CN113754613B - 一种4-烯醇的苯硫基环醚化方法 - Google Patents
一种4-烯醇的苯硫基环醚化方法 Download PDFInfo
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- CN113754613B CN113754613B CN202111134252.XA CN202111134252A CN113754613B CN 113754613 B CN113754613 B CN 113754613B CN 202111134252 A CN202111134252 A CN 202111134252A CN 113754613 B CN113754613 B CN 113754613B
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- C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
- C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
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- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
本发明涉及结构式如下所示的含苯硫基取代的环醚化产物:
Description
本发明涉及一种4-烯醇的苯硫基环醚化方法。
鉴于含硫香料独特的香气特性,研究开发新型的多官能团含硫香料分子成为近些年的研究热点之一。大量的研究表明,含1,2-氧硫结构单元的化合物普遍具有肉香、焦香味,如重要的肉香味化合物2-甲基-3-呋喃硫醇、2-甲基-3-四氢呋喃硫醇、3-巯基-2-丁酮、3-巯基-2-戊酮,重要的烤香类化合物糠硫醇等。同时,1,2-氧硫官能团除了在多官能团香料中广泛存在外,还是很多生物活性化合物的结构单元和有机合成中非常有用的合成子,因此研究开发1,2-氧硫官能团化合物的新方法具有重要的意义。
在众多的1,2-氧硫官能团化合物合成方法中,烯烃与亲电的含硫试剂作用经过氧硫基化反应是最为直接的方法。文献报道的亲电的含硫试剂主要包括次磺酰氯、二硫醚、四氟硼酸二甲基甲硫基硫鎓盐、N-烃硫基酰亚胺、次磺酸酯、磺酰肼和二甲亚砜。其中苯硫基化试剂主要有二苯基二硫醚、苯硫基氯和硫代苯磺酸苯酯。本发明方法中,开发了一种以甲基苯基亚砜和草酰氯组合试剂作为苯硫基化试剂的新的苯硫基化方法。以不饱和醇为原料,通过“一锅法”制备含有1,2-氧硫官能团的苯硫基环醚产物。
本发明的目的是提供一种新的4-烯醇的苯硫基环醚化方法。其特征是以甲基苯基亚砜和草酰氯为起始原料,然后在(±)-樟脑磺酸的催化下与4-烯醇反应,得到含有1,2-氧硫结构单元的苯硫基环醚化产物。本发明的制备方法具有原料易得、操作简便的优点。反应式如下:
本发明涉及结构式如下所示的不饱和醇的苯硫基环醚化产物:
其主要过程是:在0℃条件下,将草酰氯的乙腈溶液滴加到甲基苯基亚砜的乙腈溶液中,搅拌10min后,转移至油浴锅,加热到100℃时,将4-烯醇和(±)-樟脑磺酸加入,回流8小时,得到具有1,2-氧硫结构单元的苯硫基环醚化产物,产率60%以上。
本发明方法中制备的苯硫基环醚化产物结构通过核磁共振进行了确认。分析结果附在实施例后。
具体实施方式
(1)2-((苯硫基)甲基)四氢呋喃的制备
向三口烧瓶中加入10mL无水乙腈和甲基苯基亚砜(15mmol,1.8mL),待体系温度降至0℃以下,通过25mL的恒压滴液漏斗缓慢加入草酰氯(3.75mmol,0.33mL)的无水乙腈(10mL)溶液,滴加完毕后,在0℃下搅拌10min。然后移至油浴锅,加热至100℃时,依次加入4-戊烯-1-醇(5mmol,0.43g)和0.12g(±)-樟脑磺酸(0.5mmol),继续回流8h。TLC跟踪,烯醇反应完毕后,旋蒸除去乙腈,加入二氯甲烷,转移至分液漏斗中,分别用饱和碳酸氢钠溶液和饱和氯化钠溶液洗涤两次,无水硫酸钠干燥,过滤,旋蒸。得到的粗产物经过柱层析分离(200-300目硅胶;石油醚∶乙酸乙酯=60∶1),得到4-戊烯-1-醇的苯硫基环醚化产物2-((苯硫基)甲基)四氢呋喃0.62g,产率为64%。1H NMR(300MHz,CDCl3):δ=7.37(dd,J=7.2,1.2Hz,2H,H-o-phenyl),7.26(td,J=7.2,1.2Hz,2H,H-m-phenyl),7.16(tt,J=7.2,1.2Hz,1H,H-p-phenyl),4.05(quin.,J=6.0Hz,1H,H-C2),3.90(dt,J=9.0,6.0Hz,1H,H-C5,A part ofABX),3.75(td,J=9.0,6.0Hz,1H,H′-C5,B part ofABX),3.15(dd,J=13.0,5.8Hz,1H,H-CH2SPh),2.97(dd,J=13.0,6.8Hz,1H,H′-CH2SPh),2.14-1.98(m,1H,H-C3),1.96-1.78(m,2H,H-C4),1.71-1.62(m,1H,H′-C3)。13C NMR(75MHz,CDCl3):δ=136.3,129.1,128.8,125.9,77.5,68.2,38.8,30.8,25.7。
(2)顺式-2-戊基-3-(苯硫基)四氢-2H-吡喃的制备
向三口烧瓶中加入10mL无水乙腈和甲基苯基亚砜(15mmol,1.8mL),待体系温度降至0℃以下,通过25mL的恒压滴液漏斗缓慢加入草酰氯(3.75mmol,0.33mL)的无水乙腈(10mL)溶液,滴加完毕后,在0℃下搅拌10min。然后移至油浴锅,加热至100℃时,依次加入顺式-4-癸烯-1-醇(5mmol,0.87g)和0.12g(±)-樟脑磺酸(0.5mmol),继续回流8h。TLC跟踪,烯醇反应完毕后,旋蒸除去乙腈,加入二氯甲烷,转移至分液漏斗中,分别用饱和碳酸氢钠溶液和饱和氯化钠溶液洗涤两次,无水硫酸钠干燥,过滤,旋蒸。得到的粗产物经过柱层析分离(200-300目硅胶;石油醚∶乙酸乙酯=250∶1),得到顺式-4-癸烯-1-醇的苯硫基环醚化产物顺式-2-戊基-3-(苯硫基)四氢-2H-吡喃0.83g,产率为63%。1H NMR(300MHz,CDCl3):δ=7.41(dd,J=7.2,1.5Hz,2H,H-o-phenyl),7.26(td,J=7.2,1.5Hz,2H,H-m-phenyl),7.18(tt,J=7.2,1.5Hz,1H,H-p-phenyl),4.06-4.00(m,1H,H-C2),3.94-3.88(m,1H,H-C6,A part ofABX),3.81-3.70(m,1H,H′-C6,B part ofABX),3.18(dt,J=8.6,4.4Hz,1H,H-C3),2.05-1.20(m,12H,H-C4,H-C5,H-C1-pentyl,H-C2-pentyl,H-C3-pentyland H-C4-pentyl),0.87(t,J=6.7Hz,3H,CH3)。13C NMR(75MHz,CDCl3):δ=136.1,131.1,128.7,126.3,80.7,68.7,53.2,31.7,31.1,28.3,26.9,26.2,22.5,14.0。
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