CN105218359A - 一种k-取代芘衍生物羧酸类化合物及合成方法 - Google Patents
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- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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Abstract
一种K-取代芘衍生物的羧酸类化合物及合成方法,属于K-取代芘衍生物的羧酸类化合物。其结构式如下:
Description
技术领域
本发明涉及一种以钯的配合物为催化剂,以1,3,5,9-四溴-7-叔丁基芘化合物1和对甲氧基羰基苯硼酸为原料,合成1,3,5,9-四苯甲酸-7-叔丁基芘化合物的方法,属于K-取代芘衍生物的羧酸类化合物技术领域。
背景技术
从芘的结构式中可以看出,共有10个氢原子,因为芘的富电子性,这10个位置的氢原子都极易发生亲电取代反应。又因其具有高度对称性,使得这些反应位点分为两种:C型取代1,3,6,8-位,K型取代2,7-位和4,5,9,10-位。目前芘的衍生物大部分是C型取代物衍生而来的,而K型取代衍生物比较少。
金属催化交叉偶联反应是单取代芘化合物常用的合成方法,如:Suzuki、Heck、Sonogashira偶联等,较常见的是钯作催化剂催化C-C键的Suzuki反应。尽管大部分芘衍生物是单取代产物,也存在四取代芘化合物。如常见的1,3,6,8-四溴芘,其进一步发生Suzuki、Sonogashira等反应。随着科技的发展,金属有机骨架材料(MOFs)被人们广泛的研究,而最主要的研究方向就是支撑骨架的有机配体。基于芘的衍生物得到的有机配体因其独特的荧光性能,引起了人们极大的关注。例如利用C型衍生物1,3,6,8-四溴芘得到的四齿羧酸配体与多种金属构筑的MOFs具有很多优良的性质。最具代表性的就是NU-1000,由无水ZrCl4与1,3,6,8-tetrakis(p-benzoicacid)pyrene构筑的MOFs,其较高的水稳定性,较大的比表面积成为了MOFs领域一个非常具有意义的材料。(Mondloch,J.E.;Bury,W.;Fairen-Jimenez,D.;Kwon,S.;DeMarco,E.J.;Weston,M.H.;Sarjeant,A.A.;Nguyen,S.T.;Stair,P.C.;Snurr,R.Q.;Farha,O.K.;Hupp,J.T.J.Am.Chem.Soc.2013,135,10294)
由于2,7-位反应活性较低,这两个位置上的氢不能直接进行亲电取代反应,但是这两个位置的氢空间位阻较小,较易发生傅克化反应。而4,5,9,10-位更为特殊,从电性角度讲:芘分子HOMO轨道上的电子出现在4,5,9,10-位的概率小于1,3,6,8-位,即电子云密度小;其次从空间位阻来讲:4,5,9,10-位要比2,7,-位的位阻大。正是由于这种特殊性,使得芘K型取代物的化合物报道较少。
最近,我们设计并合成了一种新型的K-取代芘衍生物的羧酸类化合物的合成发放,以K型1,3,5,9-四溴-7-叔丁基芘化合物1和对甲氧基羰基苯硼酸为原料通过偶联反应高效的合成出了一类新型K-取代芘衍生物的羧酸类化合物。
发明内容
本发明的目的在于开发合成一种新型K-取代芘衍生物的羧酸类化合物的方法。
技术方案如下:
一种K-取代芘衍生物的羧酸类化合物,其特征在于,其结构式为:
一种K-取代芘衍生物的羧酸酯类化合物,其特征在于,其结构式为:
上述K-取代芘衍生物的羧酸类化合物是由上述K-取代芘衍生物的羧酸酯类化合物水解得到的:将上述得到的酯类化合物、碱的水溶液、溶剂加入到反应瓶中,回流条件下反应;反应停止后,减压蒸馏后并加入去离子水使其完全溶解后,逐滴加入酸溶液至无沉底析出后过滤。
碱选自氢氧化钠、氢化钠或氢氧化锂;溶剂优选为四氢呋喃、甲醇中的一种或两种;酸可以为盐酸或硝酸。
一种合成上述新型K-取代芘衍生物的羧酸酯类化合物的方法,其特征在于,包括以下步骤:在碱1类化合物存在的条件下,以钯的配位物为催化剂,溶于溶剂,在85℃~100℃的条件下,以1,3,5,9-四溴-7-叔丁基芘化合物1和对甲氧基羰基苯硼酸化合物为原料合成K-取代芘衍生物的羧酸类化合物,其反应方程式如下:
四溴叔丁基芘化合物1
溶剂优选自乙二醇二甲醚、甲苯、1,4-二氧六环中的一种或几种,碱1类化合物选自碱金属或碱土金属的碳酸盐、磷酸盐或氟化盐;1,3,5,9-四溴-7-叔丁基芘化合物与对甲氧基羰基苯硼酸化合物的摩尔比优选为1:6。四溴叔丁基芘化合物在溶剂中的浓度优选为1~10mmol/g;碱1类化合物与底物四溴叔丁基芘化合物的摩尔比为2:1~6:1。
钯催化剂优选为四三苯基膦钯、双三苯基磷二氯化钯。催化剂与四溴叔丁基芘的摩尔比优选为1:100~20:100。
将上述得到的酯类化合物水解即可得到新型K-取代芘衍生物的羧酸类化合物。
本发明的具体反应过程是:将催化剂、1,3,5,9-四溴-7-叔丁基芘化合物、对甲氧基羰基苯硼酸化合物、碱、溶剂依次加入烧瓶中,密封,85℃~100℃,反应结束后,分离提纯,得产物K-取代芘衍生物的羧酸酯类化合物,然后水解得到K-取代芘衍生物的羧酸类化合物。下面对本发明方法进行进一步的详细说明:
(1)本发明所用的对甲氧基羰基苯硼酸化合物,可直接商业购买。
(2)本发明采用普通加热,无需微波辅助加热,优选反应时间总计为48h。
(3)本发明所用的碱可以是碱金属或碱土金属的碳酸盐、磷酸盐、氟化盐;碱1与底物四溴叔丁基芘化合物1的摩尔比为2:1~6:1。
(4)本发明所用的催化剂,可以是四三苯基膦钯、双三苯基磷二氯化钯;催化剂与四溴叔丁基芘化合物1的摩尔比为1:100-20:100。
本发明合成的K-取代芘衍生物1,3,5,9-四苯甲酸-7-叔丁基芘的羧酸类化合物未见文献报道,合成方法简便,收率高,具有广泛的普适性,并且在构筑MOFs方面显示出强大的潜力。
附图说明
图1为实施例水解所得1,3,5,9-四苯甲酸-7-叔丁基芘化合物的单晶结构图(无氢原子)。
具体实施方式
下面结合实施例对本发明做进一步说明,但本发明并不限于以下实施例。
按文献报道合成出K-取代四溴芘前驱体(Org.Lett.,Vol.15,No.6,2013),后将5.00g(8.72mmol)1,3,5,6-四溴-7-叔丁基芘,14.10g(54mmol)对甲氧基羰基苯硼酸,8.15g(54mmol)氟化铯,0.18g(0.18mmol)四三苯基膦钯,300ml乙二醇二甲醚加入到500ml三口烧瓶中,密封,抽真空,氮气保护,85℃~100℃条件下反应48小时。反应停止后,用二氯甲烷萃取,水洗,无水硫酸钠干燥后,过滤,减压蒸馏,经硅胶柱柱层析分离提纯,得1,3,5,9-四苯甲酸甲酯-7-叔丁基芘5.2g,收率75%。1HNMR(300MHz,CDCl3)δ1.38(s,9H),4.01(d,12H),7.72(d,4H),7.78(d,4H),8.00(s,1H),8.10(s,2H),8.24(d,8H),8.29(s,2H)。
水解条件:将上步所得2.00g酯,3mol/L氢氧化钠溶液,200mlTHF/MeOH(v/v=2:1)加入到250ml的三口烧瓶中,回流条件下70℃~75℃反应12小时。反应停止后,减压蒸馏,加入100ml去离子水使其完全溶解后,逐滴加入稀盐酸至无沉淀析出后抽滤得1,3,5,9-四苯甲酸-7-叔丁基芘1.80g,收率90%。1HNMR(300MHz,DMSO)δ1.32(s,9H),7.79(d,4H),7.88(d,4H),8.06(d,3H),8.15(d,8H),8.27(s,2H)。
Claims (8)
1.一种K-取代芘衍生物的羧酸类化合物,其特征在于,其结构式为:
2.一种K-取代芘衍生物的羧酸酯类化合物,其特征在于,其结构式为:
3.权利要求1的K-取代芘衍生物的羧酸类化合物的制备方法,其特征在于,利用权利要求2的K-取代芘衍生物的羧酸酯类化合物水解制备得到。
4.按照权利要求3的方法,其特征在于,包括以下步骤:将K-取代芘衍生物的羧酸酯类化合物、碱2水溶液、溶剂加入到反应瓶中,回流条件下反应;反应停止后,减压蒸馏后并加入去离子水使其完全溶解后,逐滴加入酸溶液至无沉底析出后过滤。
5.按照权利要求4的方法,其特征在于,碱选自氢氧化钠、氢化钠或氢氧化锂;溶剂为四氢呋喃、甲醇中的一种或两种;酸为盐酸或硝酸。
6.制备权利要求2的K-取代芘衍生物的羧酸酯类化合物的方法,其特征在于,包括以下步骤:包括以下步骤:在碱1类化合物存在的条件下,以钯的配位物为催化剂,溶于溶剂,在85℃~100℃的条件下,以1,3,5,9-四溴-7-叔丁基芘化合物1和对甲氧基羰基苯硼酸化合物为原料合成K-取代芘衍生物的羧酸类化合物,其反应方程式如下:
四溴叔丁基芘化合物1;
溶剂优选自乙二醇二甲醚、甲苯、1,4-二氧六环中的一种或几种,碱1类化合物选自碱金属或碱土金属的碳酸盐、磷酸盐或氟化盐。
7.按照权利要求6的方法,其特征在于,1,3,5,9-四溴-7-叔丁基芘化合物与对甲氧基羰基苯硼酸化合物的摩尔比优选为1:6;四溴叔丁基芘化合物在溶剂中的浓度优选为1~10mmol/g;碱1类化合物与底物四溴叔丁基芘化合物的摩尔比为2:1~6:1。
8.按照权利要求6的方法,其特征在于,钯催化剂优选为四三苯基膦钯、双三苯基磷二氯化钯;催化剂与四溴叔丁基芘的摩尔比优选为1:100~20:100。
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