CN116239529B - 一种二氧化碳参与的n-甲基四氢喹啉类生物碱的制备方法 - Google Patents
一种二氧化碳参与的n-甲基四氢喹啉类生物碱的制备方法 Download PDFInfo
- Publication number
- CN116239529B CN116239529B CN202310279156.7A CN202310279156A CN116239529B CN 116239529 B CN116239529 B CN 116239529B CN 202310279156 A CN202310279156 A CN 202310279156A CN 116239529 B CN116239529 B CN 116239529B
- Authority
- CN
- China
- Prior art keywords
- formula
- carbon dioxide
- reaction
- alkaloid
- participation
- 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.)
- Active
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 17
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 16
- PQMWKAXQYMNZOD-UHFFFAOYSA-N 1-methyl-3,4,4a,5-tetrahydro-2h-quinoline Chemical class C1C=CC=C2N(C)CCCC21 PQMWKAXQYMNZOD-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- -1 quinoline compound Chemical class 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910007426 ZnC2 Inorganic materials 0.000 claims 1
- 125000006222 dimethylaminomethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])* 0.000 claims 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 230000000171 quenching effect Effects 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 7
- 238000007069 methylation reaction Methods 0.000 abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 150000003248 quinolines Chemical class 0.000 description 6
- QRYQKXWZOXSQAJ-UHFFFAOYSA-N 2-[2-(1,3-benzodioxol-5-yl)ethyl]-1-methyl-3,4-dihydro-2h-quinoline Chemical compound C1CC2=CC=CC=C2N(C)C1CCC1=CC=C(OCO2)C2=C1 QRYQKXWZOXSQAJ-UHFFFAOYSA-N 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 3
- 238000005580 one pot reaction Methods 0.000 description 3
- KSQZVAWGIAAZHJ-UHFFFAOYSA-N rac-angustureine Natural products C1=CC=C2N(C)C(CCCCC)CCC2=C1 KSQZVAWGIAAZHJ-UHFFFAOYSA-N 0.000 description 3
- 150000003530 tetrahydroquinolines Chemical class 0.000 description 3
- KSQZVAWGIAAZHJ-AWEZNQCLSA-N (2s)-1-methyl-2-pentyl-3,4-dihydro-2h-quinoline Chemical compound C1=CC=C2N(C)[C@@H](CCCCC)CCC2=C1 KSQZVAWGIAAZHJ-AWEZNQCLSA-N 0.000 description 2
- YVBSECQAHGIWNF-UHFFFAOYSA-N N-methyl-1,2,3,4-tetrahydroquinoline Chemical class C1=CC=C2N(C)CCCC2=C1 YVBSECQAHGIWNF-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229930013930 alkaloid Natural products 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- XIKOQBHVYFFYGH-UHFFFAOYSA-N galipeine Chemical compound C1=C(O)C(OC)=CC=C1CCC1N(C)C2=CC=CC=C2CC1 XIKOQBHVYFFYGH-UHFFFAOYSA-N 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 description 2
- LBUJPTNKIBCYBY-UHFFFAOYSA-N tetrahydroquinoline Natural products C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 2
- MBIROIXKTFTFJX-KRWDZBQOSA-N (2s)-2-[2-(3,4-dimethoxyphenyl)ethyl]-1-methyl-3,4-dihydro-2h-quinoline Chemical compound C1=C(OC)C(OC)=CC=C1CC[C@@H]1N(C)C2=CC=CC=C2CC1 MBIROIXKTFTFJX-KRWDZBQOSA-N 0.000 description 1
- HTVBVYGZKUSMHF-UHFFFAOYSA-N 1,2-dimethyl-3,4-dihydro-2h-quinoline Chemical compound C1=CC=C2N(C)C(C)CCC2=C1 HTVBVYGZKUSMHF-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 230000000078 anti-malarial effect Effects 0.000 description 1
- 239000003430 antimalarial agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- MBIROIXKTFTFJX-UHFFFAOYSA-N cuspareine Natural products C1=C(OC)C(OC)=CC=C1CCC1N(C)C2=CC=CC=C2CC1 MBIROIXKTFTFJX-UHFFFAOYSA-N 0.000 description 1
- 230000001472 cytotoxic effect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
本发明公开了一种二氧化碳参与的N‑甲基四氢喹啉类生物碱的制备方法，所述的制备方法以二氧化碳(CO2)和式I所示的喹啉类化合物为起始原料，硼氢化钠为还原剂，氨基吡咯锌化合物为催化剂，常压下实现喹啉类化合物的还原、N‑甲基化反应一步完成，合成N‑甲基‑1,2,3,4‑四氢喹啉类生物碱化合物(式Ⅱ)。本发明方法操作简便，成本较低，同时合成中不需要贵金属的参与，避免了高压反应操作，安全环保，符合绿色化学要求，拥有重要的实用价值和很好的应用前景。
Description
技术领域
本发明属于有机合成药物分子领域，具体涉及一种由二氧化碳制备N-甲基四氢喹啉生物碱类化合物的方法。
背景技术
四氢喹啉类化合物是天然生物碱中重要的组成部分，广泛应用于医药、农药、香料以及精细化学品领域。其中，N-甲基取代的四氢喹啉类化合物在生物活性分子和药物活性分子上具有非常重要意义。如含有N-甲基取代的四氢喹啉结构单元的angustureine,galipeine,galipinine，cuspareine等生物碱表现出优异的抗疟原虫和细胞毒活性，已应用于临床治疗用药。在过去的几十年里，广大科研工作者已开发出许多行之有效的合成方法来制备N-甲基四氢喹啉类化合物，其中，使用甲基化试剂与四氢喹啉类化合物进行反应是最常见的方法之一。
但是，如果以喹啉为起始原料，通过还原、N-甲基化一步合成N-甲基四氢喹啉类化合物，则提供了一种直接而有前景的N-甲基四氢喹啉类化合物制备方法。然而，迄今为止，只有少数的催化体系报道实现喹啉类化合物的N-甲基化合成N-甲基四氢喹啉类化合物。2019年，中国科学院石峰研究员报道在Pd/C催化剂存在下，利用多聚甲醛和氢气一锅还原、N-甲基化喹啉类化合物，合成N-甲基1,2,3,4-四氢喹啉类生物碱化合物。此外，中科院韩布兴院士课题组开发了一种以CO2/H2为甲基化试剂的喹啉N-甲基化的方法，采用均相Ru/三磷配合物为催化剂，在160摄氏度，PCO2/PH2(2/8MPa)压力下，N-甲基1,2,3,4-四氢喹啉类的产率可达99％。
为此，寻求一种在不使用贵金属催化剂、不采用高压反应条件的情况下能实现喹啉类化合物的还原、N-甲基一锅化反应，合成N-甲基1,2,3,4-四氢喹啉类生物碱化合物的方法，势在必行。
发明内容
本发明的目的在于提供一种常压下二氧化碳参与的N-甲基四氢喹啉类生物碱的制备方法，该方法在不使用贵金属催化剂和高压反应条件的情况下能实现喹啉类化合物的还原、N-甲基一锅化反应，合成N-甲基1,2,3,4-四氢喹啉类生物碱化合物。
本发明提供的一种二氧化碳参与的N-甲基四氢喹啉类生物碱的制备方法，包括如下步骤：将硼氢化钠、式I所示喹啉类化合物、氨基吡咯锌化合物依次加入反应釜，抽真空置换二氧化碳2-4次，加入乙腈作为反应溶剂，升温至90-120摄氏度，搅拌20-30小时反应结束后，加入氯化铵水溶液淬灭反应，用乙酸乙酯进行萃取，有机相经合并、无水硫酸钠干燥、浓缩后通过柱色谱分离即得到所述式Ⅱ所示N-甲基四氢喹啉类生物碱化合物。式I、式Ⅱ中，R可以是氢基、或烷基中的任意一种。
其中投料量按摩尔比，式I所示化合物：硼氢化钠＝1：2.5-4。
进一步，所述的烷基可以是甲基、乙基、丁基、戊基、2-(1,3-苯并二氧杂茂基)-乙基等。
与现有技术相比本发明的有益效果：
本发明以喹啉类化合物为起始原料，硼氢化钠为还原剂，氨基吡咯锌化合物为催化剂，常压下实现了喹啉类化合物的还原、N-甲基化反应一步合成N-甲基-1,2,3,4-四氢喹啉类生物碱化合物。
本发明制备方法避免了高温、高压操作，实现了喹啉类化合物的还原、N-甲基化反应一步完成。且不需要贵金属催化剂，条件相对温和、产率高、成本低，产品易分离纯化等优点。
附图说明
图1实施例1制备的N-甲基四氢喹啉的1H NMR图
图2实施例1制备的N-甲基四氢喹啉的13C NMR图
具体实施方式
以下仅仅为详细说明本发明而给出的具体实施例，这些实施例并非用于限制本发明的保护范围。实施例中所使用的实验方法如无特殊说明，均为常规方法。
实施例1
在干燥的25mL反应釜中，依次加入喹啉(0.5mmol)，NaBH4(1.5mmol)，氨基吡咯锌(0.005mmol)，利用真空泵抽真空置换二氧化碳3次，加入乙腈(1mL)作为反应溶剂，反应物在100摄氏度下搅拌24小时。反应结束后，加入氯化铵水溶液淬灭反应，用乙酸乙酯(15mL)进行萃取3次。合并有机相，无水硫酸钠干燥，粗产物经过柱色谱分离纯化，即得到目标化合物(1-甲基-1,2,3,4-四氢喹啉)。产率：98％。1H NMR(600MHz,CDCl3)δ7.07(d,J＝4.1Hz,1H),6.94(s,1H),6.59(s,2H),3.20(s,2H),2.87(s,3H),2.75(s,2H),1.97(s,2H)；13C NMR(151MHz,Chloroform-d)δ146.70,128.78,127.01,122.81,116.16,110.92,51.24,39.10,27.76,22.43.HRMS(ESI,m/z)calcd for C10H14N+:148.1121,found:148.1119.
实施例2
在干燥的25mL反应釜中，依次加入2-甲基喹啉(0.5mmol)，NaBH4(1.5mmol)，氨基吡咯锌(0.006mmol)，利用真空泵抽真空置换二氧化碳3次，加入乙腈(1mL)作为反应溶剂，反应物在110摄氏度下搅拌24小时。反应结束后，加入氯化铵水溶液淬灭反应，用乙酸乙酯(15mL)进行萃取3次。合并有机相，无水硫酸钠干燥，粗产物经过柱色谱分离纯化，即得到目标化合物(1,2-二甲基-1,2,3,4-四氢喹啉)。产率：97％。1H NMR(600MHz,CDCl3)δ7.09(m,1H),6.98(d,1H),6.61-6.55(m,2H),3.47-3.42(m,1H),2.90(s,3H),2.86-2.77(m,1H),2.72(m,1H),2.01(m,1H),1.77(m,1H),1.12(d,3H)；13C NMR(151MHz,Chloroform-d)δ145.42,128.50,127.13,122.11,115.4,110.64,53.79,37.97,28.12,23.72,17.46；HRMS(ESI,m/z)calcd for C11H16N+:162.1277,found:162.1276.
实施例3
在干燥的25mL反应釜中，依次加入2-戊基喹啉(0.5mmol)，NaBH4(2.0mmol)，氨基吡咯锌(0.01mmol)，利用真空泵抽真空置换二氧化碳3次，加入乙腈(1mL)作为反应溶剂，反应物在110摄氏度下搅拌24小时。反应结束后，加入氯化铵水溶液淬灭反应，用乙酸乙酯(15mL)进行萃取3次。合并有机相，无水硫酸钠干燥，粗产物经过柱色谱分离纯化，即得到目标化合物1-甲基-2-戊基-1,2,3,4-四氢喹啉(Angustureine)。产率：94％。1H NMR(600MHz,CDCl3)δ7.10(t,1H),7.06(d,1H),6.60(t,1H),6.51(d,1H),3.22(m,1H),2.92(s,3H),2.81(m,1H),2.65(m,1H),1.93(m,2H),1.57(m,21H),1.30(m,8H),0.86(t,3H)；13C NMR(151MHz,Chloroform-d)δ145.61,128.92,127.32,122.14,115.70,110.52,59.24,38.42,32.23,31.46,25.81,24.62,23.93,22.91,14.54.HRMS(ESI,m/z)calcd for C15H24N+:218.1903,found:218.1900.
实施例4
在干燥的25mL反应釜中，依次加入2-(2-乙基-1,3-苯并二氧杂茂)基喹啉(0.5mmol)，NaBH4(2.2mmol)，氨基吡咯锌(0.01mmol)，利用真空泵抽真空置换二氧化碳3次，加入乙腈(1mL)作为反应溶剂，反应物在110摄氏度下搅拌30小时。反应结束后，加入氯化铵水溶液淬灭反应，用乙酸乙酯(15mL)进行萃取3次。合并有机相，无水硫酸钠干燥，粗产物经过柱色谱分离纯化，即得到目标化合物2-(2-乙基-1,3-苯并二氧杂茂基)-1,2,3,4-四氢喹啉(Galipinine)。产率：91％。1H NMR(600MHz,CDCl3)δ7.10(t,1H),6.97(d,1H),6.73(d,1H),6.70(s,1H),6.62(m,2H),6.54(d,1H),5.92(s,2H),3.25(m,1H),2.91(s,3H),2.82(m,1H),2.65(m,2H),2.50(m,1H),1.91(m,3H),1.68(m,1H)；13C NMR(151MHz,Chloroform-d)δ147.61,145.59,145.29,135.82,128.67,127.10,121.71,120.93,115.42,110.59,108.57,108.16,100.76,58.21,38.05,33.13,32.04,24.35,23.54.HRMS(ESI,m/z)calcdfor C19H22NO2 +:296.1645,found:296.1643.
Claims (3)
1.一种二氧化碳参与的N-甲基四氢喹啉类生物碱的制备方法，其特征在于，包括如下步骤：将硼氢化钠、式I所示喹啉类化合物、氨基吡咯锌化合物依次加入反应釜，抽真空置换二氧化碳2-4次，加入乙腈作为反应溶剂，升温至90-120摄氏度，搅拌20-30小时反应结束后，加入氯化铵水溶液淬灭反应，用乙酸乙酯进行萃取，有机相经合并、无水硫酸钠干燥、浓缩后通过柱色谱分离即得到式Ⅱ所示四氢喹啉类生物碱化合物；
所述式I、式Ⅱ的结构式如下：
式I、式Ⅱ中的R是氢基，烷基中的任意一种，或2-(1,3-苯并二氧杂茂基)-乙基；
所述氨基吡咯锌化合物的分子式为：[C4H2N(2,5-CH2NMe2)2]ZnC2H5。
2.如权利要求1所述的一种二氧化碳参与的N-甲基四氢喹啉类生物碱的制备方法，其特征在于，所述的烷基是甲基、乙基、丁基或戊基。
3.如权利要求1所述的一种二氧化碳参与的N-甲基四氢喹啉类生物碱的制备方法，其特征在于，反应步骤中投料量按摩尔比,式I所示化合物：硼氢化钠＝1：2.5-4。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310279156.7A CN116239529B (zh) | 2023-03-21 | 2023-03-21 | 一种二氧化碳参与的n-甲基四氢喹啉类生物碱的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310279156.7A CN116239529B (zh) | 2023-03-21 | 2023-03-21 | 一种二氧化碳参与的n-甲基四氢喹啉类生物碱的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116239529A CN116239529A (zh) | 2023-06-09 |
| CN116239529B true CN116239529B (zh) | 2024-05-24 |
Family
ID=86627802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310279156.7A Active CN116239529B (zh) | 2023-03-21 | 2023-03-21 | 一种二氧化碳参与的n-甲基四氢喹啉类生物碱的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116239529B (zh) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1390991A (en) * | 1971-09-07 | 1975-04-16 | Material Vegyi Kisipari Szovet | Dihydroquinoline derivatives |
| CN104231234A (zh) * | 2014-09-26 | 2014-12-24 | 山西大学 | 氨基吡咯锌锂双金属催化剂及其制备方法和应用 |
| CN105237342A (zh) * | 2015-11-06 | 2016-01-13 | 河北师范大学 | 一种催化氢化羧酸酯还原制备醇的方法 |
| CN111675677A (zh) * | 2020-07-13 | 2020-09-18 | 江苏富比亚化学品有限公司 | 一种n-甲基吗啉的合成工艺 |
| CN113773206A (zh) * | 2021-09-06 | 2021-12-10 | 山西大学 | 一种二氧化碳参与的布替萘芬的制备方法 |
| CN115368259A (zh) * | 2022-09-30 | 2022-11-22 | 南京理工大学 | 一种n-(4-甲基苯基)甲酰胺及其制备方法 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005026165A1 (en) * | 2003-09-12 | 2005-03-24 | Warner-Lambert Company Llc | Quinolone antibacterial agents |
-
2023
- 2023-03-21 CN CN202310279156.7A patent/CN116239529B/zh active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1390991A (en) * | 1971-09-07 | 1975-04-16 | Material Vegyi Kisipari Szovet | Dihydroquinoline derivatives |
| CN104231234A (zh) * | 2014-09-26 | 2014-12-24 | 山西大学 | 氨基吡咯锌锂双金属催化剂及其制备方法和应用 |
| CN105237342A (zh) * | 2015-11-06 | 2016-01-13 | 河北师范大学 | 一种催化氢化羧酸酯还原制备醇的方法 |
| CN111675677A (zh) * | 2020-07-13 | 2020-09-18 | 江苏富比亚化学品有限公司 | 一种n-甲基吗啉的合成工艺 |
| CN113773206A (zh) * | 2021-09-06 | 2021-12-10 | 山西大学 | 一种二氧化碳参与的布替萘芬的制备方法 |
| CN115368259A (zh) * | 2022-09-30 | 2022-11-22 | 南京理工大学 | 一种n-(4-甲基苯基)甲酰胺及其制备方法 |
Non-Patent Citations (5)
| Title |
|---|
| An efficient one pot transfer hydrogenation and N-alkylation of quinolines with alcohols mediated by Pd/C/Zn;Belén Abarca et al.;《Organic & Biomolecular Chemistry》;20121231;第10卷;1826–1833 * |
| Benzimidazolylidene-Stabilized Borenium Ion for Catalytic Hydrogenation of N‑Heterocycles;Subir Maji et al.;《Inorganic Chemistry》;20220901;第61卷;14282−14287 * |
| N-methylation of quinolines with CO2 and H2 catalyzed by Ru-triphos complexes;Zhenhong He et al.;《SCIENCE CHINA Chemistry》;20170731;第60卷(第7期);927-933 * |
| Recent advances on oxazolidinones synthesize from carbon dioxide;WANG Bian-ling et al.;《燃 料 化 学 学 报 （中 英 文）》;20230131;第51卷(第1期);85-100 * |
| 硼氢化试剂在二氧化碳还原官能化 反应中的研究进展;郭志强 等;《高等学校化学学报》;20221231;第43卷(第7期);1-20 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116239529A (zh) | 2023-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101855611B1 (ko) | (r,s)-니코틴의 제조 방법 | |
| CN112300212A (zh) | 硼烷-吡啶络合物在制备nk-1受体拮抗剂中的用途 | |
| CN116239529B (zh) | 一种二氧化碳参与的n-甲基四氢喹啉类生物碱的制备方法 | |
| CA2368815A1 (en) | Novel synthesis and crystallization of piperazine ring-containing compounds | |
| WO2024045292A1 (zh) | 一种采用固载镍与有机碱组合催化工业化生产氘代医药中间体的方法 | |
| CN114249796B (zh) | 一种卡非佐米关键中间体杂质及其制备方法 | |
| CZ285139B6 (cs) | Způsob přípravy 6,9-bis[(2-aminoethyl)amino]benzo[g]isochinolin-5,10-diodimaleátu | |
| JPH03232888A (ja) | 新規なカンプトテシン誘導体 | |
| CN114181117B (zh) | 一种帕拉米韦中间体的制备方法 | |
| CN112552345A (zh) | 一种nk-1受体拮抗剂的制备方法 | |
| US20030088094A1 (en) | Novel synthesis and crystallization of piperazine ring-containing compounds | |
| CN111909098A (zh) | 六氢-5H-苯并[d]咪唑-5-酮类衍生物及其制备方法和应用 | |
| CN111440181A (zh) | 含喹啉结构的二吡唑并七元氧杂环类化合物及其合成方法 | |
| CN115385777B (zh) | 一种基于硼氢化钠还原生成的醇的纯化方法 | |
| WO1998017649A1 (en) | Process for the preparation of n-[2-(dimethylamino)ethyl]acridine-4-carboxamide | |
| CN114437050B (zh) | 一种用于常山酮中间体的脱保护剂及其应用 | |
| CN109810042B (zh) | 一种不对称双吲哚甲烷及其衍生物的制备方法 | |
| CN116478051B (zh) | 一种贝洛替康盐酸盐及其关键中间体的制备方法 | |
| CN112521298B (zh) | 一种利多卡因的合成方法 | |
| CN108558878B (zh) | 一种喹叨啉及其衍生物的合成工艺 | |
| CN110627672B (zh) | 一种磷酸二甲啡烷及其中间体的制备方法 | |
| US20030135043A1 (en) | Novel synthesis and crystallization of piperazine ring-containing compounds | |
| CN113354652A (zh) | 一种盐酸纳美芬合成方法 | |
| CN117142976A (zh) | 一种adc药物毒素伊沙替康关键中间体的制备方法 | |
| CN115490743A (zh) | 一种高立体选择性制备贝塔沙龙的方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |