Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000003029 tricyclic antidepressant agent Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种1-[2-氨基-1-(4-甲氧基苯基)乙基]环己醇的制备方法，其特征为将雷尼镍和金属的硼氢化物加入到反应溶剂中，接着加入1-[氰基(对甲氧基苯基)甲基]环己醇，进行加氢反应，反应液经过过滤，减压浓缩干后得淡黄色粘稠物即为反应产物1-[2-氨基-1-(4-甲氧基苯基)乙基]环己醇。本发明具有收率高、纯度好、成本低廉、废水产生少及适合工业化生产的优点。
Description
技术领域
本发明涉及一种1-[2-氨基-1-(4-甲氧基苯基)乙基]环己醇的制备方法，尤其涉及一种盐酸文拉法辛中间体1-[2-氨基-1-(4-甲氧基苯基)乙基]环己醇的制备方法。
背景技术
盐酸文拉法辛(Venlafaxine Hydrochloride) 是一种非三环类抗抑郁药,化学名称为1-[2-二甲氨基-1-(4-甲氧基苯基)乙基]环己醇盐酸盐，其结构式为：
文拉法辛是5-羟色胺，去甲肾上腺素和多巴胺的再摄取抑制剂，具有起效快，不良反应少的优点。而1-[2-氨基-1-(4-甲氧基苯基)乙基]环己醇是文拉法辛制备的关键中间体；
目前的制备方法有1、US4535186报道了一种制备1-[2-氨基-1-(4-甲氧基苯基)乙基]环己醇的方法,该方法以1-[氰基(对甲氧基苯基)甲基]环己醇为原料在催化剂铑-三氧化二铝作用下催化氢化制备，但催化剂铑价格昂贵.不合适大规模工业化生产；
2、中国医药工业杂志2004,35(10) 标题为 盐酸文拉法辛的合成 中报道了用红铝和氯化镍/硼氢化钾作为原料还原剂还原1-[氰基(对甲氧基苯基)甲基]环己醇制备1-[2-氨基-1-(4-甲氧基苯基)乙基]环己醇，这两种方法使用的原料红铝及氯化镍价格比较高消耗量比较大，且后处理产生大量废水。
3、CN1847219A标题为“1-[2-氨基-1-(4-甲氧基苯基)乙基]环己醇甲酸盐的合成方法”，报道了使用四氢铝锂作为还原剂进行还原；CN101503365B标题为“文拉法辛中间体1-［2-氨基-1-(4-甲氧基苯基)乙基］环己醇的制备方法”报道了在单质碘催化下用硼氢化钾或硼氢化钠为原料进行还原反应，此两种方法亦存在上述相同的问题。
4、WO03080560A1标题为Manufacture of phenyl ethyl amine compounds in particular venlafaxine，US2004181093A1标题为Process for preparation of phenethylamine derivatives，WO2007069277A2标题为A process for the preparation of venlafaxine hydrochloride等提到使用雷尼镍为催化剂，在氨/乙醇（甲醇，丁醇）溶剂中，一定压力下催化氢化得到产品，但不是收率偏低就是纯度不高。
发明内容
针对上述缺点，本发明目的在于提供一种收率高、纯度好、成本低廉、废水产生少及适合工业化生产的1-[2-氨基-1-(4-甲氧基苯基)乙基]环己醇的制备方法。
本发明的技术内容为：1-[2-氨基-1-(4-甲氧基苯基)乙基]环己醇的制备方法，其特征为将雷尼镍和金属的硼氢化物加入到反应溶剂中，接着加入1-[氰基(对甲氧基苯基)甲基]环己醇，氮气置换三次，氢气置换三次，加氢至0.5～5Mpa，于10～40℃反应，通过HPLC检测1-[氰基(对甲氧基苯基)甲基]环己醇无即反应结束；氮气置换，反应液经过过滤，减压浓缩干后得淡黄色粘稠物即为反应产物1-[2-氨基-1-(4-甲氧基苯基)乙基]环己醇；
其中反应溶剂为甲醇或乙醇或异丙醇，金属的硼氢化物为硼氢化钠或硼氢化钾；
雷尼镍用量为1-[氰基(对甲氧基苯基)甲基]环己醇重量的20%～200%，硼氢化物用量为1-[氰基(对甲氧基苯基)甲基]环己醇重量的1%～10%，溶剂用量为1-[氰基(对甲氧基苯基)甲基]环己醇重量的的4～20倍。
本发明的反应式为：
本发明中金属硼氢化物不是作为原料还原剂而是作为催化剂。
本发明与现有技术相比所具有的优点为：本发明使用雷尼镍和金属硼氢化物作为复合催化剂，其后处理简便，雷尼镍可回收套用，产物收率高，纯度好，生产成本低廉，废水产生少，适合工业化生产。
具体实施方式
例1、
向1L氢化釜中依次加入400克甲醇、30克雷尼镍、2克硼氢化钠以及50克1-[氰基(对甲氧基苯基)甲基]环己醇，氮气置换三次，氢气置换3次，然后加氢至1Mpa开始氢化，保持温度为20-30℃，加氢约5小时，HPLC检测原料1-[氰基(对甲氧基苯基)甲基]环己醇无即反应完毕，氮气置换，料液经过过滤，减压浓缩干后得淡黄色粘稠物即1-[2-氨基-1-(4-甲氧基苯基)乙基]环己醇50克，摩尔收率98.4%，纯度97.8%。
例2
向1L氢化釜中依次加入400克乙醇、40克雷尼镍、3克硼氢化钾以及50克1-[氰基(对甲氧基苯基)甲基]环己醇，氮气置换三次，氢气置换3次，然后加氢至1Mpa开始氢化，保持温度为20-30℃，加氢约5小时，HPLC检测原料1-[氰基(对甲氧基苯基)甲基]环己醇无即反应完毕，氮气置换，料液经过过滤，减压浓缩干后得淡黄色粘稠物即1-[2-氨基-1-(4-甲氧基苯基)乙基]环己醇50.5克，摩尔收率99.3%，纯度98.1%。
Claims (1)
1.一种1-[2-氨基-1-(4-甲氧基苯基)乙基]环己醇的制备方法，其特征为将雷尼镍和金属的硼氢化物加入到反应溶剂中，接着加入1-[氰基(对甲氧基苯基)甲基]环己醇，氮气置换三次，氢气置换三次，加氢至0.5～5Mpa，于10～40℃反应，通过HPLC检测1-[氰基(对甲氧基苯基)甲基]环己醇无即反应结束；氮气置换，反应液经过过滤，减压浓缩干后得淡黄色粘稠物即为反应产物1-[2-氨基-1-(4-甲氧基苯基)乙基]环己醇；
其中反应溶剂为甲醇或乙醇或异丙醇，金属的硼氢化物为硼氢化钠或硼氢化钾；
雷尼镍用量为1-[氰基(对甲氧基苯基)甲基]环己醇重量的20%～200%，硼氢化物用量为1-[氰基(对甲氧基苯基)甲基]环己醇重量的1%～10%，溶剂用量为1-[氰基(对甲氧基苯基)甲基]环己醇重量的的4～20倍。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112159330A (zh) * | 2020-09-28 | 2021-01-01 | 苏州第四制药厂有限公司 | 一种盐酸文拉法辛中间体的制备方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810766A (zh) * | 2006-01-04 | 2006-08-02 | 四川大学 | 一种还原腈制备胺的方法 |
| CN101503365A (zh) * | 2009-02-04 | 2009-08-12 | 成都樵枫科技发展有限公司 | 文拉法辛中间体1-［2-氨基-1-(4-甲氧基苯基)乙基］环己醇的制备方法 |
| WO2010046808A2 (en) * | 2008-10-21 | 2010-04-29 | Alembic Limited | A process for the preparation of venlafaxine hydrochloride |
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- 2014-09-22 CN CN201410483328.3A patent/CN104177268B/zh active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810766A (zh) * | 2006-01-04 | 2006-08-02 | 四川大学 | 一种还原腈制备胺的方法 |
| WO2010046808A2 (en) * | 2008-10-21 | 2010-04-29 | Alembic Limited | A process for the preparation of venlafaxine hydrochloride |
| CN101503365A (zh) * | 2009-02-04 | 2009-08-12 | 成都樵枫科技发展有限公司 | 文拉法辛中间体1-［2-氨基-1-(4-甲氧基苯基)乙基］环己醇的制备方法 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112159330A (zh) * | 2020-09-28 | 2021-01-01 | 苏州第四制药厂有限公司 | 一种盐酸文拉法辛中间体的制备方法 |
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