CN108997287A - 以四氟硼酸的离子液体为氟源催化合成4-氟代四氢吡喃衍生物的方法 - Google Patents

以四氟硼酸的离子液体为氟源催化合成4-氟代四氢吡喃衍生物的方法 Download PDF

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CN108997287A
CN108997287A CN201810812930.5A CN201810812930A CN108997287A CN 108997287 A CN108997287 A CN 108997287A CN 201810812930 A CN201810812930 A CN 201810812930A CN 108997287 A CN108997287 A CN 108997287A
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CN108997287B (zh
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高子伟
王芸芸
苏洁
张伟强
简亚军
孙华明
张国防
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Ningxia Normal University
Shaanxi Normal University
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Abstract

本发明公开了一种以四氟硼酸的离子液体为氟源催化合成4‑氟代四氢吡喃类化合物的方法，以二氯甲烷为溶剂，5‑磺基水杨酸和二氯二茂钛双酸体系为催化剂，1‑丁基‑2,3‑二甲基咪唑鎓四氟硼酸盐为氟源，使高烯丙醇类化合物与芳香醛在温和条件下发生Prins环化反应，制得4‑氟代四氢吡喃类化合物。本发明操作步骤简单，条件温和，催化剂用量少，成本低，底物适用性较广，目标化合物产率高，可广泛应用于酸性反应条件下4‑氟代四氢吡喃类化合物的制备。

Description

以四氟硼酸的离子液体为氟源催化合成4-氟代四氢吡喃衍生 物的方法
技术领域
本发明属于氟代四氢吡喃类化合物的合成技术领域，具体涉及一种以1-丁基-2,3-二甲基咪唑鎓四氟硼酸盐作为氟源，高烯丙醇类化合物和芳香醛作为反应底物，常温条件下，以5-磺基水杨酸与二氯二茂钛混合物为催化剂，合成4-氟代四氢吡喃类化合物的方法。
背景技术
四氢吡喃衍生物是一类很重要的含氧杂环化合物，其结构广泛存在于天然药物分子的结构中，是一类合成香精香料以及许多天然产物的重要中间体，具有广泛的生物活性以及药用价值。4-氟代四氢吡喃类化合物因其分子中引入了氟原子从而达到了同时调节药物的电子效应、亲油性能以及空间效应的作用，这些都能对药物的药效学和药代动力学特性产生决定性的影响。而天然药物分子结构中直接含氟原子的化合物较少，因此发展一种高效温和的合成4-氟代四氢吡喃类化合物方法，在有机合成领域和制药领域一直是人们关注的课题。
目前，4-氟代四氢吡喃类化合物主要是通过Prins环化反应得到，通常使用以下几种氟代策略：(1)利用氟化氢的离子液体作为氟源；(2)三氟化硼乙醚溶液作为氟源、三氯化铝作为路易斯酸催化得到；(3)四氟硼酸的乙醚溶液作为氟源；(4)四氟化钛既作为氟源又作为路易斯酸催化得到4-氟代四氢吡喃类化合物。但这些方法都存在催化剂用量大、毒性大等缺陷，且当用氟化氢的离子液体作为氟源时，由于氟化氢通常成气体状态，需将氟化氢和一些碱性的胺混合形成化合物以达到稳定氟化氢的目的，这就不利于对反应环境有酸性要求的Prins环化反应顺利进行。因而，寻找一种条件温和、安全高效的4-氟代四氢吡喃衍生物的合成方法是非常有必要的。
发明内容
本发明所要解决的技术问题在于克服现有4-氟代四氢吡喃类化合物合成方法存在的缺陷，提供一种以1-丁基-2,3-二甲基咪唑鎓四氟硼酸盐作为氟源、双酸协同催化合成4-氟代四氢吡喃类化合物的方法，该方法反应条件温和、催化剂用量少、反应时间短、安全高效。
解决上述技术问题所采用的技术方案是：以二氯甲烷为溶剂，5-磺基水杨酸和二氯二茂钛为催化剂，1-丁基-2,3-二甲基咪唑鎓四氟硼酸盐为氟源，将高烯丙醇类化合物与芳香醛在常温条件下反应4～6小时，得到4-氟代四氢吡喃类化合物。
上述的高烯丙醇类化合物为式中R1代表CH3、Cl或Br。
上述的芳香醛为2-噻吩甲醛、2-呋喃甲醛、5-甲基糠醛或肉桂醛，式中R2～R6各自独立的代表硝基、C1～C4烷基、C1～C4烷氧基、氟、氯、溴、碘中任意一种。
上述合成方法中，所述芳香醛与高烯丙醇类化合物的摩尔比为1:1.1～1.5，5-磺基水杨酸的加入量是芳香醛摩尔量的25％～35％，二氯二茂钛的加入量是芳香醛摩尔量的8％～12％，1-丁基-2,3-二甲基咪唑鎓四氟硼酸盐的加入量是芳香醛摩尔量的1.5～2.5倍。
本发明以1-丁基-2,3-二甲基咪唑鎓四氟硼酸盐作为氟源，5-磺基水杨酸协同二氯二茂钛为催化剂，使高烯丙醇l类化合物与芳香醛发生Prins环化反应生成4-氟代四氢吡喃类化合物。相对于已知的使用氟化氢的离子液体作为氟源，本发明以1-丁基-2,3-二甲基咪唑鎓四氟硼酸盐作为氟源，5-磺基水杨酸协同二氯二茂钛为催化剂催化Prins环化反应合成4-氟代四氢吡喃类化合物，反应安全高效、操作简便、毒性比较小，克服了氟化氢气体毒性比较大、操作过程不易控制或需用碱性胺来稳定等缺陷。另外，本发明所用催化剂对空气和水稳定，反应条件温和、反应时间短、原子经济性高、后处理简单，在合成其他氟代化合物的方法中具有一定的参考价值。
具体实施方式
下面结合实施例对本发明进一步详细说明，但本发明所要保护的范围不仅限于这些实施例。
实施例1
合成结构式如下的4-氟-4-甲基-2-(4-硝基苯基)-四氢吡喃
将0.1511g(1.0mmol)对硝基苯甲醛、131μL(1.3mmol)3-甲基-3-丁烯-1-醇、0.0248g(0.1mmol)二氯二茂钛、5-磺基水杨酸0.07626g(0.3mmol)、0.4800g(2.0mmol)1-丁基-2,3-二甲基咪唑鎓四氟硼酸盐、3mL干燥的二氯甲烷加入史莱克管，在常温下搅拌反应5小时，停止反应，柱色谱分离，得到固体4-氟-4-甲基-2-(4-硝基苯基)-四氢吡喃，其收率为83％，结构表征数据为：1H NMR(600MHz,CDCl3)δ8.15(d,J＝8.8Hz,4H),7.48(d,J＝8.6Hz,4H),4.75(d,J＝2.1Hz,1H),4.73(d,J＝2.1Hz,1H),4.07–4.01(m,2H),3.90(td,J＝11.6,2.7Hz,2H),2.07(ddt,J＝13.7,9.3,2.1Hz,2H),1.83-1.73(m,4H),1.54(ddd,J＝38.3,14.1,11.8Hz,2H),1.41(s,3H),1.38(s,3H)；13C NMR(151MHz,CDCl3)δ149.80(s),147.29(s),126.26(s),123.58(s),92.47(s),74.26(s),63.93(s),44.34(s),35.96(s),27.40(s).
实施例2
合成结构式如下的2-(4-氯-3-硝基苯基)-4-氟-4-甲基-四氢吡喃
本实施例中，用等摩尔4-氯-3-硝基苯甲醛替换实施例1中的对硝基苯甲醛，其他步骤与实施例1相同，得到固体2-(4-氯-3-硝基苯基)-4-氟-4-甲基四氢吡喃，其收率为77％，结构表征数据为：1H NMR(600MHz,CDCl3)δ7.89(d,J＝1.7Hz,2H),7.49(dd,J＝15.4,5.1Hz,4H),4.71(dd,J＝11.7,2.2Hz,2H),4.07-4.02(m,2H),3.94-3.88(m,2H),2.08(ddt,J＝13.8,9.0,2.3Hz,2H),1.85-1.73(m,4H),1.60-1.52(m,2H),1.43(s,3H),1.40(s,3H)；13C NMR(151MHz,CDCl3)δ148.09(s),143.25-143.11(m),131.89(s),125.87-125.74(m),73.25(s),44.00-43.87(m),36.18(s).
实施例3
合成结构式如下的4-氟-4-甲基-2-(4-甲氧基苯基)-四氢吡喃
本实施例中，用等摩尔4-甲氧基苯甲醛替换实施例1中的对硝基苯甲醛，其他步骤与实施例1相同，得到固体4-氟-4-甲基-2-(4-甲氧基苯基)-四氢吡喃，其收率为68％，结构表征数据为：1H NMR(600MHz,CDCl3)δ7.29(d,J＝8.6Hz,4H),6.89(d,J＝8.7Hz,4H),4.64(dd,J＝11.7,1.9Hz,2H),4.05-4.00(m,2H),3.97-3.90(m,2H),3.80(s,6H),2.05-1.99(m,2H),1.84-1.76(m,4H),1.73-1.65(m,2H),1.44(s,3H),1.40(s,3H)；13C NMR(151MHz,CDCl3)δ127.27(s),92.80-92.67(m),74.72(s),64.02(s),43.87(s),36.61-36.48(m),27.81(s).
实施例4
合成结构式如下的4-氟-4-甲基-2-(噻吩基)-四氢吡喃
本实施例中，用等摩尔2-噻吩甲醛替换实施例1中的对硝基苯甲醛，其他步骤与实施例1相同，得到固体4-氟-4-甲基-2-(噻吩基)-四氢吡喃，其收率为81％，结构表征数据为：1H NMR(600MHz,CDCl3)δ7.27(dd,J＝5.0,1.2Hz,2H),6.98(dd,J＝7.3,3.7Hz,4H),4.61(dd,J＝11.3,2.5Hz,2H),4.17-4.12(m,2H),3.59(td,J＝12.4,2.2Hz,2H),2.20-2.16(m,2H),2.16-2.10(m,2H),2.06(dd,J＝12.9,5.4Hz,2H),1.81(ddd,J＝10.5,4.8,2.4Hz,2H),1.59(s,3H),1.55(s,3H)；13C NMR(151MHz,CDCl3)δ126.51(s),125.17-125.04(m),123.96(s),65.80-65.67(m),45.09(s),37.35-37.22(m).
实施例5
合成结构式如下的4-氟-4-甲基-2-(呋喃基)-四氢吡喃
本实施例中，用等摩尔2-呋喃甲醛替换实施例1中的对硝基苯甲醛，其他步骤与实施例1相同，得到固体4-氟-4-甲基-2-(呋喃基)-四氢吡喃，其收率为79％，结构表征数据为：1H NMR(400MHz,CDCl3)δ7.38(s,2H),6.30(d,J＝26.4Hz,4H),4.72(d,J＝11.7Hz,2H),3.95(t,J＝15.0Hz,4H),2.00(s,4H),1.79(d,J＝20.6Hz,4H),1.46(s,3H),1.41(s,3H)；13CNMR(101MHz,CDCl3)δ154.14(s),142.38(s),107.09(s),39.71-39.51(m),36.05(s),27.53(s).
实施例6
合成结构式如下的4-氟-4-甲基-2-(2-硝基苯基)-四氢吡喃
本实施例中，用等摩尔2-硝基苯甲醛替换实施例1中的对硝基苯甲醛，其他步骤与实施例1相同，得到固体4-氟-4-甲基-2-(2-硝基苯基)-四氢吡喃，其收率为72％，结构表征数据为：1H NMR(600MHz,CDCl3)δ8.23(s,2H),8.11(d,J＝8.0Hz,2H),7.65(d,J＝7.6Hz,2H),7.49(t,J＝7.9Hz,2H),4.76(d,J＝10.5Hz,2H),4.05(dd,J＝11.5,5.3Hz,2H),3.95-3.90(m,2H),2.13-2.08(m,2H),1.82(ddd,J＝32.9,8.3,4.8Hz,4H),1.62(dd,J＝31.2,19.2Hz,2H),1.43(s,3H),1.40(s,3H)；13C NMR(151MHz,CDCl3)δ131.75(s),122.41(s),92.14-92.01(m),73.94(s),44.31(s),36.14(s),27.91(s).
实施例7
合成结构式如下的4-氟-4-甲基-2-(3-硝基苯基)-四氢吡喃
本实施例中，用等摩尔3-硝基苯甲醛替换实施例1中的对硝基苯甲醛，其他步骤与实施例1相同，得到固体4-氟-4-甲基-2-(3-硝基苯基)-四氢吡喃，其收率为80％，结构表征数据为：1H NMR(600MHz,CDCl3)δ7.88(dd,J＝8.2,1.1Hz,2H),7.76(d,J＝7.9Hz,2H),7.62(dd,J＝11.3,4.0Hz,2H),7.40(dd,J＝11.3,4.2Hz,2H),5.23(dd,J＝11.3,2.0Hz,2H),4.03-3.99(m,2H),3.94-3.90(m,2H),2.33(ddd,J＝13.5,6.6,4.4Hz,2H),1.85-1.76(m,4H),1.59(dd,J＝24.8,13.5Hz,2H),1.43(s,3H),1.40(s,3H)；13C NMR(151MHz,CDCl3)δ132.51(s),123.13(s),90.15(s),70.29(s),42.30-42.17(m).
实施例8
合成结构式如下的4-氟-4-甲基-2-(3-甲氧基苯基)-四氢吡喃
本实施例中，用等摩尔3-甲氧基苯甲醛替换实施例1中的对硝基苯甲醛，其他步骤与实施例1相同，得到固体4-氟-4-甲基-2-(3-甲氧基苯基)-四氢吡喃，其收率为65％，结构表征数据为：1H NMR(600MHz,CDCl3)δ7.28(d,J＝8.0Hz,2H),6.95(dd,J＝4.2,2.1Hz,4H),6.84(ddd,J＝8.3,2.5,0.8Hz,2H),4.68(dd,J＝11.7,2.1Hz,2H),4.08-4.04(m,2H),3.97-3.92(m,2H),3.83(s,6H),2.11-2.06(m,2H),1.86-1.77(m,4H),1.72-1.64(m,2H),1.45(s,3H),1.41(s,3H)；13C NMR(151MHz,CDCl3)δ127.27(s),92.80-92.67(m),74.72(s),64.02(s),43.87(s),36.61-36.48(m),27.81(s).
实施例9
合成结构式如下的4-氟-4-甲基-2-(2-甲氧基苯基)-四氢吡喃
本实施例中，用等摩尔2-甲氧基苯甲醛替换实施例1中的对硝基苯甲醛，其他步骤与实施例1相同，得到4-氟-4-甲基-2-(2-甲氧基苯基)-四氢吡喃，其收率为61％，结构表征数据为：1H NMR(600MHz,CDCl3)δ7.46(dd,J＝7.6,1.5Hz,1H),7.25-7.20(m,1H),6.99-6.95(m,1H),6.85(d,J＝8.2Hz,1H),4.79-4.74(m,2H),4.70(s,1H),4.13(ddd,J＝11.9,5.3,1.5Hz,1H),3.82(s,3H),3.66(td,J＝13.0,2.2Hz,1H),3.53-3.49(m,2H),2.24(t,J＝7.1Hz,2H),1.97(dt,J＝12.6,2.2Hz,1H),1.88(dt,J＝12.9,6.5Hz,1H),1.74(s,3H),1.63(dd,J＝41.5,6.8Hz,3H),1.44(s,3H),1.26(s,2H)；13C NMR(151MHz,CDCl3)δ155.26-155.13(m),142.93-142.79(m),120.65-120.52(m),65.60(s),59.19(s),55.39(s),44.06(s).
实施例10
合成结构式如下的4-氟-4-甲基-2-(5-甲基呋喃基)-四氢吡喃
本实施例中，用等摩尔5-甲基糠醛替换实施例1中的对硝基苯甲醛，其他步骤与实施例1相同，得到固体4-氟-4-甲基-2-(5-甲基呋喃基)-四氢吡喃，其收率为78％，结构表征数据为：1H NMR(400MHz,CDCl3)δ6.15(d,J＝3.0Hz,2H),5.90(d,J＝3.0Hz,2H),4.68-4.63(m,2H),3.98-3.87(m,4H),2.28(s,6H),2.03(s,2H),1.99(s,1H),1.81(s,2H),1.76(s,3H),1.46(s,3H),1.40(s,3H)；13C NMR(101MHz,CDCl3)δ152.32(s),107.87(s),106.19(s),63.77(s),36.06(s),27.56(s),13.54(s).
实施例11
合成结构式如下的(E)-4-氟-4-甲基-2-(2-苯乙烯基)-四氢吡喃
本实施例中，用等摩尔肉桂醛替换实施例1中的对硝基苯甲醛，其他步骤与实施例1相同，得到固体(E)-4-氟-4-甲基-2-(2-苯乙烯基)-四氢吡喃，其收率为75％，结构表征数据为：1H NMR(600MHz,CDCl3)δ7.29(d,J＝7.4Hz,4H),7.22(s,4H),7.15(s,2H),6.54(d,J＝15.9Hz,2H),6.09(d,J＝22.0Hz,2H),4.23(s,2H),3.89(s,2H),3.77(d,J＝23.8Hz,2H),1.88(s,2H),1.68(s,3H),1.58(s,1H),1.48(s,2H),1.33(s,3H),1.30(s,3H)；13C NMR(151MHz,CDCl3)δ129.46(s),128.59(s),127.33(s),126.58(s),125.34(s),72.37(s),35.16(s),26.66(s).

Claims (7)

1.一种以四氟硼酸的离子液体为氟源催化合成4-氟代四氢吡喃类化合物的方法，其特征在于：以二氯甲烷为溶剂，5-磺基水杨酸和二氯二茂钛为催化剂，1-丁基-2,3-二甲基咪唑鎓四氟硼酸盐为氟源，将高烯丙醇类化合物与芳香醛在常温条件下反应4～6小时，得到4-氟代四氢吡喃类化合物。
2.根据权利要求1所述的以四氟硼酸的离子液体为氟源催化合成4-氟代四氢吡喃类化合物的方法，其特征在于：所述高烯丙醇类化合物为式中R1代表CH3、Cl或Br。
3.根据权利要求1所述的以四氟硼酸的离子液体为氟源催化合成4-氟代四氢吡喃类化合物的方法，其特征在于：所述的芳香醛为2-噻吩甲醛、2-呋喃甲醛、5-甲基糠醛或肉桂醛，式中R2～R6各自独立的代表硝基、C1～C4烷基、C1～C4烷氧基、氟、氯、溴、碘中任意一种。
4.根据权利要求1～3任意一项所述的以四氟硼酸的离子液体为氟源催化合成4-氟代四氢吡喃类化合物的方法，其特征在于：所述芳香醛与高烯丙醇类化合物的摩尔比为1:1.1～1.5。
5.根据权利要求1～3任意一项所述的采以四氟硼酸的离子液体为氟源催化合成4-氟代四氢吡喃类化合物的方法，其特征在于：所述5-磺基水杨酸的加入量是芳香醛摩尔量的25％～35％。
6.根据权利要求1～3任意一项所述的以四氟硼酸的离子液体为氟源催化合成4-氟代四氢吡喃类化合物的方法，其特征在于：所述二氯二茂钛的加入量是芳香醛摩尔量的8％～12％。
7.根据权利要求1～3任意一项所述的以四氟硼酸的离子液体为氟源催化合成4-氟代四氢吡喃类化合物的方法，其特征在于：所述的1-丁基-2,3-二甲基咪唑鎓四氟硼酸盐的加入量是芳香醛摩尔量的1.5～2.5倍。
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