无金属催化快速合成2-芳酰氨基萘并[1, 2-d]噻唑

刘天宝 彭艳芬 桂美芳 章敏

引用本文: 刘天宝, 彭艳芬, 桂美芳, 章敏. 无金属催化快速合成2-芳酰氨基萘并[1, 2-d]噻唑[J]. 有机化学, 2019, 39(11): 3199-3206. doi: 10.6023/cjoc201904029 shu
Citation:  Liu Tianbao, Peng Yanfen, Gui Meifang, Zhang Min. Metal-Free Rapid Synthesis of 2-Aroylamino Naphtho[1, 2-d]thiazoles[J]. Chinese Journal of Organic Chemistry, 2019, 39(11): 3199-3206. doi: 10.6023/cjoc201904029 shu

无金属催化快速合成2-芳酰氨基萘并[1, 2-d]噻唑

    通讯作者: 刘天宝, tianbaoliu1979@126.com; 章敏, 287323206@qq.com
  • 基金项目:

    国家自然科学基金(No.21271035)、安徽省自然科学基金(No.1808085QB48)和安徽省有机化学省级教学团队(No.2017jxtd051)资助项目

摘要: 报道了在室温条件下,二醋酸碘苯促进3-[1-(4-取代萘基)]-1-芳酰基硫脲自身关环得到一系列2-芳酰氨基萘并[1,2-d]噻唑衍生物.该方法具有反应条件温和,反应迅速,操作简单,原子利用率高,无需金属催化以及底物范围广等优点.该方法也为萘并[1,2-d]噻唑衍生物的合成提供了新的高效途径.

English

  • 萘并噻唑类化合物长期以来备受人们关注, 尤其是在染料[1]和医疗诊断[2]领域.由于萘并噻唑基团存在刚性平面结构和离域的大π键, 致使萘并噻唑类化合物荧光量子产率较高, 近年来在荧光探针制备方面极受重视[3], 特别是其结构中含有N和S原子, 可与金属产生配位等作用, 使他们在荧光探针方面的应用发展迅猛.

    目前合成萘并[1, 2-d]噻唑衍生物的方法报道不多.传统的合成方法是以1, 4-萘醌为起始原料, 先与硫脲进行缩合, 然后再与羟胺反应获得萘并[1, 2-d]噻唑化合物[4]. 2012年, Zhang等[5]改进了此类化合物的合成方法, 以1-萘胺、硫和甲苯(对二甲苯)为原料, 在250~275 ℃, 无催化剂条件下, 反应1.5~3.5 h, 得到2-芳基萘并[1, 2-d]噻唑. 2017年, Jonaghani等[6]则以1-萘胺、硫和2-甲基喹啉为原料, 经四步反应得到预期结果.二醋酸碘苯(IBD)由于具有高反应性、良好稳定性和低毒性等优点[7]而备受关注, 在C—N[8], C—O[9]和C—S[10]键的构筑等方面, 都取得了令人满意的结果.然而, 却未发现它应用于萘并[1, 2-d]噻唑的合成.基于此, 本工作研究了二醋酸碘苯促进芳酰基硫脲自身关环制备2-芳酰氨基萘并[1, 2-d]噻唑的可行性.结果发现, 该方法可顺利合成一系列2-芳酰氨基萘并[1, 2-d]噻唑衍生物, 反应快速, 条件温和, 产率良好.

    以3-(1-萘基)-1-(4-甲基苯甲酰基)硫脲自身关环的反应为模板, 对该反应进行了研究(表 1).反应以3-(1-萘基)-1-(4-甲基苯甲酰基)硫脲(1a, 0.94 mmol)和IBD (0.94 mmol)为底物, 乙腈为溶剂, 在温度80 ℃条件下反应30 min, 以68%的收率得到2-(4-甲基苯甲酰氨基)萘并[1, 2-d]噻唑(2a)(表 1, Entry 1).随后, 对各种反应条件进行优化. IBD的用量筛选结果表明, 随着IBD用量的增加, 反应产率也随之增加(表 1, Entries 2, 3), 但超过1.2 equiv.时, 反应体系变得复杂, 致使产率下降(表 1, Entries 4, 5).通过温度的筛选发现, 反应温度在20 ℃以上时, 反应的产率相差不大(表 1, Entries 6~11), 在低于20 ℃时产率则下降非常明显(表 1, Entry 12), 为此, 选择20 ℃为适宜的反应温度.溶剂的筛选结果表明, 乙腈为最佳的反应溶剂(表 1, Entries 13~18).最后我们对反应时间进行了考察, 发现反应迅速, 薄层色谱(TLC)检测, 5 min原料即全部消失, 产率达到87%(表 1, Entry 21), 延长反应时间, 产率无明显变化(表 1, Entries 19, 20).因此选择5 min为最佳反应时间.通过以上筛选确定比较适宜的反应条件为: 1a (0.94 mmol), IBD (1.13 mmol), 反应时间5 min, 反应温度为20 ℃, 溶剂为乙腈.

    表 1

    表 1  2-(4-甲基苯甲酰氨基)萘并[1, 2-d]噻唑(2a)合成条件的优化a
    Table 1.  Optimization of reaction conditions on the synthesis of 2-(4-methyl benzoylamino)naphtho[1, 2-d]thiazole (2a)
    下载: 导出CSV
    Entry IBD/equiv. Temp./℃ Time/min Solvent Yieldb/%
    1 1.0 80 30 CH3CN 68
    2 1.1 80 30 CH3CN 74
    3 1.2 80 30 CH3CN 83
    4 1.3 80 30 CH3CN 75
    5 1.4 80 30 CH3CN 67
    6 1.2 70 30 CH3CN 83
    7 1.2 60 30 CH3CN 82
    8 1.2 50 30 CH3CN 86
    9 1.2 40 30 CH3CN 85
    10 1.2 30 30 CH3CN 86
    11 1.2 20 30 CH3CN 86
    12 1.2 14 30 CH3CN 44
    13 1.2 20 30 CH3CH2OH 60
    14 1.2 20 30 CH3OH 65
    15 1.2 20 30 THF 43
    16 1.2 20 30 Petroleum ether 22
    17 1.2 20 30 1, 4-Dioxane 40
    18 1.2 20 30 AcOH 80
    19 1.2 20 20 CH3CN 86
    20 1.2 20 10 CH3CN 86
    21 1.2 20 5 CH3CN 87
    a All reactions were performed in air. The mixture of 1a (0.94 mmol), catalyst, and solvent (30 mL) was placed in a three-necked round bottom flask (50 mL). b Isolated yields.

    将以上优化的反应条件应用于各种2-芳酰氨基萘并[1, 2-d]噻唑的合成, 结果如表 2所示. 3-(1-萘基)-1-芳酰基硫脲中与羰基相连的苯环上带有给电子基团CH3时, 产物2的产率均较高(2a~2c); 与羰基相连的苯环上带有卤素时, F取代物的产率明显高于Cl或Br取代物(2d~2i); 将与羰基相连的取代基换成呋喃环(2j), 或在萘环的4位碳上引入溴(2k~2n), 对反应结果没有明显影响, 均能以良好的产率得到预期产物.

    表 2

    表 2  2-芳酰氨基萘并[1, 2-d]噻唑衍生物2的合成a
    Table 2.  Synthesis of 2-aroylamino naphtho[1, 2-d]thiazoles 2
    下载: 导出CSV

    为进一步拓展反应底物的普适性, 尝试从β-萘胺出发, 首先合成得到相应的硫脲3-(2-萘基)-1-(4-甲基苯甲酰基)硫脲, 然后采用上述筛选出的最优条件进行关环尝试.实验结果表明, 上述实验的最佳条件并不能作为3-(2-萘基)-1-(4-甲基苯甲酰基)硫脲的最优关环反应条件, 薄层色谱(TLC)检测发现, 反应5 min, 体系中仍然存在大量的原料, 且体系较为复杂, 有多个新点出现, 延长反应时间或者提高反应温度, 实验结果均未得到改善.处理反应体系, 分离出主要产物, 经IR, 1H NMR, 13C NMR和HRMS表征发现主产物为2-(4-甲基苯甲酰氨基)萘并[2, 1-d]噻唑(4), 但产率仅8% (Eq. 1).

    (1)

    根据实验结果和相关文献[10c, 11], 提出3-[1-(4-取代萘基)]-1-芳酰基硫脲自身关环反应的可能机理, 如Scheme 1所示.首先, 1中的硫羰基可由酮式转为烯胺式5, 5中的巯基与IBD作用得到6, 进而发生分子内成环反应得到噻唑啉环7, 同时失去一分子碘苯和醋酸根离子.然后醋酸根离子进攻噻唑啉环上的氢原子使其脱去一分子醋酸, 即可得到目标产物2.

    图式 1

    图式 1.  生成2-芳酰氨基萘并[1, 2-d]噻唑类化合物可能的反应机理
    Scheme 1.  A plausible mechanism for the formation of 2-aroylamino naphtho[1, 2-d]thiazoles

    发展了一种在IBD作用下3-[1-(4-取代萘基)]-1-芳酰基硫脲自身关环反应合成2-芳酰氨基萘并[1, 2-d]噻唑类化合物的方法.通过对反应温度、催化剂用量、时间以及溶剂等条件的优化实现了2-芳酰氨基萘并[1, 2-d]噻唑类化合物的高效制备.该方法条件温和, 反应迅速, 操作简便, 为该类化合物提供了一种高效的合成方法.

    1H NMR和13C NMR采用AVANCE III HD 500 MHz核磁共振仪和BRUKER 400 MHz核磁共振仪测定, 内标为TMS, 溶剂为CDCl3和DMSO-d6; HRMS采用Q-Exactive型液相色谱-高分辨质谱联用仪(ESI离子源)测定; IR用Nicolet iS10型傅立叶变换红外光谱仪测定(KBr压片); 熔点采用XT-4型双目显微熔点测定仪(温度未经校正)测定.实验所用各种试剂均为市售分析纯试剂.

    3.2.1   3-[1-(4-取代萘基)]-1-芳酰基硫脲1a~1n的合成

    以3-(1-萘基)-1-(4-甲基苯甲酰基)硫脲(1a)为例, 在250 mL三颈烧瓶中依次加入KSCN (5.00 g, 51.55 mmol)和无水丙酮(60 mL), 混合物加热至回流.随后, 滴加对甲基苯甲酰氯(5.72 mL, 42.94 mmol)的无水丙酮(25 mL)溶液, 滴加完毕后出现大量白色固体, 继续反应30 min, 再缓慢加入1-萘胺(6.14 g, 42.94 mmol)的无水丙酮(30 mL)溶液, 混合物继续加热回流至反应结束(TLC检测).然后, 将反应液倒入到1000 mL去离子水中, 有大量白色固体析出, 抽滤, 粗产品用无水乙醇重结晶得到10.30 g纯净的3-(1-萘基)-1-(4-甲基苯甲酰基)硫脲(1a), 白色固体, 产率75%. m.p. 177~178 ℃; 1H NMR (500 MHz, CDCl3) δ: 12.79 (s, 1H), 9.26 (s, 1H), 8.04 (d, J=7.20 Hz, 2H), 7.90 (d, J=7.80 Hz, 1H), 7.83 (d, J=8.20 Hz, 3H), 7.51~7.59 (m, 3H), 7.34 (d, J=8.10 Hz, 2H), 2.45 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 180.2, 167.2, 145.0, 134.2, 133.6, 130.0, 128.7, 128.7, 128.6, 128.0, 127.7, 127.0, 126.5, 125.3, 123.9, 121.8, 21.8; IR (KBr) ν: 3198, 3056, 1668, 1606, 1582, 1532, 1465, 1334, 1260, 1159, 810, 803, 775, 694 cm-1; HRMS (ESI) calcd for C19H16N2NaOS [M+Na]+ 343.0881, found 343.0872.

    3-(1-萘基)-1-(3-甲基苯甲酰基)硫脲(1b):白色固体, 产率82%. m.p. 184~185 ℃; 1H NMR (500 MHz, CDCl3) δ: 12.77 (s, 1H), 9.27 (s, 1H), 8.04 (t, J=7.70 Hz, 2H), 7.91 (d, J=7.50 Hz, 1H), 7.84 (d, J=8.30 Hz, 1H), 7.72~7.75 (m, 2H), 7.52~7.59 (m, 3H), 7.42~7.47 (m, 2H), 2.45 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 180.1, 167.4, 139.4, 134.7, 134.2, 133.6, 131.6, 129.2, 128.7, 128.5, 128.2, 128.0, 127.0, 126.5, 125.3, 124.7, 123.9, 121.7, 21.4; IR (KBr) ν: 3244, 3043, 1664, 1599, 1510, 1375, 1270, 1153, 804, 775, 710 cm-1; HRMS (ESI) calcd for C19H16N2NaOS [M+Na]+ 343.0881, found 343.0873.

    3-(1-萘基)-1-(2-甲基苯甲酰基)硫脲(1c):白色固体, 产率82%. m.p. 187~188 ℃; 1H NMR (500 MHz, CDCl3) δ: 12.66 (s, 1H), 9.02 (s, 1H), 8.05 (t, J=8.30 Hz, 2H), 7.91 (d, J=8.00 Hz, 1H), 7.85 (d, J=8.20 Hz, 1H), 7.60 (t, J=7.70 Hz, 2H), 7.53~7.57 (m, 2H), 7.47 (t, J=7.50 Hz, 1H), 7.34 (d, J=7.50 Hz, 2H), 2.61 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 180.1, 169.7, 137.8, 134.2, 133.5, 132.8, 132.2, 132.0, 128.7, 128.5, 128.0, 127.1, 127.0, 126.5, 126.4, 125.3, 123.9, 121.7, 20.3; IR (KBr) ν: 3220, 3058, 1674, 1598, 1528, 1324, 1260, 807, 776, 748, 709, 672 cm-1; HRMS (ESI) calcd for C19H16N2NaOS [M+Na]+ 343.0881, found 343.0871.

    3-(1-萘基)-1-(2-氯苯甲酰基)硫脲(1d):白色固体, 产率75%. m.p. 186~188 ℃ (Lit.[12] 191.0~192.3 ℃); 1H NMR (500 MHz, CDCl3) δ: 12.53 (s, 1H), 9.46 (s, 1H), 8.03~8.07 (m, 2H), 7.92 (d, J=7.60 Hz, 1H), 7.84~7.87 (m, 2H), 7.52~7.61 (m, 5H), 7.43~7.47 (m, 1H); 13C NMR (125 MHz, CDCl3) δ: 179.4, 166.3, 134.2, 133.5, 133.4, 132.1, 131.3, 131.1, 130.7, 128.7, 128.5, 128.1, 127.6, 127.1, 126.5, 125.3, 123.9, 121.7; IR (KBr) ν: 3220, 3053, 3016, 1687, 1599, 1531, 1252, 1182, 802, 775, 703 cm-1; HRMS (ESI) calcd for C18H13ClN2NaOS [M+ Na]+ 363.0335, found 363.0320.

    3-(1-萘基)-1-(3-氯苯甲酰基)硫脲(1e):白色固体, 产率77%. m.p. 194~196 ℃; 1H NMR (500 MHz, CDCl3) δ: 12.62 (s, 1H), 9.20 (s, 1H), 8.03 (dd, J=11.00, 8.00 Hz, 2H), 7.97 (t, J=1.90 Hz, 1H), 7.92 (d, J=7.50 Hz, 1H), 7.86 (d, J=8.20 Hz, 1H), 7.80~7.82 (m, 1H), 7.64~7.66 (m, 1H), 7.50~7.61 (m, 4H); 13C NMR (125 MHz, CDCl3) δ: 179.7, 165.8, 135.8, 134.2, 133.9, 133.4, 130.6, 128.7, 128.5, 128.1, 127.1, 126.5, 125.4, 125.3, 123.9, 121.6; IR (KBr) ν: 3230, 3157, 3048, 1674, 1596, 1568, 1505, 1434, 1328, 1249, 882, 819, 790, 776, 712 cm-1; HRMS (ESI) calcd for C18H13ClN2NaOS [M+Na]+ 363.0335, found 363.0322.

    3-(1-萘基)-1-(4-氯苯甲酰基)硫脲(1f):淡黄色固体, 产率76%. m.p. 185~187 ℃; 1H NMR (500 MHz, CDCl3) δ: 12.66 (s, 1H), 9.25 (s, 1H), 8.02 (d, J=7.30 Hz, 2H), 7.91 (d, J=8.00 Hz, 1H), 7.88 (d, J=8.50 Hz, 2H), 7.85 (d, J=8.30 Hz, 1H), 7.51~7.59 (m, 5H); 13C NMR (125 MHz, CDCl3) δ: 179.9, 166.1, 140.5, 134.2, 133.5, 130.0, 129.6, 129.1, 128.7, 128.5, 128.1, 127.1, 126.5, 125.3, 123.9, 121.6; IR (KBr) ν: 3190, 3062, 1672, 1592, 1532, 1484, 1463, 1259, 843, 805, 791, 774, 744, 708 cm-1; HRMS (ESI) calcd for C18H13ClN2NaOS [M+Na]+ 363.0335, found 363.0328.

    3-(1-萘基)-1-(3-溴苯甲酰基)硫脲(1g):白色固体, 产率83%. m.p. 176~177 ℃; 1H NMR (500 MHz, CDCl3) δ: 12.62 (s, 1H), 9.22 (s, 1H), 8.12 (s, 1H), 8.02 (dd, J=11.50, 7.90 Hz, 2H), 7.92 (d, J=8.00 Hz, 1H), 7.84~7.87 (m, 2H), 7.79 (d, J=8.10 Hz, 1H), 7.53~7.60 (m, 3H), 7.43 (t, J=7.90 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ: 179.7, 165.7, 136.8, 134.2, 133.6, 133.4, 131.0, 130.7, 128.7, 128.4, 128.1, 127.1, 126.5, 125.9, 125.3, 123.8, 123.5, 121.6; IR (KBr) ν: 3235, 3152, 3047, 1673, 1596, 1564, 1505, 1435, 1326, 1248, 877, 813, 791, 748, 705 cm-1; HRMS (ESI) calcd for C18H13BrN2NaOS [M+Na]+ 406.9830, found 406.9819.

    3-(1-萘基)-1-(4-溴苯甲酰基)硫脲(1h):黄色固体, 产率78%. m.p. 184~185 ℃; 1H NMR (500 MHz, CDCl3) δ: 12.66 (s, 1H), 9.23 (s, 1H), 8.02 (dd, J=7.70, 3.70 Hz, 2H), 7.91 (d, J=7.90 Hz, 1H), 7.85 (d, J=8.20 Hz, 1H), 7.80 (d, J=8.50 Hz, 2H), 7.69 (d, J=8.40 Hz, 2H), 7.53~7.59 (m, 3H); 13C NMR (125 MHz, CDCl3) δ: 179.8, 166.3, 134.2, 133.5, 132.6, 130.4, 129.1, 128.7, 128.5, 128.1, 127.1, 126.5, 125.3, 123.9, 121.6; IR (KBr) ν: 3280, 3132, 3050, 1666, 1629, 1588, 1482, 1329, 1256, 870, 845, 772, 754, 701 cm-1; HRMS (ESI) calcd for C18H13BrN2NaOS [M+Na]+ 406.9830, found 406.9821.

    3-(1-萘基)-1-(4-氟苯甲酰基)硫脲(1i):白色固体, 产率75%. m.p. 180~182 ℃; 1H NMR (500 MHz, CDCl3) δ: 12.69 (s, 1H), 9.26 (s, 1H), 8.02 (d, J=7.60 Hz, 2H), 7.94~7.98 (m, 2H), 7.91 (d, J=7.40 Hz, 1H), 7.85 (d, J=8.30 Hz, 1H), 7.52~7.59 (m, 3H), 7.19~7.23 (m, 2H); 13C NMR (125 MHz, CDCl3) δ: 179.9, 166.1, 166.0 (1JCF=255.00 Hz), 134.2, 133.5, 130.3 (3JCF=10.00 Hz), 128.7, 128.5, 128.0, 127.8 (4JCF=3.75 Hz), 127.0, 126.5, 125.3, 123.9, 121.6, 116.5 (2JCF=22.50 Hz); IR (KBr) ν: 3213, 3062, 1668, 1626, 1600, 1575, 1504, 1237, 874, 815, 772, 737, 694 cm-1; HRMS (ESI) calcd for C18H13FN2-NaOS [M+Na]+: 347.0631, found 347.0625.

    3-(1-萘基)-1-(2-呋喃甲酰基)硫脲(1j):白色固体, 产率73%. m.p. 182~184 ℃; 1H NMR (500 MHz, CDCl3) δ: 12.47 (s, 1H), 9.37 (s, 1H), 8.02 (dd, J=15.30, 7.90 Hz, 2H), 7.90 (d, J=7.70 Hz, 1H), 7.84 (d, J=8.30 Hz, 1H), 7.62~7.63 (m, 1H), 7.51~7.58 (m, 3H), 7.43 (d, J=3.60 Hz, 1H), 6.64 (dd, J=3.60, 1.70 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ: 179.6, 157.0, 146.6, 145.0, 134.2, 133.5, 128.7, 128.6, 128.0, 127.0, 126.5, 125.3, 123.9, 121.7, 119.2, 113.5; IR (KBr) ν: 3219, 3046, 1665, 1596, 1468, 1274, 1130, 878, 783, 709 cm-1; HRMS (ESI) calcd for C16H12N2NaO2S [M+Na]+ 319.0517, found 319.0506.

    3-[1-(4-溴萘基)]-1-(2-呋喃甲酰基)硫脲(1k):淡黄色固体, 产率76%. m.p. 196~198 ℃; 1H NMR (500 MHz, DMSO-d6) δ: 12.41 (s, 1H), 11.57 (s, 1H), 8.20 (d, J=8.30 Hz, 1H), 8.12 (s, 1H), 8.04 (d, J=8.30 Hz, 1H), 7.97 (d, J=8.00 Hz, 1H), 7.93 (d, J=3.40 Hz, 1H), 7.75 (t, J=7.40 Hz, 1H), 7.70 (t, J=7.90 Hz, 2H), 6.80 (dd, J=3.40, 1.50 Hz, 1H); 13C NMR (125 MHz, DMSO-d6) δ: 181.4, 158.3, 149.0, 145.3, 135.3, 132.1, 130.7, 130.1, 128.7, 128.2, 127.4, 126.3, 123.8, 121.2, 119.3, 113.2; IR (KBr) ν: 3248, 3183, 3113, 1683, 1622, 1585, 1505, 1471, 1335, 1264, 834, 796, 748, 734, 688 cm-1; HRMS (ESI) calcd for C16H11BrN2NaO2S [M+Na]+ 396.9623, found 396.9611.

    3-[1-(4-溴萘基)]-1-(4-甲基苯甲酰基)硫脲(1l):黄色固体, 产率80%. m.p. 201~203 ℃; 1H NMR (500 MHz, CDCl3) δ: 12.79 (s, 1H), 9.25 (s, 1H), 8.30 (d, J=7.70 Hz, 1H), 8.04 (d, J=8.90 Hz, 1H), 7.91 (d, J=8.00 Hz, 1H), 7.83 (t, J=7.90 Hz, 3H), 7.61~7.66 (m, 2H), 7.35 (d, J=8.00 Hz, 2H), 2.46 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 180.2, 167.2, 145.1, 133.5, 132.5, 130.0, 129.8, 129.4, 128.5, 128.1, 127.9, 127.8, 127.7, 124.4, 122.2, 122.2, 21.8; IR (KBr) ν: 3313, 3116, 3037, 1659, 1612, 1594, 1533, 1501, 1334, 1259, 827, 772, 748, 687 cm-1; HRMS (ESI) calcd for C19H15BrN2NaOS [M+Na]+ 420.9986, found 420.9965.

    3-[1-(4-溴萘基)]-1-(3-甲基苯甲酰基)硫脲(1m):白色固体, 产率87%. m.p. 212~214 ℃; 1H NMR (500 MHz, DMSO-d6) δ: 12.64 (s, 1H), 11.74 (s, 1H), 8.21 (d, J=8.30 Hz, 1H), 8.05 (d, J=8.10 Hz, 1H), 7.98 (d, J=8.00 Hz, 1H), 7.91 (s, 1H), 7.85 (d, J=7.60 Hz, 1H), 7.70~7.78 (m, 3H), 7.50 (d, J=7.50 Hz, 1H), 7.46 (t, J=7.60 Hz, 1H), 2.42 (s, 3H); 13C NMR (125 MHz, DMSO-d6) δ: 181.9, 169.0, 138.3, 135.3, 134.3, 132.5, 132.1, 130.7, 130.1, 129.8, 128.9, 128.7, 128.2, 127.4, 126.5, 126.2, 123.8, 121.1, 21.3; IR (KBr) ν: 3214, 3127, 3051, 1660, 1595, 1585, 1505, 1324, 1241, 836, 810, 772, 723, 694 cm-1; HRMS (ESI) calcd for C19H15BrN2NaOS [M+Na]+ 420.9986, found 420.9975.

    3-[1-(4-溴萘基)]-1-(2-氯苯甲酰基)硫脲(1n):浅绿色固体, 产率79%. m.p. 186~188 ℃; 1H NMR (500 MHz, CDCl3) δ: 12.52 (s, 1H), 9.49 (s, 1H), 8.31 (dd, J=6.70, 2.70 Hz, 1H), 8.04 (dd, J=6.60, 2.70 Hz, 1H), 7.93 (d, J=8.00 Hz, 1H), 7.83~7.86 (m, 2H), 7.63~7.68 (m, 2H), 7.52 (t, J=4.10 Hz, 2H), 7.43~7.46 (m, 1H); 13C NMR (125 MHz, CDCl3) δ: 179.5, 166.4, 133.6, 133.3, 132.6, 131.9, 131.3, 131.1, 130.8, 129.7, 129.4, 128.1, 127.9, 127.9, 127.7, 124.4, 122.4, 122.2; IR (KBr) ν: 3245, 3149, 3066, 1682, 1622, 1591, 1434, 1378, 1249, 830, 775, 708 cm-1; HRMS (ESI) calcd for C18H12BrClN2NaOS [M+Na]+ 440.9440, found 440.9426.

    3.2.2   2-芳酰氨基萘并[1, 2-d]噻唑2a~2n的合成

    以2-(4-甲基苯甲酰氨基)萘并[1, 2-d]噻唑(2a)为例.将3-(1-萘基)-1-(4-甲基苯甲酰基)硫脲(1a) (0.30 g, 0.94 mmol)、IBD (0.3640 g, 1.13 mmol)和乙腈(30 mL)依次加入到50 mL三颈圆底烧瓶中后, 在20 ℃条件下反应5 min, 反应结束后溶液显浅黄色.将反应液浓缩至干得淡黄色固体, 然后用硅胶过柱提纯[洗脱剂为乙酸乙酯/石油醚(b.p. 60~90 ℃), V:V=1:10], 得0.26 g 2-(4-甲基苯甲酰氨基)萘并[1, 2-d]噻唑(2a), 白色固体, 产率87%. m.p. 169~170 ℃; 1H NMR (500 MHz, CDCl3) δ: 10.54 (s, 1H), 8.49 (dd, J=8.20, 1.20 Hz, 1H), 7.92 (dd, J=6.9, 2.3 Hz, 1H), 7.89 (d, J=8.70 Hz, 1H), 7.80 (d, J=8.20 Hz, 2H), 7.76 (d, J=8.70 Hz, 1H), 7.50~7.55 (m, 2H), 7.12 (d, J=8.00 Hz, 2H), 2.33 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 165.2, 158.3, 144.6, 143.8, 132.2, 129.5, 129.0, 128.1, 128.1, 127.5, 127.4, 126.5, 125.8, 124.7, 123.0, 118.9, 21.6; IR (KBr) ν: 3489, 3157, 3048, 2980, 1650, 1590, 1543, 1498, 1302, 1078, 805 cm-1; HRMS (ESI) calcd for C19H15N2OS [M+H]+ 319.0905, found 319.0903.

    2-(3-甲基苯甲酰氨基)萘并[1, 2-d]噻唑(2b):白色固体, 产率85%. m.p. 89~90 ℃; 1H NMR (500 MHz, CDCl3) δ: 11.34 (s, 1H), 8.39 (d, J=8.70 Hz, 1H), 7.88 (d, J=8.70 Hz, 2H), 7.76 (d, J=8.70 Hz, 1H), 7.71~7.73 (m, 1H), 7.64 (s, 1H), 7.43~7.49 (m, 2H), 7.17 (dd, J=4.60, 1.70 Hz, 2H), 2.07 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 166.8, 158.8, 144.3, 138.7, 133.6, 132.1, 131.8, 128.6, 128.1, 128.0, 127.9, 127.2, 126.4, 125.8, 124.8, 124.8, 123.0, 118.8, 20.9; IR (KBr) ν: 3488, 3157, 3051, 1644, 1591, 1541, 1499, 1368, 1300, 1078, 812, 731 cm-1; HRMS (ESI) calcd for C19H15N2OS [M+H]+ 319.0905, found 319.0909.

    2-(2-甲基苯甲酰氨基)萘并[1, 2-d]噻唑(2c):白色固体, 产率87%. m.p. 182~184 ℃; 1H NMR (500 MHz, CDCl3) δ: 10.77 (s, 1H), 8.37 (dd, J=6.00, 3.40 Hz, 1H), 7.86~7.90 (m, 2H), 7.75 (d, J=8.70 Hz, 1H), 7.49~7.52 (m, 2H), 7.35 (d, J=7.60 Hz, 1H), 7.08 (t, J=7.30 Hz, 1H), 7.03 (d, J=7.60 Hz, 1H), 6.84 (t, J=7.40 Hz, 1H), 2.52 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 167.4, 158.1, 144.4, 137.6, 132.8, 132.1, 131.3, 131.1, 128.1, 127.7, 127.3, 126.9, 126.3, 125.8, 125.6, 124.7, 123.0, 118.8, 20.1; IR (KBr) ν: 3446, 3152, 3051, 2926, 1679, 1587, 1541, 1505, 1458, 1249, 807, 781, 744 cm-1; HRMS (ESI) calcd for C19H14N2NaOS [M+Na]+ 341.0725, found 341.0719.

    2-(2-氯苯甲酰氨基)萘并[1, 2-d]噻唑(2d):白色固体, 产率78%. m.p. 194~196 ℃ (Lit.[12] m.p. 198~200 ℃); 1H NMR (500 MHz, CDCl3) δ: 11.38 (s, 1H), 8.38 (dd, J=6.40, 2.70 Hz, 1H), 7.87~7.90 (m, 2H), 7.75 (d, J=8.70 Hz, 1H), 7.56 (d, J=7.60 Hz, 1H), 7.49~7.54 (m, 2H), 7.03 (q, J=8.10 Hz, 2H), 6.96 (dd, J=11.60, 4.30 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ: 164.5, 158.1, 144.4, 132.3, 132.2, 132.1, 131.1, 130.2, 130.0, 128.0, 127.9, 127.2, 126.8, 126.5, 125.8, 124.8, 123.1, 118.8; IR (KBr) ν: 3443, 3052, 2925, 1670, 1590, 1548, 1436, 1300, 910, 799, 741 cm-1; HRMS (ESI) calcd for C18H11ClN2NaOS [M+Na]+ 361.0179, found 361.0163.

    2-(3-氯苯甲酰氨基)萘并[1, 2-d]噻唑(2e):白色固体, 产率81%. m.p. 98~100 ℃; 1H NMR (500 MHz, CDCl3) δ: 11.43 (s, 1H), 8.34 (d, J=8.10 Hz, 1H), 7.89 (dd, J=8.20, 3.80 Hz, 2H), 7.77~7.81 (m, 2H), 7.70~7.72 (m, 1H), 7.42~7.50 (m, 2H), 7.27~7.29 (m, 1H), 7.12 (t, J=7.90 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ: 164.4, 158.5, 144.2, 135.1, 133.7, 132.7, 132.2, 129.9, 128.2, 128.1, 127.8, 127.2, 126.5, 125.9, 125.6, 125.1, 122.8, 118.9; IR (KBr) ν: 3418, 3052, 1655, 1586, 1545, 1504, 1452, 1346, 1269, 806, 183, 735 cm-1; HRMS (ESI) calcd for C18H12ClN2OS [M+H]+ 339.0359, found 339.0347.

    2-(4-氯苯甲酰氨基)萘并[1, 2-d]噻唑(2f):白色固体, 产率80%. m.p. 202~203 ℃; 1H NMR (500 MHz, CDCl3) δ: 10.80 (s, 1H), 8.45 (dt, J=6.90, 3.50 Hz, 1H), 7.92~7.95 (m, 1H), 7.90 (d, J=8.70 Hz, 1H), 7.80 (t, J=8.0 Hz, 3H), 7.51~7.54 (m, 2H), 7.25~7.26 (m, 2H); 13C NMR (125 MHz, CDCl3) δ: 164.3, 158.1, 144.4, 139.4, 132.2, 130.3, 129.1, 128.9, 128.3, 128.1, 127.3, 126.6, 126.0, 125.0, 122.9, 118.9; IR (KBr) ν: 3412, 3053, 2921, 1663, 1592, 1540, 1497, 1451, 1240, 845, 800, 776, 746 cm-1; HRMS (ESI) calcd for C18H11ClN2NaOS [M+Na]+ 361.0179, found 361.0168.

    2-(3-溴苯甲酰氨基)萘并[1, 2-d]噻唑(2g):白色固体, 产率75%. m.p. 160~161 ℃; 1H NMR (500 MHz, CDCl3) δ: 11.38 (s, 1H), 8.34~8.35 (m, 1H), 7.97~7.98 (m, 1H), 7.90~7.92 (m, 2H), 7.78~7.80 (m, 2H), 7.45~7.50 (m, 3H), 7.10 (td, J=7.80, 3.70 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ: 164.3, 158.4, 144.2, 135.7, 133.9, 132.2, 130.7, 130.2, 128.2, 128.1, 127.2, 126.6, 126.1, 125.9, 125.1, 123.0, 122.8, 118.9; IR (KBr) ν: 3424, 3051, 2924, 1670, 1586, 1541, 1505, 1454, 1245, 802, 782, 729 cm-1; HRMS (ESI) calcd for C18H11BrN2NaOS [M+Na]+ 404.9673, found 404.9659.

    2-(4-溴苯甲酰氨基)萘并[1, 2-d]噻唑(2h):白色固体, 产率74%. m.p. 201~203 ℃; 1H NMR (500 MHz, CDCl3) δ: 11.40 (s, 1H), 8.41~8.43 (m, 1H), 7.94 (dd, J=8.40, 4.20 Hz, 1H), 7.89 (d, J=8.70 Hz, 1H), 7.79 (d, J=8.70 Hz, 1H), 7.73 (d, J=8.40 Hz, 2H), 7.50~7.54 (m, 2H), 7.39 (d, J=8.40 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ: 164.6, 158.5, 144.2, 132.2, 132.0, 130.7, 129.0, 128.3, 127.9, 127.9, 127.2, 126.7, 126.0, 125.1, 122.8, 118.8; IR (KBr) ν: 3414, 3052, 2920, 2851, 1661, 1590, 1541, 1505, 1450, 1280, 841, 804, 778, 742 cm-1; HRMS (ESI) calcd for C18H11BrN2NaOS [M+Na]+ 404.9673, found 404.9662.

    2-(4-氟苯甲酰氨基)萘并[1, 2-d]噻唑(2i):白色固体, 产率90%. m.p. 173~174 ℃; 1H NMR (500 MHz, CDCl3) δ: 11.13 (s, 1H), 8.48 (d, J=7.40 Hz, 1H), 7.93~7.98 (m, 3H), 7.89 (d, J=8.70 Hz, 1H), 7.79 (d, J=8.70 Hz, 1H), 7.52~7.57 (m, 2H), 7.03 (t, J=8.50 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ: 165.4 (1JCF=297.50 Hz), 164.5, 158.4, 144.3, 132.3, 130.2 (3JCF=10.00 Hz), 128.3, 128.1 (4JCF=2.50 Hz), 128.0, 127.3, 126.7, 126.0, 125.0, 122.9, 118.9, 116.1 (2JCF=21.25 Hz); IR (KBr) ν: 3426, 3053, 1667, 1604, 1588, 1537, 1503, 1453, 1237, 840, 808, 777, 752 cm-1; HRMS (ESI) calcd for C18H11FN2NaOS [M+Na]+ 345.0474, found 345.0470.

    2-(2-呋喃甲酰氨基)萘并[1, 2-d]噻唑(2j):白色固体, 产率78%. m.p. 170~171 ℃; 1H NMR (500 MHz, CDCl3) δ: 10.12 (s, 1H), 8.62 (d, J=8.20 Hz, 1H), 7.95 (d, J=8.10 Hz, 1H), 7.88 (d, J=8.70 Hz, 1H), 7.78 (d, J=8.70 Hz, 1H), 7.60~7.64 (m, 1H), 7.54~7.57 (m, 1H), 7.41 (s, 1H), 7.38 (d, J=3.50 Hz, 1H), 6.57 (dd, J=3.50, 1.70 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ: 156.7, 155.3, 145.9, 145.5, 144.8, 132.2, 128.3, 128.2, 127.6, 126.6, 125.9, 124.7, 123.3, 118.9, 117.5, 113.1; IR (KBr) ν: 3444, 3045, 2918, 1683, 1584, 1540, 1503, 1294, 844, 758 cm-1; HRMS (ESI) calcd for C16H10N2NaO2S [M+Na]+ 317.0361, found 317.0355.

    2-(2-呋喃甲酰氨基)-5-溴萘并[1, 2-d]噻唑(2k):白色固体, 产率76%. m.p. 246~247 ℃; 1H NMR (500 MHz, DMSO-d6) δ: 13.14 (s, 1H), 8.65 (d, J=7.50 Hz, 1H), 8.54~8.56 (m, 1H), 8.24 (dd, J=7.00, 1.50 Hz, 1H), 8.10 (s, 1H), 7.84 (d, J=3.20 Hz, 1H), 7.75~7.80 (m, 2H), 6.81 (dd, J=3.40, 1.60 Hz, 1H); 13C NMR (125 MHz, DMSO-d6) δ: 159.3, 156.7, 148.3, 145.8, 145.1, 130.0, 128.4, 128.1, 128.0, 127.9, 127.5, 124.0, 123.9, 117.8, 116.8, 113.0; IR (KBr) ν: 3406, 3390, 3135, 3065, 2921, 1688, 1589, 1568, 1538, 1489, 1294, 858, 770, 759 cm-1; HRMS (ESI) calcd for C16H9BrN2NaO2S [M+Na]+ 394.9466, found 394.9454.

    2-(4-甲基苯甲酰氨基)-5-溴萘并[1, 2-d]噻唑(2l):白色固体, 产率82%. m.p. 243~244 ℃; 1H NMR (500 MHz, DMSO-d6) δ: 13.09 (s, 1H), 8.67~8.69 (m, 1H), 8.58 (s, 1H), 8.25~8.27 (m, 1H), 8.11 (d, J=8.10 Hz, 2H), 7.76~7.81 (m, 2H), 7.40 (d, J=8.0 Hz, 2H), 2.42 (s, 3H); 13C NMR (125 MHz, DMSO-d6) δ: 166.2, 160.0, 145.1, 143.8, 130.0, 129.7, 129.4, 128.9, 128.4, 128.2, 128.1, 127.9, 127.6, 124.1, 124.0, 116.8, 21.7; IR (KBr) ν: 3420, 3175, 3065, 2920, 1673, 1612, 1568, 1538, 1411, 1287, 831, 789, 747 cm-1; HRMS (ESI) calcd for C19H14BrN2OS [M+H]+ 397.0010, found 397.0015.

    2-(3-甲基苯甲酰氨基)-5-溴萘并[1, 2-d]噻唑(2m):白色固体, 产率76%. m.p. 204~206 ℃; 1H NMR (500 MHz, DMSO-d6) δ: 13.10 (s, 1H), 8.68 (d, J=7.30 Hz, 1H), 8.55 (s, 1H), 8.25 (d, J=7.90 Hz, 1H), 8.04 (s, 1H), 8.00 (d, J=7.00 Hz, 1H), 7.75~7.81 (m, 2H), 7.45~7.50 (m, 2H), 2.43 (s, 3H); 13C NMR (125 MHz, DMSO-d6) δ: 166.4, 160.0, 145.1, 138.5, 134.0, 132.1, 130.0, 129.4, 129.0, 128.4, 128.2, 128.0, 127.8, 127.5, 126.0, 124.0, 123.9, 116.8, 21.4; IR (KBr) ν: 3412, 3229, 3063, 2955, 2921, 2852, 1718, 1679, 1606, 1536, 1505, 1458, 1355, 884, 822, 767, 728, 701 cm-1; HRMS (ESI) calcd for C19H13BrN2NaOS [M+Na]+ 418.9830, found 418.9818.

    2-(2-氯苯甲酰氨基)-5-溴萘并[1, 2-d]噻唑(2n):黄色固体, 产率74%. m.p. 242~244 ℃; 1H NMR (500 MHz, DMSO-d6) δ: 13.31 (s, 1H), 8.60~8.63 (m, 2H), 8.26 (dd, J=6.60, 2.60 Hz, 1H), 7.76~7.81 (m, 3H), 7.58~7.65 (m, 2H), 7.52 (dd, J=10.60, 4.20 Hz, 1H); 13C NMR (125 MHz, DMSO-d6) δ: 166.1, 160.0, 145.0, 134.4, 132.7, 130.9, 130.4, 130.1, 130.1, 128.4, 128.2, 128.1, 128.0, 127.8, 127.6, 124.1, 124.0, 117.1; IR (KBr) ν: 3398, 3065, 2923, 1670, 1572, 1537, 1495, 1450, 1296, 790, 755, 744, 732 cm-1; HRMS (ESI) calcd for C18H10BrClN2NaOS [M+Na]+ 438.9284, found 438.9261.

    3.2.3   2-(4-甲基苯甲酰氨基)萘并[2, 1-d]噻唑(4)的合成

    按照化合物2的合成方法合成2-(4-甲基苯甲酰氨基)萘并[2, 1-d]噻唑(4), 黄色固体, 产率8%. m.p. 234~236 ℃; 1H NMR (400 MHz, CDCl3) δ: 11.54 (s, 1H), 8.06 (d, J=8.10 Hz, 1H), 7.92 (t, J=7.90 Hz, 3H), 7.68 (d, J=8.80 Hz, 1H), 7.63~7.57 (m, 1H), 7.53~7.48 (m, 1H), 7.39 (d, J=8.80 Hz, 1H), 7.21 (d, J=8.00 Hz, 2H), 2.36 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 165.8, 159.1, 145.9, 143.9, 130.5, 129.7, 129.3, 128.9, 128.2, 128.0 127.9, 127.0, 126.9, 125.4, 124.1, 119.9, 21.6; IR (KBr) ν: 3439, 3051, 2924, 1671, 1655, 1631, 1610, 1590, 1560, 1541, 1295, 1257, 812, 773, 742 cm-1; HRMS (ESI) calcd for C19H15N2OS [M+H]+ 319.0905, found 319.0889.

    辅助材料(Supporting Information)   化合物1a~1n, 2a~2n41H NMR和13C NMR谱图.这些材料可以免费从本刊网站(http://sioc-journal.cn/)上下载.


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  • 图式 1  生成2-芳酰氨基萘并[1, 2-d]噻唑类化合物可能的反应机理

    Scheme 1  A plausible mechanism for the formation of 2-aroylamino naphtho[1, 2-d]thiazoles

    表 1  2-(4-甲基苯甲酰氨基)萘并[1, 2-d]噻唑(2a)合成条件的优化a

    Table 1.  Optimization of reaction conditions on the synthesis of 2-(4-methyl benzoylamino)naphtho[1, 2-d]thiazole (2a)

    Entry IBD/equiv. Temp./℃ Time/min Solvent Yieldb/%
    1 1.0 80 30 CH3CN 68
    2 1.1 80 30 CH3CN 74
    3 1.2 80 30 CH3CN 83
    4 1.3 80 30 CH3CN 75
    5 1.4 80 30 CH3CN 67
    6 1.2 70 30 CH3CN 83
    7 1.2 60 30 CH3CN 82
    8 1.2 50 30 CH3CN 86
    9 1.2 40 30 CH3CN 85
    10 1.2 30 30 CH3CN 86
    11 1.2 20 30 CH3CN 86
    12 1.2 14 30 CH3CN 44
    13 1.2 20 30 CH3CH2OH 60
    14 1.2 20 30 CH3OH 65
    15 1.2 20 30 THF 43
    16 1.2 20 30 Petroleum ether 22
    17 1.2 20 30 1, 4-Dioxane 40
    18 1.2 20 30 AcOH 80
    19 1.2 20 20 CH3CN 86
    20 1.2 20 10 CH3CN 86
    21 1.2 20 5 CH3CN 87
    a All reactions were performed in air. The mixture of 1a (0.94 mmol), catalyst, and solvent (30 mL) was placed in a three-necked round bottom flask (50 mL). b Isolated yields.
    下载: 导出CSV

    表 2  2-芳酰氨基萘并[1, 2-d]噻唑衍生物2的合成a

    Table 2.  Synthesis of 2-aroylamino naphtho[1, 2-d]thiazoles 2

    下载: 导出CSV
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  • 收稿日期:  2019-04-11
  • 修回日期:  2019-05-27
  • 网络出版日期:  2019-11-25
通讯作者: 陈斌, bchen63@163.com
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