CN111393385B - 一种苯并噻嗪甲醛衍生物的合成方法 - Google Patents
一种苯并噻嗪甲醛衍生物的合成方法 Download PDFInfo
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 7
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
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- C07D279/02—1,2-Thiazines; Hydrogenated 1,2-thiazines
Abstract
本发明属于苯并嗪噻衍生物的技术领域,公开了一种苯并噻嗪甲醛衍生物的合成方法。所述合成方法:在有机溶剂、碱性化合物、光催化剂以及添加剂的体系中,苯磺酰基炔丙胺衍生物通过光照在有氧的环境中进行反应,获得苯并噻嗪甲醛物衍生物;所述添加剂为二苯基二硫醚和苯硫酚中的一种以上。本发明实现了利用炔烃的碳氧化反应制备苯并噻嗪类化合物。本发明的方法简便、高效,区域选择性高,所用到的原料简单易得,并且无需额外加入有机氧化剂,利用空气中的氧气作为氧源,环境友好而且廉价易得。另外整个操作过程简单易行,步骤简便,产物易纯化。
Description
技术领域
本发明涉及苯并噻嗪甲醛衍生物的合成领域,具体涉及一种苯并噻嗪甲醛衍生物的合成方法。
背景技术
噻嗪类化合物是一种非常重要的分子骨架,如何快速、高效的构筑这类分子骨架在有机合成中具有重要意义。近年来,利用不饱和碳氢键的氧功能化反应构建C-O,C=O,C-X(X=C,N,O,Cl,Br)得到迅速发展,主要研究了炔烃的胺氧化,双氧化,卤氧化,硫氧化反应构建复杂的分子骨架。如(1)H.Peng,N.-G.Akhmedov,Y.-F.Liang,N.Jiao and X.Shi,Synergistic Gold and Iron dual catalysis:preferred radical addition towardvinyl-gold intermediate over alkene,J.Am.Chem.Soc.,2015,137,8912;(2)T.Miura,T.Biyajima,T.Fujii and M.Murakami,Synthesis ofα-amino ketones from terminalalkynes via rhodium catalyzed denitrogenative hydration ofN-sulfonyl-1,2,3-triazoles,J.Am.Chem.Soc.,2012,134,194;(3)E.-M.Beccalli,E.Borsini,G.Broggini,G.Palmisano and S.Sottocornola,Intramolecular Pd(II)-catalyzed cyclization ofpropargylamides:straightforward synthesis of 5-oxazolecarbaldehydes,J.Org.Chem.,2008,73,4746;(4)I.Kim and C.Lee,Rhodium-catalyzed oxygenativeaddition to terminal alkynes forthe synthesis ofesters,amides,and carboxylicacids,Angew.Chem.Int.Ed.,2013,52,10023;(5)J.-L.Li,E.Lin,X.-L.Han,Q.Li andH.Wang,Synthesis ofα-fluorinated imides via direct fluorohydroxylationofynamides,Org.Lett.,2019,21,4255.
但是,炔烃的碳氧化反应报道的相对较少。2014年,印度理工学院孟买分校的Maiti教授报道了(Maji,A.Hazra and D.Maiti,Direct synthesis ofα-trifluoromethylketone from(hetero)arylacetylene:design,intermediate trapping,andmechanisticinvestigations,Org.Lett.,2014,16,4524),杂芳基炔烃直接氧化构筑α-三氟甲基酮衍生物。
如何利用炔烃的碳氧化反应制备苯并噻嗪类化合物,并没有文献报道过。本发明以苯磺酰基炔丙胺衍生物为原料,氧气作为氧化剂,利用光催化剂,在光照条件下,实现了炔烃的碳氧化反应,制备了苯并噻嗪甲醛衍生物。本发明的方法条件温和,操作简单,一步完成,价格低廉,储量丰富,毒性较低和环境友好等优点,更具有大规模生产噻嗪类化合物的潜在优势。
发明内容
为了克服现有技术的缺点与不足,本发明的目的在于提供一种简便、高效的苯并噻嗪甲醛衍生物的合成方法,该方法所用到的原料廉价易得,整个操作过程简单易行。
本发明的目的通过下述技术方案实现:
一种苯并噻嗪甲醛衍生物的合成方法,包括以下步骤:
在有机溶剂、碱性化合物、光催化剂以及添加剂的体系中,苯磺酰基炔丙胺衍生物通过光照在有氧的环境中进行反应,获得苯并噻嗪甲醛物衍生物;
所述苯磺酰基炔丙胺化合物的结构如式A所示,所述苯并噻嗪甲醛衍生物的结构如式B所示:
在式A和式B中,R1为4-Me、4-MeO、4-CF3、4-F、4-Cl、4-Br、4-Ph、3-Cl、3-F-4-Me、3-Cl-4-Me中的一种;R2为4-Me、4-MeO、4-CF3、4-F、4-Cl、4-Br、2-Cl、3-Cl、3-Me-4-Cl、3-F-4-Me中的一种。
所述光催化剂为Eosin Y(曙红Y)、Ir(ppy)3(3-(三联吡啶)合铱(III))、Ru(bpy)3Cl2(3-(2,2'-联吡啶)二氯化钌(II))、TPP(2,4,6-三苯基吡喃鎓四氟硼酸盐)、[Mes-Acr]+ClO4 -(10-甲基-9-均三甲苯基吖啶高氯酸盐)、[Mes-Acr]+BF4 -(10-甲基-9-均三甲苯基吖啶四氟硼酸盐)中的一种以上。
所述光催化剂优选为EosinY。
所述添加剂为二苯基二硫醚和苯硫酚中的一种以上,优选为二苯基二硫醚。
所苯磺酰基炔丙胺化合物与添加剂的摩尔比为1:(0.9~1.5),优选为1:1。
所述光催化剂的用量为苯磺酰基炔丙胺衍生物摩尔用量的(2~3%)。
所述光照的光源为blue LEDs,2×30Wblue LEDs(450nm)。
所述反应的时间为12~24h;反应的温度为室温。
所述有机溶剂为1,2-二氯乙烷、乙腈、甲苯、四氢呋喃、三氯甲烷、四溴乙烷或1,2-二溴乙烷中的一种以上,优选为1,2-二氯乙烷。所述有机溶剂与苯磺酰基炔丙胺化合物用量比为(1~3)ml:0.1mmol。
所述碱性化合物为碳酸钾、碳酸铯、碳酸锂和碳酸钠中的一种以上,优选为碳酸钾。所述碱性化合物与苯磺酰基炔丙胺化合物的摩尔比为(0.1~0.15):0.1。
反应结束后,采用柱层析将产物分离纯化;所述柱层析的洗脱液为石油醚和乙酸乙酯的混合溶剂。
所述苯磺酰基炔丙胺衍生物结构式A已有文献报道。(Wang,J.J.;Li,F.;Pei,W.L.;Yang,M.;Wu,Y.;Ma,D.;Zhang,F.;Wang,J.Selective cleavage of the N-propargyl group from sulfonamides and amides under ruthenium catalysis,Tetrahedron Lett.2018,59,1902–1905;Alaoui,S.;Dufies,M.;Driowya,M.;Demange,L.;Bougrin,K.;Robert,G.;Auberger,P.;Pagès,G.;Benhida,R.Efficient synthesis andin vitro cytostatic activity of4-substituted triazolyl-nucleosides,Bioorg MedChemLett.2007,17,6656)
本发明的合成方法的反应方程式如下:
本发明相对于现有类似技术具有如下的效果及优点:
本发明的方法简便、高效,区域选择性高,所用到的原料简单易得,本制备方法无需额外加入有机氧化剂,利用空气中的氧气作为氧源,环境友好而且廉价易得。另外整个操作过程简单易行,步骤简便,产物易纯化。
附图说明
图1是实施例1制备的化合物1的氢谱图;
图2是实施例1制备的化合物1的碳谱图;
图3是实施例2制备的化合物2的氢谱图;
图4是实施例2制备的化合物2的碳谱图;
图5是实施例3制备的化合物3的氢谱图;
图6是实施例3制备的化合物3的碳谱图;
图7是实施例4制备的化合物4的氢谱图;
图8是实施例4制备的化合物4的碳谱图;
图9是实施例5制备的化合物5的氢谱图;
图10是实施例5制备的化合物5的碳谱图。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述,但本发明的实施方式不限于此。
实施例1
一种苯并噻嗪甲醛衍生物的合成方法,包括以下步骤:
在5ml是史奈特管中,依次加入苯磺酰基炔丙胺化合物(0.1mmol,30mg),EosinY(0.002mmol,1.4mg),碳酸钾(0.15mmol,20.7mg),二苯基二硫醚(0.1mmol,21.8mg),1,2-二氯乙烷(1mL);混合液在2×30Wblue LEDs下,空气中室温反应24h,反应完毕后,旋干,采用柱层析进一步分离纯化(洗脱液为石油醚和乙酸乙酯的混合溶剂,体积比为1:1),得到产品(化合物1)23.5mg,产率为:75%。
本实施例所得产品的结构表征数据如下:
1H NMR(400MHz,CDCl3)δ9.58(s,1H),8.68(s,1H),7.90(d,J=8.2Hz,1H),7.39(dd,J=17.5,8.9Hz,4H),7.31(d,J=8.0Hz,2H),2.52(s,3H),2.43(s,3H).氢谱图见图1。
13C NMR(101MHz,CDCl3)δ188.2,150.0,144.3,140.3,133.7,130.6,129.6,129.3,127.4,127.3,126.2,122.6,115.9,22.1,21.3.碳谱图见图2。
HR-MS(ESI)calcd for[M+H]+:C17H16NO3S:314.0845,found:314.0843;
根据以上数据推断所得产品的结构如下所示:
实施例2
苯并噻嗪甲醛衍生物合成方法,包括以下步骤:
在5ml是史奈特管中,依次加入苯磺酰基炔丙胺化合物(0.1mmol,30mg),EosinY(0.002mmol,1.4mg),碳酸钾(0.15mmol,20.7mg),二苯基二硫醚(0.1mmol,21.8mg),1,2-二氯乙烷(1mL);混合液在2×30Wblue LEDs下,空气中室温反应24h,反应完毕后,旋干,采用柱层析进一步分离纯化,得到产品(化合物2)16.3mg,产率为:51%。
本实施例所得产品的结构表征数据如下:
1H NMR(400MHz,CDCl3)δ9.62(s,1H),8.71(s,1H),7.93(d,J=8.1Hz,1H),7.77(d,J=7.7Hz,1H),7.60(d,J=7.9Hz,1H),7.55–7.42(m,3H),7.31(s,1H),2.55(s,3H).氢谱图见图3。
13C NMR(101MHz,CDCl3)δ188.2,149.9,144.4,133.8,133.3,131.7,131.2,131.2,129.7,129.2,128.2,127.9,126.5,122.4,116.5,22.1.碳谱图见图4。
HR-MS(ESI)calcd for[M+H]+:C16H13ClNO3S:334.0299,found:334.0302
根据以上数据推断所得产品的结构如下所示:
实施例3
苯并噻嗪甲醛衍生物的合成方法,包括以下步骤:
在5ml是史奈特管中,依次加入苯磺酰基炔丙胺化合物(0.1mmol,30mg),EosinY(0.002mmol,1.4mg),碳酸钾(0.15mmol,20.7mg),二苯基二硫醚(0.1mmol,21.8mg),1,2-二氯乙烷(1mL);混合液在2×30Wblue LEDs下,空气中室温反应24h,反应完毕后,旋干,采用柱层析进一步分离纯化,得到产品(化合物3)22.2mg,产率为:64%。
本实施例所得产品的结构表征数据如下:
1H NMR(400MHz,CDCl3)δ9.49(s,1H),8.56(s,1H),7.78(d,J=8.2Hz,1H),7.37(d,J=8.5Hz,1H),7.32(d,J=8.2Hz,1H),7.29(d,J=1.9Hz,1H),7.25(s,1H),7.20–7.16(m,1H),2.42(s,3H),2.33(s,3H).氢谱图见图5。
13C NMR(101MHz,CDCl3)δ188.1,149.3,144.5,138.3,136.1,134.6,130.4,129.8,129.1,127.3,126.3,126.1,122.6,116.3,22.1,20.2.碳谱图见图6。
HR-MS(ESI)calcd for[M+H]+:C17H15ClNO3S:348.0456,found:348.0456;
根据以上数据推断所得产品的结构如下所示:
实施例4
苯并噻嗪甲醛衍生物的合成方法,包括以下步骤:
在5ml是史奈特管中,依次加入苯磺酰基炔丙胺化合物(0.1mmol,30mg),EosinY(0.002mmol,1.4mg),碳酸钾(0.15mmol,20.7mg),二苯基二硫醚(0.1mmol,21.8mg),1,2-二氯乙烷(1mL);混合液在2×30Wblue LEDs下,空气中室温反应24h,反应完毕后,旋干,采用柱层析进一步分离纯化,得到产品(化合物4)25.1mg,产率为:67%。
本实施例所得产品的结构表征数据如下:
1H NMR(400MHz,CDCl3)δ9.63(s,1H),9.13(s,1H),8.08(d,J=8.3Hz,1H),7.81(d,J=8.2Hz,1H),7.69(d,J=7.3Hz,2H),7.50(t,J=7.3Hz,2H),7.45(d,J=7.5Hz,1H),7.41(d,J=6.2Hz,3H),7.33(d,J=7.7Hz,2H),2.44(s,3H).氢谱图见图7。
13C NMR(101MHz,CDCl3)δ188.2,150.1,146.4,140.4,139.3,133.7,130.6,129.8,129.1,128.7,128.3,127.6,127.5,127.4,124.6,123.2,116.1,21.3.碳谱图见图8。
HR-MS(ESI)calcd for[M+H]+:C22H18NO3S:376.1002,found:376.0998
根据以上数据推断所得产品的结构如下所示:
实施例5
苯并噻嗪甲醛衍生物的合成方法,包括以下步骤:
在5ml是史奈特管中,依次加入苯磺酰基炔丙胺化合物(0.1mmol,30mg),EosinY(0.002mmol,1.4mg),碳酸钾(0.15mmol,20.7mg)(碳酸钾可以以无水碳酸钾的形式加入,也可以以碳酸钾水溶液的形式加入),二苯基二硫醚(0.1mmol,21.8mg),1,2-二氯乙烷(1mL);混合液在2X 30Wblue LEDs下,室温反应24h,反应完毕后,旋干,采用柱层析进一步分离纯化,得到产品(化合物5)18.9mg,产率为:57%。
本实施例所得产品的结构表征数据如下:
1H NMR(400MHz,CDCl3)δ9.55(s,1H),8.77(d,J=6.9Hz,1H),7.64(d,J=8.2Hz,1H),7.37(d,J=7.5Hz,2H),7.32(d,J=5.4Hz,3H),2.43(s,6H).氢谱图见图9。
13C NMR(101MHz,CDCl3)δ188.1,161.7,149.4,140.5,133.5,132.1,131.9,130.6,129.7,129.6,128.8,127.5,125.4,115.9,109.4,109.1,21.3,15.2.碳谱图见图10。
HR-MS(ESI)calcd for[M+H]+:C17H15FNO3S:332.0751,found:332.0746
根据以上数据推断所得产品的结构如下所示:
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (8)
1.一种苯并噻嗪甲醛衍生物的合成方法,其特征在于:包括以下步骤:在有机溶剂、碱性化合物、光催化剂以及添加剂的体系中,苯磺酰基炔丙胺衍生物通过光照在有氧的环境中进行反应,获得苯并噻嗪甲醛衍生物;
所述苯磺酰基炔丙胺衍生物的结构如式A,所述苯并噻嗪甲醛衍生物的结构如式B:
在式A和式B中,R1为4-Me、4-MeO、4-CF3、4-F、4-Cl、4-Br、4-Ph、3-Cl、3-F-4-Me、3-Cl-4-Me中的一种;R2为4-Me、4-MeO、4-CF3、4-F、4-Cl、4-Br、2-Cl、3-Cl、3-Me-4-Cl、3-F-4-Me中的一种;
所述添加剂为二苯基二硫醚和苯硫酚中的一种以上;
所述光催化剂为Eosin Y。
2.根据权利要求1所述苯并噻嗪甲醛衍生物的合成方法,其特征在于:
所述添加剂为二苯基二硫醚。
3.根据权利要求1所述苯并噻嗪甲醛衍生物的合成方法,其特征在于:
所述苯磺酰基炔丙胺衍生物与添加剂的摩尔比为1:(0.9~1.5);
所述光催化剂的用量为苯磺酰基炔丙胺衍生物摩尔用量的(2~3%);
所述光照的光源为blue LEDs。
4.根据权利要求1所述苯并噻嗪甲醛衍生物的合成方法,其特征在于:所述反应的时间为12~24h;反应的温度为室温。
5.根据权利要求1所述苯并噻嗪甲醛衍生物的合成方法,其特征在于:所述碱性化合物为碳酸钾、碳酸铯、碳酸锂和碳酸钠中的一种以上;所述有机溶剂为1,2-二氯乙烷、乙腈、甲苯、四氢呋喃、三氯甲烷、四溴乙烷或1,2-二溴乙烷中的一种以上。
6.根据权利要求5所述苯并噻嗪甲醛衍生物的合成方法,其特征在于:所述碱性化合物为碳酸钾;所述有机溶剂为1,2-二氯乙烷。
7.根据权利要求1所述苯并噻嗪甲醛衍生物的合成方法,其特征在于:所述碱性化合物与苯磺酰基炔丙胺衍生物的摩尔比为(0.1~0.15):0.1;所述有机溶剂与苯磺酰基炔丙胺衍生物用量比为(1~3)ml:0.1mmol。
8.根据权利要求1所述苯并噻嗪甲醛衍生物的合成方法,其特征在于:反应结束后,采用柱层析将产物分离纯化;所述柱层析的洗脱液为石油醚和乙酸乙酯的混合溶剂。
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