烷氧基橋聯(lián)四香豆素的簡便合成

姚 榮

(揚(yáng)州大學(xué) 化學(xué)化工學(xué)院， 江蘇 揚(yáng)州 225002)

香豆素是廣泛存在于自然界中的內(nèi)酯類化合物，在對人體具有抗高血壓、抗凝血等藥理作用和一定的生理毒性[1-3]。

4-羥基香豆素類衍生物是很多合成工業(yè)產(chǎn)品的中間體[4]。因其具有非線性的光學(xué)特性，是很好的熒光增白劑、激光染料、熒光探針及非線性光學(xué)材料[5]。這些應(yīng)用都引起了人們的極大興趣[6-7]。

1 實(shí)驗(yàn)儀器

紅外光譜分析：Bruker Tensor27紅外光譜儀，KBr壓片法，檢測范圍為4000～400cm-1；1H-NMR分析：Bruker AV600型核磁共振儀，CDCl3或DMSO-d6為溶劑，TMS為內(nèi)標(biāo)； LWMC-205型可調(diào)功率微波反應(yīng)器(南京陵江科技開發(fā)公司)；X-4顯微熔點(diǎn)測定儀(北京泰克公司)，數(shù)據(jù)未經(jīng)校正。

2 實(shí)驗(yàn)試劑

所有試劑均為分析純試劑。2,2'-烷氧基雙苯甲醛參照文獻(xiàn)[8-9]方法合成。

3 烷氧基橋聯(lián)雙香豆素的合成

取1 mmol雙醛, 與4 mmol 4-羥基香豆素于100 mL的燒瓶中，加入 4 mL DMF，稍加熱使固體溶解，放入微波爐中，功率打到0.5 kW，每10 s作為一個(gè)加熱循環(huán)，總加熱時(shí)間控制在10 min左右。加熱過程中可以補(bǔ)入少量溶劑防止溶劑蒸干烤焦產(chǎn)品。反應(yīng)結(jié)束后在燒瓶中加 20～30 mL水，析出白色固體 (若固體較少可加入NaCl進(jìn)行鹽析)。抽濾出固體并晾干，最后用氯仿-乙醇重結(jié)晶。得到對應(yīng)白色固體1a-f。

1a, 產(chǎn)率18%,m.p.234～237℃，IR (KBr,νcm-1):3002 (w),1698 (vs),1611 (vs),1567(s)，1489 (m),1452(w),1308(s),1218 (m),1159(m),1105(m),1066 (m),902(m),805(vs);1H NMR (CDCl3, 600 MHz)δ:11.33(s,4H,OH),8.00(d,J=7.8 Hz,4H,ArH),7.59(t,J=7.2 Hz,4H,ArH),7.36～7.39(m,8H,ArH),7.29～7.32(m,4H,ArH),7.20(d,J=7.8 Hz,2H,ArH),7.12～7.15(br,2H,ArH),5.37(s,2H,OCH2);MS(m/s,%):336.13(63), 608.60(48),868.60(100),707.13(21)。

1b, 產(chǎn)率30%, m.p.235～233℃，IR (KBr, ν cm-1) : 2933 (w), 2724 (w), 2598 (w),1659 (vs), 1609 (s),1563 (s),1491 (m), 1448 (m),1348 (m), 1238(m), 1114 (w), 1054 (w), 755 (vs);1H NMR (CDCl3,600 MHz)δ: 11.54 (s, 2H, OH), 11.16 (s, 2H,OH),8.00(br,4H,ArH),7.50(br, 4H, ArH),7.38(br,8H,ArH),7.32(br,4H,ArH), 6.94 (br, 2H, ArH),6.84 (m,2H,ArH),6.03 (s, 2H, CH), 3.91 (br, 4H, OCH2);MS (m/s, %) : 335.80 (33),622.67(100),721.6(17),792.6(17),881.40 (15)。

1c, 產(chǎn)率35%, m.p. 220～224℃，IR (KBr, νcm-1) :3001 (w), 1608 (s), 1643 (s),1612 (s),1567(m),1489 (m),1462 (m),1391 (w),1342 (m), 1218 (m), 1160 (m),1067 (m), 755(vs);1H NMR (CDCl3,600 MHz)δ:11.73 (s, 2H, OH),10.87 (s, 2H, OH),7.99(m,4H,ArH),7.60(d,J=7.2 Hz, 2H, ArH),7.37(m,8H, ArH),7.25 (d, J=7.8 Hz, 2H, ArH), 7.21 (t, J=7.8 Hz, 2H, ArH), 6.93 (t, J=7.8 Hz, 2H, ArH), 6.45 (d, J=7.8 Hz, 2H, ArH), 5.97 (s, 2H, CH), 3.44 (br, 4H, OCH2),1.25 (br, 2H,CH2); MS (m/s, %) : 336.13 (90),636.53 (100),895.73 (63)。

1d, 產(chǎn)率38%, m.p. 240～243℃，IR (KBr, ν cm-1) : 3553 (s), 3478 (s), 3415 (vs), 3237 (w), 1660 (vs), 1615 (vs), 1504 (s), 1493 (m),1450 (m), 1347 (w),1308 (w), 1241 (w),1112 (w),1047 (w), 757 (s);1H NMR (CDCl3,600 MHz)δ: 11.57 (s, 2H, OH),10.94 (s, 2H, OH), 8.00 (br, 4H, ArH), 7.57 (br, 4H, ArH), 7.38 (br, 8H, ArH), 7.26 (br, 4H, ArH), 6.94 (br, 2H, ArH), 6.84 (m, 2H, ArH), 6.02(s,2H,CH),3.85(br,2H,OCH2), 3.24 (br,2H,OCH2),0.91 (br, 4H,CH2);MS(m/s,%):336.20(100),650.67 (70),821.6 (35), 910.33 (36)。

1e, 產(chǎn)率36%, m.p. 178～180℃，IR (KBr,ν cm-1) : 3553 (w), 3411 (w), 2890 (w), 1669 (s),160 (m), 1563 (m), 1495 (w), 1451 (w), 1347 (w), 1247 (w), 950 (w), 757 (s);1H NMR (CDCl3, 600 MHz)δ: 11.62 (br,2H,OH),10.84 (br,2H,OH),7.99 (d,J=7.8 Hz, 4H, ArH),7.57(br,4H,ArH),7.34～7.38 (m,8H,ArH), 7.28 (t, J=7.2 Hz, 4H, ArH),6.94(t,J=7.2 Hz,2H,ArH),6.76(d,J=7.8 Hz,2H,ArH),6.04(s,2H,CH),3.48(br, 4H, OCH2), 0.85(br,4H,CH2), 0.79(br,2H,CH2);MS(m/s,%):336.27(24),664.73(100),924.60 (42)。

1f, 產(chǎn)率32%, m.p. 234～236℃，IR (KBr,ν cm-1) : 3072 (w), 2939 (w), 2866 (w),1659 (vs),1609 (s),1564(s),1494(m),1451 (m),1347(w),1303 (w),1247(w),1092 (m),1303(w),1247(w),1092(m),1015(w),954(w),757(vs),1H NMR (CDCl3,600 MHz)δ:11.61(br,2H,OH),10.87(br,2H,OH),7.99(d,J=7.8 Hz,4H,ArH),7.59(br, 4H, ArH), 7.34～7.39(m,8H,ArH),7.28(t,J=13.8Hz, 4H, ArH),6.93(t,J=13.8Hz,2H,ArH),6.83(d,J=13.8Hz,2H,ArH),6.07(s,2H,CH),3.65(br,4H,OCH2),0.97(br,4H,CH2),0.70(br,4H,CH2);MS(m/s,%):335.73(33),678.73(67),938.33 (100)。

4 結(jié)果討論

采用微波加熱的方式，烷氧基橋聯(lián)芳醛和4-羥基香豆素的縮合反應(yīng)可以很快的完成，生成了烷氧基橋聯(lián)的四香豆素衍生物。產(chǎn)物的結(jié)構(gòu)通過IR, NMR等方法鑒定。在1H NMR中，原料中醛基氫峰已經(jīng)基本消失，目標(biāo)產(chǎn)物中羥基在11.50、11.30 ppm處，這是由于氫鍵的作用使得其化學(xué)位移向低場移動的結(jié)果。芳環(huán)氫集中在8.06～7.03 ppm處，而聯(lián)接兩個(gè)4-羥基香豆素環(huán)的橋上CH 次甲基的特征化學(xué)位移受苯環(huán)、雙鍵和酯基的影響，在6.04 ppm左右，向低場移動較大。

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