H), 9.26(s,lH,0H),9.66(s,lH,0H)。
[0063] 實施例5
[0064] 7-(3-甲氧基亞芐基)-2,2-二甲基-7,8-二氫-2H-呋喃并[3,2-h]色滿-6(3H)_酮 的制備
[O O6 6 ]按例2方法,反應(yīng)11.5 h,粗品經(jīng)柱層析[V石油醚:V乙酸乙醋= 8:1]得黃色固體,收率 57.5%,m.p.ll9~121°C</H NMR(400MHz,CDC13)S:1.54(s,6H,2XCH3),3.08(s,2H,CH2), 3.83(s,3H,0CH3),5.39(s,2H,0CH2),6.80~6.91(m,3H,C6H2,C6H4),6.92~6.99(m,lH, C6H4),7.32~7.38(m,lH,C6H4),7.56(d,J = 8.0Hz,lH,C6H2),7.83(s,lH,=CH)。
[0067] 實施例6
[0068] 7-(4-甲氧基亞芐基)-2,2-二甲基-7,8-二氫-2H-呋喃并[3,2-h]色滿-6(3H)_酮 的制備
[0070]按例2方法,反應(yīng)10.5h,粗品經(jīng)柱層析[V石湖νζιτ*=8 :1 ]得淡黃色固體,收率 46.6%,m.p.l32~134°C</HNMR(400MHz,CDCl3)S;1.54(s,6H,2XCH 3),3.08(s,2H,CH2), 3.86(s,3H,0CH3),5.42(s,2H,0CH2),6.87(d,J = 8.0Hz,lH,C6H2),6.97(d,J = 8.8Hz,2H, C6H4),7.28(d,J = 8.8Hz,2H,C6H4),7.56(d,J = 8.0Hz,lH,C6H2),7.83(s,lH,=CH)。
[0071] 實施例7
[0072] 7-(3,4,5-三甲氧基亞芐基)-2,2-二甲基-7,8-二氫-2!1-呋喃并[3,2-11]色滿-6 (3H)_酮的制備
[0074]按例2方法,反應(yīng)IOh,粗品經(jīng)柱層析[V石油釀:V乙酸乙醋=8 : 1 ]得到棕色固體,收率 46.2%,m.p.l25~127°C</H NMR(400MHz,CDC13)S:1.54(s,6H,2XCH3),3.09(s,2H,CH2), 3.88(s,6H,2X0CH3),3.91(s,3H,0CH3),5.46(s,2H,0CH2),6.54(s,2H,C 6H4),6.89(d,J = 8.0Hz,lH,C6H2),7.56(d,J = 8.0Hz,lH,C6H2),7.79(s,lH,=CH)。
[0075] 實施例8
[0076] 7-(4-羥基-3-甲氧基亞芐基)-2,2-二甲基-7,8-二氫-2H-呋喃并[3,2-h]色滿-6 (3H)-酮的制備
[0078]按例2方法,反應(yīng)IIh,粗品經(jīng)柱層析[V?麵:Vzi?i=4:1 ]得黃色固體,收率55.3%, m.p.136~138°C</H NMR(400MHz,DMS0)S:1.54(s,6H,2XCH3),3.08(s,2H,CH2),3.92(s, 3H,0CH3),5.44(s,2H,0CH2),6.83~6.89(m,3H,C6H3),6.98(d,J = 8.0Hz,lH,C6H2),7.56(d, J = 8.0Hz,1H,C6H2),7.80(s,1H,=CH)。
[0079] 實施例9
[0080] 7-(3-羥基-4-甲氧基亞芐基)-2,2-二甲基-7,8-二氫-2H-呋喃并[3,2-h]色滿-6 (3H)_酮的制備
[0082] 按例2方法,反應(yīng)IIh,乙醇重結(jié)晶得到棕黃色固體,收率59.6%,m. p. 194~196°C 。咕 NMR(400MHz,DMS0)S:1.45(s,6H,2 XCH3),3.09(s,2H,CH2),3.85(s,3H,0CH3),5.40(s, 2H,0CH2),6.90~6.92(m,2H,C6H32,6-H),6.96(d,J = 8.0Hz,lH,C6H2),7.05(d,J = 8.4Hz, 1H,C6H35-H),7.37(d,J = 8.0Hz,lH,C6H2),7.61(s,lH,=CH),9.36(s,lH,0H) ;13C 匪R (100MHz,DMS0)5:28.13,42.97,55.89,67.77,88.72,112.33,117.32,118.65,119.11, 122.18,123.28,126.80,128.80,135.69,137.13,145.45,146.45,146.51,149.58,181.19。
[0083] 實施例10
[0084] 7-(2-羥基-3-甲氧基亞芐基)-2,2-二甲基-7,8-二氫-2H-呋喃并[3,2-h]色滿-6 (3H)_酮的制備
[0086] 按例2方法,反應(yīng)11h,粗品經(jīng)柱層析[V石油醇:V乙酸乙醋=3 : 1 ]得到黃色固體,收率 48.1%,m.p.l78~180°C</HNMR(400MHz,DMS0)S:1.43(s,6H,2XCH3),3.08(s,2H,CH2), 3.84(s,3H,0CH3),5.26(s,2H,0CH2),6.70~6.73(m,lH,C6H3),6.87(t,J = 8.0Hz,lH,C6H34-H),6.93~6.97(m,lH,C6H3),7.08(d,J = 8.0Hz,lH,C6H2),7.38(d,J = 8.0Hz,lH,C6H2),7.84 (s,1H,=CH),9.41(s,1H,0H)。
[0087] 實施例11
[0088] 7-(2-硝基亞芐基)-2,2-二甲基-7,8-二氫-2H-呋喃并[3,2-h]色滿-6(3H)_酮的 制備
[0090] 按例2方法,反應(yīng)IIh,乙醇重結(jié)晶得到淡黃色固體,收率57 · I %,m· P · 142~145°C
。咕 NMR(400MHz,CDC13)S:1.44(s,6H,2 XCH3),3.10(s,2H,CH2),5.17(s,2H,0CH2),7 ·00((!, J = 8.0Hz,lH,C6H2),7.42(d,J = 8.0Hz,lH),7.43~7.48(m,lH,C6H4),7.72~7.78(m,lH, C6H4),7.85~7.90(m,lH,C6H4),7.93(s,lH,=CH),8.25~8.31(m,lH,C6H4)。
[0091] 實施例12
[0092] 7-(3-硝基亞芐基)-2,2-二甲基-7,8-二氫-2H-呋喃并[3,2-h]色滿-6(3H)_酮的 制備
[0094] I · 5mmoI 2,2-二甲基-7,8-二氫-2H-呋喃并[3,2-h ]色滿-6 (3H)-酮、5mL乙醇和適 量5 %NaOH溶液,室溫攪拌,緩慢加入1.55mmol 3-硝基苯甲醛,TLC跟蹤反應(yīng),視反應(yīng)情況補 加適量5 % NaOH水溶液。TLC監(jiān)測反應(yīng)完全后,向反應(yīng)液中加入適量冰水?dāng)嚢?5分鐘,析出黃 色沉淀,抽濾,冰水洗滌濾餅,冰乙醇淋洗濾餅,乙醇重結(jié)晶得到黃色固體,收率68.0%, m.p.231~234°C</HNMR(400MHz,DMS0)S:1.44(s,6H,2XCH3),3.09(s,2H,CH2),5.41(s, 2H,0CH 2),6.99(d,J = 8.0Hz,lH,C6H2),7.40(d,J = 8.0Hz,lH,C6H2),7·79~7.89(m,3H, C6H4),8.26~8.34(m,2H,C6H4,=CH)。
[0095] 實施例13
[0096] 7-(4-硝基亞芐基)-2,2-二甲基-7,8-二氫-2H-呋喃并[3,2-11]色滿-6(3!〇-酮的 制備
[0098] 按例2方法,反應(yīng)IOh,乙酸乙酯重結(jié)晶得到黃色固體,收率61.9%,m.p. 238~241 0Cc31H NMR(400MHz,DMS0)S:1.44(s,6H,2 XCH3),3.09(s,2H,CH2),5.39(s,2H,0CH2),6.99 (d,J = 8.0Hz,lH,C6H2),7.40(d,J = 8.0Hz,lH,C6H2),7.73(d,J = 8.0Hz,2H,C6H42,6-H), 7.81(s,lH,=CH),8.32(d,J = 8.0Hz,2H,C6H43,5-H)。
[0099] 實施例14
[0100] 7-(2-氨基亞芐基)-2,2-二甲基-7,8-二氫-2H-呋喃并[3,2-11]色滿-6(3!〇-酮的 制備
[0102] l.Ommol 7-(3_硝基亞芐基)-2,2_二甲基-7,8-二氫-2H-呋喃并[3,2-h]色滿-6 (3H)-酮,IOmL二氯甲烷和IOml乙酸攪拌溶解,加入適量鐵粉和ImL水,室溫攪拌反應(yīng)6h。過 濾,二氯甲烷洗濾餅,3 X 20mL水洗濾液,2 X 20mL飽和NaHCO3洗至無絮狀物,干燥,脫溶,乙 醇重結(jié)晶得棕黃色固體,收率82.2%,m.p.l82~184°(3</Η 匪R(400MHz,DMS0)S:1.43(s, 6H,2XCH3),3.07(s,2H,CH2),5.26(s,2H,0CH2),5.49(s,2H,NH2),6.59(t,J = 7.2Hz,lH, C6H4),6.70~6.89(m,2H,C6H4),6.95(d,J = 7.8Hz,lH,C6H2),7.13(t,J = 7.5Hz,lH,C6H4), 7.39(d,J = 7.8Hz,lH,C6H2),7.68(s,lH,=CH)。<