CN111196823A - 一种3-膦酰化苯并噻吩类化合物及制备方法 - Google Patents
一种3-膦酰化苯并噻吩类化合物及制备方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
- C07F9/655345—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a five-membered ring
- C07F9/655354—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a five-membered ring condensed with carbocyclic rings or carbocyclic ring systems
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
技术领域
本发明涉及有机合成技术领域,具体涉及一种3-膦酰化苯并噻吩类化合物及制备方法。
背景技术
含磷化合物由于在有机合成、药物和光电材料领域的广泛应用而备受关注。有机合成工作者发展了许多方法来制备含磷化合物。其中,以磷为中心的自由基引发的串联反应是最有用的策略之一,通常需要过渡金属催化剂,较高的反应温度和有机溶剂。因此,亟需开发磷自由基参与的绿色催化反应。另一方面,苯并噻吩是一种重要的杂环骨架,其衍生物广泛存在于许多天然产物,药物和功能材料中。例如,市售药物如雷洛昔芬,齐留通和舍他康唑都含有苯并噻吩骨架。由于含磷官能团对于苯并噻吩骨架的重要性,将膦酰基和苯并噻吩骨架结合起来可能是构建潜在生物活性化合物的有效途径。
最近,高玉珍课题组通过当量Ag2O促进2-甲硫基芳香炔类化合物和二芳基膦氧化物的环化反应,实现了3-膦酰化苯并噻吩的合成(Org. Lett., 2019, 21, 4605.)。其中,使用三氟乙酸作为溶剂对于抑制对苯并[b]磷氧化物的副反应至关重要。该方法使用化学计算量的过渡金属试剂,酸性溶剂和相对较高的温度,在一定程度上局限了其应用。我们推测其中副产物苯并[b]磷氧化物形成的原因,可能是银试剂活化反应底物中的叁键。因此,如果发展新型的“无银”催化体系,就可以避免形成苯并[b]磷氧化物。此外,水作为具有丰富储备的自然资源,近年来因其无毒,成本低和不易燃等特点,也广泛作为绿色溶剂用于有机合成。综上,在温和条件下,以水为溶剂,采用无金属催化体系,可见光促进下直接合成3-膦酰化苯并噻吩类化合物的方法目前尚未见报道。
发明内容
本发明提出了一种3-膦酰化苯并噻吩类化合物及制备方法,该方法操作简单,反应条件温和,反应收率较高,无需使用过渡金属试剂,是一种环境友好的绿色合成方法。
实现本发明的技术方案是:
一种3-膦酰化苯并噻吩类化合物,结构式如下:
其中R1选自烷基、烷氧基、三氟甲基、卤素取代基,R2选自烷基、卤素取代基;R3选自烷基、卤素取代基。
所述烷基选自C1~C4的烷基;所述烷氧基选自C1~C4的烷氧基;所述卤素取代基选自氟、氯或溴。
所述的3-膦酰化苯并噻吩类化合物的制备方法,将2-甲硫基芳香炔类化合物和二芳基膦氧化物在催化剂和氧化剂作用下,经过蓝光照射进行膦酰化/环化反应,得到3-膦酰化苯并噻吩类化合物。
所述2-甲硫基芳香炔类化合物的结构式如下:
R1选自烷基、烷氧基、三氟甲基、卤素取代基,R2选自烷基、卤素取代基。
所述二芳基膦氧化物的结构式如下:
其中R3选自烷基、卤素取代基。
所述催化剂为2,4,5,6-四(9-咔唑基)-间苯二腈(4CzIPN),氧化剂为过氧化十二酰(LPO)(LPO)。
所述2-甲硫基芳香炔类化合物、二芳基膦氧化物、催化剂和氧化剂的摩尔比为1:(1~3):(0.01~0.05):(1~3)。
所述反应采用水或者碳酸二甲酯作为反应介质。
采用蓝光照射,在室温25℃温度下,反应 8~18 h。
本发明所述3-膦酰化苯并噻吩类化合物的合成方法反应通式如下:
本发明的有益效果是:本发明提供了一种3-膦酰化苯并噻吩类化合物的合成方法,所述方法不需要使用过渡金属催化剂和传统挥发性有机溶剂,以绿色溶剂水为反应介质,在可见光照射下使用有机光敏剂作催化剂,通过膦酰化/环化步骤,一锅反应高效合成3-膦酰化苯并噻吩类化合物。该方法所涉及的操作简便安全、具有反应条件温和、无过渡金属、环境友好的优点。
具体实施方式
下面将结合本发明实施例,对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有付出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
3-膦酰化苯并噻吩类化合物的合成方法,步骤如下:
向装有磁子的25 mL反应管中依次加入1-(2-(甲硫基)苯基)-2-苯基乙炔(0.2 mmol),二苯基膦氧化物(0.4 mmol),过氧化十二酰(LPO)(0.4 mmol),催化剂4CzIPN(3 mol%,以1-(2-(甲硫基)苯基)-2-苯基乙炔为基准,下述所有实施例均如此);对反应管抽真空,用氮气置换三次,随后加入溶剂水(2 mL),反应管在蓝光照射下搅拌12 h。反应结束后,用乙酸乙酯萃取反应液,合并有机相之后用无水硫酸钠干燥,柱层析得到目标产物。以1-(2-(甲硫基)苯基)-2-苯基乙炔摩尔量为100%计,终产物的产率为90%。
具体结构如下:
white solid, m. p. 169.4-171.9 ℃; 1H NMR (400 MHz, Chloroform-d) δ 7.94(d, J = 8.3 Hz, 1H), 7.86 (d, J = 8.0 Hz, 1H), 7.58 (m, 4H), 7.36 (m, 3H),7.26 (m, 5H), 7.16 (d, 2H), 7.10 (t, J = 7.4 Hz, 1H), 7.00 (t, J = 7.7 Hz,2H). 13C NMR (101 MHz, Chloroform-d) δ 154.9 (d, J = 12.9 Hz), 141.4 (d, J =13.0 Hz), 139.4 (d, J = 12.7 Hz), 133.9, 132.9, 132.9 (d, J = 2.9 Hz), 131.7(d, J = 10.1 Hz), 131.5 (d, J = 2.9 Hz), 129.9, 128.4, 128.3 (d, J = 12.5Hz), 127.6, 126.0, 124.9 (d, J = 4.4 Hz), 122.8 (d, J = 105.4 Hz), 121.5. 31PNMR (162 MHz, Chloroform-d) δ 21.5。
实施例2
3-膦酰化苯并噻吩类化合物的合成方法,步骤如下:
向装有磁子的25 mL反应管中依次加入1-(2-(甲硫基)苯基)-2-(4-甲基苯基)乙炔(0.2 mmol),二苯基膦氧化物(0.2 mmol),过氧化十二酰(LPO)(0.6 mmol),催化剂4CzIPN(1 mol%);对反应管抽真空,用氮气置换三次,随后加入溶剂水(2 mL),反应管在蓝光照射下搅拌12 h。反应结束后,用乙酸乙酯萃取反应液,合并有机相之后用无水硫酸钠干燥,柱层析得到目标产物。以1-(2-(甲硫基)苯基)-2-(4-甲基苯基)乙炔摩尔量为100%计,终产物的产率为94%。
具体结构如下:
white solid, m. p. 198.2-200.7 ℃; 1H NMR (400 MHz, Chloroform-d) δ 7.9(d, J = 8.3 Hz, 1H), 7.9 (d, J = 8.0 Hz, 1H), 7.6 – 7.5 (m, 4H), 7.4 – 7.3(m, 3H), 7.2 (m, 5H), 7.0 (d, J = 8.0 Hz, 2H), 6.8 (d, J = 7.8 Hz, 2H), 2.2(s, 3H). 13C NMR (101 MHz, Chloroform-d) δ 155.1 (d, J = 12.8 Hz), 141.5 (d, J= 12.9 Hz), 139.4 (d, J = 12.6 Hz), 138.4, 134.1, 133.1, 131.7 (d, J = 10.2Hz), 131.2 (d, J = 2.9 Hz), 129.9 (d, J = 2.9 Hz), 129.8, 128.3, 128.2 (d, J= 4.1 Hz), 125.9, 124.8 (d, J = 8.3 Hz), 122.8 (d, J = 104.5 Hz), 121.5 21.2.31P NMR (162 MHz, Chloroform-d) δ 21.7。
实施例3
3-膦酰化苯并噻吩类化合物的合成方法,步骤如下:
向装有磁子的25 mL反应管中依次加入1-(2-(甲硫基)苯基)-2-(4-甲氧基苯基)乙炔(0.2 mmol),二苯基膦氧化物(0.4 mmol),过氧化十二酰(LPO)(0.2 mmol),催化剂4CzIPN(5 mol%);对反应管抽真空,用氮气置换三次,随后加入溶剂水(2 mL),反应管在蓝光照射下搅拌18 h。反应结束后,用乙酸乙酯萃取反应液,合并有机相之后用无水硫酸钠干燥,柱层析得到目标产物。以1-(2-(甲硫基)苯基)-2-(4-甲氧基苯基)乙炔摩尔量为100%计,终产物的产率为73%。
具体结果如下:
white solid; m. p. 159.4-162.7 ℃; 1H NMR (400 MHz, Chloroform-d) δ 7.86(t, J = 7.1 Hz, 2H), 7.61 – 7.54 (m, 4H), 7.37 (m, 3H), 7.27 (m, 5H), 7.10(d, J = 8.7 Hz, 2H), 6.51 (d, J = 8.7 Hz, 2H), 3.74 (s, 3H). 13C NMR (101 MHz,Chloroform-d) δ 159.7, 155.1 (d, J = 13.0 Hz), 141.5 (d, J = 13.0 Hz), 139.3(d, J = 12.8 Hz), 134.2, 133.2, 131.7, 131.6, 131.3 (d, J = 2.9 Hz), 131.2,128.3 (d, J = 12.4 Hz), 125.8, 125.1 (d, J = 3.0 Hz), 124.8 (d, J = 9.1 Hz),122.5 (d, J = 104.9 Hz), 121.5, 55.3.31P NMR (162 MHz, Chloroform-d) δ 21.5。
实施例4
3-膦酰化苯并噻吩类化合物的合成方法,步骤如下:
向装有磁子的25 mL反应管中依次加入1-(2-(甲硫基)苯基)-2-(4-乙基苯基)乙炔(0.2 mmol),二苯基膦氧化物(0.6 mmol),过氧化十二酰(LPO)(0.2 mmol),催化剂4CzIPN(3 mol%);对反应管抽真空,用氮气置换三次,随后加入溶剂水(2 mL),反应管在蓝光照射下搅拌18 h。反应结束后,用乙酸乙酯萃取反应液,合并有机相之后用无水硫酸钠干燥,柱层析得到目标产物。以1-(2-(甲硫基)苯基)-2-(4-乙基苯基)乙炔摩尔量为100%计,终产物的产率为73%。
具体结果如下:
white solid; m. p. 203.1-204.0 ℃; 1H NMR (400 MHz, Chloroform-d) δ 7.95(d, J = 8.3 Hz, 1H), 7.84 (d, J = 8.0 Hz, 1H), 7.62 – 7.51 (m, 4H), 7.38 –7.31 (m, 3H), 7.27 – 7.19 (m, 5H), 7.06 (d, J = 8.1 Hz, 2H), 6.80 (d, J = 8.1Hz, 2H), 2.52 (q, J = 7.6 Hz, 2H), 1.18 (t, J = 7.6 Hz, 3H). 13C NMR (101 MHz,Chloroform-d) δ 155.1 (d, J = 13.1 Hz), 144.5, 141.5 (d, J = 12.8 Hz), 139.4(d, J = 12.6 Hz), 134.1, 133.0, 131.7 (d, J = 10.2 Hz), 131.3 (d, J = 2.8Hz), 130.1 (d, J = 2.8 Hz), 129.9, 128.2 (d, J = 12.5 Hz), 127.1, 125.9,124.8 (d, J = 7.5 Hz), 122.6 (d, J = 104.6 Hz), 121.4, 28.6, 15.4. 31P NMR(162 MHz, Chloroform-d) δ 21.7。
实施例5
3-膦酰化苯并噻吩类化合物的合成方法,步骤如下:
向装有磁子的25 mL反应管中依次加入1-(2-(甲硫基)苯基)-2-(4-苯基苯基)乙炔(0.2 mmol),二苯基膦氧化物(0.4 mmol),过氧化十二酰(LPO)(0.4 mmol),催化剂4CzIPN(3 mol%);对反应管抽真空,用氮气置换三次,随后加入溶剂水(2 mL),反应管在蓝光照射下搅拌8 h。反应结束后,用乙酸乙酯萃取反应液,合并有机相之后用无水硫酸钠干燥,柱层析得到目标产物。以1-(2-(甲硫基)苯基)-2-(4-苯基苯基)乙炔摩尔量为100%计,终产物的产率为85%。
具体结果如下:
yellow solid; m. p. 210.6-211.4 ℃; 1H NMR (400 MHz, Chloroform-d) δ 7.98(d, J = 8.2 Hz, 1H), 7.88 (d, J = 8.0 Hz, 1H), 7.60 (dd, J = 12.3, 7.5 Hz,4H), 7.48 (d, J = 3.4 Hz, 4H), 7.38 (m, 4H), 7.32 – 7.13 (m, 9H). 13C NMR (101MHz, Chloroform-d) δ 154.4 (d, J = 12.8 Hz), 141.4 (d, J = 12.8 Hz), 141.2,140.4, 139.4 (d, J = 12.7 Hz), 134.0, 132.9, 131.8, 131.7, 131.4 (d, J = 2.9Hz), 130.4, 128.9, 128.3 (d, J = 12.5 Hz), 127.6, 127.0, 126.3, 126.0, 125.0(d, J = 2.7 Hz), 123.2 (d, J = 104.5 Hz), 121.5. 31P NMR (162 MHz, Chloroform-d) δ 21.7。
实施例6
3-膦酰化苯并噻吩类化合物的合成方法,步骤如下:
向装有磁子的25 mL反应管中依次加入1-(2-(甲硫基)苯基)-2-(4-氟苯基)乙炔(0.2mmol),二苯基膦氧化物(0.4 mmol),过氧化十二酰(LPO)(0.4 mmol),催化剂4CzIPN(3mol%);对反应管抽真空,用氮气置换三次,随后加入溶剂水(2 mL),反应管在蓝光照射下搅拌8 h。反应结束后,用乙酸乙酯萃取反应液,合并有机相之后用无水硫酸钠干燥,柱层析得到目标产物。以1-(2-(甲硫基)苯基)-2-(4-氟苯基)乙炔摩尔量为100%计,终产物的产率为89%。
具体结果如下:
white solid; m. p. 186.7-187.8 ℃; 1H NMR (400 MHz, Chloroform-d) δ 7.86(t, J = 7.8 Hz, 2H), 7.57 (dd, J = 12.4, 8.3 Hz, 4H), 7.43 – 7.32 (m, 3H),7.27 (m, 5H), 7.16 (m, 2H), 6.68 (t, J = 8.7 Hz, 2H). 13C NMR (101 MHz,Chloroform-d) δ 162.7 (d, J = 249.1 Hz), 153.6 (d, J = 12.8 Hz), 141.3 (d, J= 12.8 Hz), 139.3 (d, J = 12.5 Hz), 133.9, 132.9, 131.7 (d, J = 24.5 Hz),131.6 (d, J = 10.9 Hz), 128.9, 128.4 (d, J = 12.5 Hz), 125.9, 125.0, 123.5(d, J = 103.7 Hz), 121.5, 114.6 (d, J = 22.0 Hz). 31P NMR (162 MHz,Chloroform-d) δ 21.29. 19F NMR (376 MHz, Chloroform-d) δ -112.6。
实施例7
3-膦酰化苯并噻吩类化合物的合成方法,步骤如下:
向装有磁子的25 mL反应管中依次加入1-(2-(甲硫基)苯基)-2-(4-氯苯基)乙炔(0.2mmol),二苯基膦氧化物(0.4 mmol),过氧化十二酰(LPO)(0.4 mmol),催化剂4CzIPN(3mol%);对反应管抽真空,用氮气置换三次,随后加入溶剂水(2 mL),反应管在蓝光照射下搅拌8 h。反应结束后,用乙酸乙酯萃取反应液,合并有机相之后用无水硫酸钠干燥,柱层析得到目标产物。以1-(2-(甲硫基)苯基)-2-(4-氯苯基)乙炔摩尔量为100%计,终产物的产率为81%。
具体结果如下:
white solid; m. p.216.9-218.1 ℃ 1H NMR (400 MHz, Chloroform-d) δ 7.88(dd, J = 12.9, 8.2 Hz, 2H), 7.60 – 7.52 (m, 4H), 7.47 – 7.41 (m, 2H), 7.36(t, 1H), 7.25 (m,5 H), 7.08 (d, J = 8.4 Hz, 2H), 6.95 (d, J = 8.4 Hz, 2H). 13CNMR (101 MHz, Chloroform-d) δ 153.2 (d, J = 12.5 Hz), 141.2 (d, J = 12.6 Hz),139.4 (d, J = 12.6 Hz), 134.8, 133.8, 132.8, 131.7 (d, J = 10.2 Hz), 131.6(d, J = 2.9 Hz), 131.3 (d, J = 2.9 Hz), 131.2, 128.4 (d, J = 12.5 Hz), 127.7,126.0, 125.1 (d, J = 2.5 Hz), 123.8 (d, J = 103.6 Hz), 121.5. 31P NMR (162MHz, Chloroform-d) δ 21.4。
实施例8
3-膦酰化苯并噻吩类化合物的合成方法,步骤如下:
向装有磁子的25 mL反应管中依次加入1-(2-(甲硫基)苯基)-2-(4-溴苯基)乙炔(0.2mmol),二苯基膦氧化物(0.4 mmol),过氧化十二酰(LPO)(0.4 mmol),催化剂4CzIPN(3mol%);对反应管抽真空,用氮气置换三次,随后加入溶剂水(2 mL),反应管在蓝光照射下搅拌12 h。反应结束后,用乙酸乙酯萃取反应液,合并有机相之后用无水硫酸钠干燥,柱层析得到目标产物。以1-(2-(甲硫基)苯基)-2-(4-溴苯基)乙炔摩尔量为100%计,终产物的产率为81%。
具体结果如下:
white solid; m. p. 240.6-241.9 ℃; 1H NMR (400 MHz, Chloroform-d) δ 7.91(d, J = 8.3 Hz, 1H), 7.86 (d, J = 8.1 Hz, 1H), 7.56 (dd, J = 12.5, 7.5 Hz,4H), 7.48 – 7.40 (m, 2H), 7.37 (t, J = 7.6 Hz, 1H), 7.28 (m, 5H), 7.10 (d, J= 8.1 Hz, 2H), 7.01 (d, J = 8.4 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ153.1 (d, J = 12.5 Hz), 141.2 (d, J = 12.7 Hz), 139.4 (d, J = 12.6 Hz),133.8, 132.7, 131.8 (d, J = 2.9 Hz), 131.7 (d, J = 10.2 Hz), 131.6 (d, J =2.9 Hz), 131.4, 130.7, 128.4 (d, J = 12.5 Hz), 126.0, 125.1 (d, J = 2.9 Hz),123.8 (d, J = 103.4 Hz), 123.1, 121.5. 31P NMR (162 MHz, Chloroform-d) δ 21.5。
实施例9
3-膦酰化苯并噻吩类化合物的合成方法,步骤如下:
向装有磁子的25 mL反应管中依次加入1-(2-(甲硫基)苯基)-2-(4-三氟甲基苯基)乙炔(0.2 mmol),4-甲基苯膦氧化物(0.4 mmol),过氧化十二酰(LPO)(0.4 mmol),催化剂4CzIPN(3 mol%);对反应管抽真空,用氮气置换三次,随后加入溶剂水(2 mL),反应管在蓝光照射下搅拌18 h。反应结束后,用乙酸乙酯萃取反应液,合并有机相之后用无水硫酸钠干燥,柱层析得到目标产物。以1-(2-(甲硫基)苯基)-2-(4-三氟甲基苯基)乙炔摩尔量为100%计,终产物的产率为72%。
具体结果如下:
white solid; m. p. 210.2-212.5 ℃; 1H NMR (400 MHz, Chloroform-d) δ 7.96(d, J = 8.3 Hz, 1H), 7.88 (d, J = 8.0 Hz, 1H), 7.59 – 7.52 (m, 4H), 7.43 –7.36 (m, 3H), 7.32 – 7.22 (m, 9H). 13C NMR (101 MHz, Chloroform-d) δ 152.3 (d,J = 12.4 Hz), 141.2 (d, J = 12.5 Hz), 139.4 (d, J = 12.4 Hz), 136.6, 133.6,132.6, 131.8 (d, J = 2.9 Hz),130.1 (q, J = 325.22). 130.3, 130.1 (d, J =32.32). 128.4 (d, J = 12.5 Hz), 126.2, 125.3 (d, J = 9.8 Hz), 125.0 (d, J =21.5 Hz), 124.3 (q, J = 8.08), 123.1 (d, J = 147.9 Hz), 121.6.31P NMR (162MHz, Chloroform-d) δ 21.3. 19F NMR (376 MHz, Chloroform-d) δ -63.2。
实施例10
3-膦酰化苯并噻吩类化合物的合成方法,步骤如下:
向装有磁子的25 mL反应管中依次加入1-(2-(甲硫基)苯基)-2-(2-甲氧基苯基)乙炔(0.2 mmol),4-甲氧基苯膦氧化物(0.4 mmol),过氧化十二酰(LPO)(0.4 mmol),催化剂4CzIPN(3 mol%);对反应管抽真空,用氮气置换三次,随后加入溶剂水(2 mL),反应管在蓝光照射下搅拌18 h。反应结束后,用乙酸乙酯萃取反应液,合并有机相之后用无水硫酸钠干燥,柱层析得到目标产物。以1-(2-(甲硫基)苯基)-2-(2-甲氧基苯基)乙炔摩尔量为100%计,终产物的产率为70%。
具体结果如下:
white solid; m. p. 190.0-191.9 ℃; 1H NMR (400 MHz, Chloroform-d) δ 8.06(d, J = 8.2 Hz, 1H), 7.85 (d, J = 8.1 Hz, 1H), 7.57 (s, 4H), 7.43 – 7.19 (m,8H), 7.17 – 7.01 (m,2H), 6.71 (t, J = 7.2 Hz, 1H), 6.35 (d, J = 8.2 Hz, 1H),3.52 (s, 3H). 13C NMR (101 MHz, Chloroform-d) δ 156.0, 150.1 (d, J = 13.1 Hz),141.3 (d, J = 12.8 Hz), 139.7 (d, J = 12.5 Hz), 133.5, 132.4, 131.8 (d, J =10.4 Hz), 131.6, 131.5 (d, J = 2.9 Hz), 130.5, 127.9 (d, J = 12.5 Hz), 125.8(d, J = 1.5 Hz), 124.7 (d, J = 9.8 Hz), 123.9 (d, J = 106.1 Hz), 121.7 (d, J= 2.7 Hz), 121.4, 119.7, 109.9, 54.5. 31P NMR (162 MHz, Chloroform-d) δ 23.1.HRMS Calcd for C27H22O2PS [M + H]+ : m/z 441.1073, found: 441.1077。
实施例11
3-膦酰化苯并噻吩类化合物的合成方法,步骤如下:
向装有磁子的25 mL反应管中依次加入1-(2-(甲硫基)苯基)-2-(2-氟苯基)乙炔(0.2mmol),二苯基膦氧化物(0.4 mmol),过氧化十二酰(LPO)(0.4 mmol),催化剂4CzIPN(3mol%);对反应管抽真空,用氮气置换三次,随后加入溶剂水(2 mL),反应管在蓝光照射下搅拌18 h。反应结束后,用乙酸乙酯萃取反应液,合并有机相之后用无水硫酸钠干燥,柱层析得到目标产物。以1-(2-(甲硫基)苯基)-2-(2-氟苯基)乙炔摩尔量为100%计,终产物的产率为73%。
具体结果如下:
white solid; m. p. 191.3-193.6 ℃; 1H NMR (400 MHz, Chloroform-d) δ 8.05(d, J = 8.3 Hz, 1H), 7.86 (d, J = 8.0 Hz, 1H), 7.61 (dd, J = 12.5, 7.4 Hz,4H), 7.32 (m, 8H), 7.10 (m, 2H), 6.85 (t, J = 7.6 Hz, 1H), 6.64 (t, J = 8.9Hz, 1H). 13C NMR (101 MHz, Chloroform-d) δ 158.9 (d, J = 247.2 Hz), 146.5 (d,J = 13.4 Hz), 141.0 (d, J = 12.6 Hz), 139.8 (d, J = 11.8 Hz), 133.2, 132.1,131.9, 131.8, 131.8, 130.9 (d, J = 7.9 Hz), 128.2 (d, J = 12.6 Hz), 126.1,125.4 (d, J = 103.9 Hz), 125.1 (d, J = 11.9 Hz), 123.5, 121.5, 120.9 (d, J =16.3 Hz), 115.3 (d, J = 21.5 Hz). 31P NMR (162 MHz, DMSO-d 6) δ 21.8. 19F NMR(376 MHz, Chloroform-d) δ -109.8. HRMS Calcd for C26H19FOPS [M + H]+ : m/z429.0873, found: 429.0874。
实施例12
3-膦酰化苯并噻吩类化合物的合成方法,步骤如下:
向装有磁子的25 mL反应管中依次加入1-(2-(甲硫基)苯基)-2-(3-甲基苯基)乙炔(0.2 mmol),二苯基膦氧化物(0.4 mmol),过氧化十二酰(LPO)(0.4 mmol),催化剂4CzIPN(3 mol%);对反应管抽真空,用氮气置换三次,随后加入溶剂水(2 mL),反应管在蓝光照射下搅拌18 h。反应结束后,用乙酸乙酯萃取反应液,合并有机相之后用无水硫酸钠干燥,柱层析得到目标产物。以1-(2-(甲硫基)苯基)-2-(3-甲基苯基)乙炔摩尔量为100%计,终产物的产率为74%。
具体结果如下:
yellow solid; m. p. 176.5-179.1 ℃; 1H NMR (400 MHz, Chloroform-d) δ 7.96(d, J = 8.2 Hz, 1H), 7.86 (d, J = 8.0 Hz, 1H), 7.58 (dd, J = 12.4, 7.3 Hz,4H), 7.42 – 7.33 (m, 3H), 7.26 (m, 5H), 7.03 (d, J = 7.4 Hz, 1H), 6.97 – 6.84(m, 3H), 2.12 (s, 3H). 13C NMR (101 MHz, Chloroform-d) δ 155.0 (d, J = 13.0Hz), 141.5 (d, J = 13.0 Hz), 139.3 (d, J = 12.6 Hz), 137.1, 134.1, 133.0,132.7 (d, J = 2.7 Hz), 131.6 (d, J = 10.2 Hz), 131.4 (d, J = 2.9 Hz), 130.9,129.3, 128.2 (d, J = 12.5 Hz), 127.6, 126.9, 126.0, 124.8 (d, J = 5.9 Hz),122.7 (d, J = 104.8 Hz), 121.4, 21.1. 31P NMR (162 MHz, Chloroform-d) δ 21.6。
实施例13
3-膦酰化苯并噻吩类化合物的合成方法,步骤如下:
向装有磁子的25 mL反应管中依次加入1-(2-(甲硫基)苯基)-2-(3-氯苯基)乙炔(0.2mmol),二苯基膦氧化物(0.4 mmol),过氧化十二酰(LPO)(0.4 mmol),催化剂4CzIPN(3mol%);对反应管抽真空,用氮气置换三次,随后加入溶剂水(2 mL),反应管在蓝光照射下搅拌18 h。反应结束后,用乙酸乙酯萃取反应液,合并有机相之后用无水硫酸钠干燥,柱层析得到目标产物。以1-(2-(甲硫基)苯基)-2-(3-氯苯基)乙炔摩尔量为100%计,终产物的产率为90%。
具体结果如下:
white solid; m. p. 193.1-195.2 ℃; 1H NMR (400 MHz, Chloroform-d) δ 7.94(d, J = 8.2 Hz, 1H), 7.86 (d, J = 8.0 Hz, 1H), 7.58 (dd, J = 12.4, 7.4 Hz,4H), 7.38 (q, J = 8.4, 8.0 Hz, 3H), 7.29 (m, 5H), 7.14 – 7.01 (m, 3H), 7.00 –6.92 (m, 1H). 13C NMR (101 MHz, Chloroform-d) δ 152.5 (d, J = 12.6 Hz), 141.2(d, J = 12.5 Hz), 139.3 (d, J = 12.5 Hz), 134.6 (d, J = 2.9 Hz), 133.6,133.4, 132.6, 131.8 (d, J = 2.9 Hz), 131.6 (d, J = 10.2 Hz), 130.1, 128.8,128.7, 128.4 (d, J = 12.6 Hz), 128.1, 126.1, 125.1 (d, J = 8.5 Hz), 123.8 (d,J = 103.3 Hz), 121.5. 31P NMR (162 MHz, Chloroform-d) δ 21.4. HRMS Calcd forC26H18ClNaOPS [M + Na]+ : m/z 467.0397, found: 467.0400。
实施例14
3-膦酰化苯并噻吩类化合物的合成方法,步骤如下:
向装有磁子的25 mL反应管中依次加入1-(2-(甲硫基)-4-甲基苯基)-2-苯基乙炔(0.2mmol),二苯基膦氧化物(0.4 mmol),过氧化十二酰(LPO)(0.4 mmol),催化剂4CzIPN(5mol%);对反应管抽真空,用氮气置换三次,随后加入溶剂水(2 mL),反应管在蓝光照射下搅拌18 h。反应结束后,用乙酸乙酯萃取反应液,合并有机相之后用无水硫酸钠干燥,柱层析得到目标产物。以1-(2-(甲硫基)-4-甲基苯基)-2-苯基乙炔摩尔量为100%计,终产物的产率为70%。
具体结果如下:
white solid; m. p. 207.6-209.6 ℃; 1H NMR (400 MHz, Chloroform-d) δ 7.76(d, J = 8.5 Hz, 1H), 7.65 (s, 1H), 7.62 – 7.53 (m, 4H), 7.40 – 7.33 (m, 2H),7.25 (m, 4H), 7.19 – 7.14 (m, 2H), 7.08 (t, 2H), 6.97 (t,2 H), 2.45 (s, 3H).13C NMR (101 MHz, Chloroform-d) δ 153.8 (d, J = 12.8 Hz), 139.7 (d, J = 12.6Hz), 139.2 (d, J = 12.9 Hz), 134.9, 134.1, 133.0, 133.0 (d, J = 2.9 Hz),131.7 (d, J = 10.1 Hz), 131.4 (d, J = 2.9 Hz), 130.0, 128.3 (d, J = 12.7 Hz),127.5, 126.6, 125.5 (d, J = 1.4 Hz), 122.5 (d, J = 104.4 Hz), 121.2, 21.4. 31PNMR (162 MHz, Chloroform-d) δ 21.5. HRMS Calcd for C27H21OPS [M + H]+ : m/z425.1123, found: 425.1122。
实施例15
3-膦酰化苯并噻吩类化合物的合成方法,步骤如下:
向装有磁子的25 mL反应管中依次加入1-(2-(甲硫基)-4-氯苯基)-2-苯基乙炔(0.2mmol),二苯基膦氧化物(0.4 mmol),过氧化十二酰(LPO)(0.4 mmol),催化剂4CzIPN(5mol%);对反应管抽真空,用氮气置换三次,随后加入溶剂水(2 mL),反应管在蓝光照射下搅拌18 h。反应结束后,用乙酸乙酯萃取反应液,合并有机相之后用无水硫酸钠干燥,柱层析得到目标产物。以1-(2-(甲硫基)-4-氯苯基)-2-苯基乙炔摩尔量为100%计,终产物的产率为60%。
具体结果如下:
white solid; m. p. 209.2-211.1 ℃; 1H NMR (400 MHz, Chloroform-d) δ 7.90(d, J = 8.9 Hz, 1H), 7.84 (s, 1H), 7.55 (dd, J = 12.4, 7.4 Hz, 4H), 7.37 (t,J = 7.0 Hz, 2H), 7.30 – 7.19 (m, 5H), 7.11 (dd, J = 16.2, 7.4 Hz, 3H), 6.98(t, J = 7.6 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ 155.0 (d, J = 12.7 Hz),140.4 (d, J = 12.4 Hz), 140.0 (d, J = 12.6 Hz), 133.7, 132.6, 132.4 (d, J =2.7 Hz), 131.6 (d, J = 10.0 Hz), 131.1, 129.8, 128.6, 128.4 (d, J = 12.5 Hz),127.7, 126.9, 125.7, 122.8 (d, J = 103.5 Hz), 121.1. 31P NMR (162 MHz,Chloroform-d) δ 21.1. HRMS Calcd for C26H19ClOPS [M + H]+ : m/z 445.0577,found: 445.0579。
实施例16
3-膦酰化苯并噻吩类化合物的合成方法,步骤如下:
向装有磁子的25 mL反应管中依次加入1-(2-(甲硫基)苯基)-2-苯基乙炔(0.2 mmol),二(对甲苯基)膦氧化物(0.4 mmol),过氧化十二酰(LPO)(0.4 mmol),催化剂4CzIPN(5mol%);对反应管抽真空,用氮气置换三次,随后加入溶剂水(2 mL),反应管在蓝光照射下搅拌18 h。反应结束后,用乙酸乙酯萃取反应液,合并有机相之后用无水硫酸钠干燥,柱层析得到目标产物。以1-(2-(甲硫基)苯基)-2-苯基乙炔摩尔量为100%计,终产物的产率为75%。
white solid; m. p. 176.5-178.1 ℃; 1H NMR (400 MHz, Chloroform-d) δ 8.02(d, J = 8.2 Hz, 1H), 7.85 (d, J = 8.0 Hz, 1H), 7.43 (dd, J = 12.3, 8.1 Hz,4H), 7.36 (t, J = 7.6 Hz, 1H), 7.30 – 7.27 (m, 1H), 7.12 (d, J = 12.7 Hz,3H), 7.04 (dd, J = 8.0, 2.5 Hz, 4H), 7.00 – 6.95 (m, 2H). 13C NMR (101 MHz,Chloroform-d) δ 154.3 (d, J = 12.8 Hz), 141.8 (d, J = 2.9 Hz), 141.5 (d, J =12.6 Hz), 139.3 (d, J = 12.4 Hz), 133.1 (d, J = 2.7 Hz), 131.7 (d, J = 10.6Hz), 130.8, 129.9, 129.7, 129.0 (d, J = 12.9 Hz), 127.8, 127.4, 126.2 (d, J =1.3 Hz), 124.8 (d, J = 7.8 Hz), 123.5 (d, J = 103.9 Hz), 121.3, 21.5. 31P NMR(162 MHz, Chloroform-d) δ 22.2。
实施例17
3-膦酰化苯并噻吩类化合物的合成方法,步骤如下:
向装有磁子的25 mL反应管中依次加入1-(2-(甲硫基)苯基)-2-苯基乙炔(0.2 mmol),二(对氟苯基)膦氧化物(0.4 mmol),过氧化十二酰(LPO)(0.4 mmol),催化剂4CzIPN(5mol%);对反应管抽真空,用氮气置换三次,随后加入溶剂水(2 mL),反应管在蓝光照射下搅拌18 h。反应结束后,用乙酸乙酯萃取反应液,合并有机相之后用无水硫酸钠干燥,柱层析得到目标产物。以1-(2-(甲硫基)苯基)-2-苯基乙炔摩尔量为100%计,终产物的产率为70%。
具体结果如下:
white solid; m. p. 149.1-152.6 ℃; 1H NMR (400 MHz, Chloroform-d) δ 7.95(d, J = 8.3 Hz, 1H), 7.87 (d, J = 8.1 Hz, 1H), 7.54 (m, 4H), 7.42 – 7.35 (m,1H), 7.33 – 7.26 (m, 1H), 7.18 (t, J = 7.4 Hz, 1H), 7.15 – 7.09 (m, 2H), 7.04(t, J = 7.6 Hz, 2H), 6.94 (m, 4H). 13C NMR (101 MHz, Chloroform-d) δ 164.8(dd, J = 253.5, 3.4 Hz), 154.9 (d, J = 13.3 Hz), 141.1 (d, J = 12.9 Hz),139.4 (d, J = 12.8 Hz), 134.1 (dd, J = 11.7, 8.8 Hz), 132.7 (d, J = 2.8 Hz),129.9, 129.8 (d, J = 3.3 Hz), 128.7 (d, J = 3.4 Hz), 128.6, 127.7, 125.8 (d,J = 1.7 Hz), 125.1 (d, J = 1.8 Hz), 122.5 (d, J = 106.6 Hz), 121.6, 115.8(dd, J = 21.5, 13.7 Hz).31P NMR (162 MHz, Chloroform-d) δ 19.8. 19F NMR (376MHz, Chloroform-d) δ -107.6. HRMS Calcd for C26H18F2PS [M + H]+ : m/z 447.0779,found: 447.0780。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (9)
2.根据权利要求1所述的3-膦酰化苯并噻吩类化合物,其特征在于:所述烷基选自C1~C4的烷基;所述烷氧基选自C1~C4的烷氧基;所述卤素取代基的卤素选自氟、氯或溴。
3.权利要求1或2所述的3-膦酰化苯并噻吩类化合物的制备方法,其特征在于:将2-甲硫基芳香炔类化合物和二芳基膦氧化物在催化剂和氧化剂作用下,经过蓝光照射进行膦酰化/环化反应,得到3-膦酰化苯并噻吩类化合物。
6.根根权利要求3所述的3-膦酰化苯并噻吩类化合物的制备方法,其特征在于,所述催化剂为2,4,5,6-四(9-咔唑基)-间苯二腈,氧化剂为过氧化十二酰。
7.根据权利要求4-6任一项所述的3-膦酰化苯并噻吩类化合物的制备方法,其特征在于:所述2-甲硫基芳香炔类化合物、二芳基膦氧化物、催化剂和氧化剂的摩尔比为1:(1~3):(0.01~0.05):(1~3)。
8.根据权利要求7所述的3-膦酰化苯并噻吩类化合物的制备方法,其特征在于:所述反应采用水或者碳酸二甲酯作为反应介质。
9.根据权利要求7所述的3-膦酰化苯并噻吩类化合物的制备方法,其特征在于:采用蓝光照射,在室温25℃温度下,反应 8~18 h。
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