含长叶烯结构硫氰酸烯丙酯和异硫氰酸烯丙酯的合成

Synthesis of allyl thiocyanate and allyl isothiocyanate containing the structure of longifolene

研究ω-氯甲基长叶烯与不同硫氰酸盐的取代反应,选择性合成了含长叶烯结构的ω-硫氰甲基长叶烯和ω-异硫氰甲基长叶烯,采用FTIR、UPLC-QTOF/MS、^(1)H NMR和^(13)C NMR对产物进行结构表征。结果表明,硫氰酸盐类型和反应体系对产物的选择性有较大影响。在60℃加热搅拌条件下,硬酸型阳离子K^(+)、Na^(+)和NH_(4)^(+)的硫氰酸盐,在以水或正己烷为溶剂的反应体系中,主要产物是ω-硫氰甲基长叶烯,选择性大于75.0%,而在室温无溶剂研磨反应体系中主要产物没有生成;软酸型阳离子Ag^(+)和交界酸型阳离子Pb^(2+)的硫氰酸盐,在以水为溶剂和室温无溶剂研磨两种反应体系中,主要产物为ω-硫氰甲基长叶烯,选择性均大于80.0%,而在以正己烷为溶剂反应体系中,主要产物为ω-异硫氰甲基长叶烯,选择性大于70.0%。

ω-thiocyanatomethyl longifolene(Ⅱ)and ω-isothiocyanatomethyl longifolene(Ⅲ)were selectively synthesized by substitution reaction between ω-chloromethyl longifolene(Ⅰ)and a series of thiocyanates.The products were characterized by FTIR,UPLC-QTOF/MS,^(1)H NMR and ^(13)C NMR.The results showed that the types of thiocyanates and reaction systems had remarkable effects on the selectivity of compounds Ⅱ and Ⅲ.Compound Ⅱ as the main product was obtained from compound Ⅰ and thiocyanates containing hard-acidic cations such as potassium, sodium and ammonium in the reaction system with the use of water or n-hexane as solvent at 60 ℃.The selectivity of compound Ⅱ was higher than 75%,but the reaction mentioned above was unable to work in a solvent-free reaction system at room temperature.Moreover, it was shown that compound Ⅱ could be achieved from soft-acidic silver thiocyanate and borderline acidic lead thiocyanate in a reaction system with water as solvent at 60 ℃ and a solvent-free grinding reaction system at room temperature, respectively.The selectivity of compound Ⅱ in these two reaction systems were both over 80.0%,whereas the selectivity of the compound Ⅲ in a reaction system with the use of n-hexane as solvent was higher than 70.0%.