CN112920156A - 一种酸催化环1,3-二酮异戊烯基化反应的方法 - Google Patents

一种酸催化环1,3-二酮异戊烯基化反应的方法 Download PDF

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CN112920156A
CN112920156A CN201911232213.6A CN201911232213A CN112920156A CN 112920156 A CN112920156 A CN 112920156A CN 201911232213 A CN201911232213 A CN 201911232213A CN 112920156 A CN112920156 A CN 112920156A
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陈庆安
李莹
呼延成
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Abstract

本发明涉及环1,3‑二酮与不同的异戊烯基源发生具有化学选择性的异戊烯基化反应。具体为,以1,3‑环己二酮和异戊二烯为原料,在固体酸催化的条件下,可以实现C上的异戊烯基化反应得[3+3]环化的5‑色烯酮衍生物。在Lewis酸催化时可以得到氧原子上异戊烯基化产物。本发明有以下优点,异戊二烯是一种绿色的大宗化学品,简单易得,价格便宜;环1,3‑二酮廉价易得,性质稳定。只需在催化量固体酸或Lewis酸条件下存在条件下使用不同的异戊烯基源即可发生具有化学选择性的反应,且操作简单,原子经济性高,产物具有潜在的应用价值。

Description

一种酸催化环1,3-二酮异戊烯基化反应的方法
技术领域
本发明涉及一种环1,3-二酮与不同的异戊烯基源发生具有化学选择性的异戊烯基化反应的方法。具体为,以1,3-环己二酮和异戊二烯为原料,在固体酸催化剂促进下,可以在1,3-环己二酮选择性引入环化的异戊烯基。以1,3-环己二酮和异戊烯基醇为原料,在Lewis催化剂促进下,可以得到氧原子上的异戊烯基化产物。基本发明有以下优点,异戊二烯和1,3-环己二酮及异戊烯基醇都可直接商业获得,价格便宜,直接一步就可高选择性引入异戊烯基;简单的1,3-环己二酮即可参与反应;底物上不需要离去基团,原子经济性高。
背景技术
5-色烯酮是一类重要的药物分子核心骨架,例如,具有生物活性的分子(式1)。因此,探索简单、高效的催化体系来实现在4-羟基香豆素骨架上引入异戊烯基,具有重要的研究意义。
Figure BDA0002303868640000011
式1.含有5-色烯酮结构的生物活性分子
通过文献检索发现(式2),Ashwell小组在2008年报道了4-羟基香豆素和异戊烯基溴在NaI和Et3N存在下,可以在4-羟基香豆素C3位引入异戊烯基,再经过硫酸酸化得到目标产物(Yang,R-Y.;Kizer,D;Wu,H.;Ashwell,Mark A.Bioorg.Med.Chem.2008,16,5635.)。在该工作的基础上,2018年,梁永民小组发展了一种Lewis酸催化4-羟基香豆素与炔丙醇反应(Han,Y-P;Li,X-S;Liang,Y-M.Adv.Synth.Catal.2018,360,2796)。但这些方法原子经济性不好。因此,选择合适的原料来提高反应的原子经济性显得尤为重要。
Figure BDA0002303868640000021
式2.文献中报道生成5-色烯酮结构的反应
发明内容
本发明目的在于以1,3-环己二酮与不同的异戊烯基源发展一种酸催化体系,具有较好的化学选择性。
本发明是通过以下技术方案实现的:
1,3-环己二酮与异戊二烯环化反应的方法,
1,3-环己二酮与不同的异戊烯基源在固体酸或Lewis酸催化剂作用下,可以发生具有化学选择性的异戊烯基化反应,反应式如下所示:
Figure BDA0002303868640000022
具体操作步骤如下:
在氩气或氮气气氛下,于反应器中加入1,3-环己二酮、固体酸催化剂,加入溶剂溶解,加入异戊二烯,反应生成目标产物3。而向反应器中加入1,3-环己二酮、Lewis酸3催化剂,加入溶剂溶解,加入异戊烯基醇生成目标产物5。
点板监测反应体系,反应结束后,旋干溶剂,柱层析流动相:石油醚/乙酸乙酯(体积比20:1-4:1)固体酸催化条件得到目标产物3,Lewis酸催化的条件主要得到产物5
反应物1,3-环己二酮环上的取代基R可以是氢、C1-C8烷基、C1-C8烷氧基、苯氧基及、苯基、苄基、萘基、酰基、-F、-Cl、-Br、-NO2中的一种、二种、三种或四种;
取代的异戊二烯上的R1可以是连在1、3或4位置中的一个、二个或三个位置,分别包括氢、C1-C8烷基、苯基及取代的苯基、苄基及取代的苄基或萘基,取代的苯基中的取代基为-F、-Cl、-Br、-NO2,取代的苄基中的取代基为-F、-Cl、-Br、-NO2
所用固体酸催化剂为下述中的一种或二种以上:H-MOR、H-USY、Amberlyst-15、Amberlyst-36、Nafion、HY、H-β、2,4-二硝基苯磺酸二水合物。其中,催化剂优选Nafion催化剂与1,3-环己二酮的摩尔比为0.001-1,优选范围为0.01-0.2。
所用Lewis酸催化剂为下述中的一种或二种以上:三氯化铝(AlCl3)、三氯化铁FeCl3)、三氯化铟(InCl3)、三溴化铟(InBr3)、三氟甲磺酸铜[Cu(OTf)2]、三氟甲磺酸镱[Yb(OTf)3]、三氟甲磺酸钇[Y(OTf)3]、三氟甲磺酸钪[Sc(OTf)3]、三氟甲磺酸锌[Zn(OTf)2]、三氟甲磺酸铁[Fe(OTf)3]、三氟甲磺酸钐[Sm(OTf)3]、其中,催化剂优选三氯化铝(AlCl3),催化剂与1,3-环己二酮的摩尔比为0.001-1,优选范围为0.01-0.2。
所用溶剂为,以甲醇、乙醇、异丙醇、叔丁醇、乙腈、甲苯、环己烷、四氢呋喃、2-甲基四氢呋喃、乙二醇二甲醚、甲基叔丁基醚、二氯甲烷、1,2-二氯乙烷、1,4-二氧六环、乙酸乙酯、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、二甲亚砜中的一种或二种以上为溶剂,溶剂优选1,2-二氯乙烷、甲苯中的一种或两种,1,3-环己二酮于溶剂中优选浓度范围0.01-1.5mol/L。
异戊烯基醇用量是摩尔量的0.5-10倍之间,优选2-5倍之间;
反应温度在25-120℃之间;优选温度100-120℃,反应时间在0.5-36h之间,优选反应时间16-24h。
本发明以1,3-环己二酮和异戊二烯为原料,在固体酸催化的条件下,可以实现C上的异戊烯基化反应得[3+3]环化的5-色烯酮衍生物。在Lewis酸催化时可以得到氧原子上异戊烯基化产物。
本发明具有如下优点:
本发明有以下优点,异戊二烯和1,3-环己二酮都可直接商业获得,价格便宜,直接一步就可高选择性引入异戊烯基;催化量的固体酸Nafion即可促进反应的进行,不需要其他添加剂;操作简单,原子经济性高。因此,本专利在合成具有生物活性类分子方面有着潜在的应用前景。
附图说明
图1为化合物3a的1H NMR和13C NMR图;
图2为化合物3b的1H NMR和13C NMR图;
图3为化合物3c的1H NMR和13C NMR图;
图4为化合物3d的1H NMR和13C NMR图;
图5为化合物3e的1H NMR和13C NMR图;
图6为化合物3e'的1H NMR和13C NMR图;
图7为化合物5a的1H NMR和13C NMR图;
图8为化合物5b的1H NMR和13C NMR图;
图9为化合物5c的1H NMR和13C NMR图;
图10为化合物5d的1H NMR和13C NMR图;
图11为化合物5e的1H NMR和13C NMR图;
具体实施方式
下面将以具体的实施例来对本发明加以说明,但本发明的保护范围不局限于这些实例。
1.酸催化4-羟基香豆素和异戊二烯的反应
在2.0mL封管中,依次加入酸催化剂、4-羟基香豆素1a(0.4mmol,64.8mg),用1mL溶剂溶解,然后加入异戊二烯2(1.2mmol,120μL),在90℃反应24h,结束后加入均三甲氧基苯作为内标,HPLC检测目标产物收率。
Figure BDA0002303868640000041
表1.催化剂、溶剂、温度对反应的影响
Figure BDA0002303868640000042
Figure BDA0002303868640000051
Figure BDA0002303868640000052
表2.催化剂、溶剂、温度对反应的影响
Figure BDA0002303868640000053
2.底物类型(1)在手套箱中,向2.0mL封管中,依次加入1(0.4mmol)、Nafion(10wt%,),用1.0mL 1,2-二氯乙烷溶解,然后加入异戊二烯2(1.2mmol),在110℃反应24h。反应结束后旋干,柱层析分离,流动相为石油醚/乙酸乙酯(体积比)可得到目标产物3。
Figure BDA0002303868640000054
Figure BDA0002303868640000055
3H),3.32(tt,J=10.4,5.1Hz,1H),2.74–2.49(m,4H),2.40–2.14(m,2H),1.69(h,J=7.6Hz,2H),1.34(s,3H),1.25(s,3H).13C NMR(100MHz,CDCl3)δ197.2,169.7,143.1,128.7,126.9,126.7,109.8,77.5,43.8,39.1,36.6,32.2,27.7,25.5,15.7.HRMS calculated forC17H21O2[M+H]+257.1536,found 257.1543
Figure BDA0002303868640000061
1.93–1.84(m,1H),1.60(td,J=6.6,1.3 Hz,1H),1.22(d,J=1.6Hz,3H).13C NMR(100 MHz,CDCl3)δ198.2,170.6,110.0,77.0,36.7,32.3,29.2,26.6,21.0,15.7.HRMS calculatedfor C11H17O2[M+H]+181.1223,found 181.1225.
Figure BDA0002303868640000062
3H),2.10–1.96(m,2H),1.69–1.55(m,2H),1.28(s,3H),1.21(s,3H),1.02(d,J=6.3Hz,3H).13C NMR(100MHz,CDCl3)δ198.2,170.0,109.5,77.1,45.1,37.4,32.2,28.6,27.5,25.7,21.1,15.7.HRMScalculated for C12H19O2[M+H]+195.1380,found 195.1385.
Figure BDA0002303868640000063
1.22(s,6H),0.99(s,6H).13C NMR(100 MHz,CDCl3)δ197.9,168.9,108.7,77.1,50.7,43.0,32.3,32.2,28.4,26.6,15.5.HRMScalculated for C13H21O2[M+H]+209.1536,found209.1531.
Figure BDA0002303868640000064
(q,J=6.4Hz,2H),1.63(t,J=6.6Hz,2H),1.25(s,6H),1.09(s,6H).13C NMR(100MHz,CDCl3)δ203.1,168.4,108.1,76.7,39.9,34.8,32.4,26.7,26.2,25.0,16.2.HRMScalculated for C13H21O2[M+H]+209.1536,found 209.1538.
Figure BDA0002303868640000065
(m,2H),1.59(t,J=6.7Hz,2H),1.22(s,6H),1.12(s,6H).13C NMR(100MHz,CDCl3)13C NMR(101MHz,Chloroform-d)δ198.0,175.8,108.4,76.4,35.7,35.2,33.6,32.0,26.4,25.6,16.1.HRMS calculated for C13H21O2[M+H]+209.1536,found 209.1538.
Figure BDA0002303868640000071
(2)在手套箱中,向2.0mL封管中,依次加入1(0.4mol)、AlCl3(0.04mmol,5.4mg),用1.0mL DCE溶解,然后加入异戊烯基醇4(1.2mmol),在70℃反应24h。反应结束后旋干,柱层析分离,流动相为石油醚/乙酸乙酯(体积比)可得到主要的目标产物4。
Figure BDA0002303868640000072
7.28–7.21(m,3H),5.47(s,1H),5.44–5.35(m,1H),4.49–4.35(m,2H),3.32–3.40(m,1H),2.76–2.49(m,4H),1.79(d,J=1.4Hz,3H),1.71(d,J=1.4Hz,3H).13C NMR(100MHz,CDCl3)δ198.8,176.9,142.8,139.8,128.8,127.0,126.7,117.9,102.8,65.8,43.9,39.4,36.7,25.8,18.3.HRMS calculated for C17H21O2[M+H]+257.1536,found 257.1541.
Figure BDA0002303868640000073
(t,J=6.3Hz,2H),2.32–2.27(m,2H),1.93(p,J=6.5Hz,2H),1.74(s,3H),1.66(s,3H).13CNMR(100MHz,CDCl3)δ199.9,177.9,139.6,117.9,103.0,65.4,36.7,29.2,25.8,21.3,18.2.HRMS calculated for C11H17O2[M+H]+181.1223,found 181.1227.
Figure BDA0002303868640000074
2.44–2.32(m,2H),2.25–2.06(m,2H),2.04–1.94(m,1H),1.74(s,3H),1.66(s,3H),1.03(d,J=6.4Hz,3H).13C NMR(100MHz,CDCl3)δ199.8,177.3,139.6,118.0,102.6,65.5,45.1,37.3,28.9,25.8,20.9,18.2.HRMS calculated for C12H19O2[M+H]+195.1380,found195.1382.
Figure BDA0002303868640000081
=6.8Hz,2H),2.25(s,2H),2.18(s,2H),1.76(s,3H),1.67(s,3H),1.04(s,6H).13C NMR(100MHz,CDCl3)δ199.7,176.2,139.6,118.0,101.8,65.6,50.8,43.0,32.6,28.4,25.9,18.3.HRMS calculated for C13H21O2[M+H]+209.1536,found 209.1541.
Figure BDA0002303868640000082
Hz,2H),2.40(t,J=6.4Hz,2H),1.81–1.73(m,5H),1.67(s,3H),1.08(s,6H).13C NMR(100MHz,CDCl3)δ204.6,175.8139.5,118.1,101.3,65.5,40.2,35.1,26.4,25.8424.6,18.2.HRMS calculated for C13H21O2[M+H]+209.1536,found 209.1530.

Claims (8)

1.一种酸催化环1,3-环二酮异戊烯基化反应的方法,其特征在于:
1,3-环己二酮与不同的异戊烯基源在固体酸或Lewis酸催化剂作用下,可以发生具有化学选择性的异戊烯基化反应,具体操作步骤如下:在氩气或氮气气氛下,
于反应器中加入1,3-环己二酮、固体酸催化剂,加入溶剂溶解,加入异戊二烯,反应生成目标产物3;
或,向反应器中加入1,3-环己二酮、Lewis酸催化剂,加入溶剂溶解,加入异戊烯基醇生成目标产物5。
2.根据权利要求1所述的方法,其特征在于:
点板监测反应体系,反应结束后,旋干溶剂,柱层析流动相:石油醚/乙酸乙酯(体积比20:1-4:1);固体酸催化条件得到目标产物3,Lewis酸催化的条件主要得到产物5。
3.根据权利要求1所述的方法,其特征在于:
反应式如下所示:
Figure FDA0002303868630000011
反应物1,3-环己二酮环上的取代基R可以是氢、C1-C8烷基、C1-C8烷氧基、苯氧基及、苯基、苄基、萘基、酰基、-F、-Cl、-Br、-NO2中的一种、二种、三种或四种;
取代的异戊二烯上的R1可以是连在1、3或4位置中的一个、二个或三个位置,分别包括氢、C1-C8烷基、苯基及取代的苯基、苄基及取代的苄基或萘基,取代的苯基中的取代基为-F、-Cl、-Br、-NO2中的一种或二种以上,取代的苄基中的取代基为-F、-Cl、-Br、-NO2中的一种或二种以上。
4.根据权利要求1所述的方法,其特征在于:
所用固体酸催化剂为下述中的一种或二种以上:H-MOR、H-USY、Amberlyst-15、Amberlyst-36、Nafion、HY、H-β、2,4-二硝基苯磺酸二水合物;其中,催化剂优选Nafion;
催化剂与1,3-环己二酮的摩尔比为0.001-1,优选范围为0.01-0.2。
5.根据权利要求1所述的方法,其特征在于:
所用Lewis酸催化剂为下述中的一种或二种以上:三氯化铝(AlCl3)、三氯化铁FeCl3)、三氯化铟(InCl3)、三溴化铟(InBr3)、三氟甲磺酸铜[Cu(OTf)2]、三氟甲磺酸镱[Yb(OTf)3]、三氟甲磺酸钇[Y(OTf)3]、三氟甲磺酸钪[Sc(OTf)3]、三氟甲磺酸锌[Zn(OTf)2]、三氟甲磺酸铁[Fe(OTf)3]、三氟甲磺酸钐[Sm(OTf)3];其中,催化剂优选三氯化铝(AlCl3);
催化剂与1,3-环己二酮的摩尔比为0.001-1,优选范围为0.01-0.2。
6.根据权利要求1-5任一所述的方法,其特征在于:
所用溶剂为,以甲醇、乙醇、异丙醇、叔丁醇、乙腈、甲苯、环己烷、四氢呋喃、2-甲基四氢呋喃、乙二醇二甲醚、甲基叔丁基醚、二氯甲烷、1,2-二氯乙烷、1,4-二氧六环、乙酸乙酯、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、二甲亚砜中的一种或二种以上为溶剂,溶剂优选1,2-二氯乙烷、甲苯中的一种或两种,1,3-环己二酮于溶剂中优选浓度范围0.01-1.5mol/L。
7.根据权利要求1-5任一所述的方法,其特征在于:
异戊烯基醇用量是1,3-环己二酮摩尔量的0.5-10倍之间,优选2-5倍之间;异戊二烯是1,3-环己二酮摩尔量的0.5-10倍之间,优选2-5倍之间。
8.根据权利要求1-5任一所述的方法,其特征在于:
反应温度在25-120℃之间;优选温度100-120℃,反应时间在0.5-36h之间,优选反应时间16-24h。
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102675071A (zh) * 2012-05-24 2012-09-19 江苏康恒化工有限公司 一种3-甲氧基-2-环己烯-1-酮的制备方法
CN103102261A (zh) * 2013-02-06 2013-05-15 上海药明康德新药开发有限公司 一种螺[2.5]辛烷-5-羧酸的合成方法
CN107501287A (zh) * 2017-08-22 2017-12-22 中国科学院华南植物园 Myrtuco mmulone J和Myrtucommuacetalone及其类似物的制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102675071A (zh) * 2012-05-24 2012-09-19 江苏康恒化工有限公司 一种3-甲氧基-2-环己烯-1-酮的制备方法
CN103102261A (zh) * 2013-02-06 2013-05-15 上海药明康德新药开发有限公司 一种螺[2.5]辛烷-5-羧酸的合成方法
CN107501287A (zh) * 2017-08-22 2017-12-22 中国科学院华南植物园 Myrtuco mmulone J和Myrtucommuacetalone及其类似物的制备方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
M. CURINI ET AL.: "Ytterbium triflate catalyzed synthesis of b-keto enol ethers", 《TETRAHEDRON LETTERS》, vol. 47, 31 December 2006 (2006-12-31), pages 4697 - 4700, XP025004382, DOI: 10.1016/j.tetlet.2006.04.121 *
P. SRIHARI等: "PMA-SiO2 catalyzed synthesis of b-keto enol ethers", 《CHINESE CHEMICAL LETTERS》, vol. 19, 31 December 2008 (2008-12-31), pages 767 - 770, XP022762634, DOI: 10.1016/j.cclet.2008.05.006 *
YING LI等: "Acid-catalyzed chemoselective C- and O-prenylation of cyclic 1,3-diketones", 《CHINESE JOURNAL OF CATALYSIS》, vol. 41, 5 September 2020 (2020-09-05), pages 1401 - 1409, XP086150138, DOI: 10.1016/S1872-2067(20)63575-6 *

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