CN107011294B - 二糠基醚的一种合成方法 - Google Patents

二糠基醚的一种合成方法 Download PDF

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CN107011294B
CN107011294B CN201710340935.8A CN201710340935A CN107011294B CN 107011294 B CN107011294 B CN 107011294B CN 201710340935 A CN201710340935 A CN 201710340935A CN 107011294 B CN107011294 B CN 107011294B
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furfuryl
ether
furfuryl ether
synthetic method
molybdate
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CN107011294A (zh
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杨绍祥
田红玉
刘永国
孙宝国
郝颜峰
王嘉琳
王皓
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Beijing Technology and Business University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Abstract

本发明公开了二糠基醚的一种合成方法，具体是以糠醇为原料，在硫钼酸盐催化下选择性脱水，合成二糠基醚。本发明与现有的方法相比，合成步骤少、环境污染小。

Description

二糠基醚的一种合成方法
技术领域
本发明涉及二糠基醚的一种合成方法，具体是以糠醇为原料，在硫钼酸盐催化下选择性脱水，合成二糠基醚。
背景技术
二糠基醚(2，2′-Difurfuryl ether)是一种重要的香料化合物，具有咖啡、坚果、蘑菇香味，已经被美国食品香料和萃取物制造者协会(FEMA)和食品添加剂联合专家委员会(JECFA)列为可食用香料，FEMA编号为3337，JECFA编号为1522，同时也进入我国食品添加剂使用标准(GB2760-2014)允许使用的食品香料名单中，编号为S1108。
二糠基醚的化学合成方法主要是以糠醇为起始原料，与三溴化磷通过溴代反应得2-溴乙基呋喃、然后在氢氧化钾或氢氧化钠作用下与糠醇通过醚化反应得到二糠基醚。
该合成路线使用了三溴化磷、强碱等对环境具有较大污染的化学试剂。为了使反应路线更加简捷，反应条件更加绿色化，广大的研究人员将研究的重点转移到采用新型的催化剂进行催化反应，使二糠基醚的合成更加符合当今社会发展对环境友好化的要求。
发明内容
本发明目的是克服上述二糠基醚合成方法的缺点，提供一种工艺步骤少、无环境污染的新合成方法。
为实现上述的目的，本发明采用的技术方案是，以糠醇为原料，在硫钼酸盐催化下选择性脱水，一步反应合成二糠基醚，合成路线如下式所示。
本发明中所述硫钼酸盐为{[(CH3CH2CH2CH2)4N]2[SMo12O40]}、{[(CH3CH2CH2CH2)4N][HSMo12O40]}、{[(CH3)4N]2[SMo12O40]}、{[(CH3)3C16H33N]2[SMo12O40]}、{[C5H5NC16H33]2[SMo12O40]}。所述反应温度为50℃-150℃。所述催化剂硫钼酸盐用量为10％-0.1％。所述反应时间为5小时-24小时。
本发明与现有的方法相比，工艺步骤少、无环境污染。
具体实施方式
实施例1：
在50mL圆底烧瓶中分别加入0.98g(10mmol)糠醇，催化剂硫钼酸盐{[(CH3CH2CH2CH2)4N]2[SMo12O40]}0.23g(0.1mmol)，10mL甲苯，混匀后100℃加热9小时，乙醚萃取。旋蒸，除去溶剂，柱层析分离提纯，得0.50g无色液体，产率30.0％。
本专业领域的普通技术人员可以根据本发明方法，参照上述实施例，对催化剂硫钼酸盐的选择及其用量、反应温度、反应时间在本发明的范围内任意选取，给出一种或多种具体的合成方法，均在本发明的保护范围内。
产物经过核磁氢谱、核磁碳谱、质谱表征。
1H NMR(300MHz，CDCl3)δ：4.48(4H，s，-CH2-O)，6.34(4H，s，-CH＝CH-)，7.42(2H，d，J＝ 0.9Hz，C＝CH-O).
13C NMR(75MHz，CDCl3)δ：63.38，109.54，110.19，142.81，151.30.
MS，m/z：178.1[M]+，147.0，119.0，91.1，53.1。

Claims (1)

1.一种二糠基醚的合成方法，其特征是：以糠醇为原料，在硫钼酸盐{[(CH3CH2CH2CH2)4N]2[SMo12O40] } 催化下选择性脱水，合成二糠基醚。
CN201710340935.8A 2017-05-16 2017-05-16 二糠基醚的一种合成方法 Active CN107011294B (zh)

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CN112221465B (zh) * 2020-09-10 2021-07-16 昆明理工大学 一种无废生物精炼制备多孔生物炭的方法及应用
CN115322166B (zh) * 2021-05-10 2024-01-30 中国科学院大连化学物理研究所 一种合成二糠基醚的方法

Citations (1)

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Publication number Priority date Publication date Assignee Title
CN106366055A (zh) * 2016-08-26 2017-02-01 安徽金邦医药化工有限公司 一种制备四氢糠醇乙醚的工艺

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106366055A (zh) * 2016-08-26 2017-02-01 安徽金邦医药化工有限公司 一种制备四氢糠醇乙醚的工艺

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Crystal structure of bis(tetra-n-butylammonium)dodecamolybdosulfate(VI)-(2-), [NBun4]2[SMo12O40];Toshitaka Hori等;《J. Chem. Soc.,Dalton Trans.》;19960101;第2083页摘要
Polymerization of furfuryl alcohol with trifluoroacetic acid, 2 The formation of difurfuryl ether;Regino Gonzalez等;《Makromol. Chem., Rapid Commun.》;19921231;第13卷;第517页第4段，第518页第1段
Selective catalytic dehydration of furfuryl alcohol to 2,2′-difurfuryl ether using a polyoxometalate catalyst;ShaoxiangYang等;《Scientific Reports 》;20171011;第7卷;第12954，1至6页

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