CN110734389B - 一种二烷基砜类化合物的制备方法 - Google Patents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/02—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
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Abstract
本发明属于有机化学技术领域,具体涉及一种二烷基砜类化合物的制备方法。本发明提供的二烷基砜类化合物的制备方法,是在可见光催化下,通过简便的操作,以各种简单或复杂烷基取代的N‑烷基吡啶盐和光催化剂作用生成烷基自由基,继而串联二氧化硫得到磺酰基自由基,再进攻烯醇硅醚,从而高效构建一系列二烷基砜类化合物的方法。该方法能够高效、简便的合成二烷基砜类化合物,且反应所需的磺酰基来源焦亚硫酸钾为廉价易得化工原料,避免了传统磺酰类化合物合成中强酸性磺酸、磺酰氯的使用,具有大规模工业制备的优势。
Description
技术领域
本发明属于有机化学技术领域,具体涉及一种二烷基砜类化合物的制备方法。
背景技术
在过去的几年中,使用光反应来催化有机转化的策略迅速发展(T.P.Yoon,M.A.Ischay,J.Du,Nat.Chem.2010,2,527;J.M.R.Narayanam,C.R.J.Stephenson,Chem.Soc.Rev.2011,40,102;J.Xuan,W.-J.Xiao,Angew.Chem.Int.Ed.2012,51,6828;L.Shi,W.-J.Xia,Chem.Soc.Rev.2012,41,7687;C.K.Prier,D.A.Rankic,D.W.C.MacMillan,Chem.Rev.2013,113,5322;D.M.Schultz,T.P.Yoon,Science.2014,343,985)。在大多数情况下,光催化过程需要由激发态光催化剂与底物发生单电子转移生成作为反应中间体的自由基物种。目前在此研究领域中,铱配合物光催化剂以其用量小、效率高、应用范围广的优点被广泛应用。
N-烷基吡啶盐类化合物近年来作为优秀的自由基前体被广泛研究(C.H.Basch,J.Liao,J.Xu,J.J.Piane,M.P.Watson,J.Am.Chem.Soc.2017,139,5313;J.Liao,W.Guan,B.P.Boscoe,J.W.Tucker,J.W.Tomlin,M.R.Garnsey,M.P.Watson,Org.Lett.2018,20,3030;Z.-F.Zhu,M.-M.Zhang,F.Liu,Org.Biomol.Chem.2019,17,1531;J.Wu,P.S.Grant,X.Li,A.Noble,V.K.Aggarwal,Angew.Chem.,Int.Ed.2019,58,5697)。此类N-烷基吡啶盐可由相应烷基伯胺为原料高效制备,过程简单,廉价易得(A.R.Katritzky,G.De Ville,R.C.Patel,Tetrahedron.1981,37,25;A.R.Katritzky,C.M.Marson,Angew.Chem.,Int.Ed.Engl.1984,23,420),同时具有空气稳定、不易分解、易于保存、反应后处理简单等优点。
天然产物骨架中广泛存在如砜、磺酰胺等磺酰基官能团,并且部分此类化合物具有良好的生物活性和优秀的药用价值。通过二氧化硫的直接插入合成砜类和磺酰类化合物的策略也已经得到了化学家们的广泛关注。二氧化硫插入反应是一种简单高效、绿色环保的有机合成策略(P.Bisseret,N.Blanchard,Org.Biomol.Chem.2013,11,5393;G.Liu,C.Fan,J.Wu,Org.Biomol.Chem.2015,13,1592;G.Qiu,K.Zhou,L.Gao,J.Wu,Org.Chem.Front.2018,5,691;J.Zhu,W.-C.Yang,X.-D.Wang,L.Wu,Adv.Synth.Catal.2018,360,386),其优势在于避免了传统含磺酰基化合物合成过程中强酸性磺酸或磺酰氯的使用与制备,而可通过串联反应一步直接完成磺酰基官能团的构建。在这类反应体系中,利用自由基引发的二氧化硫插入反应合成一些具有生物活性的化合物的发展尤为迅速。
但在各种砜类化合物的合成方法中,二烷基砜类化合物的合成仍有一定局限性,且已有合成方法难以适用于各种不同烷基取代的目标产物。
发明内容
本发明的目的在于解决现有技术问题的不足,提供一种二烷基砜类化合物的制备方法,本发明提供的制备方法能够简便、高效的合成二烷基砜类化合物。
为了实现上述发明目的,本发明提供以下技术方案:
本发明提供了一种二烷基砜类化合物的制备方法,包括如下步骤:
(1)在保护气氛下,在可见光照射下,N-烷基吡啶盐类化合物与光催化剂发生单电子转移产生烷基自由基;
(2)上述烷基自由基在二氧化硫供体的作用下得到磺酰基自由基,所述磺酰基自由基进攻烯醇硅醚后发生加成脱硅反应,反应完全后对反应液进行后处理,得到二烷基砜类化合物。
优选的,本发明中所述的保护气氛包括氮气和氩气,更优选为高纯氮气或者氩气(高纯为纯度>99.999%),优选操作方式为加入溶剂前在高纯氮气或者氩气中置换气。
优选的,步骤(1)中所述的N-烷基吡啶盐类化合物包括N-烷基-2,4,6-三芳基吡啶四氟硼酸盐,所述烷基优选为环烷基。
优选的,步骤(1)中所述的光催化剂为铱配合物光催化剂,包括Ir[dF(CF3)ppy]2(bpy)PF6、Ir[dF(CF3)ppy]2(dtbbpy)PF6、Ir(4-Fppy)2(bpy)PF6和Ir(ppy)2(dtbbpy)PF6,更优选为Ir[dF(CF3)ppy]2(bpy)PF6:
优选的,步骤(1)中所述的可见光为蓝光。
优选的,步骤(2)中所述的二氧化硫供体包括焦亚硫酸钾和焦亚硫酸钠,更优选为焦亚硫酸钾。
优选的,步骤(2)中所述的烯醇硅醚中的(Het)Ar为含有吸电子基团或供电子基团的苯基或杂环取代基,所述吸电子基团包括氟、氯、溴和三氟甲基取代基团,所述供电子基团包括烷基和甲氧基基团,所述杂环为富电子或缺电子杂环。
优选的,本发明中所述的N-烷基吡啶盐、二氧化硫供体、烯醇硅醚、光催化剂的摩尔比为1:(1.25-2.25):(2-3.5):(0.01-0.02),更优选为1:2:3:0.015。
优选的,本发明中所用的溶剂为有机溶剂,包括二甲亚砜、二甲基甲酰胺和二甲基乙酰胺,更优选为二甲亚砜,更优选为干燥的二甲亚砜。
优选的,本发明中的加料顺序为:加入N-烷基吡啶盐、二氧化硫供体和光催化剂后,在高纯氮气或氩气中置换气,使体系处于无水无氧条件,再加入溶剂和烯醇硅醚,所述溶剂用量为使反应均匀进行的常规用量。
优选的,本发明中反应温度为室温,优选在搅拌条件下进行反应。
优选的,步骤(2)中所述的反应完全的监测方法包括TLC监测,所述反应后处理包括依次进行萃取、干燥、浓缩、柱层析和溶剂去除;所述萃取剂为水和有机溶剂,所述有机溶剂包括乙酸乙酯、乙醚、二氯甲烷和三氯甲烷;所述干燥方式为对有机相进行干燥,干燥剂包括无水硫酸钠;所述浓缩方式包括减压浓缩;所述柱层析分离溶剂包括石油醚与乙酸乙酯的混合液。
本发明提供的二烷基砜类化合物的制备方法,是利用N-烷基吡啶盐、二氧化硫供体和烯醇硅醚,在光催化剂作用下,在可见光照射及室温下光催化的自由基反应,高效构建二烷基砜类化合物。
本发明优选反应式如下所示:
本发明与现有技术相比,其有益效果主要体现在:本发明反应在非常温和简单的条件下,通过简便的操作,以各种简单或复杂烷基取代的N-烷基吡啶盐生成烷基自由基,继而串联二氧化硫得到磺酰基自由基,再进攻烯醇硅醚,从而高效构建了一系列二烷基砜类化合物;该反应所需的磺酰基来源焦亚硫酸钾为廉价易得化工原料,该反应避免了传统磺酰类化合物合成中强酸性磺酸、磺酰氯的使用,可以用于大规模的工业制备,在科研和工业领域具有很好的指导意义和应用前景。
具体实施方式
下面结合具体实施例对本发明提供的一种二烷基砜类化合物的制备方法进行详细的说明,但是不能把它们理解为对本发明保护范围的限定。
实施例1
向干燥的试管中加入0.2mmol的N-环己基-2,4,6-三苯基吡啶四氟硼酸盐、0.4mmol焦亚硫酸钾、0.003mmol(1.5mol%)的铱光敏剂Ir[dF(CF3)ppy]2(bpy)PF6,用塞子塞好反应管后置于高纯氮气中置换气,使得体系处于无水无氧条件后加入2.5mL的干燥二甲亚砜和0.6mmol的1-苯基-1-三异丙基硅氧乙烯,置于可见光反应装置中搅拌至完全反应为止。TCL监测反应完毕后将反应液倒入50mL水中,用20mL乙酸乙酯萃取三次,合并有机相后用无水硫酸钠干燥,减压浓缩,并采用石油醚和乙酸乙酯的混合液作为流动相进行柱层析分离,即可得到相应2-(环己基磺酰基)-1-苯基-1-乙酮(2-(Cyclohexylsulfonyl)-1-phenylethan-1-one)例1。
化合物例1的结构表征:1H NMR(400MHz,Chloroform-d)δ8.03(d,J=7.8Hz,2H),7.65(t,J=7.4Hz,1H),7.53(t,J=7.5Hz,2H),4.57(s,2H),3.31(t,J=12.1Hz,1H),2.23(d,J=12.2Hz,2H),1.95(d,J=13.2Hz,2H),1.75(d,J=12.5Hz,1H),1.67–1.57(m,2H),1.41–1.23(m,3H).13C NMR(101MHz,Chloroform-d)δ189.34,135.86,134.50,129.34,128.90,61.27,56.81,25.01,24.91,24.75.
实施例2
向干燥的试管中加入0.2mmol的N-环己基-2,4,6-三苯基吡啶四氟硼酸盐、0.25mmol焦亚硫酸钾、0.002mmol(1.5mol%)的铱光敏剂Ir[dF(CF3)ppy]2(bpy)PF6,用塞子塞好反应管后置于高纯氩气中置换气,使得体系处于无水无氧条件后加入2.5mL的干燥二甲亚砜和0.4mmol的1-(4-甲基苯基)-1-三异丙基硅氧乙烯,置于可见光反应装置中搅拌至完全反应为止。TCL监测反应完毕后将反应液倒入50mL水中,用20mL乙醚萃取三次,合并有机相后用无水硫酸钠干燥,减压浓缩,并采用石油醚和乙酸乙酯的混合液作为流动相进行柱层析分离,即可得到相应2-(环己基磺酰基)-1-(4-甲基苯基)-1-乙酮(2-(Cyclohexylsulfonyl)-1-(p-tolyl)ethan-1-one)例2。
化合物例2的结构表征:1H NMR(400MHz,Chloroform-d)δ7.90(d,J=7.8Hz,2H),7.29(d,J=7.8Hz,2H),4.52(s,2H),3.28(t,J=12.1Hz,1H),2.42(s,3H),2.21(d,J=12.0Hz,2H),1.92(d,J=12.9Hz,2H),1.72(d,J=12.2Hz,1H),1.59(q,J=10.8Hz,2H),1.39–1.20(m,3H).13C NMR(101MHz,Chloroform-d)δ188.97,145.88,133.58,129.72,129.62,61.34,56.88,25.15,25.03,24.85,21.89.
实施例3
向干燥的试管中加入0.2mmol的N-环己基-2,4,6-三苯基吡啶四氟硼酸盐、0.45mmol焦亚硫酸钾、0.004mmol(1.5mol%)的铱光敏剂Ir[dF(CF3)ppy]2(bpy)PF6,用塞子塞好反应管后置于高纯氮气中置换气,使得体系处于无水无氧条件后加入2.5mL的干燥二甲亚砜和0.7mmol的1-(4-三氟甲基苯基)-1-三异丙基硅氧乙烯,置于可见光反应装置中搅拌至完全反应为止。TCL监测反应完毕后将反应液倒入50mL水中,用20mL乙酸乙酯萃取三次,合并有机相后用无水硫酸钠干燥,减压浓缩,并采用石油醚和乙酸乙酯的混合液作为流动相进行柱层析分离,即可得到相应2-(环己基磺酰基)-1-(4-三氟甲基苯基)-1-乙酮(2-(Cyclohexylsulfonyl)-1-(4-(trifluoromethyl)phenyl)ethan-1-one)例3。
化合物例3的结构表征:1H NMR(400MHz,Chloroform-d)δ8.14(d,J=7.9Hz,2H),7.77(d,J=8.0Hz,2H),4.58(s,2H),3.23(t,J=12.0Hz,1H),2.22(d,J=12.0Hz,2H),1.95(d,J=12.9Hz,2H),1.75(d,J=12.4Hz,1H),1.60(q,J=12.1Hz,2H),1.40–1.22(m,3H).13CNMR(101MHz,Chloroform-d)δ188.78,138.57,135.66(d,JF=33.1Hz),129.92,126.08(q,JF=3.6Hz),123.46(q,JF=274.0Hz),61.78,57.28,25.11,25.05,24.94.
实施例4
向干燥的试管中加入0.2mmol的N-环己基-2,4,6-三苯基吡啶四氟硼酸盐、0.4mmol焦亚硫酸钾、0.003mmol(1.5mol%)的铱光敏剂Ir[dF(CF3)ppy]2(bpy)PF6,用塞子塞好反应管后置于高纯氮气中置换气,使得体系处于无水无氧条件后加入2.5mL的干燥二甲亚砜和0.6mmol的1-(2-噻吩基)-1-三异丙基硅氧乙烯,置于可见光反应装置中搅拌至完全反应为止。TCL监测反应完毕后将反应液倒入50mL水中,用20mL乙酸乙酯萃取三次,合并有机相后用无水硫酸钠干燥,减压浓缩,并采用石油醚和乙酸乙酯的混合液作为流动相进行柱层析分离,即可得到相应2-(环己基磺酰基)-1-(2-噻吩基)-1-乙酮(2-(Cyclohexylsulfonyl)-1-(thiophen-2-yl)ethan-1-one)例4。
化合物例4的结构表征:1H NMR(400MHz,Chloroform-d)δ7.87(d,J=3.0Hz,1H),7.79(d,J=4.7Hz,1H),7.20(t,J=3.6Hz,1H),4.46(s,2H),3.28(t,J=12.1Hz,1H),2.22(d,J=12.2Hz,2H),1.93(d,J=12.9Hz,2H),1.73(d,J=12.2Hz,1H),1.60(q,J=12.2Hz,2H),1.39–1.21(m,3H).13C NMR(101MHz,Chloroform-d)δ181.59,143.46,136.90,135.66,128.99,61.37,58.07,25.16,25.05,24.91.
实施例5
向干燥的试管中加入0.2mmol的N-(4-四氢噻喃基)-2,4,6-三苯基吡啶四氟硼酸盐、0.4mmol焦亚硫酸钾、0.003mmol(1.5mol%)的铱光敏剂Ir[dF(CF3)ppy]2(bpy)PF6,用塞子塞好反应管后置于高纯氮气中置换气,使得体系处于无水无氧条件后加入2.5mL的干燥二甲亚砜和0.6mmol的1-(3-甲氧基苯基)-1-三异丙基硅氧乙烯,置于可见光反应装置中搅拌至完全反应为止。TCL监测反应完毕后将反应液倒入50mL水中,用20mL乙酸乙酯萃取三次,合并有机相后用无水硫酸钠干燥,减压浓缩,并采用石油醚和乙酸乙酯的混合液作为流动相进行柱层析分离,即可得到相应1-(3-甲氧基苯基)-2-((4-四氢噻喃基)磺酰基)-1-乙酮(1-(3-Methoxyphenyl)-2-((tetrahydro-2H-thiopyran-4-yl)sulfonyl)ethan-1-one)例5。
化合物例5的结构表征:1H NMR(400MHz,Chloroform-d)δ7.58(d,J=7.6Hz,1H),7.50(s,1H),7.43(t,J=7.9Hz,1H),7.19(d,J=8.1Hz,1H),4.56(s,2H),3.86(s,3H),3.35(t,J=11.8Hz,1H),2.81–2.70(m,4H),2.53(d,J=12.8Hz,2H),2.00(qd,J=12.4,4.0Hz,2H).13C NMR(101MHz,Chloroform-d)δ189.21,160.15,137.12,130.14,122.33,121.60,113.15,61.01,56.86,55.66,27.51,26.28.
实施例6
向干燥的试管中加入0.2mmol的N-(4-环戊烯基)-2,4,6-三苯基吡啶四氟硼酸盐、0.4mmol焦亚硫酸钾、0.003mmol(1.5mol%)的铱光敏剂Ir[dF(CF3)ppy]2(bpy)PF6,用塞子塞好反应管后置于高纯氮气中置换气,使得体系处于无水无氧条件后加入2.5mL的干燥二甲亚砜和0.6mmol的1-(3-甲氧基苯基)-1-三异丙基硅氧乙烯,置于可见光反应装置中搅拌至完全反应为止。TCL监测反应完毕后将反应液倒入50mL水中,用20mL乙酸乙酯萃取三次,合并有机相后用无水硫酸钠干燥,减压浓缩,并采用石油醚和乙酸乙酯的混合液作为流动相进行柱层析分离,即可得到相应2-(4-环戊烯基磺酰基)-1-(3-甲氧基苯基)-1-乙酮(2-(Cyclopent-3-en-1-ylsulfonyl)-1-(3-methoxyphenyl)ethan-1-one)例6。
化合物例6的结构表征:1H NMR(400MHz,Chloroform-d)δ7.50(d,J=7.6Hz,1H),7.42(s,1H),7.32(t,J=7.9Hz,1H),7.08(d,J=8.2Hz,1H),5.61(s,2H),4.45(s,2H),4.01(p,J=8.0Hz,1H),3.76(s,3H),2.85(dd,J=15.8,6.4Hz,2H),2.72(dd,J=15.6,9.7Hz,2H).13C NMR(101MHz,Chloroform-d)δ188.93,160.12,137.22,130.08,128.39,122.42,121.51,113.20,59.97,58.87,55.64,33.66.
本技术领域中的技术人员应当认识到,以上的实例仅是用来说明本发明,而非用作为对本发明的限定,只要在本发明的实质精神范围内,对以上所述实施例的变化,变型都将落在本发明的权利要求范围内。
Claims (7)
1.一种二烷基砜类化合物的制备方法,其特征在于,包括如下步骤:
(1)在保护气氛下,在可见光照射下,N-烷基吡啶盐类化合物与光催化剂发生单电子转移产生烷基自由基;
(2)上述烷基自由基在二氧化硫供体的作用下得到磺酰基自由基,所述磺酰基自由基进攻烯醇硅醚后发生加成脱硅反应,反应完全后对反应液进行后处理,得到二烷基砜类化合物;
其中,步骤(1)中所述的N-烷基吡啶盐类化合物为N-烷基-2,4,6-三芳基吡啶四氟硼酸盐;
步骤(1)中所述的光催化剂为铱配合物光催化剂,所述铱配合物光催化剂为Ir[dF(CF3)ppy]2(bpy)PF6;
步骤(2)中所述的二氧化硫供体为焦亚硫酸钾或焦亚硫酸钠的至少一种;
步骤(2)中所述的烯醇硅醚中的硅醚取代基为三异丙基硅基、三甲基硅基、三乙基硅基、叔丁基二甲基硅基或叔丁基二苯基硅基中的至少一种;烯醇硅醚中的(Het)Ar为含有或不含有吸电子基团或供电子基团的苯基或杂环取代基,所述吸电子基团为氟、氯、溴或三氟甲基取代基团中的至少一种,所述供电子基团为烷基或甲氧基基团中的至少一种,所述杂环为富电子或缺电子杂环。
2.根据权利要求1所述一种二烷基砜类化合物的制备方法,其特征在于,步骤(1)中所述的N-烷基-2,4,6-三芳基吡啶四氟硼酸盐的烷基为环烷基。
3.根据权利要求1所述一种二烷基砜类化合物的制备方法,其特征在于,所述的N-烷基吡啶盐、二氧化硫供体、烯醇硅醚、光催化剂的摩尔比为1:(1.25-2.25):(2-3.5):(0.01-0.02)。
4.根据权利要求1所述一种二烷基砜类化合物的制备方法,其特征在于,所用的溶剂为有机溶剂。
5.根据权利要求4所述一种二烷基砜类化合物的制备方法,其特征在于,所述有机溶剂为二甲亚砜、二甲基甲酰胺或二甲基乙酰胺中的至少一种。
6.根据权利要求1所述一种二烷基砜类化合物的制备方法,其特征在于,所述的保护气氛为氮气或氩气中的至少一种,反应温度为室温。
7.根据权利要求1所述一种二烷基砜类化合物的制备方法,其特征在于,所述的可见光为蓝光。
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