CN112939883A - 一种多取代1,3恶唑烷化合物的制备方法 - Google Patents
一种多取代1,3恶唑烷化合物的制备方法 Download PDFInfo
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
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- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/04—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/04—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D263/06—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hydrocarbon radicals, substituted by oxygen atoms, attached to ring carbon atoms
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Abstract
多取代1,3恶唑烷化合物具有广泛的药物活性,同时也属于有机制备范畴内的一类重要中间体,可以用于合成多种具有生物活性的天然产物和生物活性分子,具有很高的有机合成应用价值。本发明提供了一种极为简洁的可见光催化的1,3恶唑烷化合物的制备方法,具体过程为:以甘氨酸衍生物和环氧化合物为原料,以廉价的催化剂氢碘酸、氢溴酸或N‑溴代丁二酰亚胺为催化剂,在室温及可见光照射下反应10‑20h,分离纯化后得到一系列多取代1,3恶唑烷化合物。与现有技术相比,该制备方法具有步骤简洁、原料和催化剂廉价易得、无金属、无额外光催化剂、反应条件温和、反应操作简单等优点,更适合于中试放大与大规模制备多取代1,3恶唑烷化合物。
Description
技术领域
本发明属于有机化合物合成制备技术领域,尤其涉及了一种多取代1,3恶唑烷化合物的制备方法。
背景技术
多取代1,3恶唑烷是一种十分重要的五元氮杂环化合物,它不仅是很多天然产物和生物活性分子(如Erchinines A and B、(-)-Quinocarcin、GSK1265744等)的重要骨架,还可以作为有机合成中间体,参与复杂天然产物和活性功能分子的合成。此外,该结构骨架还可以作为不对称催化反应中的手性助剂和过渡金属催化反应中的配体而在化学反应中得以广泛应用。
已报道的合成多取代1,3恶唑烷类化合物的方法主要有:(1)氨基醇或氮杂环丙烷与醛酮的反应;(2)具有环张力的三元环或四元环的扩环反应;(3)过渡金属催化的偶极[3+2]环加成反应;(4)氧化剂作用下的氧化脱氢[2+3]环加成反应;(5)可见光催化下自由基加成环化反应等。
虽然构建恶唑烷骨架的方法已经被广泛研究,但已报道的策略通常具有起始原料复杂、反应条件苛刻以及须使用昂贵的金属催化剂等不足。这使得已报道方法的应用性受到了限制。
在此,本发明提供一种可见光催化的甘氨酸衍生物与环氧化合物间的氧化脱氢形式[2+3]环化反应来合成多取代1,3恶唑烷化合物的新方法。该方法以廉价、丰富、绿色的可见光作为能源,以空气中的氧气作为绿色氧化剂,此外,其还具有原料便宜易得、反应条件温和绿色、操作简便等优点,可以以70%-80%的产率高效地制备一系列多取代1,3恶唑烷类化合物。尤为重要的是,此反应无需额外的光催化剂,仅以廉价易得的氢碘酸、氢溴酸或N-溴代丁二酰亚胺为催化剂,大大降低了反应成本。
发明内容
本发明旨在提供一种反应条件温和、绿色、高效、成本低的多取代1,3恶唑烷类化合物的合成方法。
反应方程式如下式所示。
其中R1取代基可以是甲基、甲氧基等;R2取代基可以是烷氧基、苯基、取代氨基等;R3取代基可以是各种取代芳基等。
该制备过程主要包括以下步骤:向烧瓶中依次加入甘氨酸衍生物、环氧乙烷衍生物、催化剂和适量溶剂,在可见光照射下室温搅拌10-20小时,然后减压蒸除溶剂,柱层析得到多取代1,3恶唑烷化生物。
在上述步骤中,催化剂优选为氢碘酸、氢溴酸或N-溴代丁二酰亚胺其中一种。
在上述步骤中,可见光光源优选为26W节能灯、太阳光或5W蓝色LED灯其中一种。
在上述步骤中,溶剂优选为二氯甲烷、甲苯、1,2-二氯乙烷或1,2-二氯乙烷与乙腈的混合溶剂其中一种。
在上述步骤中,甘氨酸衍生物、环氧乙烷衍生物与催化剂的摩尔比优选为1:1.2:0.3。
在上述步骤中,反应过程中温度优选为室温。
与现有技术相比,本发明具有以下优点:
1.反应原料及催化剂廉价易得。
2.反应仅需一步转化,收率较好(70-80%)。
3.不使用额外的光催化剂、氧化剂以及金属试剂等,反应在室温、空气和可见光照射下进行,反应条件温和,操作简便,环境友好、绿色环保,克服了传统方法条件苛刻、原料或催化剂昂贵等缺点。
附图说明
图1为3-(4-甲氧基苯基)-4-苯基恶唑烷-2-羧酸乙酯的1H NMR图谱
图2为3-(4-甲氧基苯基)-4-苯基恶唑烷-2-羧酸乙酯的13C NMR图谱
具体实施方式
下面的实例可以使本专业的技术人员更了解本发明,但不以任何方式限制本发明。本发明所用原料均为已知化合物,可由市场购得或可采用本领域已知方法制备得到。
实施例1:3-(4-甲氧基苯基)-4-苯基恶唑烷-2-羧酸乙酯的制备
在100mL烧瓶中,将1.05g(5mmol)(4-甲氧基苯基)甘氨酸乙酯溶于50.0mL二氯甲烷,然后依次加入721mg(6mmol)氧化苯乙烯、253mg(30mol%)氢溴酸,在26W节能灯照射下室温搅拌12小时。然后减压蒸除溶剂,柱层析(石油醚/乙酸乙酯=16:1)得到1.31g产品,产率80%。淡黄色液体。1H NMR(400MHz,CDCl3)δ7.34–7.29(m,4H),7.27–7.22(m,1H),6.70(d,J=9.1Hz,2H),6.50(d,J=9.1Hz,2H),5.79(s,1H),4.98(dd,J=7.4,3.7Hz,1H),4.79(t,J=7.6Hz,1H),4.22–4.10(m,2H),4.01(dd,J=7.8,3.7Hz,1H),3.67(s,3H),1.20(t,J=7.1Hz,3H);13C NMR(100MHz,CDCl3)δ170.0,152.5,141.1,136.7,128.8,127.5,126.2,115.4,114.6,89.1,75.9,61.2,61.0,55.4,14.1.HRMS(ESI):calcd for C19H21NO4Na(M+Na+)350.1363;found 350.1369.
实施例2:(3-(4-甲氧基苯基)-4-苯基恶唑烷-2-羰基)甘氨酸乙酯的制备
在100mL烧瓶中,将1.33g(5mmol)(4-甲氧基苯基)甘氨酰甘氨酸乙酯溶于50.0mL 1,2-二氯乙烷,然后依次加入721mg(6mmol)氧化苯乙烯、337mg(30mol%)氢碘酸,在5W蓝色LED灯照射下室温搅拌15小时。然后减压蒸除溶剂,柱层析(石油醚/乙酸乙酯=4:1)得到1.50g产品,产率78%。白色固体。1H NMR(400MHz,CDCl3)δ7.30–7.21(m,3H),7.16(d,J=6.9Hz,2H),7.06(s,1H),6.69(d,J=9.0Hz,2H),6.49(d,J=9.0Hz,2H),5.66(s,1H),5.05(d,J=4.6Hz,1H),4.59(dd,J=8.1,6.2Hz,1H),4.20–4.08(m,3H),4.04(dd,J=8.2,1.7Hz,1H),3.94(dd,J=18.3,4.9Hz,1H),3.65(s,3H),1.25(t,J=7.1Hz,3H).13C NMR(100MHz,CDCl3)δ169.41,169.37,152.5,140.3,136.3,128.7,127.5,126.6,115.7,114.5,89.3,74.6,61.7,61.5,55.3,41.0,14.0.HRMS-ESI:calcd for C21H24N2O5(M+H)+385.1758,found385.1765.
实施例3:苯基(4-苯基-3-(对甲苯基)恶唑烷-2-基)甲酮的制备
在100mL烧瓶中,将1.13g(5mmol)1-苯基-2-(对甲苯胺基)乙-1-酮溶于50.0mL甲苯,然后依次加入721mg(6mmol)氧化苯乙烯、267mg(30mol%)N-溴代丁二酰亚胺,在5W蓝色LED灯照射下室温搅拌20小时。然后减压蒸除溶剂,柱层析(石油醚/乙酸乙酯=16:1)得到1.36g产品,产率79%。黄色固体。1H NMR(400MHz,CDCl3)δ8.13(d,J=7.5Hz,2H),7.64–7.60(m,1H),7.53–7.49(m,2H),7.36–7.31(m,4H),7.27–7.24(m,1H),6.85(d,J=8.3Hz,2H),6.68(s,1H),6.26(d,J=8.4Hz,2H),5.08(dd,J=7.1,1.9Hz,1H),4.47(t,J=7.7Hz,1H),4.04(dd,J=8.3,2.0Hz,1H),2.13(s,3H).13C NMR(100MHz,CDCl3)δ194.3,142.1,140.8,134.9,133.7,129.7,128.9,128.8,127.5,126.7,126.2,113.4,88.3,75.1,61.5,20.2.HRMS-ESI:calcd for C23H21NO2(M+H)+344.1645,found 344.1652.
实施例4:3-(3-氟-4-甲基苯基)-4-苯基恶唑烷-2-羧酸乙酯的制备
在100mL烧瓶中,将1.06g(5mmol)(3-氟-4-甲基苯基)甘氨酸乙酯溶于50.0mL(1,2-二氯乙烷/乙腈=15:1),然后依次加入721mg(6mmol)氧化苯乙烯、337mg(30mol%)氢碘酸,在26W节能灯照射下室温搅拌20小时。然后减压蒸除溶剂,柱层析(石油醚/乙酸乙酯=16:1)得到1.17g产品,产率71%。淡棕色液体。1H NMR(400MHz,CDCl3)δ7.34–7.30(m,2H),7.29–7.23(m,3H),6.91–6.87(m,1H),6.23–6.16(m,2H),5.74(s,1H),4.95(dd,J=7.2,2.7Hz,1H),4.79(t,J=7.6Hz,1H),4.27–4.16(m,2H),4.04(dd,J=8.0,2.7Hz,1H),2.08(s,3H),1.26(t,J=7.1Hz,3H).13C NMR(100MHz,CDCl3)δ169.6,161.6(d,JC-F=241.3Hz),142.1(d,JC-F=10.5Hz),141.0,131.7(d,JC-F=7.0Hz),128.9,127.7,126.1,114.0(d,JC-F=17.5Hz),109.2,101.1(d,JC-F=27.1Hz),88.4,75.7,61.5,61.0,14.1,13.5(d,JC-F=3.2Hz).19F NMR(376MHz,CDCl3)δ-115.86(s,F).HRMS-ESI:calcd for C19H20FNO3(M+H)+330.1500,found 330.1508.
实施例5:3-(4-溴苯基)-4-苯基恶唑烷-2-羧酸乙酯的制备
在100mL烧瓶中,将1.29g(5mmol)(4-溴苯基)甘氨酸乙酯溶于50.0mL(1,2-二氯乙烷/乙腈=20:1),然后依次加入721mg(6mmol)氧化苯乙烯、337mg(30mol%)氢碘酸,在5W蓝色LED灯照射下室温搅拌15小时。然后减压蒸除溶剂,柱层析(石油醚/乙酸乙酯=16:1)得到1.35g产品,产率72%。淡黄色液体。1H NMR(400MHz,CDCl3)δ7.33–7.24(m,5H),7.20(d,J=9.0Hz,2H),6.38(d,J=9.0Hz,2H),5.76(s,1H),4.96(dd,J=7.2,2.6Hz,1H),4.80(dd,J=8.0,7.2Hz,1H),4.25–4.17(m,2H),4.05(dd,J=8.1,2.7Hz,1H),1.26(t,J=7.1Hz,3H).13CNMR(100MHz,CDCl3)δ169.4,141.5,140.7,131.9,128.9,127.8,126.1,115.3,110.5,88.2,75.7,61.6,60.9,14.1.HRMS-ESI:calcd for C18H18BrNO3(M+Na)+398.0362,found398.0372.
实施例6:4-(4-氟苯基)-3-(4-甲氧基苯基)恶唑烷-2-羧酸乙酯的制备
在100mL烧瓶中,将1.05g(5mmol)(4-甲氧基苯基)甘氨酸乙酯溶于50.0mL(1,2-二氯乙烷/乙腈=25:1),然后依次加入828mg(6mmol)(4-氟苯基)环氧乙烷、337mg(30mol%)氢碘酸,在太阳光照射下室温搅拌10小时。然后减压蒸除溶剂,柱层析(石油醚/乙酸乙酯=16:1)得到1.33g产品,产率77%。淡棕色液体。1H NMR(400MHz,CDCl3)δ7.32–7.25(m,2H),7.03–6.95(m,2H),6.71(d,J=9.0Hz,2H),6.49(d,J=9.0Hz,2H),5.78(s,1H),4.97(dd,J=7.4,3.7Hz,1H),4.77(t,J=7.6Hz,1H),4.21–4.11(m,2H),3.98(dd,J=7.9,3.6Hz,1H),3.68(s,3H),1.20(t,J=7.1Hz,3H).13C NMR(100MHz,CDCl3)δ169.9,162.1(d,JC-F=244.1Hz),152.6,136.8(d,JC-F=2.9Hz),136.4,127.8(d,JC-F=8.0Hz),115.7(d,JC-F=21.4Hz),115.5,114.6,89.1,75.8,61.3,60.3,55.4,14.1.19F NMR(376MHz,CDCl3)δ-114.87(s,F).HRMS-ESI:calcd for C19H20FNO4(M+H)+346.1449,found 346.1450.
实施例7:4-(4-乙酰氧基苯基)-3-(4-甲氧基苯基)恶唑烷-2-羧酸乙酯的制备
在100mL烧瓶中,将1.05g(5mmol)(4-甲氧基苯基)甘氨酸乙酯溶于50.0mL(1,2-二氯乙烷/乙腈=20:1),然后依次加入1.07g(6mmol)(4-乙酰氧基苯基)环氧乙烷、337mg(30mol%)氢碘酸,在5W蓝色LED灯照射下室温搅拌16小时。然后减压蒸除溶剂,柱层析(石油醚/乙酸乙酯=16:1)得到1.39g产品,产率72%。淡棕色液体。1H NMR(400MHz,CDCl3)δ7.32(d,J=8.5Hz,2H),7.04(d,J=8.5Hz,2H),6.71(d,J=9.0Hz,2H),6.50(d,J=9.0Hz,2H),5.78(s,1H),4.98(dd,J=7.4,3.6Hz,1H),4.77(t,J=7.6Hz,1H),4.20–4.10(m,2H),4.01(dd,J=7.9,3.6Hz,1H),3.68(s,3H),2.27(s,3H),1.20(t,J=7.1Hz,3H).13C NMR(100MHz,CDCl3)δ169.9,169.3,152.6,149.9,138.6,136.5,127.3,121.9,115.5,114.6,89.1,75.7,61.2,60.4,55.4,21.0,14.0.HRMS-ESI:calcd for C21H23NO6(M+H)+386.1598,found386.1599。
Claims (5)
2.根据权利要求1所述的多取代1,3恶唑烷化合物的制备方法,其特征在于:催化剂为氢碘酸、氢溴酸或N-溴代丁二酰亚胺其中一种。
3.根据权利要求1所述的多取代1,3恶唑烷化合物的制备方法,其特征在于:可见光光源为26W节能灯、太阳光或5W蓝色LED灯其中一种。
4.根据权利要求1所述的多取代1,3恶唑烷化合物的制备方法,其特征在于:溶剂为二氯甲烷、甲苯、1,2-二氯乙烷或1,2-二氯乙烷与乙腈的混合溶剂其中一种。
5.根据权利要求1所述的多取代1,3恶唑烷化合物的制备方法,其特征在于:甘氨酸衍生物、环氧乙烷衍生物与催化剂的摩尔比为1:1.2:0.3。
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