CN1069642C - 一种2－甲基－3－甲硫基呋喃的制备方法 - Google Patents
一种2－甲基－3－甲硫基呋喃的制备方法 Download PDFInfo
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- CN1069642C CN1069642C CN96106592A CN96106592A CN1069642C CN 1069642 C CN1069642 C CN 1069642C CN 96106592 A CN96106592 A CN 96106592A CN 96106592 A CN96106592 A CN 96106592A CN 1069642 C CN1069642 C CN 1069642C
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- thiomethylfuran
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OQVAOEIMSKZGAL-UHFFFAOYSA-N 2-methyl-3-methylsulfanylfuran Chemical compound CSC=1C=COC=1C OQVAOEIMSKZGAL-UHFFFAOYSA-N 0.000 title claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- RUYNUXHHUVUINQ-UHFFFAOYSA-N 2-Methyl-3-furanthiol Chemical compound CC=1OC=CC=1S RUYNUXHHUVUINQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 12
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 6
- 238000010992 reflux Methods 0.000 abstract description 5
- 239000000796 flavoring agent Substances 0.000 abstract description 4
- 235000013599 spices Nutrition 0.000 abstract description 4
- 235000009508 confectionery Nutrition 0.000 abstract description 3
- 235000019634 flavors Nutrition 0.000 abstract description 3
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- TUBOBUVDNZENEO-UHFFFAOYSA-N [Na].CC=1OC=CC1S Chemical compound [Na].CC=1OC=CC1S TUBOBUVDNZENEO-UHFFFAOYSA-N 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 235000013882 gravy Nutrition 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 235000013372 meat Nutrition 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- -1 organic bases sodium methylate Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
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Abstract
本发明提供一种2-甲基-3-甲硫基呋喃的制备方法。该方法步骤：在常压-10℃至回流温度下使2-甲基-3-呋喃硫醇在氢氧化钠水溶液中与硫酸二甲酯反应；得到具有肉香、甜的、肉汁谷物样香味的2-甲基-3-甲硫基呋喃。该香料可用于食用香精，尤其是调味香精的调配。
Description
本发明涉及一种2-甲基-3-甲硫基呋喃的制备方法，该化合物具有肉香、甜的、肉汁谷物样香味，可用于各种食用香精配方中。
2-甲基-3-甲硫基呋喃天然发现于煮牛肉香成分中，是一种很有发展前途的新型食用香料，是调配各种食用香精、尤其是各种调味香精不可多得的关键性香料，
现有的以2-甲基-3-呋喃硫醇为原料制备2-甲基-3-甲硫基呋喃的方法(美国专利USP4031256)可用如下反应方程式表示：
其主要过程是：首先在用无水甲醇做溶剂、氮气保护下使2-甲基-3-呋喃硫醇与甲醇钠反应，生成2-甲基-3-呋喃硫醇钠；然后，加入碘甲烷的无水甲醇溶液使之与2-甲基-3-呋喃硫醇钠反应，生成2-甲基-3-甲硫基呋喃。制备过程主要经历以下几个步骤：
上述方法存在的主要问题：一是反应不完全，产物中含有未反应的2-甲基-3-呋喃硫醇；二是反应在甲醇溶液中进行，使用强有机碱甲醇钠和价格昂贵的碘甲烷，使成本升高。
本发明的目的是提供一种改进的2-甲基-3-甲硫基呋喃的制备方法，以解决上述方法存在的问题。
本发明的制备方法可以使2-甲基-3-呋喃硫醇全部反应，
本发明涉及式(Ⅰ)的2-甲基-3-甲硫基呋喃的制备方法：
(Ⅰ)2-甲基-3-甲硫基呋喃其特征是以2-甲基-3-呋喃硫醇和硫酸二甲酯为原料制备2-甲基-3-甲硫基呋喃，反应方程式为：
本发明的制备方法，反应在氢氧化钠或氢氧化钾的水溶液中进行，反应操作非常方便。反应器中加入2-甲基-3-呋喃硫醇和氢氧化钠或氢氧化钾水溶液，保持温度在-10℃至回流温度之间，搅拌或回流下加入硫酸二甲酯，反应完毕后，通过减压蒸馏或水蒸汽蒸馏得到具有肉香、甜的、肉汁谷物样香味的2-甲基-3-甲硫基呋喃。产率达到82％。
本发明的制备方法中所述的无机碱为氢氧化钠和氢氧化钾。当采用减压蒸馏法分离产品时，需要先用溶剂萃取，所述的溶剂为乙醚、二氯甲烷、三氯甲烷和苯。
对用本发明所得到的2-甲基-3-甲硫基呋喃经过色谱-质谱联机分析证实了其结构。质谱分析结果见附图。
本发明的制备方法克服了现有制备方法的缺点，主要优点在于：
1、本发明的制备方法是在反应过程中用硫酸二甲酯作烷基化剂，降低了反应成本，
2、反应是在氢氧化钠或氢氧化钾的水溶液中进行，操作方便，成本低，
本发明的2-甲基-3-甲硫基呋喃的制备方法将通过下面的实施例而得到更具体的描述。本发明中所用原料2-甲基-3-呋喃硫醇是按现有的方法制备而成(文献：美国专利USP3922288)，
实施例1
在带有电动搅拌器、氮气导入管、温度计和滴液漏斗的1000ml四口烧瓶中，加入580ml蒸馏水、30g氢氧化钠、57g2-甲基-3-呋喃硫醇。通入氮气，搅拌使混合物冷却至-10℃，从滴液漏斗中滴加48ml硫酸二甲酯。加完后继续搅拌1小时，然后将反应混合物加热至60℃、再搅拌1小时，冷却、用10％的硫酸调至微酸性，分别用50ml乙醚萃取三次，萃取液用无水硫酸钠干燥。常压蒸除乙醚，减压蒸馏，收集61～63℃/16～18mmHg的馏分，产品为淡黄色透明液体。
实施例2
在带有回流冷凝器、氮气导入管、温度计和滴液漏斗的1000ml四口烧瓶中，加入600ml蒸馏水、42g氢氧化钾、57g2-甲基3-呋喃硫醇。通入氮气，加热至回流，开始滴加47ml硫酸二甲酯，加完后继续回流0.5小时，用10％的硫酸调至微酸性，进行水蒸汽蒸馏，至馏出液中无油状物馏出为止，馏出液冷却后，分出下层淡黄色液体，用无水硫酸钠干燥后即得产品。
实施例3
在带有电动搅拌器、温度计和滴液漏斗的1000ml四口烧瓶中，加入500ml蒸馏水、30g氢氧化钠、47ml硫酸二甲酯，室温下搅拌0.5小时，然后从滴液漏斗中滴加57g2-甲基-3-呋喃硫醇，加完后继续搅拌4小时、用l0％的盐酸调至微酸性，分别用40ml苯萃取三次，萃取液用无水碳酸钾干燥1小时，常压蒸除苯，减压蒸馏，收集61～63℃/16～18mmHg的馏分，产品为淡黄色液体。
Claims (2)
1、一种2-甲基-3-甲硫基呋喃的制备方法，其特征是以2-甲基-3-呋喃硫醇和硫酸二甲酯为原料制备2-甲基-3-甲硫基呋喃，反应方程式为：
反应是在氢氧化钠或氢氧化钾水溶液中进行。
2、根据权利要求1所述的一种2-甲基-3-甲硫基呋喃的制备方法，其特征在于反应是在氢氧化钠的水溶液中进行。
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| CN96106592A CN1069642C (zh) | 1996-06-28 | 1996-06-28 | 一种2－甲基－3－甲硫基呋喃的制备方法 |
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| CN96106592A CN1069642C (zh) | 1996-06-28 | 1996-06-28 | 一种2－甲基－3－甲硫基呋喃的制备方法 |
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| Publication Number | Publication Date |
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| CN1141296A CN1141296A (zh) | 1997-01-29 |
| CN1069642C true CN1069642C (zh) | 2001-08-15 |
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| CN103588737B (zh) * | 2013-11-27 | 2016-05-04 | 北京工商大学 | 一种2-甲基-3-四氢呋喃硫醇乙酸酯顺反异构体的制备方法 |
| CN115340513B (zh) * | 2022-09-26 | 2023-03-10 | 济南悟通生物科技有限公司 | 一种2-甲基-3-甲巯基呋喃的制备方法 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4031256A (en) * | 1975-02-19 | 1977-06-21 | International Flavors & Fragrances Inc. | Foodstuff flavor compositions comprising 3-furyl alkyl sulfides and processes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4031256A (en) * | 1975-02-19 | 1977-06-21 | International Flavors & Fragrances Inc. | Foodstuff flavor compositions comprising 3-furyl alkyl sulfides and processes |
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| CN1141296A (zh) | 1997-01-29 |
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