CN103664961A - 一种西地那非的合成工艺 - Google Patents
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- BNRNXUUZRGQAQC-UHFFFAOYSA-N sildenafil Chemical compound CCCC1=NN(C)C(C(N2)=O)=C1N=C2C(C(=CC=1)OCC)=CC=1S(=O)(=O)N1CCN(C)CC1 BNRNXUUZRGQAQC-UHFFFAOYSA-N 0.000 title abstract description 9
- 238000000034 method Methods 0.000 title abstract description 6
- 229960003310 sildenafil Drugs 0.000 title abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 claims abstract description 6
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- 241000405119 Virga Species 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- -1 ethoxyl Chemical group 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- RVVOSOSBFSYZDM-UHFFFAOYSA-N 4-ethoxy-3-(1-methyl-7-oxo-3-propyl-4h-pyrazolo[4,3-d]pyrimidin-5-yl)benzenesulfonyl chloride Chemical compound CCCC1=NN(C)C(C(N=2)=O)=C1NC=2C1=CC(S(Cl)(=O)=O)=CC=C1OCC RVVOSOSBFSYZDM-UHFFFAOYSA-N 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 abstract 1
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- ZOOGRGPOEVQQDX-KHLHZJAASA-N cyclic guanosine monophosphate Chemical compound C([C@H]1O2)O[P@](O)(=O)O[C@@H]1[C@H](O)[C@H]2N1C(N=C(NC2=O)N)=C2N=C1 ZOOGRGPOEVQQDX-KHLHZJAASA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 102000004861 Phosphoric Diester Hydrolases Human genes 0.000 description 2
- 108090001050 Phosphoric Diester Hydrolases Proteins 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- 238000003825 pressing Methods 0.000 description 1
- 231100000872 sexual dysfunction Toxicity 0.000 description 1
- DEIYFTQMQPDXOT-UHFFFAOYSA-N sildenafil citrate Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O.CCCC1=NN(C)C(C(N2)=O)=C1N=C2C(C(=CC=1)OCC)=CC=1S(=O)(=O)N1CCN(C)CC1 DEIYFTQMQPDXOT-UHFFFAOYSA-N 0.000 description 1
- 229960002639 sildenafil citrate Drugs 0.000 description 1
- 210000002460 smooth muscle Anatomy 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 229940094720 viagra Drugs 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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Abstract
本发明公开了一种西地那非的制备方法，所述西地那非制备方法是采用5-（5-卤磺酰基-2-乙氧基苯基）-1-甲基-3-正丙基-1,6-二氢-7H-吡唑并（4.3-d）嘧啶-7-酮与N-甲基哌嗪反应，所得产物经浓缩后加水析晶直接得到符合药用标准的纯净产物。与现有公开技术相比，该合成工艺具有反应时间短，反应容易，产物不需纯化，产率高等特点。
Description
技术领域
本发明涉及一种治疗性功能障碍的原料药—枸橼酸西地那非的制备方法，属于医药技术领域，特别涉及一种西地那非的生产工艺。
背景技术
西地那非(Sildenafil)的化学名为：5-[2-乙氧基-5-(4-甲基哌嗪-1-磺酰基)苯基]-1-甲基-3-正丙基-1，6-二氢-7H-吡唑并[4，3-d]嘧啶-7-酮。该化合物能选择性抑制cGMP PDE，而不抑制cAMP PDE，早期是一种治疗心血管疾病的原料药物，曾在EP-A-0463756中公开。近年来研究发现，西地那非临床上有治疗男性勃起功能障碍的作用，见WO-A-94／28902和CN1124926A；其作用机理是通过对5型磷酸二酯酶(PDE5)的高度选择性抑制，提高环鸟苷酸(cGMP)水平，增强阴茎释放的NO的作用，使海绵体平滑肌松弛，增加阴茎血流量而勃起，其药物制剂被称为喜勃酮或Viagra。
发明内容
本发明的主要目的在于公开一种新的合成西地那非的方法，该方法具有步骤简单，反应无需后处理，直接得到符合药用的产品。
现有技术中酰氯与胺反应生成酰胺的反应的比较困难，而本专利发明人意外发现，磺酰氯可以很容易与铵盐反应得到磺酰胺，且反应收率很高，不产生副反应。
本发明提供以下技术方案：
一种西地那非的制备方法，包括下述步骤：将5-（5-卤磺酰基-2-乙氧基苯基）-1-甲基-3-正丙基-1,6-二氢-7H-吡唑并（4.3-d）嘧啶-7-酮与N-甲基哌嗪反应，所得产物经浓缩后加水析晶得西地那非。
进一步，5-（5-卤磺酰基-2-乙氧基苯基）-1-甲基-3-正丙基-1,6-二氢-7H-吡唑并（4.3-d）嘧啶-7-酮中的卤磺酰基的卤素为F、Cl、Br、I其中的一种。
进一步，卤磺酰基的卤素为氯。
进一步，将5-（5-氯磺酰基-2-乙氧基苯基）-1-甲基-3-正丙基-1,6-二氢-7H-吡唑并（4.3-d）嘧啶-7-酮加入到乙醇中，降温搅拌，至0℃以下，滴加N-甲基哌嗪，反应3小时，反应完毕将反应液浓缩至干，再加水搅拌析晶；抽滤，水洗，真空干燥，得西地那非。
进一步，真空干燥是在五氧化二磷存在的情况下进行的。
与现有技术相比，本发明的有益效果是：通过酰基氯与铵盐的反应得到磺酰胺，反应选择性好，收率高，不产生副反应。
附图说明：
图1－西地那非红外图谱；
图2－西地那非高效液相色谱测试图谱。
具体实施方式
下面结合试验例及具体实施方式对本发明作进一步的详细描述。但不应将此理解为本发明上述主题的范围仅限于以下的实施例，凡基于本发明内容所实现的技术均属于本发明的范围。
实施例1
本实施例涉及的是5-[2-乙氧基-5-(4-甲基哌嗪-1-磺酰基)苯基]-1-甲基-3-正丙基-1，6-二氢-7H-吡唑并[4，3-d]嘧啶-7-酮的制备方法，具体如下：
将化合物5-（5-氯磺酰基-2-乙氧基苯基）-1-甲基-3-正丙基-1,6-二氢-7H-吡唑并（4.3-d）嘧啶-7-酮7.5g（0.018mol）加入125ml乙醇中，搅拌降温，缓慢滴加N-甲基哌嗪6g，滴完后反应3小时，反应完毕将反应液减压浓缩至干，加水40ml，搅拌析晶，抽滤，滤饼水洗并在五氧化二磷存在下真空干燥，得标题化合物8.2g，收率92%。
测试例
溴化钾压片测试红外图谱见图1。
高效液相色谱测试，精密称取本品约35mg，置50ml量瓶中，加流动相溶解并稀释至刻度，摇匀，作为供试品溶液。精密量取供试品溶液适量，加流动相制成相当于供试品溶液浓度0.1%溶液，作为对照溶液。照含量测定项下的色谱条件，精密量取对照溶液及供试溶液各20ul，分别注入液相色谱仪，记录色谱图至主成分峰保留时间的3倍。供试品溶液中除溶剂和主成分峰外，如显杂质峰（相对保留时间为1.6～1.8），其峰面积不得大于对照溶液主峰面积的3倍（0.3%），如显其他未知杂质峰，其单个杂质峰面积不得大于对照溶液的主峰面积（0.1%），未知杂质峰峰面积的和不得大于对照溶液主峰面积的3倍（0.3%），总杂质峰峰面积的和不得大于对照溶液主峰面积的5倍（0.5%），测试结果见图2。
Claims (5)
1.一种西地那非的制备方法，包括下述步骤：将5-（5-卤磺酰基-2-乙氧基苯基）-1-甲基-3-正丙基-1,6-二氢-7H-吡唑并（4.3-d）嘧啶-7-酮与N-甲基哌嗪反应，所得产物经浓缩后加水析晶得西地那非。
2.根据权利要求1所述的制备方法，其特征在于，5-（5-卤磺酰基-2-乙氧基苯基）-1-甲基-3-正丙基-1,6-二氢-7H-吡唑并（4.3-d）嘧啶-7-酮中的卤磺酰基的卤素为F、Cl、Br、I其中的一种。
3.根据权利要求2所述的制备方法，其特征在于，5-（5-卤磺酰基-2-乙氧基苯基）-1-甲基-3-正丙基-1,6-二氢-7H-吡唑并（4.3-d）嘧啶-7-酮为5-（5-氯磺酰基-2-乙氧基苯基）-1-甲基-3-正丙基-1,6-二氢-7H-吡唑并（4.3-d）嘧啶-7-酮。
4.根据权利要求3所述的制备方法，其特征在于，将5-（5-氯磺酰基-2-乙氧基苯基）-1-甲基-3-正丙基-1,6-二氢-7H-吡唑并（4.3-d）嘧啶-7-酮加入到乙醇中，降温搅拌，至0℃以下，滴加N-甲基哌嗪，反应3小时，反应完毕将反应液浓缩至干，再加水搅拌析晶；抽滤，水洗，真空干燥，得西地那非。
5.根据权利要求4所述的制备方法，其特征在于，真空干燥是在五氧化二磷存在的情况下进行的。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370915A (zh) * | 2014-11-06 | 2015-02-25 | 成都医路康医学技术服务有限公司 | 枸橼酸西地那非的制备方法 |
| CN104940166A (zh) * | 2015-07-23 | 2015-09-30 | 青岛蓝盛洋医药生物科技有限责任公司 | 一种治疗男性阳痿的药物枸橼酸西地那非组合物胶囊 |
| CN104940154A (zh) * | 2015-07-23 | 2015-09-30 | 青岛蓝盛洋医药生物科技有限责任公司 | 一种治疗泌尿外科疾病的药物枸橼酸西地那非组合物片剂 |
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| CN1377884A (zh) * | 2001-03-30 | 2002-11-06 | 杭州中美华东制药有限公司 | 制备西地那非的方法 |
| CN1925860A (zh) * | 2004-01-05 | 2007-03-07 | 特瓦制药工业有限公司 | 制备西地那非碱及其柠檬酸盐的方法 |
| WO2007141805A2 (en) * | 2006-06-05 | 2007-12-13 | Matrix Laboratories Limited | Novel process for the preparation of sildenafil citrate |
-
2013
- 2013-12-18 CN CN201310698852.8A patent/CN103664961B/zh active Active
Patent Citations (3)
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| CN1377884A (zh) * | 2001-03-30 | 2002-11-06 | 杭州中美华东制药有限公司 | 制备西地那非的方法 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370915A (zh) * | 2014-11-06 | 2015-02-25 | 成都医路康医学技术服务有限公司 | 枸橼酸西地那非的制备方法 |
| CN104940166A (zh) * | 2015-07-23 | 2015-09-30 | 青岛蓝盛洋医药生物科技有限责任公司 | 一种治疗男性阳痿的药物枸橼酸西地那非组合物胶囊 |
| CN104940154A (zh) * | 2015-07-23 | 2015-09-30 | 青岛蓝盛洋医药生物科技有限责任公司 | 一种治疗泌尿外科疾病的药物枸橼酸西地那非组合物片剂 |
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