Process for the preparation of optical antipode of vincamine and new indole derivatives
阅读：652发布：2023-07-29
专利汇可以提供Process for the preparation of optical antipode of vincamine and new indole derivatives专利检索，专利查询，专利分析的服务。并且A process is described for the preparation of the optical antipode of vincamine from (+)-vincadifformine. The process comprises (i) oxidation with a per-compound to form (+)-N-oxyvincadifformine, (ii) oxidation of the latter with a per-compound to form (+)-1,2-dehydro-16-carbomethoxy-16-hydroxy-N-oxyaspidospermidine, and (iii) reducing the latter with a reducing agent for the N-oxy group in acidic medium, whereby reduction and rearrangement simultaneously occur to give a mixture of the optical antipodes of vincamine, 16-epi-vincamine, and apovincamine, which can be separated into its constituents. The products of steps (i) and (ii) are novel and other analogous novel compounds are obtained by reactions with (+)vincadifformine, which analogous compounds can also be rearranged in acidic medium to form a mixture of the optical antipodes of vincamine, 16-epi-vincamine and apo-vincamine.，下面是Process for the preparation of optical antipode of vincamine and new indole derivatives专利的具体信息内容。
1. A PROCESS FOR THE PREPARATION OF THE OPTICAL ANTIPODE OF VINCAMINE, WHICH COMPRISES THE STEPS OF: A. OXIDIZING (+)-VINCADIFFORMINE WIH A PERACID UNDER NITROGEN, IN THE ABSENCE OF LIGHT AND IN THE PRESENCE OF A WATER-IMMISCIBLE SOLVENT SELECTED FROM THE GROUP CONSISTING OF AROMATIC SOLVENTS, ALIPHATIC CHLORINATED HYDROCARBONS AND ETHER FOR A TIME AT LEAST SUFFICIENT FOR PRODUCING (+)-1,2-DEHYDRO-16-CARBOMETHOXY-16-HYDROXY-NOXYASPIDOSPERMIDINE, AND B. REDUCING THE (+)-1,2-DEHYDRO-16-CARBOMETHOXY-16HYDROXY-N-OXYASPIDOSPERMIDINE OF STEP (A) IN THE PRESENCE OF A LIQUID LOW MOLECULAR WEIGHT ORGANIC ACID WITH TRIPHENYLPHOSPHINE FOR A TIME AT LEAST SUFFICIENT FOR FORMING A PRODUCT COMPRISING A MIXTURE OF THE OPTICAL ANTIPODES OF:
1. VICAMINE, 2. 16-EPI-VICAMINE, AND
2. 16-epi-vicamine, and
2. 16-epi-vincamine, and
2. The process of claim 1 which comprising oxidizing (+) vincadifformine with an equal molar quantity of a peracid for a time at least sufficient to produce (+)-N-oxy-vincadifformine and then treating the (+)-N-oxy-vincadifformiNe with an equal molar quantity of a peracid for a time at least sufficient to produce the (+)-1,2-dehydro-16-carbomethoxy-16-hydroxy-N-oxyaspidospermidine.
3. The process of claim 2 which comprises treating the (+)-N-oxy-vincadifformine with an equimolar quantity of a peracid for 1 to 5 days.
3. apo-vincamine.
3. apo-vincamine.
3. APO-VINCAMINE.
4. The process of claim 1 which further comprises isolating the optical antipode of vincamine from the mixture by crystallization from a member selected from the group of acetone, methanol, ethanol and propanol.
5. The process of claim 4 wherein the products of step (b) are separated into fractions by a plurality of successive crystallizations.
6. The process of claim 1 which further comprises isolating the optical antipode of vincamine from the mixture by chromatography with aluminum-oxide and then crystallization from acetone.
7. The process of claim 6 wherein the product mixture of step (b) is separated by chromatography into two fractions wherein the more polar fraction consisting essentially to a major extent of said antipode of vincamine and to a minor extent of the optical antipode of 16-epi-vincamine and the less polar fraction consisting essentially of the optical antipode of apo-vincamine, and wherein the constituents of the more polar fraction are separated by crystallization.
8. The process of claim 1 which comprises reducing the (+)-1,2-dehydro-16-carbomethoxy-16-hydroxy-N-oxyaspidospermidine with an approximately equimolar quantity of the reducing agent in solution in a liquid organic acid of low molecular weight at an elevated temperature for 1 to 2 hours under nitrogen.
9. The process of claim 1 which comprises oxidizing (+)-vincadifformine with about two molar equivalents of a peroxide for a time at least sufficient to form the (+)-1,2-dehydro-16-carbomethoxy-16-hydroxy-N-oxy-aspidospermidine.
10. The process of claim 1 which comprises oxidizing (+)-vincadifformine with about 2 molar equivalents of a peroxide for 1 to 5 days.
11. A process of claim 1 which comprises oxidizing (+)-vincadifformine for 1 to 5 hours with an equimolar quantity of a peracid at room temperature under nitrogen and in the absence of light.
12. A process of claim 11 which further comprises washing the reaction solution with aqueous alkaline solution to remove the major part of the peracid and its conversion products, and then distilling the reaction solution to obtain a residue containing (+)-N-oxy-vincadifformine.
13. The process of claim 11 which comprises treating the (+)-N-oxy-vincadifformine with an equimolar quantity of a peracid for 1 to 5 days.
14. The process of claim 1 wherein said liquid low molecular weight organic acid is acetic acid.
15. The process of claim 1 wherein said peracid is selected from the group of peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, p-nitroperbenzoic acid, trifluoro-peracetic acid, performic acid and perphthalic acid.
16. A process for the preparation of the optical antipode of vincamine, which comprises the steps of a. oxidizing (+)-vincadifformine with an equal molar quantity of a peracid for about 1 to 5 hours under nitrogen, in the absence of light, and in the presence of a water-immiscible organic solvent selected from the group consisting of aromatic solvents, ethers and chlorinated aliphatic hydrocarbons, to produce (+)-N-oxy-vincadifformine; b. washing the reaction solution with aqueous alkaline solution to remove the major part of the peracid and its conversion products; c. distilling the reaction solution to obtain a residue containing (+)-N-oxy-vincadifformine; d. oxidizing the (+)-N-oxy-vincadifformine with an equal molar quantity of a peracid for between 1 and 5 days under nitrogen, in the absence of light, and in the presence of a water-immiscible organic solvent selected from the group consisting of aromatic solvents, ethers, and chlorinated aliphatic hydrocarbons, to produce (+)-1,2-dehydro-16-carbomethoxy-16-hydroxy-N-oxy-aspidospermidine; e. the peracid of steps (a) and (d) being selected from the group of peracetic acid, perbenzoic acid, m-chloro-perbenzoic acid, p-nitroperbenzoic acid, trifluoroperacetic acid, performic acid and perphthalic acid; f. reducing the (+)-1,2-dehydro-16-carbomethoxy-16-hydroxy-N-oxyaspidospermidine of step (e) with triphenylphosphine in the presence of acetic acid for a time at least sufficient for forming a product comprising a mixture of the optical antipodes of:
17. The process of claim 16 wherein said aqueous alkaline solution is aqueous sodium bicarbonate solution.
| 标题 | 发布/更新时间 | 阅读量 |
|---|---|---|
| 寡核苷酸组合物及其使用方法 | 2020-05-11 | 253 |
| 精密仪器用高耐磨钨合金粉末冶金材料及其制备方法 | 2020-05-08 | 557 |
| 半导体结构及其形成方法 | 2020-05-11 | 829 |
| 电磁波吸收颗粒、电磁波吸收颗粒分散液、电磁波吸收颗粒的制造方法 | 2020-05-11 | 604 |
| 利用含水气流活化硅质载体上的贵金属催化剂 | 2020-05-11 | 422 |
| 一种光驱动制氧型角膜接触镜及其制备方法和应用 | 2020-05-11 | 86 |
| 使用至少一种蓝色、紫色或绿色染料和至少一种二硫化物、硫醇或受保护硫醇荧光染料染色角蛋白材料的方法 | 2020-05-08 | 621 |
| 金属互连结构的形成方法 | 2020-05-08 | 321 |
| 柔性传感器电极制备方法、柔性传感器电极及柔性传感器 | 2020-05-08 | 143 |
| 无外部电压偏置的水溶液中的选择性无电电化学电原子层沉积 | 2020-05-08 | 751 |
高效检索全球专利专利汇是专利免费检索,专利查询,专利分析-国家发明专利查询检索分析平台，是提供专利分析，专利查询，专利检索等数据服务功能的知识产权数据服务商。
我们的产品包含105个国家的1.26亿组数据，免费查、免费专利分析。
分析报告
专利汇分析报告产品可以对行业情报数据进行梳理分析，涉及维度包括行业专利基本状况分析、地域分析、技术分析、发明人分析、申请人分析、专利权人分析、失效分析、核心专利分析、法律分析、研发重点分析、企业专利处境分析、技术处境分析、专利寿命分析、企业定位分析、引证分析等超过60个分析角度，系统通过AI智能系统对图表进行解读，只需1分钟，一键生成行业专利分析报告。
QQ群二维码
意见反馈
意见反馈