CN111606915B - 一种螺吡喃类光致变色材料的制备方法 - Google Patents
一种螺吡喃类光致变色材料的制备方法 Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/10—Spiro-condensed systems
- C07D491/107—Spiro-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
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- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
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Abstract
本发明公开了一种螺吡喃类光致变色材料的制备方法,以式2所示的2,3,3‑三甲基‑3H‑吲哚类化合物为起始物,甲醇为烷基化试剂,在硫酰氟气氛、缚酸剂和有机溶剂存在下,室温下进行烷基化反应,反应结束后,向体系中加入式3所示水杨醛及乙醇,加热至回流反应,反应产物经分离提纯,获得式1所示的螺吡喃类光致变色材料。该方法以安全低毒的醇类化合物为烷基化试剂,在低毒硫酰氟气体的原位活化下,通过一锅两步反应完成螺吡喃类光致变色材料的合成,具有反应条件温和,操作简便,收率高的优点。
Description
技术领域
本发明涉及有机合成技术领域,特别涉及一种螺吡喃类光致变色材料的制备方法。
背景技术
光致变色材料(Photochromism materials)是指一种在光的作用下,颜色能够发生可逆变化的一类物质。螺吡喃类光致变色材料是目前研究最为广泛的变色材料之一,被用于包括“智能电极”、光控酶活性、光控制释放治疗剂以及纳米粒子光控溶解在内领域中。该螺吡喃类化合物结构中,含有两组共享一个sp3杂化碳原子的稠环结构,故形成螺环结构,相互正交且不形成共轭体系,具体化合物结构通式1以及光致变色过程如下所示:
现有技术路线中,螺吡喃类光致变色材料的合成方法主要如下:以2,3,3-三甲基-3H-吲哚类化合物为底物,在加热条件下与碘甲烷反应,生成相应的铵盐;铵盐在碱的作用下发生消除反应,形成1,3,3-三甲基-2-亚甲基吲哚啉类中间体;最后与水杨醛进行环化反应,得到目标产物。该方法所使用的碘甲烷属于一种具有毒性、污染性很强的试剂;此外该方法需要三步反应,总产率低于40%,操作不方便。该路线具体如下:
除此路线外,在其改进后的反应中可选用其他类型的N-烷基化试剂,例如卤代烷烃、硫酸二烷基酯类以及三氟磺酸酯等类,但该类优化工作并未从根本解决其环境不友好,操作复杂,反应效率的问题。
发明内容
本发明的目的在于提供一种螺吡喃类光致变色材料的制备方法,该方法以安全低毒的醇类化合物为烷基化试剂,在低毒硫酰氟气体的原位活化下,通过一锅两步反应完成螺吡喃类光致变色材料的合成,具有反应条件温和,操作简便,收率高的优点。
本发明解决其技术问题所采用的技术方案是:
一种螺吡喃类光致变色材料的制备方法,以式2所示的2,3,3-三甲基-3H-吲哚类化合物为起始物,甲醇为烷基化试剂,在硫酰氟气氛、缚酸剂和有机溶剂存在下,室温下进行烷基化反应,反应结束后,向体系中加入式3所示水杨醛及乙醇,加热至回流反应,反应产物经分离提纯,获得式1所示的螺吡喃类光致变色材料;
本发明利用硫酰氟对醇类化合物进行原位活化,实现2,3,3-三甲基-3H-吲哚类化合物的烷基化反应,并在同一反应体系中与水杨醛进行反应,实现高效一锅法螺吡喃类变色材料的合成,操作简单,三步反应总收率可达到87%。本发明烷基化反应后加入乙醇作为脱水剂,用于提高反应效率。
作为优选,所述硫酰氟气氛指含一个大气压硫酰氟的气体环境。
作为优选,所述R为对位或邻位的甲基、卤素、三氟甲基、甲氧基、苯基中的一种。
作为优选,所述缚酸剂为NaOH、KOH、Na2CO3、K2CO3、Cs2CO3、NEt3、DBU或咪唑。优选NaOH、KOH、Cs2CO3,更优选NaOH。
作为优选,所述2,3,3-三甲基-3H-吲哚类化合物选自5-甲氧基-2,3,3-三甲基-3-H-吲哚、5-氟-2,3,3-三甲基-3-H-吲哚、5-氯-2,3,3-三甲基-3-H-吲哚、5-溴-2,3,3-三甲基-3-H-吲哚、5-三氟甲基-2,3,3-三甲基-3-H-吲哚、2,3,3-三甲基苯并[e]吲哚、2,3,3,5-四甲基-3-H-吲哚、7-溴-2,3,3-三甲基-3-H-吲哚中的一种。
作为优选,按摩尔比计,2,3,3-三甲基-3H-吲哚类化合物:烷基化试剂:缚酸剂:水杨醛为1:1-5:1-5:1-3。优选为1:4:3:1。
作为优选,所述有机溶剂为二氯甲烷、四氢呋喃、1,4-二氧六环、甲醇、甲苯、N,N-二甲基甲酰胺或二甲基亚砜。优选四氢呋喃、1,4-二氧六环,更优选1,4-二氧六环。
作为优选,所述乙醇的用量为:每1摩尔2,3,3-三甲基-3H-吲哚类化合物使用1-10mL。优选5mL。
本发明的有益效果是:
采用醇类化合物为烷基化试剂,具有原料安全低毒、廉价易得、原子利用率高等优点;
所采用技术路线在常规实验室条件下完成,分步一锅法反应无需中途替换溶剂,且反应时间短,产率高,对反应操作简单;
工艺方法普适性好,可用于多种螺吡喃类光致变色材料的制备。
具体实施方式
下面通过具体实施例,对本发明的技术方案作进一步的具体说明。
本发明中,若非特指,所采用的原料和设备等均可从市场购得或是本领域常用的。下述实施例中的方法,如无特别说明,均为本领域的常规方法。
实施例1 5'-氟-1',3',3'-三甲基螺[色烯-2,2'-二氢吲哚]的合成
于25mL干燥的三口烧瓶中,称取氢氧化钠(60mg,1.5mmol,3eq),5-氟-2,3,3-三甲基-3-H-吲哚(89mg,0.5mmol),用硫酰氟置换反应体系中气体;随后加入1,4-二氧六环(4mL),甲醇(80μL,2mmol,4eq),室温搅拌反应3小时,至原料转化完全;之后用氮气置换反应体系中气体,加入乙醇(5mL)脱水剂,水杨醛(52μL,0.5mmol,1eq),回流搅拌反应5小时。
反应结束后,加水淬灭,二氯甲烷萃取,有机相饱和食盐水洗涤,经Na2SO4干燥后浓缩,随后通过硅胶柱纯化(PE:EA=50:1,Rf=0.4)得105mg黄色固体,产率71%。
1H NMR(500MHz,CDCl3)δ7.10(td,J=7.7,1.7Hz,1H),7.04(dd,J=7.6,1.7Hz,1H),6.85(d,J=10.4Hz,2H),6.83–6.77(m,2H),6.71(d,J=8.1Hz,1H),6.40(dd,J=8.3,4.1Hz,1H),5.66(d,J=10.2Hz,1H),2.69(s,3H),1.28(s,3H),1.17(s,3H);13C NMR(126MHz,CDCl3)δ157.6(d,J=235.5Hz),154.5,144.5,138.7(d,J=7.3Hz),129.8(d,J=27.8Hz),126.9,120.3,119.2,118.9,115.1,113.2(d,J=22.9Hz),109.7(d,J=24.4Hz),106.9(d,J=8.2Hz),104.7,52.0,29.9,29.4,25.8,20.2;;HRMS-ESI(m/z)calcd for[M+H+](C19H19FNO):296.1445 found 296.1438。
同样条件下,从各取代的2,3,3-三甲基-3H-吲哚类化合物出发,在上述条件下得到化合物1(式1所示的螺吡喃类光致变色材料),其结果如下表所示:
实施例2 5'-氟-1',3',3'-三甲基螺[色烯-2,2'-二氢吲哚]的合成
方法同实施例1,不同之处在于将氢氧化钠换为碳酸铯,溶剂为二甲基亚砜,产率65%。
实施例3 5'-氟-1',3',3'-三甲基螺[色烯-2,2'-二氢吲哚]的合成
方法同实施例1,不同之处在于将氢氧化钠换为氢氧化钾,溶剂为二氯甲烷,产率60%。
实施例4 5'-氟-1',3',3'-三甲基螺[色烯-2,2'-二氢吲哚]的合成
方法同实施例1,不同之处在于5-氟-2,3,3-三甲基-3-H-吲哚、甲醇和氢氧化钠投料比为1:2:4,溶剂为1,4-二氧六环,产率58%。
实施例5 5'-氟-1',3',3'-三甲基螺[色烯-2,2'-二氢吲哚]的合成
方法同实施例1,不同之处在于5-氟-2,3,3-三甲基-3-H-吲哚、甲醇和氢氧化钠投料比为1:3:4,溶剂为1,4-二氧六环,产率66%。
实施例6 5'-氟-1',3',3'-三甲基螺[色烯-2,2'-二氢吲哚]的合成
方法同实施例1,不同之处在于5-氟-2,3,3-三甲基-3-H-吲哚、甲醇和氢氧化钠投料比为1:5:4,溶剂为1,4-二氧六环,产率55%。
实施例7 5'-氟-1',3',3'-三甲基螺[色烯-2,2'-二氢吲哚]的合成
方法同实施例1,不同之处在于5-氟-2,3,3-三甲基-3-H-吲哚、甲醇和氢氧化钠投料比为1:4:4,溶剂为1,4-二氧六环,产率67%。
实施例8 5'-氯-1',3',3'-三甲基螺[色烯-2,2'-二氢吲哚]的合成
方法同实施例1,不同之处在于将底物换为5-氯-2,3,3-三甲基-3-H-吲哚,产率87%。1H NMR(500MHz,CDCl3)δ7.14–7.09(m,2H),7.05(dd,J=7.5,1.7Hz,1H),7.02(d,J=2.1Hz,1H),6.89–6.82(m,2H),6.71(d,J=8.1Hz,1H),6.43(d,J=8.2Hz,1H),5.66(d,J=10.2Hz,1H),2.71(s,3H),1.30(s,3H),1.17(s,3H);13C NMR(126MHz,CDCl3)δ154.4,147.0,138.9,130.0,129.8,127.4,126.9,123.8,122.2,120.3,118.9,118.8,115.1,107.8,104.4,51.9,29.1,25.8,20.1;HRMS-ESI(m/z)calcd for[M+H+](C19H19ClNO):312.1150found 312.1142。
实施例9 5'-溴-1',3',3'-三甲基螺[色烯-2,2'-二氢吲哚]的合成
方法同实施例1,不同之处在于将底物换为5-溴-2,3,3-三甲基-3-H-吲哚,产率51%。1H NMR(500MHz,CDCl3)δ7.28–7.25(m,1H),7.15(d,J=2.0Hz,1H),7.10(td,J=7.7,1.7Hz,1H),7.05(dd,J=7.6,1.7Hz,1H),6.88–6.81(m,2H),6.71(d,J=8.1Hz,1H),6.39(d,J=8.2Hz,1H),5.65(d,J=10.3Hz,1H),2.70(s,3H),1.28(s,3H),1.16(s,3H);13C NMR(126MHz,CDCl3)δ154.3,147.5,139.3,130.3,130.0,129.8,126.9,124.9,120.3,118.8,118.7,115.1,110.9,108.4,104.3,29.1,25.8,20.1;HRMS-ESI(m/z)calcd for[M+H+](C19H19BrNO):356.0645 found 356.0638。
实施例10 1',3',3',5'-四甲基螺[色烯-2,2'-二氢吲哚]的合成
方法同实施例1,不同之处在于底物换为2,3,3,5-四甲基-3-H-吲哚,产率84%。1HNMR(500MHz,CDCl3)δ7.11(td,J=7.8,1.7Hz,1H),7.06(dd,J=7.5,1.6Hz,1H),7.02–6.99(m,1H),6.93(d,J=1.7Hz,1H),6.88–6.81(m,2H),6.75(d,J=8.1Hz,1H),6.46(d,J=7.8Hz,1H),5.70(d,J=10.2Hz,1H),2.73(s,3H),2.35(s,3H),1.33(s,3H),1.20(s,3H);13CNMR(126MHz,CDCl3)δ154.7,146.3,137.1,129.8,129.4,128.4,127.9,126.7,122.5,120.0,119.5,119.0,115.1,106.8,104.5,51.8,29.2,26.0,21.2,20.3;HRMS-ESI(m/z)calcd for[M+H+](C20H22NO):292.1696 found 292.1687。
实施例11 5'-甲氧基-1',3',3'-三甲基螺[色烯-2,2'-二氢吲哚]的合成
方法同实施例1,不同之处在于底物换为5-甲氧基-2,3,3-三甲基-3-H-吲哚,产率49%。1H NMR(500MHz,CDCl3)δ7.10(td,J=7.7,1.7Hz,1H),7.05(dd,J=7.5,1.7Hz,1H),6.87–6.81(m,2H),6.75–6.70(m,3H),6.45(d,J=8.1Hz,1H),5.68(d,J=10.2Hz,1H),3.81(s,3H),2.70(s,3H),1.31(s,3H),1.19(s,3H);13C NMR(126MHz,CDCl3)δ154.7,153.9,142.7,138.6,129.8,129.4,126.8,120.1,119.5,118.9,115.1,111.3,109.7,107.0,104.7,56.0,52.0,29.4,25.9,20.2。
实施例12 5'-三氟甲基-1',3',3'-三甲基螺[色烯-2,2'-二氢吲哚]的合成方法同实施例1,不同之处在于底物换为5-三氟甲基-2,3,3-三甲基-3-H-吲哚,产率64%。1HNMR(500MHz,CDCl3)δ7.46(dd,J=8.2,1.8Hz,1H),7.28(d,J=1.8Hz,1H),7.13(td,J=7.8,1.7Hz,1H),7.08(dd,J=7.5,1.6Hz,1H),6.90(d,J=10.2Hz,1H),6.86(td,J=7.4,1.2Hz,1H),6.73(d,J=8.1Hz,1H),6.54(d,J=8.1Hz,1H),5.68(d,J=10.2Hz,1H),2.79(s,3H),1.35(s,3H),1.20(s,3H);13C NMR(126MHz,CDCl3)δ154.2,150.9,137.4,130.0,130.0,128.5,126.9,125.8(q,J=4.1Hz),124.2,121.0(q,J=32.1Hz),120.5,118.8(q,J=3.6Hz),118.7,118.7,115.1,106.0,104.3,51.7,28.9,25.9,20.2。
实施例13 7'-溴-1',3',3'-三甲基螺[色烯-2,2'-二氢吲哚]的合成
方法同实施例1,不同之处在于底物换为7-溴-2,3,3-三甲基-3-H-吲哚,产率82%。1H NMR(500MHz,CDCl3)δ7.29(dd,J=8.1,1.2Hz,1H),7.12(td,J=7.7,1.7Hz,1H),7.06(dd,J=7.5,1.7Hz,1H),6.99(dd,J=7.2,1.2Hz,1H),6.90–6.82(m,2H),6.74(d,J=8.2Hz,1H),6.69(dd,J=8.0,7.2Hz,1H),5.65(d,J=10.2Hz,1H),3.16(s,3H),1.30(s,3H),1.14(s,3H);13C NMR(126MHz,CDCl3)δ154.4,144.9,140.4,133.3,130.0,130.0,126.9,120.8,120.8,120.3,119.3,118.6,115.1,105.1,101.5,51.3,32.2,26.1,20.3;HRMS-ESI(m/z)calcd for[M+H+](C19H19BrNO):356.0645 found 356.0639。
实施例14 1,1,3-三甲基-1,3-二氢螺[苯并[e]吲哚-2,2'-色烯]的合成方法同实施例1,不同之处在于底物换为化合物2,3,3-三甲基苯并[e]吲哚,产率82%。1H NMR(500MHz,CDCl3)δ7.99(dd,J=8.6,1.1Hz,1H),7.84(dt,J=8.3,0.9Hz,1H),7.78(d,J=8.6Hz,1H),7.44(ddd,J=8.4,6.7,1.4Hz,1H),7.26(td,J=7.6,7.2,1.2Hz,1H),7.14–7.08(m,2H),7.01(d,J=8.6Hz,1H),6.94(dd,J=10.2,0.7Hz,1H),6.86(td,J=7.4,1.1Hz,1H),6.71(d,J=8.1Hz,1H),5.79(d,J=10.2Hz,1H),2.88(s,3H),1.71(s,3H),1.40(s,3H);13C NMR(126MHz,CDCl3)δ154.8,146.1,130.2,129.9,129.9,129.7,129.5,129.1,126.9,126.4,125.9,121.6,121.6,120.1,119.0,118.8,115.0,110.4,105.3,53.5,29.4,24.2,21.9;HRMS-ESI(m/z)calcd for[M+H+](C23H22NO):328.1696 found 328.1686。
以上所述的实施例只是本发明的一种较佳的方案,并非对本发明作任何形式上的限制,在不超出权利要求所记载的技术方案的前提下还有其它的变体及改型。
Claims (7)
2.根据权利要求1所述的一种螺吡喃类光致变色材料的制备方法,其特征在于:所述硫酰氟气氛指含一个大气压硫酰氟的气体环境。
3.根据权利要求1所述的一种螺吡喃类光致变色材料的制备方法,其特征在于:所述缚酸剂为NaOH、KOH、Na2CO3、K2CO3、Cs2CO3、NEt3、DBU或咪唑。
4.根据权利要求1所述的一种螺吡喃类光致变色材料的制备方法,其特征在于:所述2,3,3-三甲基-3H-吲哚类化合物选自5-甲氧基-2,3,3-三甲基-3-H-吲哚、5-氟-2,3,3-三甲基-3-H-吲哚、5-氯-2,3,3-三甲基-3-H-吲哚、5-溴-2,3,3-三甲基-3-H-吲哚、5-三氟甲基-2,3,3-三甲基-3-H-吲哚、2,3,3-三甲基苯并[e]吲哚、2,3,3,5-四甲基-3-H-吲哚、7-溴-2,3,3-三甲基-3-H-吲哚中的一种。
5.根据权利要求1所述的一种螺吡喃类光致变色材料的制备方法,其特征在于:按摩尔比计,2,3,3-三甲基-3H-吲哚类化合物:烷基化试剂:缚酸剂:水杨醛为1:1-5:1-5:1-3。
6.根据权利要求1所述的一种螺吡喃类光致变色材料的制备方法,其特征在于:所述乙醇的用量为:每1摩尔2,3,3-三甲基-3H-吲哚类化合物使用1-10mL。
7.根据权利要求1所述的一种螺吡喃类光致变色材料的制备方法,其特征在于:所述有机溶剂为二氯甲烷、四氢呋喃、1,4-二氧六环、甲醇、甲苯、N,N-二甲基甲酰胺或二甲基亚砜。
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