CN116262976B - 一种苯甲醛类衍生物的电化学合成方法 - Google Patents
一种苯甲醛类衍生物的电化学合成方法 Download PDFInfo
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
本申请提供一种苯甲醛类衍生物的电化学合成方法,涉及医药化工中间体合成技术领域。苯甲醛类衍生物的电化学合成方法,包括:将包括甲苯类化合物、电解质和溶剂在内的原料混合得到反应溶液,然后在不分立电解槽中,将正极和负极分别***到所述反应溶液中,恒定电流进行反应,然后柱层析得到苯甲醛类衍生物;所述甲苯类化合物的结构通式为:所述苯甲醛类衍生物的结构通式为:其中,R1为H、C1‑C4烷基、C3‑C6环烷基、C6‑C8芳基或杂环芳基;R2为H、C1‑C4烷基、卤素、C3‑C6环烷基、C6‑C8芳基或杂环芳基。本申请提供的苯甲醛类衍生物的电化学合成方法,原料易得、操作简单、选择性高、安全快速。
Description
技术领域
本申请涉及医药化工中间体合成技术领域,尤其涉及一种苯甲醛类衍生物的电化学合成方法。
背景技术
苯甲醛类衍生物作为重要的药物中间体,被广泛应用于各种天然产物、药物、农用化学品、生物活性化合物的合成中,例如:制备月桂醛、月桂酸、苯乙醛和苯甲酸苄酯等的重要化工原料,同时也是除草剂野燕枯、植物生长调节剂抗倒胺的中间体。因此,其高效合成是当前研究的热点之一。传统合成方法主要是通过甲苯氯化再水解法、苯甲醇氧化法、甲苯直接氧化法以及以苯为原料,在加压和三氯化铝作用下,苯与一氧化碳和氯化氢反应来合成苯甲醛类衍生物。然而,这些方法要获得各种取代的苯甲醛来说并非易事。
在过去的几十年,定向的C-H直接选择性氧化反应取得了相当大的进展,其中烯丙位、苄位(活性C-H)、杂原子(O,N等)的邻α位的C-H活性较高,比较容易被选择性的氧化,从而彻底改变骨架来对化合物进行开发,这也使得C-H键氧化反应成为新药开发的强有力手段。因此,目前通过C-H键直接选择性氧化反应来合成苯甲醛类衍生物是较为高效简洁的方法。例如:2019年,Wu等报道了一种在氧化剂K2S2O8存在的情况下,以Co(OAc)2·4H2O催化甲苯类化合物在三氟乙酸和三氟乙酸酐的溶剂中,苄位C-H键被氧化合成苯甲醛类衍生物的方法(RSC Adv.,2019,9,20879-20883.)。此外,2022年,Wang等报道使用电化学催化氧化甲苯类化合物,随后经过盐酸的水解得到苯甲醛类衍生物的方法(J.Org.Chem.,2022,87,7806-7817.)。上述氧化方法存在着一些不足:金属催化剂和化学计量的氧化剂的使用增加了成本,步骤繁琐,底物适用性差等。
因此,开发一种原料易得、操作简单、选择性高、安全快速的苯甲醛类衍生物的合成方法尤为必要。
发明内容
本申请的目的在于提供一种苯甲醛类衍生物的电化学合成方法,以解决上述问题。
为实现以上目的,本申请采用以下技术方案:
一种苯甲醛类衍生物的电化学合成方法,包括:
将包括甲苯类化合物、电解质和溶剂在内的原料混合得到反应溶液,然后在不分立电解槽中,将正极和负极分别***到所述反应溶液中,恒定电流进行反应,然后柱层析得到苯甲醛类衍生物;
所述甲苯类化合物的结构通式为:
所述苯甲醛类衍生物的结构通式为:
其中,R1为H、C1-C4烷基、C3-C6环烷基、C6-C8芳基或杂环芳基;R2为H、C1-C4烷基、卤素、C3-C6环烷基、C6-C8芳基或杂环芳基。
优选地,所述正极和所述负极各自独立的选自铂电极、镍电极、镁电极、不锈钢电极、锌电极、网状玻璃态碳电极、石墨毡电极中的任一种。
优选地,所述电解质包括高氯酸锂、四丁基四氟硼酸铵、四丁基六氟磷酸铵、四丁基碘化铵、四丁基溴化铵、四丁基氟化铵中的至少一种。
优选地,所述电解质的用量为所述甲苯类化合物的用量的80-150mol%。
优选地,所述溶剂包括甲醇、乙醇、异丙醇、三氟乙醇、六氟异丙醇、甲苯、氯苯、乙腈、二甲基亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二氧六环、二氯甲烷、1,2-二氯乙烷、丙酮、四氢呋喃、乙酸乙酯、正己烷中的一种或多种。
优选地,所述恒定电流为5-40mA。
优选地,所述反应的温度为25-75℃。
优选地,所述甲苯类化合物在所述反应溶液中的摩尔浓度为0.1 -0.5mol/L。
优选地,所述甲苯类化合物在所述反应溶液中的摩尔浓度为0.2 -0.6mol/L。
优选地,所述柱层析采用硅胶柱层析,洗脱剂为体积比为10:1的正己烷和乙酸乙酯混合溶液。
与现有技术相比,本申请的有益效果包括:
本申请提供的苯甲醛类衍生物的电化学合成方法,甲苯类化合物经氧化生成苯甲醛类衍生物,是一种绿色电化学合成方法,解决了现有技术中原料不易得的缺点,并且无需使用任何金属催化剂和氧化剂,而是使用电催化氧化,副产物仅为氢气,更加绿色环保,原料易得、操作简单、反应化学选择性高、环境友好等特点,具有较大的实施价值和社会经济效益,符合绿色化学以及社会的发展。
具体实施方式
下面将结合具体实施例对本申请的实施方案进行详细描述,但是本领域技术人员将会理解,下列实施例仅用于说明本申请,而不应视为限制本申请的范围。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
实施例1:对乙酰基苯甲醛(Ia)的制备
将对甲基苯乙酮(68mg,0.5mmol),四丁基四氟硼酸铵(165mg,0.5mmol)和六氟异丙醇(5mL)加入反应瓶中,并***网状玻璃态碳电极和铂电极,电流调整为恒流5mA,25℃反应6小时,经硅胶柱层析(洗脱剂为正己烷:乙酸乙酯=10:1,体积比)分离得到无色液体对乙酰基苯甲醛(Ia)61mg,收率:82%,Ia结构式为:
表征信息如下:
1H NMR(500MHz,CDCl3)δ10.10(s,1H),8.09(d,J=7.1Hz,2H),7.97(d,J=7.1Hz,2H),2.66(s,3H).13C NMR(125MHz,CDCl3)δ197.51,191.72,141.35,139.18,129.95,128.95,27.10.HRMS(ESI-TOF):m/z calcd for C9H9O2[M+1]+:149.0597,found 149.0599。
实施例2:对乙酰基苯甲醛(Ia)的制备
将对甲基苯乙酮(68mg,0.5mmol),四丁基六氟磷酸铵(194mg,0.5mmol)和六氟异丙醇(5mL)加入反应瓶中,并***网状玻璃态碳电极和铂电极,电流调整为恒流5mA,25℃反应6小时,经硅胶柱层析(洗脱剂为正己烷:乙酸乙酯=10:1,体积比)分离得到无色液体对乙酰基苯甲醛(Ia)58mg,收率:78%。
实施例3:对乙酰基苯甲醛(Ia)的制备
将对甲基苯乙酮(68mg,0.5mmol),四丁基四氟硼酸铵(165mg,0.5mmol)和乙腈(5mL)加入反应瓶中,并***网状玻璃态碳电极和铂电极,电流调整为恒流5mA,25℃反应6小时,经硅胶柱层析(洗脱剂为正己烷:乙酸乙酯=10:1,体积比)分离得到无色液体对乙酰基苯甲醛(Ia)11mg,收率:15%。
实施例4:对乙酰基苯甲醛(Ia)的制备
将对甲基苯乙酮(68mg,0.5mmol),四丁基四氟硼酸铵(165mg,0.5mmol)和六氟异丙醇(5mL)加入反应瓶中,并***石墨毡电极和铂电极,电流调整为恒流5mA,25℃反应6小时,经硅胶柱层析(洗脱剂为正己烷:乙酸乙酯=10:1,体积比)分离得到无色液体对乙酰基苯甲醛(Ia)60mg,收率:80%。
实施例5:对乙酰基苯甲醛(Ia)的制备
将对甲基苯乙酮(68mg,0.5mmol),四丁基四氟硼酸铵(165mg,0.5mmol)和六氟异丙醇(5mL)加入反应瓶中,并***网状玻璃态碳电极和铂电极,电流调整为恒流10mA,25℃反应6小时,经硅胶柱层析(洗脱剂为正己烷:乙酸乙酯=10:1,体积比)分离得到无色液体对乙酰基苯甲醛(Ia)41mg,收率:55%。
实施例6:对乙酰基苯甲醛(Ia)的制备
将对甲基苯乙酮(68mg,0.5mmol),四丁基四氟硼酸铵(165mg,0.5mmol)和六氟异丙醇(5mL)加入反应瓶中,并***网状玻璃态碳电极和铂电极,电流调整为恒流5mA,50℃反应6小时,经硅胶柱层析(洗脱剂为正己烷:乙酸乙酯=10:1,体积比)分离得到无色液体对乙酰基苯甲醛(Ia)47mg,收率:63%。
实施例7:3-乙酰基苯甲醛(Ib)的制备
将3'-甲基苯乙酮(68mg,0.5mmol),四丁基四氟硼酸铵(165mg,0.5mmol)和六氟异丙醇(5mL)加入反应瓶中,并***网状玻璃态碳电极和铂电极,电流调整为恒流5mA,25℃反应6小时,经硅胶柱层析(洗脱剂为正己烷:乙酸乙酯=10:1,体积比)分离得到无色液体3-乙酰基苯甲醛(Ib)55mg,收率:74%,Ib的结构式为:
1H NMR(500MHz,CDCl3)δ10.10(s,1H),8.44(s,1H),8.23(d,J=7.7Hz,1H),8.09(d,J=7.6Hz,1H),7.73-7.60(m,1H),2.68(s,3H).13C NMR(125MHz,CDCl3)δ192.52,191.61,137.96,136.82,133.88,133.78,129.71,129.67,26.85.HRMS(ESI-TOF):m/zcalcd for C9H9O2[M+1]+:149.0597,found149.0595。
实施例8:2-乙酰基苯甲醛(Ic)的制备
将2'-甲基苯乙酮(68mg,0.5mmol),四丁基四氟硼酸铵(165mg,0.5mmol)和六氟异丙醇(5mL)加入反应瓶中,并***网状玻璃态碳电极和铂电极,电流调整为恒流5mA,25℃反应6小时,经硅胶柱层析(洗脱剂为正己烷:乙酸乙酯=10:1,体积比)分离得到无色液体2-乙酰基苯甲醛(Ic)48mg,收率:66%,Ic的结构式为:
1H NMR(500MHz,CDCl3)δ10.22(s,1H),7.86(d,J=7.6Hz,1H),7.72(d,J=7.4Hz,1H),7.70-7.57(m,2H),2.64(s,3H).13C NMR(125MHz,CDCl3)δ201.10,192.32,140.68,136.33,133.12,131.97,129.77,128.58,28.91.HRMS(ESI-TOF):m/z calcd for C9H9O2[M+1]+:149.0597,found 149.0598。
实施例9:4-乙酰基-3,5-二甲基苯甲醛(Id)的制备
将2',4',6'-三甲基苯乙酮(81mg,0.5mmol),四丁基四氟硼酸铵(165mg,0.5mmol)和六氟异丙醇(5mL)加入反应瓶中,并***网状玻璃态碳电极和铂电极,电流调整为恒流5mA,25℃反应6小时,经硅胶柱层析(洗脱剂为正己烷:乙酸乙酯=10:1,体积比)分离得到无色液体4-乙酰基-3,5-二甲基苯甲醛(Id)60mg,收率:68%,Id的结构式为:
1H NMR(500MHz,CDCl3)δ9.95(s,1H),7.54(s,2H),2.50(s,3H),2.32(s,6H).13CNMR(125MHz,CDCl3)δ207.27,192.10,148.04,136.31,133.56,129.33,31.84,19.11.HRMS(ESI-TOF):m/z calcd for C11H13O2[M+1]+:177.0910,found 177.0911。
实施例10:4-乙酰基-2-甲基苯甲醛(Ie)的制备
将2,4-二甲基苯乙酮(74mg,0.5mmol),四丁基四氟硼酸铵(165mg,0.5mmol)和六氟异丙醇(5mL)加入反应瓶中,并***网状玻璃态碳电极和铂电极,电流调整为恒流5mA,25℃反应6小时,经硅胶柱层析(洗脱剂为正己烷:乙酸乙酯=10:1,体积比)分离得到无色液体4-乙酰基-2-甲基苯甲醛(Ie)47mg,收率:58%,Ie的结构式为:
1H NMR(500MHz,CDCl3)δ10.31(s,1H),8.37(s,1H),8.06(d,J=5.5Hz,1H),7.38(d,J=5.5Hz,1H),2.73(s,4H),2.64(s,3H).13C NMR(100MHz,CDCl3)δ196.81,191.99,145.88,135.53,134.14,132.77,132.36,131.99,26.58,19.86.HRMS(ESI-TOF):m/z calcdfor C10H11O2[M+1]+:163.0754,found 163.0752。
实施例11:1,4-二乙酰基苯(If)的制备
将对乙基苯乙酮(74mg,0.5mmol),四丁基四氟硼酸铵(165mg,0.5mmol)和六氟异丙醇(5mL)加入反应瓶中,并***网状玻璃态碳电极和铂电极,电流调整为恒流5mA,25℃反应6小时,经硅胶柱层析(洗脱剂为正己烷:乙酸乙酯=10:1,体积比)分离得到无色液体1,4-二乙酰基苯(If)61mg,收率:75%,If的结构式为:
1H NMR(500MHz,CDCl3)δ8.02(s,4H),2.64(s,6H).13C NMR(125MHz,CDCl3)δ197.61,140.30,128.62,27.02.HRMS(ESI-TOF):m/z calcd for C10H11O2[M+1]+:163.0754,found 163.0755。
实施例12:4-乙酰基-2-溴苯甲醛(Ig)的制备
将3'-溴-4'-甲基苯乙酮(107mg,0.5mmol),四丁基四氟硼酸铵(165mg,0.5mmol)和六氟异丙醇(5mL)加入反应瓶中,并***网状玻璃态碳电极和铂电极,电流调整为恒流5mA,25℃反应6小时,经硅胶柱层析(洗脱剂为正己烷:乙酸乙酯=10:1,体积比)分离得到无色液体4-乙酰基-2-溴苯甲醛(Ig)66mg,收率:58%,Ig的结构式为:
1H NMR(500MHz,CDCl3)δ10.41(s,1H),8.21(s,1H),8.06-7.92(m,2H),2.64(s,3H).13C NMR(125MHz,CDCl3)δ191.33,186.19,153.69,137.75,133.83,130.28,127.52,127.26,27.05.HRMS(ESI-TOF):m/z calcd for C9H7BrO2[M+1]+:226.9702,found226.9705。
实施例13:4-乙酰基-2-硝基苯甲醛(Ih)的制备
将3-硝基-4-甲基苯乙酮(90mg,0.5mmol),四丁基四氟硼酸铵(165mg,0.5mmol)和六氟异丙醇(5mL)加入反应瓶中,并***网状玻璃态碳电极和铂电极,电流调整为恒流5mA,25℃反应6小时,经硅胶柱层析(洗脱剂为正己烷:乙酸乙酯=10:1,体积比)分离得到无色液体4-乙酰基-2-硝基苯甲醛(Ih)50mg,收率:52%,Ih的结构式为:
1H NMR(500MHz,CDCl3)δ10.47(s,1H),8.65(s,1H),8.32(d,J=7.0Hz,1H),8.04(d,J=7.5Hz,1H),2.72(s,3H).13C NMR(125MHz,CDCl3)δ194.94,187.57,149.78,141.03,134.21,133.31,130.55,124.35,27.03.HRMS(ESI-TOF):m/z calcd for C9H7NO4[M+1]+:194.0448,found 194.0445。
实施例14:1-(4-甲酰基苯基)丙-1-酮(Ii)的制备
将对甲基苯丙酮(74mg,0.5mmol),四丁基四氟硼酸铵(165mg,0.5mmol)和六氟异丙醇(5mL)加入反应瓶中,并***网状玻璃态碳电极和铂电极,电流调整为恒流5mA,25℃反应6小时,经硅胶柱层析(洗脱剂为正己烷:乙酸乙酯=10:1,体积比)分离得到无色液体1-(4-甲酰基苯基)丙-1-酮(Ii)65mg,收率:80%,Ii的结构式为:
1H NMR(500MHz,CDCl3)δ10.10(s,1H),8.10(d,J=8.6Hz,2H),7.97(d,J=8.7Hz,2H),3.04(q,J=7.3Hz,2H),1.24(t,3H).13C NMR(125MHz,CDCl3)δ200.29,191.79,141.29,139.07,129.97,128.63,32.49,8.17.HRMS(ESI-TOF):m/z calcd for C10H10O2[M+1]+:163.0754,found 163.0758。
实施例15:对苯二甲醛(Ij)的制备
将对甲基苯甲醛(60mg,0.5mmol),四丁基四氟硼酸铵(165mg,0.5mmol)和六氟异丙醇(5mL)加入反应瓶中,并***网状玻璃态碳电极和铂电极,电流调整为恒流5mA,25℃反应6小时,经硅胶柱层析(洗脱剂为正己烷:乙酸乙酯=10:1,体积比)分离得到无色液体对苯二甲醛(Ij)48mg,收率:71%,Ij的结构式为:
1H NMR(500MHz,CDCl3)δ10.14(s,2H),8.06(s,4H).13C NMR(125MHz,CDCl3)δ191.62,140.18,130.29.HRMS(ESI-TOF):m/z calcd for C8H6O2[M+1]+:135.0441,found135.0444。
实施例16:4-苯甲酰苯甲醛(Ik)的制备
将4-甲基二苯甲酮(98mg,0.5mmol),四丁基四氟硼酸铵(165mg,0.5mmol)和六氟异丙醇(5mL)加入反应瓶中,并***网状玻璃态碳电极和铂电极,电流调整为恒流5mA,25℃反应6小时,经硅胶柱层析(洗脱剂为正己烷:乙酸乙酯=10:1,体积比)分离得到无色液体4-苯甲酰苯甲醛(Ik)68mg,收率:65%,Ik的结构式为:
1H NMR(500MHz,CDCl3)δ10.13(s,1H),8.00(d,J=7.5Hz,2H),7.92(d,J=7.7Hz,2H),7.80(d,J=7.6Hz,2H),7.63(t,J=7.3Hz,1H),7.56-7.45(m,2H).13C NMR(125MHz,CDCl3)δ195.94,191.75,142.69,138.60,136.86,133.26,130.44,130.24,129.62,128.67.HRMS(ESI-TOF):m/z calcd for C14H10O2[M+1]+:211.0754,found 211.0750。
实施例17:9,10-二氧-9,10-二氢蒽-2-甲醛(Il)的制备
将2-甲基蒽醌(111mg,0.5mmol),四丁基四氟硼酸铵(165mg,0.5mmol)和六氟异丙醇(5mL)加入反应瓶中,并***网状玻璃态碳电极和铂电极,电流调整为恒流5mA,25℃反应6小时,经硅胶柱层析(洗脱剂为正己烷:乙酸乙酯=10:1,体积比)分离得到无色液体9,10-二氧-9,10-二氢蒽-2-甲醛(Il)80mg,收率:68%,Il的结构式为:
1H NMR(500MHz,CDCl3)δ10.23(s,1H),8.79(s,1H),8.47(d,J=7.8Hz,1H),8.40-8.32(m,2H),8.30(d,J=7.9Hz,1H),7.93-7.79(m,2H).13CNMR(125MHz,CDCl3)δ190.95,182.56,182.28,140.01,137.05,134.79,134.75,134.30,133.50,133.48,133.22,129.68,128.34,127.66.HRMS(ESI-TOF):m/z calcd for C15H9O3[M+1]+:237.0546,found237.0548。
实施例18:对甲酰基苯甲酸甲酯(Im)的制备
将对甲基苯甲酸甲酯(75mg,0.5mmol),四丁基四氟硼酸铵(165mg,0.5mmol)和六氟异丙醇(5mL)加入反应瓶中,并***网状玻璃态碳电极和铂电极,电流调整为恒流5mA,25℃反应6小时,经硅胶柱层析(洗脱剂为正己烷:乙酸乙酯=10:1,体积比)分离得到无色液体对甲酰基苯甲酸甲酯(Im)71mg,收率:86%,Im的结构式为:
1H NMR(500MHz,CDCl3)δ10.10(s,1H),8.19(d,J=7.9Hz,2H),7.95(d,J=8.1Hz,2H),3.96(s,3H).13C NMR(125MHz,CDCl3)δ191.82,166.23,139.29,135.25,130.35,129.68,128.39,52.74.HRMS(ESI-TOF):m/z calcd for C9H9O3[M+1]+:165.0546,found165.0548。
实施例19:4-甲酰基苯甲酰胺(In)的制备
将对甲苯酰胺(68mg,0.5mmol),四丁基四氟硼酸铵(165mg,0.5mmol)和六氟异丙醇(5mL)加入反应瓶中,并***网状玻璃态碳电极和铂电极,电流调整为恒流5mA,25℃反应6小时,经硅胶柱层析(洗脱剂为正己烷:乙酸乙酯=10:1,体积比)分离得到无色液体4-甲酰基苯甲酰胺(In)66mg,收率:88%,In的结构式为:
1H NMR(500MHz,CDCl3)δ10.10(s,1H),8.15-7.78(m,4H),6.18(s,1H),5.86(s,1H).13C NMR(125MHz,CDCl3)δ191.47,169.23,140.98,138.16,129.90,128.08.HRMS(ESI-TOF):m/z calcd for C8H8NO2[M+1]+:150.0550,found 150.0553。
实施例20:2-(4-甲酰基苯基)-2-氧代乙酸乙酯(Io)的制备
将乙基-4-甲基苯甲酰(96mg,0.5mmol),四丁基四氟硼酸铵(165mg,0.5mmol)和六氟异丙醇(5mL)加入反应瓶中,并***网状玻璃态碳电极和铂电极,电流调整为恒流5mA,25℃反应6小时,经硅胶柱层析(洗脱剂为正己烷:乙酸乙酯=10:1,体积比)分离得到无色液体2-(4-甲酰基苯基)-2-氧代乙酸乙酯(Io)77mg,收率:75%,Io的结构式为:
1H NMR(500MHz,CDCl3)δ10.13(s,1H),8.19(d,J=8.2Hz,2H),8.02(d,J=8.3Hz,2H),4.48(q,J=7.2Hz,2H),1.44(t,J=7.2Hz,3H).13C NMR(125MHz,CDCl3)δ191.48,185.54,163.06,140.16,136.85,130.76,129.95,62.92,14.23.HRMS(ESI-TOF):m/z calcdfor C11H11O4[M+1]+:207.0652,found 207.0655。
实施例21:对溴苯甲醛(Ip)的制备
将对溴甲苯(86mg,0.5mmol),四丁基四氟硼酸铵(165mg,0.5mmol)和六氟异丙醇(5mL)加入反应瓶中,并***网状玻璃态碳电极和铂电极,电流调整为恒流5mA,25℃反应6小时,经硅胶柱层析(洗脱剂为正己烷:乙酸乙酯=10:1,体积比)分离得到无色液体对溴苯甲醛(Ip)40mg,收率:43%,Ip的结构式为:
1H NMR(500MHz,CDCl3)δ9.97(s,1H),7.74(d,J=8.6Hz,2H),7.68(d,J=8.1Hz,2H).13C NMR(125MHz,CDCl3)δ191.18,135.21,132.57,131.10,129.91.HRMS(ESI-TOF):m/zcalcd for C7H6BrO[M+H]+:184.9597,found184.9595。
实施例21:对硝基苯甲醛(Iq)的制备
将对硝基甲苯(69mg,0.5mmol),四丁基四氟硼酸铵(165mg,0.5mmol)和六氟异丙醇(5mL)加入反应瓶中,并***网状玻璃态碳电极和铂电极,电流调整为恒流5mA,25℃反应6小时,经硅胶柱层析(洗脱剂为正己烷:乙酸乙酯=10:1,体积比)分离得到无色液体对溴苯甲醛(Iq)42mg,收率:56%,Iq的结构式为:
1H NMR(500MHz,CDCl3)δ10.16(s,1H),8.39(d,J=8.3Hz,2H),8.07(d,J=8.3Hz,2H).13C NMR(125MHz,CDCl3)δ190.42,151.26,140.18,130.61,124.44.HRMS(ESI-TOF):m/zcalcd for C7H6NO3[M+H]+:152.0342,found 152.0344。
最后应说明的是:以上各实施例仅用以说明本申请的技术方案,而非对其限制;尽管参照前述各实施例对本申请进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本申请各实施例技术方案的范围。
此外,本领域的技术人员能够理解,尽管在此的一些实施例包括其它实施例中所包括的某些特征而不是其它特征,但是不同实施例的特征的组合意味着处于本申请的范围之内并且形成不同的实施例。例如,在上面的权利要求书中,所要求保护的实施例的任意之一都可以以任意的组合方式来使用。公开于该背景技术部分的信息仅仅旨在加深对本申请的总体背景技术的理解,而不应当被视为承认或以任何形式暗示该信息构成已为本领域技术人员所公知的现有技术。
Claims (1)
1.一种甲酰基苯甲酰胺的制备方法包括:将对甲苯酰胺68mg,0.5mmol,四丁基四氟硼酸铵165mg,0.5mmol和六氟异丙醇5mL加入反应瓶中,并***网状玻璃态碳电极和铂电极,电流调整为恒流5mA,25℃反应6小时,经硅胶柱层析,其中洗脱剂为体积比正己烷:乙酸乙酯=10:1,分离得到无色液体4-甲酰基苯甲酰胺66mg,收率:88%,结构式为:。
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