阅读说明：本技术 一种3-烯醇的苯硫基环醚化方法 (Method for etherifying thiophenyl ring of 3-enol ) 是由 刘永国 王皓 田红玉 梁森 杨绍祥 邱果 白宇辰 孙宝国 于 2021-09-27 设计创作，主要内容包括：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：该方法步骤：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3-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。(The invention relates to a phenylthio-substituted cyclic etherification product with a structural formula shown as follows:)

1. A method for etherifying thiophenyl ring of 3-enol is characterized in that methyl phenyl sulfoxide and oxalyl chloride are used as initial raw materials, and then react with 3-enol under the catalysis of (+/-) -camphorsulfonic acid to obtain a thiophenyl ring etherified product containing 1, 2-oxysulfide structural unit, and the reaction formula is as follows,

Detailed Description

(1) Preparation of 2- ((phenylthio) methyl) tetrahydrofuran

10mL of anhydrous acetonitrile and methyl phenyl sulfoxide (15mmol, 1.8mL) were added to a three-necked flask, and when the temperature of the system was lowered to 0 ℃ or below, a solution of oxalyl chloride (3.75mmol, 0.33mL) in anhydrous acetonitrile (10mL) was slowly added through a 25mL constant pressure dropping funnel, and after completion of the addition, the mixture was stirred at 0 ℃ for 10 min. Then, the mixture was transferred to an oil bath, and when it was heated to 100 ℃ 4-penten-1-ol (5mmol, 0.43g) and 0.12g (. + -.) -camphorsulfonic acid (0.5mmol) were added in this order, followed by refluxing for 8 hours. TLC tracking, after enol reaction is finished, removing acetonitrile by rotary evaporation, adding dichloromethane, transferring to a separating funnel, washing twice with saturated sodium bicarbonate solution and saturated sodium chloride solution respectively, drying with anhydrous sodium sulfate, filtering and rotary evaporation. The crude product thus obtained was subjected to column chromatography (200-300 mesh silica gel; petroleum ether: ethyl acetate: 60: 1) to give 0.62g of the phenylthio cycloetherified product of 4-penten-1-ol, 2- ((phenylthio) methyl) tetrahydrofuran, in 64% yield.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 of ABX)，3.75(td，J＝9.0，6.0Hz，1H，H′-C5，B part of ABX)，3.15(dd，J＝13.0，5.8 Hz，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) Preparation of cis-2-pentyl-3- (phenylthio) tetrahydro-2H-pyran

10mL of anhydrous acetonitrile and methyl phenyl sulfoxide (15mmol, 1.8mL) were added to a three-necked flask, and when the temperature of the system was lowered to 0 ℃ or below, a solution of oxalyl chloride (3.75mmol, 0.33mL) in anhydrous acetonitrile (10mL) was slowly added through a 25mL constant pressure dropping funnel, and after completion of the addition, the mixture was stirred at 0 ℃ for 10 min. Then moved to an oil bath and heated to 100 ℃ and then cis-4-decen-1-ol (5mmol, 0.87g) and 0.12g (. + -.) -camphorsulfonic acid (0.5mmol) were added in that order and reflux continued for 8 h. TLC tracking, after enol reaction is finished, removing acetonitrile by rotary evaporation, adding dichloromethane, transferring to a separating funnel, washing twice with saturated sodium bicarbonate solution and saturated sodium chloride solution respectively, drying with anhydrous sodium sulfate, filtering and rotary evaporation. The crude product was separated by column chromatography (200-mesh 300-mesh silica gel; petroleum ether: ethyl acetate: 250: 1) to give 0.83g of cis-2-pentyl-3- (phenylthio) tetrahydro-2H-pyran, a phenylthio cycloetherification product of cis-4-decen-1-ol, in 63% yield.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 of ABX)，3.81-3.70(m，1H，H′-C6，B part of ABX)，3.18(dt，J＝8.6，4.4Hz，1 H，H-C3)，2.05-1.20(m，12H，H-C4，H-C5，H-C1-pentyl，H-C2-pentyl，H-C3-pentyl and 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。