CN108440457A - 一种2-甲基四氢呋喃-3-硫醇的制备方法及其应用 - Google Patents
一种2-甲基四氢呋喃-3-硫醇的制备方法及其应用 Download PDFInfo
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- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims abstract description 9
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- BGCWDXXJMUHZHE-UHFFFAOYSA-N 5-methyl-2,3-dihydrofuran Chemical class CC1=CCCO1 BGCWDXXJMUHZHE-UHFFFAOYSA-N 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 15
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- 238000000034 method Methods 0.000 claims description 10
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 3
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- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 abstract 4
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- DBPHPBLAKVZXOY-UHFFFAOYSA-N Tetrahydro-2-methyl-3-furanthiol Chemical compound CC1OCCC1S DBPHPBLAKVZXOY-UHFFFAOYSA-N 0.000 description 1
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- GRTOGORTSDXSFK-XJTZBENFSA-N ajmalicine Chemical compound C1=CC=C2C(CCN3C[C@@H]4[C@H](C)OC=C([C@H]4C[C@H]33)C(=O)OC)=C3NC2=C1 GRTOGORTSDXSFK-XJTZBENFSA-N 0.000 description 1
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Classifications
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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
- C07D307/04—Heterocyclic compounds containing five-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
- C07D307/18—Heterocyclic compounds containing five-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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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/20—Synthetic spices, flavouring agents or condiments
- A23L27/26—Meat flavours
-
- 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
- C07D307/04—Heterocyclic compounds containing five-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
- C07D307/06—Heterocyclic compounds containing five-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 only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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- Health & Medical Sciences (AREA)
- Nutrition Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Furan Compounds (AREA)
Abstract
本发明公开了一种2‑甲基四氢呋喃‑3‑硫醇的制备方法，以5‑羟基‑2‑戊酮为原料通过散布反应制得2‑甲基四氢呋喃‑3‑硫醇。本发明的优点是：以5‑羟基‑2‑戊酮(I)和磷酸为原料制备4,5‑二氢‑2‑甲基呋喃(II)产生的异构体少，能够有效减少反应过程中副产物的生成，大大提高产品质量；之后4,5‑二氢‑2‑甲基呋喃(II)再与硫代乙酸反应得到中间体2‑甲基四氢呋喃‑3‑硫醇乙酸酯(III)后制备2‑甲基四氢呋喃‑3‑硫醇，这条路线反应时间短。
Description
技术领域
本发明属有机合成方法学领域，尤其涉及一种2-甲基四氢呋喃-3-硫醇的制备方法及其应用。
背景技术
【背景技术】
2-甲基四氢呋喃-3-硫醇(2-Methyltetrahydrofuran-3-thiol,FEMA号3787)是一种重要的含硫香料，其化学结构如下：
在食用香料中，含硫香料占有非常重要的地位。由于含硫香料香气阈值低、特征性强，用量小，可广泛用于食用香精尤其是肉味香精的调配，对提高香精的质量和档次具有重要作用，是非常重要的一类食用香料，产品售价往往在每千克几千元至几万元，具有明显的经济效益。含硫香料往往是食品的微量香成分，随着分析技术的不断发展，越来越多的含硫化合物在食品中被检测出来，由于含硫香料具有用量小、售价高、香气特征性强的特点，日益受到人们的重视。
硫醇的制备方法很多，常用的方法为用醇或卤代烷与硫脲反应生成S-烷基代异硫酸盐，然后和碱作用制得。专利申请CN103694094报道了物质II的合成方法，需要在一定压力下，使用钯碳/氢气进行反应得到产品。
这个方法具有一定的危险性，并且成本较高。
也有报道在手套箱中将炔醇与氘代试剂进行混合，之后60-120℃加热反应，通过核磁鉴定产品。
这个方法会产生较多的异构体，为后续反应带来影响。
也有公开了2-甲基四氢呋喃-3-硫醇(IV)的主要制备方法，制备路线如下：
这个方法IV的制备方法路线长，使用硼氢化钠危险系数较高的化学品，成本高。
这些方法存在原料难得、步骤较多及成本较高等缺陷。显然，这样的合成思路不符合现代绿色化学关于原子经济学的理念。针对现存的工艺缺陷，开发出工艺简洁、经济环保且质量上乘的制备技术，尤其是寻求能够适应工业化生产的工艺技术，对该产物的经济和社会效益提高有着重要的现实意义。
发明内容
有鉴于此，本发明的目的是为2-甲基四氢呋喃-3-硫醇的制备提供一种新的合成方法，反应选择性好，合成路线安全环保。为达到上述目的，本发明创造的技术方案是这样实现的：
一种2-甲基四氢呋喃-3-硫醇的制备方法，以5-羟基-2-戊酮为原料，按如下反应路线制备而成：
具体反应步骤如下：
(一)4,5-二氢-2-甲基呋喃(II)的制备
在5-羟基-2-戊酮(I)中投入磷酸，油浴200℃中加热，常压蒸馏，收集馏出温度70-90℃的馏分得到4,5-二氢-2-甲基呋喃(II)；
(二)2-甲基四氢呋喃-3-硫醇乙酸酯(III)的制备
在4,5-二氢-2-甲基呋喃(II)中投入硫代乙酸，滴加六氢吡啶，室温搅拌，TLC监测，反应完后，用酸调pH至中性，加入异丙醚搅拌，用饱和食盐水洗涤一次，低于30℃除去异丙醚溶剂制得2-甲基四氢呋喃-3-硫醇乙酸酯(III)；
(三)2-甲基四氢呋喃-3-硫醇(IV)的制备
在乙酸溶液中，投入2-甲基四氢呋喃-3-硫醇乙酸酯(III)，常温搅拌，TLC监测，反应完后分液去除水相，得到2-甲基四氢呋喃-3-硫醇粗品，减压蒸馏，在1.4KPa下，收集内温88-115℃的馏分得到2-甲基四氢呋喃-3-硫醇(IV)。
优选的，步骤(一)中所述磷酸浓度为0.2-0.6mol/L。
优选的，步骤(一)中所述5-羟基-2-戊酮(I)和磷酸的摩尔比为：326-327:1。
优选的，步骤(二)中所述4,5-二氢-2-甲基呋喃(II)、硫代乙酸和六氢吡啶的摩尔比为1:1-2：0.1。
优选的，步骤(二)中所述的酸为盐酸、硫酸或醋酸中的一种。
优选的，步骤(二)中所述异丙醚加入的质量是4,5-二氢-2-甲基呋喃(II)质量的5倍。
优选的，步骤(三)中所述乙酸溶液与2-甲基四氢呋喃-3-硫醇乙酸酯(IV)的体积质量比为5ml：1g。
本发明的方法制得的2-甲基四氢呋喃-3-硫醇用于高档食用香料。
TLC监测是进行化学反应时，利用薄层色谱观察原料斑点的逐步消失来判断反应是否完成。
本发明的优点是：以5-羟基-2-戊酮(I)和磷酸为原料制备4,5-二氢-2-甲基呋喃(II)产生的异构体少，能够有效减少反应过程中副产物的生成，大大提高产品质量；之后4,5-二氢-2-甲基呋喃(II)再与硫代乙酸反应得到中间体2-甲基四氢呋喃-3-硫醇乙酸酯(III)后制备2-甲基四氢呋喃-3-硫醇，这条路线反应时间短。简化了生产工艺、大大减轻了工人的劳动强度，收率高，避开使用高危险、高毒原料，反应选择性好，合成路线安全环保，物料用量大幅较少，同时降低废水量，符合绿色环保生产理念。优化反应体系，可以实现异丙醚溶剂的回收。
附图说明
构成本发明创造的一部分的附图用来提供对本发明创造的进一步理解，本发明创造的示意性实施例及其说明用于解释本发明创造，并不构成本发明创造的不当限定。在附图中：
图1是4,5-二氢-2-甲基呋喃的1H NMR谱图。
图2是2-甲基四氢呋喃-3-硫醇的1H NMR谱图。
具体实施方式
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。
实施例中使用的试剂均是由试剂公司购买的,冰乙酸为试剂公司买的纯度99％的乙酸溶液。
实施例1
在500ml的四口烧瓶中投入5-羟基-2-戊酮(I)100g(979.1mmol)，投入0.3mol/L磷酸10ml，油浴200℃中加热，常压蒸馏，收集馏出温度70-90℃的馏分得到4,5-二氢-2-甲基呋喃(II)，产率95％。如图1谱图为制得的4,5-二氢-2-甲基呋喃的1H NMR谱图。
实施例2
在500ml的四口烧瓶中投入5-羟基-2-戊酮(I)100g(979.1mmol)，投入0.6mol/L磷酸5ml，油浴200℃中加热，常压蒸馏，收集馏出温度70-90℃的馏分得到4,5-二氢-2-甲基呋喃(II)，产率92％。
实施例3
在500ml的四口烧瓶中投入5-羟基-2-戊酮(I)100g(979.1mmol)，投入0.2mol/L磷酸15ml，油浴200℃中加热，常压蒸馏，收集馏出温度70-90℃的馏分得到4,5-二氢-2-甲基呋喃(II)，产率90％。
实施例4
在250ml的三口烧瓶中投入实施例1制得的4,5-二氢-2-甲基呋喃(II)30g(356.6mmol)，投入硫代乙酸29.86g(392.3mmol)，滴加六氢吡啶3g(35.6mmol)，室温搅拌，反应1.5小时后采用TLC监测,反应完后，用乙酸调pH至中性，加入异丙醚30ml搅拌，用饱和食盐水洗涤一次，低于30℃除去溶剂制得化合物2-甲基四氢呋喃-3-硫醇乙酸酯(III)，产率86％。
实施例5
在250ml的三口烧瓶中投入实施例1制得的4,5-二氢-2-甲基呋喃(II)30g(356.6mmol)，投入硫代乙酸29.86g(392.3mmol)，滴加六氢吡啶3g(35.6mmol)，室温搅拌，反应1小时后采用TLC监测,反应完后，用1N HCl调pH至中性，加入异丙醚30ml搅拌，用饱和食盐水洗涤一次，低于30℃除去溶剂制得化合物2-甲基四氢呋喃-3-硫醇乙酸酯(III)，产率88％。
实施例6
在250ml的三口烧瓶中投入4,5-二氢-2-甲基呋喃(II)30g(356.6mmol)，投入硫代乙酸59.72g(784.6mmol)，滴加六氢吡啶3g(35.6mmol)，室温搅拌，反应2小时后采用TLC监测,反应完后，用硫酸调pH至中性，加入异丙醚30ml搅拌，用饱和食盐水洗涤一次，低于30℃除去溶剂制得化合物2-甲基四氢呋喃-3-硫醇乙酸酯(III)，产率79％。
实施例7
在100ml的三口烧瓶中投入50ml冰乙酸，滴加实施例5得到的2-甲基四氢呋喃-3-硫醇乙酸酯(III)10g(62.41mmol)，室温搅拌，反应30分钟后采用TLC监,。反应完后分液去除水相，得到2-甲基四氢呋喃-3-硫醇粗品，减压蒸馏，在1.4KPa下，收集内温88-115℃的馏分得到化合物2-甲基四氢呋喃-3-硫醇(IV)，产率87％。图2为制得的2-甲基四氢呋喃-3-硫醇的1H NMR谱图。
以上所述仅为本发明创造的较佳实施例而已，并不用以限制本发明创造，凡在本发明创造的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明创造的保护范围之内。
Claims (8)
1.一种2-甲基四氢呋喃-3-硫醇的制备方法，其特征在于，以5-羟基-2-戊酮为原料，按如下反应路线制备而成：
具体反应步骤如下：
(一)4,5-二氢-2-甲基呋喃(II)的制备
在5-羟基-2-戊酮(I)中投入磷酸，油浴200℃中加热，常压蒸馏，收集馏出温度70-90℃的馏分得到4,5-二氢-2-甲基呋喃(II)；
(二)2-甲基四氢呋喃-3-硫醇乙酸酯(III)的制备
在4,5-二氢-2-甲基呋喃(II)中投入硫代乙酸，滴加六氢吡啶，室温搅拌，TLC监测，反应完后，用酸调pH至中性，入异丙醚搅拌，用饱和食盐水洗涤一次，低于30℃除去异丙醚溶剂制得2-甲基四氢呋喃-3-硫醇乙酸酯(III)；
(三)2-甲基四氢呋喃-3-硫醇(IV)的制备
在乙酸溶液中，投入2-甲基四氢呋喃-3-硫醇乙酸酯(IV)，常温搅拌，TLC监测，反应完后分液去除水相，得到2-甲基四氢呋喃-3-硫醇粗品，减压蒸馏，在1.4KPa下，收集内温88-115℃的馏分得到2-甲基四氢呋喃-3-硫醇(IV)。
2.根据权利要求1所述一种2-甲基四氢呋喃-3-硫醇的制备方法，其特征在于，步骤(一)中所述磷酸浓度为0.2-0.6mol/L。
3.根据权利要求1所述一种2-甲基四氢呋喃-3-硫醇的制备方法，其特征在于，步骤(一)中所述5-羟基-2-戊酮(I)和磷酸的摩尔比为：326-327:1。
4.根据权利要求1所述一种2-甲基四氢呋喃-3-硫醇的制备方法，其特征在于，步骤(二)中的4,5-二氢-2-甲基呋喃(II)、硫代乙酸和六氢吡啶的摩尔比为1:1-2：0.1。
5.根据权利要求1所述一种2-甲基四氢呋喃-3-硫醇的制备方法，其特征在于，步骤(二)中所述的酸为盐酸、硫酸或醋酸中的一种。
6.根据权利要求1所述一种2-甲基四氢呋喃-3-硫醇的制备方法，其特征在于，步骤(二)中所述异丙醚加入的质量是4,5-二氢-2-甲基呋喃(II)质量的5倍。
7.根据权利要求1所述一种2-甲基四氢呋喃-3-硫醇的制备方法，其特征在于，步骤(三)中所述乙酸溶液与2-甲基四氢呋喃-3-硫醇乙酸酯(IV)的体积质量比为5ml：1g。
8.权利要求1-7任一权利要求的方法制得的2-甲基四氢呋喃-3-硫醇用于高档食用香料。
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