CN109422634B - 一种3-羰基茚酮类化合物的合成方法 - Google Patents
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- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
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Abstract
本发明提供了一种3‑羰基茚酮类化合物的制备方法。所述合成方法是以式(I)所示的二炔化合物为原料,在金属铜参与的条件下,以Selectcfluor为氧化剂,乙腈为溶剂,在25℃的条件下反应6‑12小时,制备得到式(Ⅱ)茚酮类化合物。本发明的合成方法具有对环境危害小,反应条件相对温和,节约能源消耗,产物选择性高,操作简便等特点。
Description
技术领域
本发明涉及一种有机化合物的合成方法,具体地说涉及与一种3-羰基茚酮类化合物的合成方法。
背景技术
茚酮是天然产物中的重要结构,广泛地存在于染料、医药、农药等化合物分子结构当中。此外,3-羰基茚酮类化合物是一类含多种生物活性的有机化合物。目前发现包括茚酮结构的天然产物有100多种有药物活性,最具有代表性的天然产物为从海洋海藻青菌中分离纯化得到的Pterosin B、Pterosin C,含有茚酮结构或相关结构的药物分子会表现出其生物活性。例如平滑肌松弛活性、环氧化酶抑制活性等。目前Friedel-Crafts环化法是制备3-羰基茚酮类化合物的主要途径。但是,传统的Friedel-Crafts环化法对芳香酮的制备受芳环上的取代基影响较大,当芳环上有强吸电子基团(如硝基、羰基等)时,不发生该反应。从而使得反应原料受限,底物普适性差。同时工业制备3-羰基茚酮类化合物时产生大量的废酸和含有机物的酸性废水而导致环境污染,增加了治理费用,另外该方法的选择性差,造成原材料的浪费,并存在多种副反应,导致总体产率不高。
目前文献报道了许多改进的Friedel-Crafts环化法制备3-羰基茚酮类化合物以及Nazarov环化法、多聚磷酸(PPA)环化法、Pinacol重排法等等。但这些方法体系中均需要贵金属参与反应,且后处理均相对较麻烦,产生较多的废酸,对环境影响较大,产率也不高。因此,因此,鉴于3-羰基茚酮类化合物在药物化学和有机精细化工生产方面的重要应用,探索一种简便、高效茚酮类化合物的合成方法是具有重要意义的。
发明内容
针对现有技术存在的不足,本发明旨在提供一种制备3-羰基茚酮类化合物的方法,克服现有技术的缺点,在低价金属铜参与的条件下,在室温的温度下制备得到3-羰基茚酮类化合物。
为了达到上述发明目的,本发明采用的技术方案是:
一种制备式(Ⅱ)所示的3-羰基茚酮类化合物的方法:以式(Ⅰ)所示的二炔类化合物为起始原料,在金属铜为催化剂条件下,以Selectcfluor为氧化剂,于溶剂中,在20~80℃的反应温度下反应5~48小时,反应液经分离纯化制备得到式(Ⅱ)所示的3-羰基茚酮类化合物;
式(Ⅰ)或式(Ⅱ)中,R为H、甲基、溴、丙基中的一种。
反应式如下:
本发明使用的原料式(Ⅰ)所示的二炔类化合物,本领域技术人员可以根据现有文献公开的方法自行制备。
本发明所述的反应是在铜的参与下,其特点是价廉易得,低毒高效,且无需额外配体辅助。所述金属铜为粉末状,其物质的量为式(Ⅰ)所示的二炔类化合物物质的量的1-10%,优选为5%。
本发明所述的氧化剂为Selectcfluor(1-氯甲基-4-氟-1,4-重氮化二环2.2.2辛烷双(四氟硼酸))。所述Selectcfluor的物质的量为式(Ⅰ)所示的二炔类化合物物质的量的100%~200%,优选为120%。
本发明所述的有剂为乙腈、硝基甲烷、水、甲苯、四氢呋喃或N,N-二甲基甲酰胺中的一种或两种,优选乙腈为溶剂。
进一步,所述溶剂体积以式(Ⅰ)所示的二炔类化合物的物质的量计为10~30mL/mmol。
本发明所述的反应,优选在25℃条件下进行,反应时间优选为12小时。
进一步,本发明所述的后处理为:反应液中加入柱层析硅胶,并通过减压蒸馏除去溶剂,再通过柱色谱分离,以石油醚与乙酸乙酯体积比为30:1的混合液作为洗脱剂洗脱,收集含目标产物的洗脱液,蒸除溶剂得到式(Ⅱ)所示的3-羰基茚酮类化合物。
更进一步,所述的柱层析硅胶为100~200目;所述柱层析硅胶的质量以式(Ⅰ)所示的二炔类化合物的物质的量计为0.5g/mmol。
本发明具体推荐所述的3-羰基茚酮类化合物的合成方法,其特征在于:所述的合成方法包括如下步骤:以式(Ⅰ)所示的二炔类化合物为起始原料,在金属铜为催化剂条件下,以Selectcfluor为氧化剂,乙腈为溶剂,在25℃的反应温度下反应6-12小时,反应液经分离纯化制备得到式(Ⅱ)所示的3-羰基茚酮类化合物;所述金属铜为粉末状,其物质的量为式(Ⅰ)所示的二炔类化合物物质的量的5%;所述Selectcfluor的物质的量为式(Ⅰ)所示的二炔类化合物物质的量的120%。
进一步,本发明式(Ⅰ)所示的二炔类化合物优选为下列化合物之一:
本发明通过二炔化合物在Cu/Selectcfluor体系作用下,通过羟铜化反应过程制得3-羰基茚酮类化合物,有益效果:与现有的制备3-羰基茚酮类化合物方法相比,使用低价金属铜参与反应,对环境危害小;反应温度为在室温,条件相对温和,节约能源消耗;产物选择性高;此外,还具有底物普适性强,操作简便等特点。
具体实施方式
下面结合具体实施例对本发明作进一步详细说明,本发明的保护范围不限于此。
实施例1
将0.3mmol 1,2-双(苯基乙炔基)苯、0.3mmol Selectcfluor、0.015mmol铜粉加入到10mL耐压反应器中,再加入4mL乙腈作溶剂。接着,于25℃条件下磁力搅拌5h。然后,在反应液中加入两药匙柱层析硅胶(100-200目),并通过减压蒸馏除去溶剂,再通过柱色谱分离得到如结构式所示的产物纯品3-苯甲酰基-2-苯基-1H-茚-1-酮(以石油醚/乙酸乙酯=30:1作为洗脱剂)。该物质为黄色固体,产率为85%。
表征数据:1H NMR(500MHz,CDCl3):δ7.94(dd,J1=8Hz,J2=1Hz,2H),7.35(d,J=7Hz,1H),7.54-7.50(m,1H),7.50-7.43(m,2H),7.40-7.35(m,3H),7.32-7.29(m,1H),7.25-7.23(m,3H),7.06(d,J=7Hz,1H),13C NMR(125MHz,CDCl3):δ195.99,194.56,150.39,144.06,135.17,134.64,134.39,134.36,129.68,129.55,129.35,129.33,128.96,128.80,128.29,123.86,121
实施例2
将0.3mmol 1,2-双(苯基乙炔基)苯、0.36mmol Selectcfluor、0.003mmol铜粉加入到10mL耐压反应器中,再加入4mL硝基甲烷作溶剂。接着,于25℃条件下磁力搅拌48h。然后,在反应液中加入两药匙柱层析硅胶(100-200目),并通过减压蒸馏除去溶剂,再通过柱色谱分离得到如结构式所示的产物纯品3-苯甲酰基-2-苯基-1H-茚-1-酮(以石油醚/乙酸乙酯=30:1作为洗脱剂)。该物质为黄色固体,产率为78%。
表征数据:1H NMR(500MHz,CDCl3):δ7.94(dd,J1=8Hz,J2=1Hz,2H),7.35(d,J=7Hz,1H),7.54-7.50(m,1H),7.50-7.43(m,2H),7.40-7.35(m,3H),7.32-7.29(m,1H),7.25-7.23(m,3H),7.06(d,J=7Hz,1H),13C NMR(125MHz,CDCl3):δ195.99,194.56,150.39,144.06,135.17,134.64,134.39,134.36,129.68,129.55,129.35,129.33,128.96,128.80,128.29,123.86,121
实施例3
将0.3mmol 1,2-双(苯基乙炔基)苯、0.6mmol Selectcfluor、0.03mmol铜粉加入到10mL耐压反应器中,再加入4mL乙腈作溶剂。接着,于50℃条件下磁力搅拌12h。然后,在反应液中加入两药匙柱层析硅胶(100-200目),并通过减压蒸馏除去溶剂,再通过柱色谱分离得到如结构式所示的产物纯品3-苯甲酰基-2-苯基-1H-茚-1-酮(以石油醚/乙酸乙酯=30:1作为洗脱剂)。该物质为黄色固体,产率为73%。
表征数据:1H NMR(500MHz,CDCl3):δ7.94(dd,J1=8Hz,J2=1Hz,2H),7.35(d,J=7Hz,1H),7.54-7.50(m,1H),7.50-7.43(m,2H),7.40-7.35(m,3H),7.32-7.29(m,1H),7.25-7.23(m,3H),7.06(d,J=7Hz,1H),13C NMR(125MHz,CDCl3):δ195.99,194.56,150.39,144.06,135.17,134.64,134.39,134.36,129.68,129.55,129.35,129.33,128.96,128.80,128.29,123.86,121
实施例4
将0.3mmol 1,2-双(苯基乙炔基)苯、0.36mmol Selectcfluor、0.015mmol铜粉加入到10mL耐压反应器中,再加入9mL乙腈、1mL水作溶剂。接着,于20℃条件下磁力搅拌6h。然后,在反应液中加入两药匙柱层析硅胶(100-200目),并通过减压蒸馏除去溶剂,再通过柱色谱分离得到如结构式所示的产物纯品3-苯甲酰基-2-苯基-1H-茚-1-酮(以石油醚/乙酸乙酯=30:1作为洗脱剂)。该物质为黄色固体,产率为70%。
表征数据:1H NMR(500MHz,CDCl3):δ7.94(dd,J1=8Hz,J2=1Hz,2H),7.35(d,J=7Hz,1H),7.54-7.50(m,1H),7.50-7.43(m,2H),7.40-7.35(m,3H),7.32-7.29(m,1H),7.25-7.23(m,3H),7.06(d,J=7Hz,1H),13C NMR(125MHz,CDCl3):δ195.99,194.56,150.39,144.06,135.17,134.64,134.39,134.36,129.68,129.55,129.35,129.33,128.96,128.80,128.29,123.86,121
实施例5
将0.3mmol 1,2-双(对-甲苯基乙炔基)苯、0.36mmol Selectcfluor、0.003mmol铜粉加入到10mL耐压反应器中,再加入3mL乙腈作溶剂。接着,于25℃条件下磁力搅拌12h。然后,在反应液中加入两药匙柱层析硅胶(100-200目),并通过减压蒸馏除去溶剂,再通过柱色谱分离得到如结构式所示的产物纯品3-(4-甲基苯甲酰基)-2-(对甲苯基)-1H-茚-1-酮(以石油醚/乙酸乙酯=30:1作为洗脱剂)。该物质为黄色固体,产率为86%。
表征数据:1H NMR(500MHz,CDCl3):δ7.87(d,J=3.5Hz,2H),7.65(d,J=7Hz,1H),7.60-7.34(m,3H),7.29-7.26(m,1H),7.19(d,J=8Hz,2H),7.07(d,J=8Hz,2H),6.99(d,J=7Hz),2.37(s,3H),2.28(s,3H)13C NMR(125MHz,CDCl3)δ:196.05,194.18,149.58,149.71,143.86,143.56,134.47,134.17,133.26,129.99,128.58,128.34,128.21,127.85,127.60,127.49,127.13,125.65,122.68,38.51,37.89
实施例6
将0.3mmol 1,2-双(对-甲苯基乙炔基)苯、0.36mmol Selectcfluor、0.015mmol铜粉加入到10mL耐压反应器中,再加入4mL四氢呋喃作溶剂。接着,于25℃条件下磁力搅拌12h。然后,在反应液中加入两药匙柱层析硅胶(100-200目),并通过减压蒸馏除去溶剂,再通过柱色谱分离得到如结构式所示的产物纯品3-(4-甲基苯甲酰基)-2-(对甲苯基)-1H-茚-1-酮(以石油醚/乙酸乙酯=30:1作为洗脱剂)。该物质为黄色固体,产率为66%。
表征数据:1H NMR(500MHz,CDCl3):δ7.87(d,J=3.5Hz,2H),7.65(d,J=7Hz,1H),7.60-7.34(m,3H),7.29-7.26(m,1H),7.19(d,J=8Hz,2H),7.07(d,J=8Hz,2H),6.99(d,J=7Hz),2.37(s,3H),2.28(s,3H)13C NMR(125MHz,CDCl3)δ:196.05,194.18,149.58,149.71,143.86,143.56,134.47,134.17,133.26,129.99,128.58,128.34,128.21,127.85,127.60,127.49,127.13,125.65,122.68,38.51,37.89
实施例7
将0.3mmol 1,2-双(对-甲苯基乙炔基)苯、0.36mmol Selectcfluor、0.015mmol铜粉加入到10mL耐压反应器中,再加入4mL N,N-二甲基甲酰胺作溶剂。接着,于25℃条件下磁力搅拌12h。然后,在反应液中加入两药匙柱层析硅胶(100-200目),并通过减压蒸馏除去溶剂,再通过柱色谱分离得到如结构式所示的产物纯品3-(4-甲基苯甲酰基)-2-(对甲苯基)-1H-茚-1-酮(以石油醚/乙酸乙酯=30:1作为洗脱剂)。该物质为黄色固体,产率为73%。
表征数据:1H NMR(500MHz,CDCl3):δ7.87(d,J=3.5Hz,2H),7.65(d,J=7Hz,1H),7.60-7.34(m,3H),7.29-7.26(m,1H),7.19(d,J=8Hz,2H),7.07(d,J=8Hz,2H),6.99(d,J=7Hz),2.37(s,3H),2.28(s,3H)13C NMR(125MHz,CDCl3)δ:196.05,194.18,149.58,149.71,143.86,143.56,134.47,134.17,133.26,129.99,128.58,128.34,128.21,127.85,127.60,127.49,127.13,125.65,122.68,38.51,37.89
实施例8
将0.3mmol 1,2-双((4-溴苯基)乙炔基)苯、0.36mmol Selectcfluor、0.015mmol铜粉加入到10mL耐压反应器中,再加入4mL乙腈作溶剂。接着,于25℃条件下磁力搅拌12h。然后,在反应液中加入两药匙柱层析硅胶(100-200目),并通过减压蒸馏除去溶剂,再通过柱色谱分离得到如结构式所示的产物纯品3-(4-溴苯甲酰基)-2-(4-溴苯基)-1H-茚-1-酮(以石油醚/乙酸乙酯=30:1作为洗脱剂)。该物质为棕红色固体,产率为77%。
表征数据:1H NMR(500MHz,CDCl3):δ7.98(d,J=8.5Hz,2H),7.62(d,J=7Hz,1H),7.53(d,J=8.5Hz,2H),7.40-7.37(m,3H),7.33-7.28(m,3H),7.02(d,J=7Hz,1H)13C NMR(125MHz,CDCl3):δ195.35,193.15,150.06,143.58,134.57,133.67,133.44,132.37,131.72,130.75,130.66,130.20,129.69,129.32,128.37,124.12,123.78,121.83
实施例9
将0.3mmol 1,2-双((4-溴苯基)乙炔基)苯、0.36mmol Selectcfluor、0.015mmol铜粉加入到10mL耐压反应器中,再加入6mL硝基甲烷作溶剂。接着,于50℃条件下磁力搅拌12h。然后,在反应液中加入两药匙柱层析硅胶(100-200目),并通过减压蒸馏除去溶剂,再通过柱色谱分离得到如结构式所示的产物纯品3-(4-溴苯甲酰基)-2-(4-溴苯基)-1H-茚-1-酮(以石油醚/乙酸乙酯=30:1作为洗脱剂)。该物质为棕红色固体,产率为47%。
表征数据:1H NMR(500MHz,CDCl3):δ7.98(d,J=8.5Hz,2H),7.62(d,J=7Hz,1H),7.53(d,J=8.5Hz,2H),7.40-7.37(m,3H),7.33-7.28(m,3H),7.02(d,J=7Hz,1H)13C NMR(125MHz,CDCl3):δ195.35,193.15,150.06,143.58,134.57,133.67,133.44,132.37,131.72,130.75,130.66,130.20,129.69,129.32,128.37,124.12,123.78,121.83
实施例10
将0.3mmol 1,2-双((4-溴苯基)乙炔基)苯、0.36mmol Selectcfluor、0.015mmol铜粉加入到10mL耐压反应器中,再加入4mL甲苯作溶剂。接着,于25℃条件下磁力搅拌12h。然后,在反应液中加入两药匙柱层析硅胶(100-200目),并通过减压蒸馏除去溶剂,再通过柱色谱分离得到如结构式所示的产物纯品3-(4-溴苯甲酰基)-2-(4-溴苯基)-1H-茚-1-酮(以石油醚/乙酸乙酯=30:1作为洗脱剂)。该物质为棕红色固体,产率为57%。
表征数据:1H NMR(500MHz,CDCl3):δ7.98(d,J=8.5Hz,2H),7.62(d,J=7Hz,1H),7.53(d,J=8.5Hz,2H),7.40-7.37(m,3H),7.33-7.28(m,3H),7.02(d,J=7Hz,1H)13C NMR(125MHz,CDCl3):δ195.35,193.15,150.06,143.58,134.57,133.67,133.44,132.37,131.72,130.75,130.66,130.20,129.69,129.32,128.37,124.12,123.78,121.83
实施例11
将0.3mmol 1,2-双((4-丙基苯基)乙炔基)苯、0.36mmol Selectcfluor、0.015mmol铜粉加入到10mL耐压反应器中,再加入4mL乙腈作溶剂。接着,于50℃条件下磁力搅拌12h。然后,在反应液中加入两药匙柱层析硅胶(100-200目),并通过减压蒸馏除去溶剂,再通过柱色谱分离得到如结构式所示的产物纯品3-(4-溴苯甲酰基)-2-(4-丙基苯基)-1H-茚-1-酮(以石油醚/乙酸乙酯=30:1作为洗脱剂)。该物质为棕红色固体,产率为64%。
表征数据:1H NMR(500MHz,CDCl3):δ7.86(d,J=5Hz,2H),7.61(d,J=5Hz,1H),7.38(d,J=10Hz,2H),7.35(d,J=5Hz,1H),7.28-7.25(m,1H),7.16(d,J=10Hz,2H),7.06-7.02(m,3H),2.58(t,J=10Hz,2H),2.50(t,J=10Hz,2H),1.64-0.85(m,6H)13C NMR(125MHz,CDCl3)δ:196.35,194.28,149.98,149.91,144.36,143.66,134.37,134.27,133.06,129.62,129.48,129.24,129.01,128.85,128.60,128.39,127.13,123.65,121.58,38.01,37.69,24.11,23.93,13.59(2C).
实施例12
将0.3mmol 1,2-双((4-丙基苯基)乙炔基)苯、0.36mmol Selectcfluor、0.020mmol铜粉加入到10mL耐压反应器中,再加入4mL乙腈作溶剂。接着,于20℃条件下磁力搅拌12h。然后,在反应液中加入两药匙柱层析硅胶(100-200目),并通过减压蒸馏除去溶剂,再通过柱色谱分离得到如结构式所示的产物纯品3-(4-溴苯甲酰基)-2-(4-丙基苯基)-1H-茚-1-酮(以石油醚/乙酸乙酯=30:1作为洗脱剂)。该物质为棕红色固体,产率为74%。
表征数据:1H NMR(500MHz,CDCl3):δ7.86(d,J=5Hz,2H),7.61(d,J=5Hz,1H),7.38(d,J=10Hz,2H),7.35(d,J=5Hz,1H),7.28-7.25(m,1H),7.16(d,J=10Hz,2H),7.06-7.02(m,3H),2.58(t,J=10Hz,2H),2.50(t,J=10Hz,2H),1.64-0.85(m,6H)13C NMR(125MHz,CDCl3)δ:196.35,194.28,149.98,149.91,144.36,143.66,134.37,134.27,133.06,129.62,129.48,129.24,129.01,128.85,128.60,128.39,127.13,123.65,121.58,38.01,37.69,24.11,23.93,13.59(2C).
实施例13
将0.3mmol 1,2-双((3-溴苯基)乙炔基)苯、0.36mmol Selectcfluor、0.020mmol铜粉加入到10mL耐压反应器中,再加入4mL硝基甲烷作溶剂。接着,于20℃条件下磁力搅拌12h。然后,在反应液中加入两药匙柱层析硅胶(100-200目),并通过减压蒸馏除去溶剂,再通过柱色谱分离得到如结构式所示的产物纯品3-(3-溴苯甲酰基)-2-(3-溴苯基)-1H-茚-1-酮(以石油醚/乙酸乙酯=30:1作为洗脱剂)。该物质为棕红色固体,产率为58%。
表征数据:1H NMR(500MHz,CDCl3):δ8.02(t,J=2Hz,1H),7.78-7.76(m,1H),7.64-7.62(m,2H),7.56(t,J=1.5Hz,1H),7.43-7.40(m,1H),7.37-7.32(m,2H),7.28-7.26(m,1H),7.23(t,J=8Hz,1H),7.10(t,J=8Hz,2H)13C NMR(125MHz,CDCl3):δ195.09,192.71,150.13,143.31,137.20,136.72,134.61,133.79,132.18,131.94,131.43,130.34,129.84,129.32,127.90,127.84,124.21,123.16,122.43,122.14
实施例14
将0.3mmol 1,2-双((3-溴苯基)乙炔基)苯、0.36mmol Selectcfluor、0.020mmol铜粉加入到10mL耐压反应器中,再加入4mL乙腈作溶剂。接着,于20℃条件下磁力搅拌12h。然后,在反应液中加入两药匙柱层析硅胶(100-200目),并通过减压蒸馏除去溶剂,再通过柱色谱分离得到如结构式所示的产物纯品(以石油醚/乙酸乙酯=30:1作为洗脱剂)。该物质为棕红色固体,产率为64%。
表征数据:1H NMR(500MHz,CDCl3):δ8.02(t,J=2Hz,1H),7.78-7.76(m,1H),7.64-7.62(m,2H),7.56(t,J=1.5Hz,1H),7.43-7.40(m,1H),7.37-7.32(m,2H),7.28-7.26(m,1H),7.23(t,J=8Hz,1H),7.10(t,J=8Hz,2H)13C NMR(125MHz,CDCl3):δ195.09,192.71,150.13,143.31,137.20,136.72,134.61,133.79,132.18,131.94,131.43,130.34,129.84,129.32,127.90,127.84,124.21,123.16,122.43,122.14。
Claims (9)
2.如权利要求1所述的方法,其特征在于:所述金属铜物质的量为式(Ⅰ)所示的二炔类化合物物质的量的1-10%。
3.如权利要求1所述的方法,其特征在于:所述1-氯甲基-4-氟-1,4-重氮化二环2.2.2辛烷双(四氟硼酸)的物质的量为式(Ⅰ)所示的二炔类化合物物质的量的100%~200%。
4.如权利要求1所述的方法,其特征在于:所述溶剂为乙腈、硝基甲烷、甲苯、水、四氢呋喃或N,N-二甲基甲酰胺中的一种或两种。
5.如权利要求1所述的方法,其特征在于:所述溶剂体积以式(Ⅰ)所示的二炔类化合物的物质的量计为10~30mL/mmol。
6.如权利要求1所述的方法,其特征在于:所述反应温度为25℃,反应的反应时间为6-12小时。
7.如权利要求1~6之一所述的方法,其特征在于:所述后处理为反应液中加入柱层析硅胶,并通过减压蒸馏除去溶剂,再通过柱色谱分离,以石油醚与乙酸乙酯体积比为30:1的混合液作为洗脱剂洗脱,收集含目标产物的洗脱液,蒸除溶剂得到式(Ⅱ)所示的3-羰基茚酮类化合物。
8.如权利要求7所述的方法,其特征在于:所述的柱层析硅胶为100~200目,所述柱层析硅胶的质量以式(Ⅰ)所示的二炔类化合物的物质的量计为0.5g/mmol。
9.如权利要求1所述的方法,其特征在于所述方法为:以式(Ⅰ)所示的二炔类化合物为起始原料,在金属铜为催化剂条件下,以1-氯甲基-4-氟-1,4-重氮化二环2.2.2辛烷双(四氟硼酸)为氧化剂,乙腈为溶剂,在25℃的反应温度下反应6-12小时,反应液经分离纯化制备得到式(Ⅱ)所示的3-羰基茚酮类化合物;所述金属铜为粉末状,其物质的量为式(Ⅰ)所示的二炔类化合物物质的量的5%;所述1-氯甲基-4-氟-1,4-重氮化二环2.2.2辛烷双(四氟硼酸)的物质的量为式(Ⅰ)所示的二炔类化合物物质的量的120%。
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