CN115785148A - 一种硫代膦(磷)酸酯取代苯并芴化合物的制备方法 - Google Patents
一种硫代膦(磷)酸酯取代苯并芴化合物的制备方法 Download PDFInfo
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Abstract
本发明公开一种硫代膦(磷)酸酯取代苯并芴化合物的制备方法,所述的方法是以如式(I)所示的1,6‑二炔醇化合物为原料,于室温条件下加入有机溶剂充分溶解,而后加入含P(O)‑SH类化合物,在80℃下反应1‑10小时,反应结束后,反应产物经硅胶柱层析分离纯化得到如式(II)所示的硫代膦(磷)酸酯取代苯并芴化合物。本发明原料简单易得、条件温和、操作简便、底物适用性好、产率良好等特点;此外,制备得到的目标产物硫代膦(磷)酸酯取代苯并芴化合物在有机合成、药学、材料科学等领域具有潜在的应用价值,具有较好的推广应用前景的化学合成方法。
Description
技术领域
本发明属于有机合成技术领域,具体涉及一种硫代膦(磷)酸酯取代苯并芴化合物的制备方法。
背景技术
含有(RO)2P(O)S-C(SP2)键结构的硫代磷酸酯类化合物,在药物方面可以作为医药中间体、杀虫剂、杀菌剂、固化促进剂、抗静电剂及一种胆碱酯酶抑制剂。在功能材料方面,作为表面活性剂、光电材料、含磷阻燃剂。同样,硫代磷酸酯类化合物作为合成中间体在有机合成领域具有重要作用。
此外,苯并芴化合物是多环芳烃中非常重要的一类碳环骨架,此类骨架是众多天然代谢产物和抗肿瘤类抗生素家族的核心结构单元,具有优良的生物和药理活性,在医药领域具有广泛的应用和发展前景,如Kinamycin D是从链霉菌蛋白酶中分离得到的天然重氮化合物,该物质对革兰氏阳性细菌生物体具有抗肿瘤性能和抗生素活性;Kinobscurinone是一种合成醌那霉素类药物的关键中间体;Stealthin C系列化合物则是从S.murayamaensis培养中分离得到的一类天然产物。此外,因其新颖的刚性结构和大的π共轭体系,具有独特的光电性质,使得苯并芴类化合物的合成与应用一直都是化学与材料、化学与生物等交叉领域的研究热点。虽然目前构建苯并芴化合物的方法有很多,但主要是在过渡金属、高温或强氧化剂条件下进行,而在无金属催化剂或强氧化剂下合成苯并芴骨架化合物的研究鲜有报道,尤其是对于构建硫代膦(磷)酸酯取代苯并芴化合物的文献还未见报道。
基于硫代磷酸酯类化合物和苯并芴化合物在有机合成、药物化学及材料科学等领域的广泛应用,发展一种无金属、原子经济性、高效、绿色的合成策略来构建成硫代膦(磷)酸酯取代苯并芴化合物是非常重要且极具挑战性。
发明内容
本发明是利用1,6-二炔醇化合物为底物在含P(O)-SH类化合物促进下一步实现构建成硫代膦(磷)酸酯取代苯并芴化合物的合成,目的是提供一种原料易得、条件温和、无金属、原子经济性、高效、绿色、具有较好应用前景的硫代膦(磷)酸酯取代苯并芴化合物的制备方法。
本发明所采用的技术方案如下:
一种如式(II)所示的硫代膦(磷)酸酯取代苯并芴化合物的合成方法,所述的方法是以式(I)所示的1,6-二炔醇化合物为原料,于室温条件下加入有机溶剂充分溶解,而后加入含P(O)-SH类化合物,加热反应1-10小时,反应结束后,反应产物经分离纯化得到如式(II)所示的硫代膦(磷)酸酯取代苯并芴化合物;
式(I)所示的1,6-二炔醇化合物和式(II)所示的硫代膦(磷)酸酯取代苯并芴化合物的化学结构如下所示:
其中,式(Ⅰ)和式(II)中的R1为强给电子基团,R2为芳基、烷基,R3~R6各自独立为H、CH3、X(X为F、Cl、Br中的一种)、OCH3等基团中的一种,R7为芳基。
所述反应的反应式如下:
其中,所述的有机溶剂为下列之一:1,2-二氯乙烷、乙腈、硝基甲烷、二氯甲烷、四氢呋喃。所述的有机溶剂的质量为1,6-二炔醇化合物质量的10-30倍。
本发明中,所述的1,6-二炔醇化合物、含P(O)-SH类化合物的物质的量之比为1:2.0~3.0。进一步优选地,所述的1,6-二炔醇化合物、含P(O)-SH类化合物的物质的量之比为1:2.5。
本发明反应过程中以TCL跟踪反应进度时间,所述反应时间为1-10小时,不同底物所需反应时间不一样。
进一步优选地,所述方法的反应加热温度为80℃。
本发明中所述的分离纯化可采用如下步骤:将反应液加入饱和碳酸氢酸钠溶液,再加入乙酸乙酯,充分搅拌后静置分层;分出的水层用乙酸乙酯萃取,将乙酸乙酯的萃取物与分出的有机层合并后分别用饱和食盐水洗涤、无水硫酸钠干燥;蒸除乙酸乙酯溶剂,其后经硅胶柱层析得到硫代膦(磷)酸酯取代苯并芴化合物。
本发明与现有技术相比,其有益效果体现在:(1)提供一种新的合成策略来构建硫代膦(磷)酸酯取代苯并芴化合物;(2)本发明的反应无需金属催化剂、额外的酸促进剂、条件温和;(3)本发明方法不仅原子经济性高,而且操作简便,底物适用性也广,得到硫代膦(磷)酸酯取代苯并芴化合物;(4)本发明无需金属催化剂、无额外酸参与,原料简单易得、产率良好。
综上所述,本发明具有试剂廉价易得、无需催化剂、反应条件温和、工艺操作简单、高效、绿色污染少等优点,是一种具有较好推广应用前景的硫代膦(磷)酸酯取代苯并芴化合物合成方法。
具体实施方式
通过以下实施例进一步详细说明本发明,但本发明的保护范围并并不仅限于此。
实施例一:硫代膦(磷)酸酯取代苯并芴化合物1的制备,硫代膦(磷)酸酯取代苯并芴化合物1的化学结构式如下所示:
代表性的实施过程:室温下,依次向反应瓶中加入1,6-二炔醇化合物I-1(67.6mg,0.2mmol)和2ml干燥硝基甲烷,然后将硫代磷酸二乙酯(0.5mmol)加入到反应瓶中,随后将反应置于80℃下反应5小时。TLC跟踪反应进度,反应结束后,将反应液加入饱和碳酸氢钠溶液,再加入乙酸乙酯,充分搅拌后静置分层;分出的水层用乙酸乙酯萃取,将乙酸乙酯的萃取物与分出的有机层合并后分别用饱和食盐水洗涤、无水硫酸钠干燥;蒸除乙酸乙酯溶剂,其后经硅胶柱层析分离纯化得到硫代膦(磷)酸酯取代苯并芴化合物1(78.1mg,80%)。
1H NMR(400MHz,CDCl3):δppm 1.24(t,J=7.2Hz,6H),3.72(s,3H),4.10-4.22(m,4H),4.42(d,J=2.8Hz,2H),6.41(d,J=7.6Hz,1H),6.87(d,J=2.4Hz,1H),7.04(t,J=7.6Hz,1H),7.24-7.30(m,2H),7.41-7.43(m,2H),7.55-7.66(m,4H),8.61(d,J=9.2Hz,1H).13C NMR(100MHz,CDCl3):16.1(d,JC-P=6.8Hz),38.2,55.1,64.4(d,JC-P=7.2Hz),105.8,117.6(d,JC-P=8.4Hz),118.1,123.7,124.8,126.5,127.3,127.5,128.0,129.3,129.6(d,JC-P=3.1Hz),129.7,134.7(d,JC-P=4.1Hz),135.1(d,JC-P=2.4Hz),138.2(d,JC-P=3.6Hz),138.5,141.2,144.0,147.4(d,JC-P=6.2Hz),157.4.31P NMR(162MHz,CDCl3):δppm 22.89.HRMS(ESI,m/z):calcd for C28H27O4PS:M+H=491.1441;found:491.1433。
实施例二:硫代膦(磷)酸酯取代苯并芴化合物2的制备,硫代膦(磷)酸酯取代苯并芴化合物2的化学结构式如下所示:
代表性的实施过程:室温下,依次向反应瓶中加入1,6-二炔醇化合物I-2(73.6mg,0.2mmol)和2ml干燥硝基甲烷,然后将硫代磷酸二乙酯(0.5mmol)加入到反应瓶中,随后将反应置于80℃下反应1小时,TLC跟踪反应进度。分离纯化步骤同实施例1,得到硫代膦(磷)酸酯取代苯并芴化合物2(65.5mg,63%)。
1H NMR(400MHz,CDCl3):δppm 1.24(t,J=6.8Hz,6H),3.76(s,3H),4.01(s,3H),4.08-4.24(m,4H),4.43(d,J=2.8Hz,2H),6.54(d,J=8.0Hz,1H),6.93(s,1H),7.08(t,J=7.6Hz,1H),7.18(d,J=8.4Hz,2H),7.29(d,J=7.6Hz,2H),7.34(d,J=8.0Hz,2H),7.57(d,J=7.2Hz,1H),8.61(d,J=9.2Hz,1H).13C NMR(100MHz,CDCl3):16.1(d,JC-P=6.5Hz),38.3,55.2,55.4,64.5(d,JC-P=7.1Hz),106.0,114.7,118.1,123.8,124.9,126.5,127.3,127.6,129.8,130.7,130.9,134.5,135.6,138.7,141.4,144.0,147.5(d,JC-P=6.2Hz),157.5,159.4.31P NMR(162MHz,CDCl3):δppm 21.81.HRMS(ESI,m/z):calcd for C29H29O5PS:M+H=521.1546;found:521.1544。
实施例三:硫代膦(磷)酸酯取代苯并芴化合物3的制备,硫代膦(磷)酸酯取代苯并芴化合物3的化学结构式如下所示:
代表性的实施过程:室温下,依次向反应瓶中加入1,6-二炔醇化合物I-3(73.2mg,0.2mmol)和2ml干燥硝基甲烷,然后将硫代磷酸二乙酯(0.5mmol)加入到反应瓶中,随后将反应置于80℃下反应3小时,TLC跟踪反应进度。分离纯化步骤同实施例1,得到硫代膦(磷)酸酯取代苯并芴化合物3(88.1mg,85%)。
1H NMR(400MHz,CDCl3):δppm 1.19(t,J=7.2Hz,6H),2.41(s,6H),3.73(s,3H),4.04-4.17(m,4H),4.39(d,J=3.2Hz,2H),6.47(d,J=7.6Hz,1H),6.92(d,J=2.4Hz,1H),6.99(s,2H),7.04(t,J=7.2Hz,1H),7.19(s,1H),7.24-7.26(m,2H),7.53(d,J=7.2Hz,1H),8.58(d,J=9.2Hz,1H).13C NMR(100MHz,CDCl3):16.1(d,JC-P=6.5Hz),21.4,38.3,55.3,64.5(d,JC-P=7.2Hz),106.4,117.3(d,JC-P=6.7Hz),117.8,123.9,124.4(d,JC-P=8.5Hz),124.8,126.5,127.3,127.5,129.5,129.7,135.2,138.2,138.3,138.7,141.4,144.0,147.5(d,JC-P=5.8Hz),157.4.31P NMR(162MHz,CDCl3):δppm 22.25.HRMS(ESI,m/z):calcd for C30H31O4PS:M+H=519.1759;found:519.1757。
实施例四:硫代膦(磷)酸酯取代苯并芴化合物4的制备,硫代膦(磷)酸酯取代苯并芴化合物4的化学结构式如下所示:
代表性的实施过程:室温下,依次向反应瓶中加入1,6-二炔醇化合物I-4(74.4mg,0.2mmol)和2ml干燥硝基甲烷,然后将硫代磷酸二乙酯(0.5mmol)加入到反应瓶中,随后将反应置于80℃下反应10小时,TLC跟踪反应进度。分离纯化步骤同实施例1,硫代膦(磷)酸酯取代苯并芴化合物4(77.6mg,74%)。
1H NMR(400MHz,CDCl3):δppm 1.22(t,J=7.2Hz,6H),3.72(s,3H),4.07–4.19(m,4H),4.39(d,J=2.8Hz,2H),6.46(d,J=8.0Hz,1H),6.77(d,J=2.0Hz,1H),7.06(t,J=7.2Hz,1H),7.24-7.27(m,2H),7.35(d,J=8.4Hz,2H),7.55(d,J=7.6Hz,1H),7.60(d,J=8.4Hz,2H),8.59(d,J=9.2Hz,1H).13C NMR(100MHz,CDCl3):16.1(d,JC-P=6.8Hz),38.3,55.3,64.5(d,JC-P=7.2Hz),105.6,118.2,123.6,125.0,126.6,127.6,127.7,129.7,131.4,133.2(d,JC-P=3.8Hz),134.1,135.0,137.2,138.4(d,JC-P=3.6Hz),141.0,144.2,147.4(d,JC-P=6.3Hz),157.7.31P NMR(162MHz,CDCl3):δppm 21.70.HRMS(ESI,m/z):calcdfor C28H26ClO4PS:M+H=525.1051;found:525.1042。
Claims (7)
2.根据权利要求1所述的制备方法,其特征在于,步骤一中所述的有机溶剂为下列之一:1,2-二氯乙烷、乙腈、硝基甲烷、二氯甲烷。
3.根据权利要求1所述的制备方法,其特征在于,步骤一中所述的1,6-二炔醇化合物、含P(O)-SH类化合物的物质的量之比为1:2.0~3.0。
4.根据权利要求3所述的制备方法,其特征在于,步骤一中所述的1,6-二炔醇化合物、含P(O)-SH类化合物的物质的量之比为1:2.5。
5.根据权利要求1所述的制备方法,其特征在于,步骤一中所述的有机溶剂的质量为1,6-二炔醇化合物质量的10-30倍。
6.根据权利要求1所述的制备方法,其特征在于,步骤二中所述加热温度为80℃。
7.根据权利要求1所述的制备方法,其特征在于,步骤三中所述的分离纯化步骤为:将反应液加入饱和碳酸氢酸钠溶液,再加入乙酸乙酯,充分搅拌后静置分层;分出的水层用乙酸乙酯萃取,将乙酸乙酯的萃取物与分出的有机层合并后分别用饱和食盐水洗涤、无水硫酸钠干燥;蒸除乙酸乙酯溶剂,其后经硅胶柱层析得到硫代膦(磷)酸酯取代苯并芴化合物。
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