CN105693671A - 一种制备3-卤代-2h-吡喃衍生物的方法 - Google Patents

一种制备3-卤代-2h-吡喃衍生物的方法 Download PDF

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CN105693671A
CN105693671A CN201410687061.XA CN201410687061A CN105693671A CN 105693671 A CN105693671 A CN 105693671A CN 201410687061 A CN201410687061 A CN 201410687061A CN 105693671 A CN105693671 A CN 105693671A
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halosuccinimides
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CN105693671B (zh
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万伯顺
信晓义
李新成
吴凡
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Dalian Institute of Chemical Physics of CAS
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Abstract

本发明涉及一种制备3-卤代-2H-吡喃衍生物的方法。具体地说在碱的催化下是由炔丙醇衍生物、丁炔二酸二烷基酯和N-卤代丁二酰亚胺制备3-卤代-2H-吡喃化合物的方法。本发明使用的方法不使用过渡金属催化剂，由简单易得和商业可得的原料出发经简单的操作步骤就得到其它方法难以得到的多取代的3-卤代-2H-吡喃衍生物。

Description

一种制备3-卤代-2H-吡喃衍生物的方法
技术领域
本发明涉及一种由炔丙醇衍生物、丁炔二酸二烷基酯和N-卤代丁二酰亚胺制备3-卤代-2H-吡喃化合物的方法。
背景技术
2H-吡喃及其衍生物广泛应用在医药、农药和材料等领域(文献1：(a)Hu,H.；Harrison,T.J.；Wilson,P.D.J.Org.Chem.2004,69,3782；(b)Rao,M.R.；Shen,X.H.；Zhou,X.Eur.J.Pharmacol.1988,155,293；(c)Sharma,H.；Santra,S.；Debnath,J.；Antonio,T.；Reith,M.；Dutta,A.Bioorg.Med.Chem.2014,22,311；(d)Zhao,H.；Lan,Y.B.；Liu,Z.M.；Wang,Y.；Wang,X.W.；Tao,J.C.Eur.J.Org.Chem.2012,1935；(e)Alberti,G.；Bernard,A.M.；Floris,C.；Frongia,A.；Piras,P.P.；Secci,F.；Spiga,M.Org.Biomol.Chem.2009,7,3512.)。卤代的2H-吡喃作为反应前体可以用来合成其它的取代的2H-吡喃衍生物(文献1：(a)Biftu,T.；Qian,X.X.；Chen,P.；Feng,D.；Scapin,G.；Gao,Y.D.；Cox,J.；Roy,R.S.；Eiermann,G.；He,H.B.Bioorg.Med.Chem.Lett.2013,23,5361；(b)Iwata,N.；Wang,N.；Yao,X.；Kitanaka,S.J.Nat.Prod.2004,67,1106；(c)Verhoest,P.R.；Fonseca,K.R.；Hou,X.J.；Proubc-LaFrance,C.；Corman,M.；Helal,C.J.；Claffey,M.M.；Tuttle,J.B.；Coffman,K.J.；Liu,S.P.J.Med.Chem.2012,55,9045；(d)Liu,Y.C；Dong,D.W.；Liu,Q.；Qi,Y.M.；Wang,Z.Org.Biomol.Chem.2004,2,28.)。因而，通过简单易得的原料来合成这类化合物有着重要的实际意义。本文描述了一种以简单易得的炔丙醇衍生物、商业可得的丁炔二酸二烷基酯和N-卤代丁二酰亚胺为原料来直接合成多取代的3-卤代-2H-吡喃衍生物。
发明内容
本发明的目的在于提供一种合成3-卤代-2H-吡喃衍生物的新方法。
反应方程式1：由炔丙醇衍生物、丁炔二酸二烷基酯和N-卤代丁二酰亚胺制备3-卤代-2H-吡喃化合物
具体操作步骤如下(反应方程式1)：
于反应器中进行反应，反应器抽真空后通氩气置换，依次加入炔丙醇衍生物1、丁炔二酸二烷基酯2和催化剂，然后将N-卤代丁二酰亚胺3溶解在指定的溶剂中缓慢滴入反应器中。滴加完后于20℃-80℃下反应2-12小时。反应结束后，用抽掉溶剂，固体溶于二氯甲烷上样进行硅胶柱层析，得到3-卤代-2H-吡喃衍生物4。
本发明有以下优点：
1.反应物炔丙醇衍生物1由廉价易得的端炔和醛经简单反应步骤得到(文献3：Yan,W.M.；Wang,Q.Y.；Chen,Y.F.；Petersen,J.L.；Shi,X.D.Org.Lett.2011,12,3308.)。丁炔二酸二烷基酯2和N-卤代丁二酰亚胺3商业可得。原料来源广泛，廉价易得。
2.反应操作简单，不使用过渡金属催化剂，环境友好。
具体实施方式
为了更好地理解本发明，通过以下实例进行说明。
于反应器中进行反应，反应器抽真空后通氩气置换，依次加入炔丙醇衍生物1(0.5mmol)、丁炔二酸二烷基酯2(0.5mmol)和催化剂DABCO(0.025mmol)，然后将N-卤代丁二酰亚胺3(0.75mmol)溶解在2mLCH2Cl2溶剂中缓慢滴入反应器中。滴加完后于40℃(X为碘)或50℃(X为溴或氯)下反应12小时。反应结束后，用旋转蒸发仪抽掉溶剂，固体溶于二氯甲烷上样进行硅胶柱层析，洗脱剂为石油醚:乙酸乙酯＝4:1(体积比)的混合溶剂，得到3-卤代-2H-吡喃衍生物4。
下表给出21个实施例的情况：
各产物的的表征数据如下：
(d,J＝7.5Hz,2H),6.10(s,1H),3.74(s,3H),3.41(s,3H)；13CNMR(100MHz,CDCl3)δ165.3,162.0,140.3,140.0,138.6,138.3,135.3,130.2,128.8,128.7,128.5,118.8,96.3,93.3,85.3,52.9,52.4；HRMS(Q-TOF,ESI)calcdforC21H17I2O5 +[M+H]+602.9160,found602.9175.
3.77(m,2H),2.41(s,3H),1.24(t,J＝7.1Hz,3H),0.88(t,J＝7.1Hz,3H)；13CNMR(100MHz,CDCl3)δ165.1,161.8,140.8,139.8,139.2,138.6,135.7,130.6,129.7,128.9,128.7,128.6,128.4,125.5,118.5,94.0,85.9,62.1,61.4,21.7,14.0,13.6；HRMS(Q-TOF,ESI)calcdforC24H24IO5 +[M+H]+519.0663,found519.0699.
3.94–3.72(m,2H),2.39(s,3H),1.24(t,J＝7.1Hz,3H),0.88(t,J＝7.1Hz,3H)；13CNMR(100MHz,CDCl3)δ165.1,161.8,140.8,139.9,139.7,139.2,132.8,129.81,129.77,128.6,128.5,128.4,118.45,94.0,85.8,62.1,61.4,21.5,14.05,13.6；HRMS(Q-TOF,ESI)calcdforC24H24IO5 +[M+H]+519.0663,found519.0669.
2H),7.51(s,1H),7.45–7.18(m,5H),6.90(s,1H),4.04(q,J＝7.0Hz,2H),3.86(q,J＝7.0Hz,2H),1.09(t,J＝7.0Hz,3H),0.88(t,J＝7.0Hz,3H)；13CNMR(100MHz,CDCl3)δ165.0,161.6,141.1,141.0,139.2,134.45,132.1,130.7,129.5,129.3,128.9,128.53,128.47,127.0,126.8,126.1,125.2,124.3,119.1,92.65,82.6,61.8,61.4,13.8,13.6；HRMS(Q-TOF,ESI)calcdforC27H24IO5 +[M+H]+555.0663found555.0685.
(m,1H),7.56–7.51(m,2H),7.44–7.37(m,3H),7.30(d,J＝6.2Hz,2H),6.33(s,1H),4.17(q,J＝7.1Hz,2H),3.86(q,J＝7.1Hz,2H),1.22(t,J＝7.1Hz,3H),0.89(t,J＝7.1Hz,3H)；13CNMR(100MHz,CDCl3)δ165.1,161.8,140.8,140.1,139.2,134.1,133.2,129.2,128.8,128.8,128.7,128.5,128.4,127.9,127.1,126.6,125.6,118.6,110.1,93.9,86.0,62.1,61.4,14.0,13.6；HRMS(Q-TOF,ESI)calcdforC27H24IO5 +[M+H]+555.0663,found555.0685.
Hz,1H),4.20(m,2H),3.87(m,2H),1.38–1.19(m,3H),0.99–0.81(m,3H)；13CNMR(100MHz,CDCl3)δ165.0,161.65,161.1(d,J＝251.2Hz),140.5,139.1,131.8(d,J＝8.4Hz),129.6(d,J＝3.0Hz),128.9,128.7,128.4,124.7(d,J＝4.0Hz),118.2,116.2(d,J＝21.6Hz),115.5(d,J＝22.3Hz),92.8,84.9,79.5(d,J＝4.2Hz),62.1,61.5,14.0,13.6；19FNMR(377MHz,CDCl3)δ-116.4；HRMS(Q-TOF,ESI)calcdforC23H21FIO5 +[M+H]+523.0412,found523.0416.
(d,J＝6.1Hz,2H),7.13(d,J＝6.1Hz,1H),6.14(s,1H),4.21(d,J＝7.1Hz,2H),4.00–3.60(m,2H),1.34–1.17(m,3H),0.87(t,J＝7.1Hz,3H)；13CNMR(100MHz,CDCl3)δ164.8,162.95(d,J＝271.4Hz),161.6,140.8,140.3,138.9,138.4(d,J＝6.6Hz),130.6(d,J＝8.1Hz),128.9,128.7,128.5,124.1(d,J＝3.0Hz),118.7,116.8(d,J＝21.2Hz),115.5(d,J＝22.4Hz),92.8,84.8(d,J＝1.7Hz),62.2,61.5,14.0,13.5；19FNMR(377MHz,CDCl3)δ-111.7；HRMS(Q-TOF,ESI)calcdforC23H21FIO5 +[M+H]+523.0412,found523.0450.
Hz,3H),0.87(t,J＝7.1Hz,3H)；13CNMR(100MHz,CDCl3)δ164.6,161.4,141.1,140.7,138.6,132.9,132.5,129.1,128.9,128.8,128.6,118.5,113.7,92.0,84.5,62.4,61.6,14.0,13.5；HRMS(Q-TOF,ESI)calcdforC23H21ClIO5 +[M+H]+539.0117,found539.0126.
(m,3H),6.66(s,1H),3.73(s,3H),3.43(s,3H)；13CNMR(100MHz,CDCl3)δ165.3,162.0,140.8,140.6,138.5,135.1,134.4,133.3,131.9,128.8,128.6,128.5,127.91,127.86,118.6,93.0,82.4,52.9,52.4；HRMS(Q-TOF,ESI)calcdforC21H16Cl2IO5 +[M+H]+544.9414,found544.9424.
0.89(t,J＝6.9Hz,3H)；13CNMR(100MHz,CDCl3)δ164.8,161.4,141.02,140.97,138.8,135.2,134.3,133.3,131.8,128.8,128.7,128.5,127.9,127.8,118.4,92.6,82.3,62.1,61.5,14.0,13.5；HRMS(Q-TOF,ESI)calcdforC23H20Cl2IO5 +[M+H]+572.9727,found572.9682.
2H),6.11(s,1H),4.20(q,J＝7.1Hz,2H),3.85(q,J＝7.1,2H),1.25(t,J＝7.1Hz,3H),0.88(t,J＝7.1Hz,3H).)；13CNMR(100MHz,CDCl3)δ164.9,161.6,140.7,140.2,138.9,134.9,132.3,130.1,129.0,128.9,128.8,128.5,124.2,118.7,93.0,85.05,62.2,61.5,14.0,13.6；HRMS(Q-TOF,ESI)calcdforC24H21INO5 +[M+H]+530.0459,found530.0450.
2H),3.87(m,2H),2.37(s,3H),1.24(t,J＝7.1Hz,3H),0.92(t,J＝7.1Hz,3H)；13CNMR(100MHz,CDCl3)δ165.1,161.8,140.7,139.8,138.5,136.2,135.9,129.8,129.1,129.0,128.8,128.5,118.7,93.8,85.8,62.1,61.4,21.5,14.0,13.6；HRMS(Q-TOF,ESI)calcdforC24H24IO5 +[M+H]+519.0663,found519.0690.
(400MHz,CDCl3)δ7.58(m,2H),7.53–7.32(m,5H),7.20(m,2H),6.15(s,1H),4.18(m,2H),3.99–3.79(m,2H),1.23(t,J＝7.1Hz,3H),0.93(t,J＝7.1Hz,3H)；13CNMR(100MHz,CDCl3)δ164.8,161.6,141.4,138.7,137.5,135.6,134.6,130.4,129.8,129.0,128.7,128.3,117.8,94.1,85.7,62.1,61.4,14.0,13.6；HRMS(Q-TOF,ESI)calcdforC23H21ClIO5 +[M+H]+539.0117,found539.0142.
7.26(m,3H),7.23(m,1H),6.04(s,1H),4.21(q,J＝7.1Hz,2H),3.87(m,2H),2.40(s,3H),1.25(t,J＝7.1Hz,3H),0.89(t,J＝7.1Hz,3H)；13CNMR(100MHz,CDCl3)δ165.0,161.6,140.3,138.7,135.8,135.6,134.1,130.6,129.1,129.0,128.9,128.6,128.4,125.1,119.0,115.9,82.7,62.1,61.4,21.65,14.0,13.6；HRMS(Q-TOF,ESI)calcdforC24H24BrO5 +[M+H]+471.0802,found471.0816.
2H),3.97–3.76(m,2H),1.09(t,J＝7.1Hz,3H),0.88(t,J＝7.1Hz,3H)；13CNMR(100MHz,CDCl3)δ165.0,161.5,135.8,135.6,134.4,132.0,130.8,129.4,129.1,128.9,128.7,128.4,126.9,126.6,126.2,125.2,124.2,123.5,119.6,114.8,79.6,61.9,61.5,13.8,13.6；HRMS(Q-TOF,ESI)calcdforC27H24BrO5 +[M+H]+507.0802,found507.0846.
1H),6.06(s,1H),4.23(q,J＝7.1Hz,2H),3.88(q,J＝7.1Hz,2H),1.27(t,J＝7.1Hz,3H),0.88(t,J＝7.1Hz,3H)；13CNMR(100MHz,CDCl3)δ164.7,163.1(d,J＝247.4Hz),161.5,140.4,138.4(d,J＝6.6Hz),135.5,134.7,130.6(d,J＝8.1Hz),129.0,128.7,128.4,123.7(d,J＝3.0Hz),119.3,116.9(d,J＝21.0Hz),115.2(d,J＝22.0Hz),115.1,81.7(d,J＝1.6Hz),62.2,61.5,14.0,13.5；19FNMR(377MHz,CDCl3)δ-111.3；HRMS(Q-TOF,ESI)calcdforC23H21FBrO5 +[M+H]+475.0556,found475.0589.
3H)；13CNMR(100MHz,CDCl3)δ164.7,161.3,140.6,135.4,135.0,134.3,133.3,131.9,128.9,128.8,128.6,128.4,127.8,127.7,119.0,114.5,79.3,62.1,61.5,13.9,13.5；HRMS(Q-TOF,ESI)calcdforC23H20Cl2BrO5 +[M+H]+524.9866,found524.9874.
1.25(t,J＝7.1Hz,3H),0.95(t,J＝7.1Hz,3H)；13CNMR(100MHz,CDCl3)δ164.8,161.5,141.0,135.6,134.7,134.1,133.1,130.6,129.9,129.1,128.7,128.0,118.3,116.1,82.6,62.2,61.6,14.0,13.6；HRMS(Q-TOF,ESI)calcdforC23H21BrClO5 +[M+H]+491.0255,found491.0264.
2.3Hz,2H),1.26(t,J＝7.1Hz,3H),0.96(t,J＝7.1Hz,3H)；13CNMR(100MHz,CDCl3)δ164.7,162.9(d,J＝248.6Hz),161.3,140.6,134.9,134.45(d,J＝9.7Hz),133.3,132.0,131.2,131.0(d,J＝8.3Hz),127.9,127.6,118.7,115.7(d,J＝22.0Hz),115.6(d,J＝21.8Hz),115.1,79.4,62.3,61.7,14.0,13.7；19FNMR(377MHz,CDCl3)δ-112.2；HRMS(Q-TOF,ESI)calcdforC23H19Cl2BrFO5 +[M+H]+542.9771,found542.9778.
142.2,139.4,138.3,132.1,128.7,128.5,120.1,90.2,75.9,53.1,52.4；HRMS(Q-TOF,ESI)calcdforC15H14IO5 +[M+H]+400.9880,found400.9886.
1.19(m,3H),1.20–0.73(m,3H)；13CNMR(100MHz,CDCl3)δ167.3,164.3,134.2,133.7,131.8,130.8,129.8,129.7,129.6,128.9,128.8,128.3,127.4,127.1,127.1,126.5,109.0,97.5,62.7,57.1,14.0,13.8；HRMS(Q-TOF,ESI)calcdforC23H19Cl3O5[M+H]+481.0371,found481.0360.
本发明使用的方法不使用过渡金属催化剂，由简单易得和商业可得的原料出发经简单的操作步骤就得到其它方法难以得到的多取代的3-卤代-2H-吡喃衍生物。

Claims (4)

1.一种制备3-卤代-2H-吡喃衍生物的方法，是由炔丙醇衍生物、丁炔二酸二烷基酯和N-卤代丁二酰亚胺制备3-卤代-2H-吡喃化合物的方法，其特征在于：
以下式所示的炔丙醇衍生物(1)、丁炔二酸二烷基酯(2)和N-卤代丁二酰亚胺(3)为原料生成3-卤代-2H-吡喃化合物(4)，反应式如下：
其中R1、R2分别为苯基、取代的苯基或萘基，苯基上的取代基为C1-C8烷基、C1-C8烷氧基、氟、氯、溴、碘、三氟甲基、硝基、氰基中的一种、或二种、或三种，取代基的个数为1-5个；R3为甲基或乙基；
具体操作步骤如下：
于反应器中进行反应，反应器抽真空后通氩气置换，依次加入炔丙醇1、丁炔二酸二烷基酯2和催化剂，然后将N-卤代丁二酰亚胺3溶解在指定的溶剂中缓慢滴入反应器中。滴加完后于20℃-80℃下反应2-12小时；反应结束后，用抽掉溶剂，固体溶于二氯甲烷上样进行硅胶柱层析，得到3-卤代-2H-吡喃衍生物4。
2.按照权利要求1所述的方法，其特征在于：
催化剂为1,4-二氮杂二环[2.2.2]辛烷(DABCO)和/或碳酸铯；催化剂用量按摩尔比算为炔丙醇衍生物(1)的5mol％-100mol％。
3.按照权利要求1所述的方法，其特征在于：
溶剂为二氯甲烷、1,2-二氯乙烷、N,N-二甲基甲酰胺、1,4-二氧六环、乙腈、四氢呋喃中的一种或两种以上，溶剂的用量为每毫摩尔反应物炔丙醇1用溶剂1–10毫升。
4.按照权利要求1所述的方法，其特征在于：炔丙醇1、丁炔二酸二烷基酯2和N-卤代丁二酰亚胺(3)的用量摩尔比为1:1:1.5。
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