具体实施方式
所用试剂均为市售产品,溶剂经常规干燥处理,敏感化合物的合成即操作采用标准真空线技术;采用试剂说明:PE—石油醚;DCM—二氯甲烷;THF—四氢呋喃;EtOH—乙醇;KOH—氢氧化钾;EtOAc—乙酸乙酯;TBAB—四正丁基溴化铵;MeOH—甲醇;NaOH—氢氧化钠。
参阅图1,本发明制备方法按下述步骤进行:
芴及螺芴并噻吩系列衍生物的制备
化合物1,3-二苯基-茚[a]并环戊二烯-2,8-二酮参照文献制得(Ried, W.; Freitag, D. Chem. Ber. 1966, 99, 2675-2677)。
将水合茚三酮(4.86 g, 27.3 mmol)和1,3-二苯基丙酮(5.73 g, 27.3 mmol)溶解在40 ml热的乙醇中,缓慢滴加3.5 ml 10% KOH/MeOH 溶液,滴加完毕后在75 ℃下搅拌3h,待溶液由黄色变成深红棕色并有大量固体产生时停止反应,滤出反应产生固体,用甲苯重结晶,得到红棕色晶体7.43 g,产率81.9 %; 熔点:204 ~ 206 ℃(文献m. p204~206℃ ), 1H NMR (CDCl3, 500 MHz) δ: 8.61(dd, J=7.6 Hz, J=1.0 Hz, 1H), 8.23-8.19(m, 1H), 8.08-8.07 (m, 1H), 7.76-7.73(m, 4H), 7.52-7.48(m, 6H)。
二苯基-2,3-二羟甲基-9-芴酮(1a)
将4g (12 mmol)1,3-二苯基-茚[a]并环戊二烯-2,8-酮与1.3 g (14.3 mmol) 1,4-丁炔二醇置于50 mL圆底烧瓶中,在搅拌下将固体加热到240℃,待反应5min后终止反应,将体系冷却至室温后,产物用DCM:EtOAc =10:1展开剂柱层析,旋干后,固体用正己烷洗涤,得到2 g黄色固体粉末。产率43 %。熔点:224-225℃。1H NMR (CDCl3, 500MHz,ppm) δ:7.57-7.51(m, 3H), 7.48-7.42(m, 4H), 7.40-7.38(m, 2H), 7.32-7.30(m, 2H), 7.11(t, J = 7.5 Hz, 1H), 7.03(td, J = 7.5 Hz, J = 1.0 Hz, 1H), 5.98(d, J = 5.0 Hz, 1H), 4.56(d, J = 5.0 Hz, 4H), 2.99(br.s, 1H), 2.67(br.s, 1H); 13C NMR (125 MHz, CDCl3, ppm) δ:192.53, 145.16, 143.27, 142.29, 139.56, 187.82, 137.70, 136.18, 134.67, 134.17, 130.40, 129.22, 129.12, 128.79, 128.72, 128.36, 128.10, 127.82, 123.72, 123.14, 59.75, 59.30。
二甲基-6,12-二苯基-1,5亚甲基-芴酮[3,2-e]并[1,3]氧杂环庚烷(1b)
将双苄醇原料(1a) 11.26 g(28.7 mmol),2,2-二甲氧基丙烷3.47 g(34.4 mmol)以及对甲苯磺酸2.6g (14.4 mmol)溶于200 mL THF中加热回流4小时,之后产物倒入200 mL的20 %NaOH溶液中,二氯甲烷(3×50 mL)萃取,合并有机相,无水硫酸镁干燥,旋干后粗产物PE:DCM=1:1柱层析得到10.5g黄色固体,产率85%,熔点:211-213℃; 1H NMR (CDCl3, 500MHz,ppm)δ:7.56-7.49(m, 3H), 7.48-7.41(m, 4H), 7.33-7.31(m, 2H), 7.24-7.22(m, 2H), 7.09(t, J = 7.5 Hz, 1H), 7.03(td, J = 7.5 Hz, J = 1.0 Hz, 1H), 5.93(d, J = 5.0 Hz, 1H), 4.62(d, J = 5.0 Hz, 4H), 1.39(s, 6H); 13C NMR (125 MHz, CDCl3, ppm) δ:192.59, 143.56, 143.33, 140.80, 138.95, 138.00, 137.59, 136.11, 135.05, 134.94, 133.94, 129.49, 129.34, 128.73, 128.41, 128.33, 128.31, 127.77, 123.63, 122.80, 120.13, 63.13, 62.25, 23.54。
二甲基-6,12-二苯基-1,5,7-亚甲基-芴[3,2-e]并[1,3]氧杂环庚烷(1c)
将原料(1b) 6.48g (15mmol)悬浮在150 ml的一缩二乙二醇溶液中,加入13.5 mL (85%, 202 mmol)水合肼溶液,将其加热到180℃,保持2小时后,将体系冷却到室温,向其中加入1.3g (22.5mmol) KOH,升温到180℃后,反应至体系变为白色即停止加热,待冷却到室温后,将溶液倾入200mL冰水中,用二氯甲烷(3×50 mL)萃取,合并有机相,无水硫酸镁干燥,旋干,粗产物用乙醇重结晶,得到5.2g白色固体,产率83%,熔点:173-175℃。1H NMR (CDCl3, 500MHz,ppm)δ:7.55-7.47(m, 5H), 7.42(t, J = 7.2 Hz, 1H), 7.34(d, J = 7.0 Hz, 3H), 7.31(d, J = 7.0 Hz, 2H), 7.11(t, J = 7.2 Hz, 1H), 6.94(t, J = 7.8 Hz, 1H), 6.22(d, J = 7.6 Hz, 1H), 4.73(d, J = 9.0 Hz, 4H), 3.57(s, 2H), 1.42(s, 6H); 13C NMR (125 MHz, CDCl3, ppm) δ:143.99, 141.59, 141.06, 139.26, 139.19, 137.68, 136.52, 135.25, 134.25, 134.17, 129.18, 129.09, 128.87, 128.74, 127.69, 127.36, 126.24, 126.09, 124.52, 122.67, 102.01, 36.52, 23.73。
二苯基-2,3-二(溴甲基)芴(1d)
将原料(1c) 1.9g (4.5mmol)溶解于50 mL的氯仿中,同时,依次加入0.6 g ( 2 mmol)的TBAB, 10 mL浓氢溴酸,以及0.8mL的浓硫酸,在60℃下回流72 h,将反应体系倾倒入水中,将溶液倾入200mL水中,用二氯甲烷(3×50mL)萃取,合并有机相,无水硫酸镁干燥,旋干,粗产物PE:DCM=3∶1柱层析得到1.8g白色固体,产率78.6%, 熔点:180-182℃。1H NMR (CDCl3, 500MHz,ppm)δ: 7.62-7.55(m, 5H), 7.50-7.49(m, 5H), 7.37(d, J = 7.5Hz, 1H), 7.17(t, J = 7.4Hz, 1H), 6.98(t, J = 7.6Hz, 1H), 6.22(d, J = 7.9Hz, 1H), 4.68(s, 4H), 3.63(s, 2H); 13C NMR (125 MHz, CDCl3, ppm) δ:144.03, 143.81, 140.97, 140.41, 140.11, 138.27, 138.04, 137.82, 134.49, 132.89, 129.21, 129.08, 128.90, 128.70, 128.26, 127.92, 126.91, 126.52, 124.56, 123.14, 37.17, 29.52, 28.87。
二苯基-1,3,9-亚甲基-芴[2,3-c]并硫杂环戊烷(1e)
于100 mL三颈烧瓶中将Na2S·9H2O (0.3g, 1.2mmol)加入18mL THF/EtOH =1:5(体积比)的混合溶剂中,氮气保护下加热至回流,待体系呈悬浮状态时,将原料1d 0.4g(0.8mmol)溶于5mLTHF中,缓慢滴加至反应体系中,保持加热回流状态3小时,常温搅拌过夜,反应结束后将反应混合物倾入水中,二氯甲烷萃取,合并有机相,无水硫酸镁干燥,过滤旋干,粗产物PE: DCM = 3:1柱层析得到0.15g白色固体1e,产率50%,熔点:163-165℃。1H NMR (CDCl3, 500 MHz,ppm) δ:7.56-7.53(m, 2H), 7.51-7.48(m, 3H), 7.44-7.39(m, 6H), 7.15(t, J = 7.2 Hz, 1H), 6.99(t, J = 7.5 Hz, 1H), 6.51(d, J = 7.9 Hz, 1H), 4.16(s, 2H), 4.07(s, 2H), 3.71(s, 2H); 13C NMR (125 MHz, CDCl3, ppm) δ:144.17, 141.79, 141.24, 139.41, 139.16, 138.56, 137.36, 134.94, 132.98, 129.10, 128.71, 128.53, 127.80, 127.53, 126.31, 126.27, 124.67, 122.64, 37.77, 37.72, 36.07。
二苯基-9H-芴[2,3-c]噻吩(1f)
于100 mL三颈烧瓶中加入原料1e 0.15g(0.4mmol),70%钯/碳(质量百分数)0.06g,加入溶剂二甲苯15mL,氮气保护下加热回流24小时,反应结束后硅藻土抽滤除去钯炭,旋干溶剂,初产物PE: DCM = 5:1柱层析得到0.06g固体1f,产率40%,熔点:165-167℃。1H NMR (CDCl3, 500 MHz,ppm) δ: 7.62-7.59(m, 4H),7.57-7.54(m, 5H),7.48-7.46(m, 1H), 7.43-7.42(m, 1H), 7.37(d, J = 7.5 Hz, 1H), 7.28-7.27(m, 1H), 7.18(t, J = 7.5 Hz, 1H), 7.01(t, J = 7.7 Hz, 1H), 6.71(d, J = 7.9 Hz, 1H), 3.94(s, 2H); 13C NMR (125 MHz, CDCl3, ppm) δ:144.31, 140.75, 138.96, 129.63, 129.29, 129.08, 128.68, 127.82, 127.47, 127.16, 126.41, 124.85, 123.64, 117.05, 115.09, 30.89。
二甲基-7,7-二乙基-6,12-二苯基-1,5亚甲基-芴[3,2-e]并[1,3]氧杂环庚烷(2d)
在氮气保护下,将原料1c 2.22 g(5.3 mmol)溶解于50 ml干燥的THF中,在-78℃条件下向反应体系中缓慢滴加3.2 mL(2.5 M, 7.9mmol)n-BuLi溶液,搅拌半小时后再向其中加入0.63mL(7.9mmol)溴代乙烷,将反应瓶升温到室温,搅拌1小时后,重复以上操作,待搅拌6小时后用饱和氯化铵溶液终止反应,二氯甲烷 (3×50mL)萃取,合并有机相,无水硫酸镁干燥,过滤旋干,粗产物PE:DCM=3:1柱层析,过柱产物旋干,乙醇洗涤,得到1.9 g白色固体2d,产率75.4%,熔点:181-182℃。1H NMR (CDCl3, 500 MHz,ppm) δ:7.54-7.49(m, 3H), 7.46-7.42(m, 3H), 7.33(d, J = 7.0 Hz, 2H), 7.28(d, J = 6.5 Hz, 2H), 7.11(t, J = 7.0 Hz, 2H), 6.87-6.85(m, 1H), 6.05(d, J = 8.0 Hz, 1H), 4.68(s, 2H), 4.51(s, 2H), 1.63(q, J=7.0Hz, 4H), 1.39(s, 6H), 0.25(t, J=7.0Hz, 6H); 13C NMR (125 MHz, CDCl3, ppm) δ:151.12, 143.25, 141.01, 139.46, 138.64, 138.44, 136.36, 135.12, 135.00, 134.33, 129.21, 129.17, 129.09, 128.13, 127.62, 127.47, 126.56, 126.09, 122.24, 121.43, 101.90, 63.08, 62.86, 57.43, 31.90, 23.66, 8.27。
二苯基-2,3-(溴甲基)-9,9-二乙基芴(2e)
将原料2d 1.9g (4.0mmol)溶解于50 mL氯仿中,同时,依次加入0.68g (2.25 mmol)的TBAB,12.5mL浓氢溴酸,以及1mL浓硫酸,在60℃下回流70 h,将反应体系倾倒入水中,将溶液倾入200mL水中,用二氯甲烷(3×50mL)萃取,合并有机相,无水硫酸镁干燥,旋干,粗产物PE:DCM=4:1柱层析得白色固体产物1.8 g,产率80%,熔点:181-183℃。1H NMR (CDCl3, 500MHz,ppm) δ: 7.56-7.48(m, 8H), 7.48-7.40(m, 2H), 7.18-7.13(m, 2H), 6.90(t, J=7.0Hz , 1H), 6.05(d, J=8.0Hz, 1H), 4.60(s, 2H), 4.49(s, 2H), 1.67-1.63(m,4H), 0.25(t, J=7.0Hz, 6H);13C NMR (125 MHz, CDCl3, ppm) δ:151.20, 146.23, 141.23, 140.29, 139.83, 138.19, 137.59, 137.04, 134.34, 133.99, 129.36, 128.97, 128.12, 128.00, 127.78, 127.34, 126.35, 122.74, 121.50, 57.91, 31.76, 29.36, 28.88, 8.28。
二苯基-1,3-亚甲基-9,9-二乙基芴[2,3-c]并硫杂环戊烷(2f)
于250 mL三颈烧瓶中将Na2S· 9H2O 1.2g(4.8mmol)加入24mLTHF/EtOH =1:5(体积比)的混合溶剂中,氮气保护下加热至回流,待体系呈悬浮状态时,将原料2e 1.8g(3.2mmol)溶于10mL THF中,缓慢滴加至反应体系中,保持加热回流状态3小时,常温搅拌过夜,反应结束后将反应混合物倾入水中,二氯甲烷萃取,合并有机相,无水硫酸镁干燥,过滤旋干,粗产物DCM:PE = 1:3柱层析得到0.76g白色固体2f,产率55%,熔点:131-133℃。1H NMR (CDCl3, 500MHz,ppm)δ:7.55-7.48(m, 3H), 7.46-7.43(m, 3H), 7.40-7.39(m, 2H),7.32-7.30(m, 2H), 7.16-7.15(m, 2H), 6.94-6.91(m, 1H), 6.36(d, J=7.9Hz, 1H),4.05(s, 2H),3.90(s, 2H), 1.72(q, J=7.3Hz , 4H), 0.30(t, J=7.7Hz , 6H); 13C NMR (125 MHz, CDCl3, ppm) δ:151.17, 144.57, 140.77, 139.71, 139.27, 139.20, 138.69, 138.41, 135.14, 132.85, 129.05, 128.78, 128.47, 128.18, 127.69, 127.51, 126.69, 126.17, 122.18, 121.65, 57.10, 38.28, 37.95, 32.03, 8.33。
二苯基-9,9-二乙基芴[2,3-c]并噻吩(2g)
于100 mL三颈烧瓶中加入原料2f 0.6g(1.38mmol),70%钯/碳(质量百分数)0.2g,加入溶剂二甲苯15mL,氮气保护下加热回流24小时,反应结束后硅藻土抽滤除去钯炭,旋干溶剂,初产物DCM:PE = 1:5柱层析得到0.27g白色固体,产率46%。熔点:133-135℃。1H NMR (CDCl3, 500MHz,ppm)δ:7.61-7.58(m, 2H), 7.55-7.47(m, 6H), 7.45-7.43(m, 2H),7.21-7.14(m, 3H), 6.96-6.92(m, 2H), 6.58(d, J=7.9Hz, 1H), 1.82-1.76(m, 2H), 1.75-1.70(m, 2H), 0.42(t, J=7.3Hz, 6H); 13C NMR (125 MHz, CDCl3, ppm) δ:151.16, 141.06, 140.74, 140.31, 139.21, 136.16, 129.72, 129.63, 129.40, 129.09, 127.99, 127.74, 127.54, 127.46, 126.32, 123.08, 122.00, 116.46, 56.19, 33.19, 8.64。
二甲基-7-羟基-7-(2’-联苯基)-6,12-二苯基-1,5亚甲基-芴[3,2-e]并[1,3]氧杂环庚烷(2c)
在氮气保护下,将(2g, 8.6 mmol)2-溴联苯溶解于15 ml干燥的THF中,将体系降温到-78°C,之后向其中滴入3.44 mL(2.5M,8.6 mmol)正丁基锂溶液,搅拌一小时,之后,将15 mL干燥的原料1b (2.3 g, 5.75 mmol)THF溶液缓慢滴加进反应体系,保持-78℃搅拌1小时,之后在室温下继续搅拌1小时,反应结束后加入50mL饱和NH4Cl溶液淬灭反应,二氯甲烷(3×20mL)萃取,无水硫酸镁干燥、旋干,PE:DCM=1:1柱层析,过柱产物正己烷洗涤,得到2.7g白色固体,产率86.5 %, 熔点:257-259℃。1H NMR (CDCl3, 500MHz,ppm) δ:7.45-7.43(m, 1H), 7.41-7.28(m, 3H), 7.30(d, J=8.0Hz, 1H), 7.27(d, J=7.0Hz , 1H), 7.23(t, J = 7.0 Hz, 1H), 7.17-7.13(m, 2H), 7.10(t, J = 7.5Hz, 1H), 7.02-6.97(m, 5H), 6.88(d, J=7.0Hz, 1H), 6.77(d, J=6.5Hz, 2H) 6.52-6.49(m, 3H), 5.83(s, 1H), 5.60(d, J=8.0Hz, 1H), 4.63-4.43(m, 4H), 2.34(s, 1H); 1.41(s, 3H), 1.36(s, 3H);13C NMR (125 MHz, CDCl3, ppm) δ:151.21, 145.87, 141.00, 137.34, 136.63, 130.90, 129.13, 129.05, 128.67, 128.57, 128.13, 127.90, 127.84, 127.64, 127.37, 126.89, 126.73, 125.96, 125.70, 125.40, 123.95, 122.94, 101.92, 82.14, 62.81, 62.78, 23.85, 23.63。
二苯基-2,3-二甲酸亚甲酯基-9,9’-螺二芴(3d)
将原料2c(2.7 g, 4.6mmol)悬浮于150ml甲酸中,同时向其中加入1.75g (25 mmol)的甲酸钠,反应体系回流24h,之后将其倾入500 mL的冰水中,二氯甲烷(3×50 mL)萃取,水洗至上层水相pH接近7.0,合并有机相,无水硫酸镁干燥,旋干,产品用乙醇重结晶,得到2 g白色固体,产率74 %,熔点:150-152℃。1H NMR (CDCl3, 500MHz,ppm) δ: 7.98(s, 1H), 7.79(s, 1H), 6.64-6.59(m, 3H), 7.53(d, J=7.5Hz , 2H), 7.32(d, J= 7.5Hz, 2H), 7.20(t, J = 7.2Hz, 2H), 7.07(t, J= 7.5Hz, 2H), 6.95-6.93(m, 2H), 6.88(t, J=7.5Hz, 1H) 6.79(d, J= 7.5Hz, 2H), 6.62(t, J= 7.8Hz, 2H), 6.49-6.47(m, 1H), 6.27-6.26(m, 1H), 6.07(d, J= 7.0Hz, 2H); 5.15(s, 2H), 4.85(s, 2H);13C NMR (125 MHz, CDCl3, ppm) δ:178.04, 160.14, 159.99, 149.98, 147.60, 147.45, 142.06, 141.66, 140.23, 138.46, 138.07, 134.58, 132.86, 132.38, 129.43, 129.13, 128.78, 128.37, 128.04, 127.28, 127.21, 127.17, 126.60, 125.95, 123.63, 123.52, 123.29, 119.90, 65.64, 60.35, 60.32。
二苯基-2,3-二(羟甲基)-9,9’-螺二芴(3e)
将原料3d 2g(3.45 mmol)溶解于50 mL的THF中,向其中加入10 mL10% KOH溶液,搅拌半小时,将反应混合物倾入水中,用二氯甲烷(3×50 mL)萃取,水洗3次,合并有机相,无水硫酸镁干燥过滤后旋干,正己烷重结晶,得到1.6 g白色粉末,产率88%,熔点:279-280℃。1H NMR (CDCl3, 500MHz,ppm) δ:7.64-7.55(m, 5H), 7.44(d, J=5.0Hz, 2H), 7.20(t, J= 7.5Hz, 2H), 7.06(t, J=7.3Hz , 2H), 6.92-6.82(m, 3H), 6.79(d, J = 7.5Hz, 2H), 6.64(t, J= 7.5Hz, 2H), 6.47(d, J= 7.0Hz, 1H), 6.28(d, J=7.0Hz, 1H) 6.10(d, J= 7.5Hz, 2H), 4.64(s, 2H), 4.35(s, 2H), 2.97(br.s, 1H), 2.45(br.s, 1H);13C NMR (125 MHz, CDCl3, ppm) δ:149.91, 148.06, 145.84, 142.03, 140.82, 139.99, 139.11, 138.32, 137.14, 135.75, 129.57, 129.05, 128.82, 127.94, 127.52, 127.16, 127.12, 127.01, 126.61, 125.59, 123.69, 123.40, 123.10, 119.81, 107.95, 65.64, 59.99, 59.91。
二苯基-2,3-二(溴甲基)-9,9’-螺二芴(3f)
将原料3e 1.6g (3.0mmol)溶解于50 mL的氯仿中,同时,依次加入0.6 g(2 mmol)的TBAB, 8mL浓氢溴酸,以及0.6mL浓硫酸,在60℃下回流72 h,将反应体系倾倒入水中,将溶液倾入200mL水中,用二氯甲烷(3×50mL)萃取,合并有机相,无水硫酸镁干燥,旋干,粗产物PE:DCM=3:1柱层析得到1.8g白色固体,产率90%,熔点:145-148℃。1H NMR (CDCl3, 500MHz,ppm)δ:7.69-7.62(m, 5H), 7.33(d, J=7.5Hz, 2H), 7.21(t, J= 7.5Hz, 2H), 7.09(t, J=7.4Hz , 2H), 6.94-6.91(m, 3H), 6.81(d, J = 7.5Hz, 2H), 6.68(t, J= 7.5Hz, 2H), 6.48-6.46(m, 1H), 6.23-6.20(m, 1H), 6.17(d, J= 7.1Hz, 2H), 4.65(s, 2H), 4.37(s, 2H);13C NMR (125 MHz, CDCl3, ppm) δ:159.96, 147.65, 142.02, 140.96, 140.28, 137.93, 135.25, 134.72, 134.40, 129.41, 129.13, 128.84, 128.40, 127.94, 127.25, 127.23, 127.16, 126.58, 125.97, 123.71, 123.47, 123.19, 119.85, 109.65, 65.61, 28.86, 28.65。
二苯基-1,3-亚甲基-9,9’-螺二芴[2,3-c]并硫杂环戊烷(3g)
于250 mL三颈烧瓶中将Na2S·9H2O(0.75g, 3.1mmol)加入24mLTHF/EtOH =1:5(体积比)的混合溶剂中,氮气保护下加热至回流,待体系呈悬浮状态时,将原料3f 1.4g(2.1mmol)溶于10mLTHF中,缓慢滴加至反应体系中,保持加热回流状态3小时,常温搅拌过夜,反应结束后将反应混合物倾入水中,二氯甲烷萃取,合并有机相,无水硫酸镁干燥,过滤旋干,粗产物DCM:PE = 1:4柱层析得到0.6g白色固体,产率53%,熔点:269-271℃。1H NMR (CDCl3, 500MHz,ppm)δ:7.63-7.60(m, 2H), 7.57-7.55(m, 3H), 7.32(d, J= 7.5Hz, 2H), 7.20(t, J= 7.4Hz, 2H), 7.08(t, J= 7.4Hz, 2H), 6.97-6.87(m, 3H), 6.83(d, J= 7.5Hz, 2H), 6.67(t, J= 7.5Hz, 2H), 6.52(q, J= 7.5Hz, 2H), 6.08(d, J= 7.5Hz, 2H), 4.09(s, 2H), 3.77(s, 2H); 13C NMR (125 MHz, CDCl3, ppm) δ:149.90, 148.38, 145.43, 142.02, 140.75, 139.62, 139.37, 139.22, 136.36, 132.90, 129.18, 128.85, 128.00, 127.96, 127.32, 127.19, 127.15, 127.02, 126.91, 125.69, 123.71, 123.60, 122.67, 119.77, 37.87。
二苯基-9,9’-螺二芴[2,3-c]并噻吩(3h)
于100 mL三颈烧瓶中加入原料(3g) 0.6g(1.14mmol),70%钯/碳(质量百分数)0.4g,加入溶剂二甲苯20mL,氮气保护下加热回流24小时,反应结束后用硅藻土抽滤除去钯炭,旋干溶剂,初产物DCM:PE = 1:5柱层析得到0.25g白色固体,产率42%。熔点:279-280℃。1H NMR (CDCl3, 500MHz,ppm)δ:7.70-7.64(m, 4H), 7.60-7.58(m, 1H), 7.34(d, J= 7.4Hz, 2H), 7.27-7.26(m, 1H), 7.19(t, J= 7.1Hz, 2H),7.07(t, J= 7.2Hz, 2H), 6.99-6.90(m, 6H), 6.79-6.72(m,3H), 6.49(d, J= 6.9Hz, 1H), 6.23(d, J= 6.9Hz, 2H); 13C NMR (125 MHz, CDCl3, ppm) δ:150.82, 150.12, 141.70, 141.58, 140.54, 140.36, 138.93, 136.07, 135.51, 131.22, 129.81, 129.25, 128.97, 128.08, 128.04, 127.72, 127.31, 127.22, 127.10, 126.89, 125.83, 124.24, 124.01, 123.64, 119.66, 117.13, 117.06, 64.18。
二苯基-2,3-二(溴甲基)-9-芴酮(2b)
将双羟甲基芴酮原料1a(2.1g,5mmol)溶于50 mL的氯仿中,同时,依次加入0.6 g (2 mmol)的TBAB, 10mL浓氢溴酸,以及1mL浓硫酸,在60℃下回流72 h,将反应体系倾倒入水中,将溶液倾入200mL水中,用二氯甲烷(3×50mL)萃取,合并有机相,无水硫酸镁干燥,旋干,粗产品DCM:PE = 1:1柱层析得黄色固体产物2.2 g,产率79%,熔点:191-193℃。1H NMR (CDCl3, 500MHz,ppm) δ: 7.62-7.61(m, 3H), 7.55-7.53(m, 3H), 7.50-7.47(m, 3H), 7.42-7.40(m, 2H), 7.15(t, J= 7.5Hz, 1H), 7.09(t, J= 7.5Hz, 1H), 5.95(d, J= 7.5Hz, 1H), 4.52(s, 4H); 13C NMR (125 MHz, CDCl3, ppm) δ:191.96, 143.22, 142.86, 142.12, 141.83, 138.20, 136.90, 136.57, 135.19, 134.59,134.36, 131.16, 129.36, 129.13, 128.98, 128.86, 128.52, 128.23, 123.91, 123.28, 27.49, 27.19。
氧代-4,10-二苯基-芴[2,3-c]并硫杂环戊烷(3c)
于250 mL三颈烧瓶中将Na2S·9H2O 1.5g(6.2 mmol)加入36mL THF/EtOH =1:5(体积比)的混合溶剂中,氮气保护下加热至回流,待体系呈悬浮状态时,将原料(2b)2g(3.86mmol)溶于20mLTHF中,缓慢滴加至反应体系中,保持加热回流状态3小时,常温搅拌过夜,反应结束后将反应混合物倾入水中,二氯甲烷萃取,合并有机相,无水硫酸镁干燥,过滤旋干,粗产物柱层析(DCM:PE = 3:2)得到0.7黄色固体,产率47%,熔点.:270-272℃。1H NMR (CDCl3, 500MHz,ppm)δ: 7.58-7.53(m, 3H), 7.50-7.44(m, 4H), 7.40-7.38(m, 2H), 7.34-7.32(m, 2H), 7.15-7.08(m, 2H), 6.24(d, J= 7.3Hz, 1H); 4.04-4.00(m, 4H); 13C NMR (125 MHz, CDCl3, ppm) δ:192.14, 146.59, 143.05, 141.67, 141.03, 137.68, 137.44, 136.22, 135.06, 133.91, 133.63, 130.21, 129.21, 128.40, 128.28, 128.24, 128.08, 127.82, 123.64, 122.60, 37.85, 37.30. MS( EI):m/z=390[M+]。
氧代-4,10-二苯基-芴[2,3-c]并噻吩(4d)
于100 mL三颈烧瓶中加入0.7g(1.80mmol)原料3c,70%钯/碳(质量百分数)0.5g,加入溶剂二甲苯20mL,氮气保护下加热回流24小时,反应结束后硅藻土抽滤除去钯炭,旋干溶剂,初产物柱层析(DCM:PE = 1:1)得到0.26g金黄色固体,产率37%。熔点:265-267℃。1H NMR (CDCl3, 500MHz,ppm)δ: 7.65-7.53(m, 12H), 7.22-7.20(m, 3H), 6.61(d, J=6.5Hz, 1H); 13C NMR (125 MHz, CDCl3, ppm) δ:191.67, 143.99, 141.62, 139.65, 137.75, 137.60, 137.03, 135.61, 134.13, 132.02, 129.31, 129.29, 128.42, 128.38, 128.09, 127.35, 124.73, 123.78, 123.65, 119.59。