CN113979906B - 一种简便的制备二甲基二硫醚及氘代二甲基二硫醚的方法 - Google Patents
一种简便的制备二甲基二硫醚及氘代二甲基二硫醚的方法 Download PDFInfo
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- dimethyl disulfide
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- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 22
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- JWMLCCRPDOIBAV-UHFFFAOYSA-N chloro(methylsulfanyl)methane Chemical compound CSCCl JWMLCCRPDOIBAV-UHFFFAOYSA-N 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000012544 monitoring process Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 125000003963 dichloro group Chemical group Cl* 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 4
- 239000000796 flavoring agent Substances 0.000 description 4
- 235000019634 flavors Nutrition 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
- C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/05—Isotopically modified compounds, e.g. labelled
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种简便的制备二甲基二硫醚及氘代二甲基二硫醚的方法。本发明涉及的两个结构式如下所示:
Description
本发明涉及一种二甲基二硫醚及氘代二甲基二硫醚的制备方法。
含硫化合物是食品中一类重要的挥发性化合物,其阈值低,具有独特的感官特性,在食品风味中有着非常重要的作用。越来越多的含硫化合物通过安全评价,被批准作为食用香料用于各种食用香精的配方中。开发实用的合成路线,对这些香料在食用香精配方中的应用至关重要。此外,这些含硫化合物在食品挥发性成分中含量通常很低,利用稳定同位素稀释法是这些痕量风味化合物准确定量的重要手段。探索这些重要含硫香料的实用合成方法及其氘代化合物的合成方法,是香料化学家的重要研究方向之一。
二甲基二硫醚作为食品中的挥发性成分广泛存在。其典型的制备方法包括硫酸二甲酯与Na2S2反应、甲硫醇在催化剂的作用下与液态硫单质的反应、甲硫醇或其盐的氧化等。但这些制备方法或多或少都有一些缺点,如试剂或溶剂的高毒性、昂贵的催化剂或低产率等。目前仍需非常有效、便捷的制备方法。
本发明的目的是提供一种新的制备二甲基二硫醚和氘代二甲基二硫醚的方法。其特征是草酰氯/二甲亚砜或草酰氯/氘代二甲亚砜反应产生氯甲基甲硫醚或氘代氯甲基甲硫醚中间体,随后在水的作用下得到二甲基二硫醚或氘代二甲基二硫醚。本发明的制备方法具有反应时间短、操作简便等优点。反应式如下:
本发明涉及的两个结构式如下所示:
其主要过程是:在0℃将草酰氯的二氯溶液滴加到二甲亚砜或氘代二甲亚砜的二氯甲烷溶液中,搅拌一段时间后转移到室温继续搅拌,然后加入水,反应一段时间,得到二甲基二硫醚或氘代二甲基二硫醚,产率38%左右。
本发明方法中制备的二甲基二硫醚或氘代二甲基二硫醚的结构都通过核磁共振进行了确认,其中氘代二甲基二硫醚也通过高分辨质谱进行了确认。分析结果附在实施例后。
具体实施方式
(1)二甲基二硫醚的制备
向装有磁力搅拌子和恒压滴液漏斗的250mL三口烧瓶内,加入草酰氯(0.11mol,1.1eq)和40mL无水二氯甲烷,搅拌,低温浴槽冷却至0℃,滴加二甲亚砜(0.1mol,1eq)的二氯甲烷(40mL)溶液。滴加完毕,在0℃左右搅拌15min后,转移到室温搅拌,然后加入H2O(1mol,10eq)并在室温下继续搅拌反应。使用GC/MS监测氯甲基甲硫醚,反应约4h氯甲基甲硫醚消失。反应混合物用饱和氯化钠溶液洗涤三次,水相用CH2Cl2萃取。将合并的有机相用无水Na2SO4干燥。在50℃的大气压下浓缩得到二甲基二硫醚(1.774g,38%)的纯品。1H NMR(300MHz,CDCl3)δ2.32(s,6H)。13C{1H}NMR(75MHz,CDCl3)821.7。所有测量值与商业标准样品的相同。
(2)氘代二甲基二硫醚的制备
向装有磁力搅拌子和恒压滴液漏斗的100mL三口烧瓶内,加入草酰氯(16.5mmol,1.1eq)和10mL无水二氯甲烷,搅拌,低温浴槽冷却至0℃,滴加氘代二甲亚砜(15mmol,1eq)的二氯甲烷(10mL)溶液。滴加完毕,在0℃左右搅拌30min后,转移到室温搅拌,然后加入H2O(150mmol,10eq)并在室温下继续搅拌反应。使用GC/MS监测氘代氯甲基甲硫醚,反应约4h氘代氯甲基甲硫醚消失。反应混合物用饱和氯化钠溶液洗涤三次,水相用CH2Cl2萃取。将合并的有机相用无水Na2SO4干燥。在50℃的大气压下浓缩得到氘代二甲基二硫醚(0.29g,39%)的纯品。13C{1H}NMR(75MHz,CDCl3)δ20.7(七重峰,J=21.2Hz)。HRMS(EI)m/z:[M]+C2D6S2Calculated for 100.0282;Found 100.0282。
Claims (1)
1.一种制备二甲基二硫醚的方法,其特征在于,向装有磁力搅拌子和恒压滴液漏斗的250mL三口烧瓶内,加入0.11mol草酰氯和40mL无水二氯甲烷,搅拌,低温浴槽冷却至0℃,滴加0.1mol二甲亚砜的40mL二氯甲烷溶液,滴加完毕,在0℃左右搅拌15min后,转移到室温搅拌,然后加入1mol H2O,并在室温下继续搅拌反应,使用GC/MS监测氯甲基甲硫醚,反应约4h氯甲基甲硫醚消失,反应混合物用饱和氯化钠溶液洗涤三次,水相用CH2Cl2萃取,将合并的有机相用无水Na2SO4干燥,在50℃的大气压下浓缩得到二甲基二硫醚的纯品,产率38%。
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GB825347A (en) * | 1957-05-06 | 1959-12-16 | Rech S Et Propagande Scient | Improvements in the production of bis-chloromethyl bisulphide |
CN1188759A (zh) * | 1998-02-24 | 1998-07-29 | 北京轻工业学院 | 一种甲基烃基二硫醚的制备方法 |
JP2007238517A (ja) * | 2006-03-09 | 2007-09-20 | Hamamatsu Kagaku Gijutsu Kenkyu Shinkokai | ジスルフィド化合物の製造方法 |
FR2935142A1 (fr) * | 2008-08-20 | 2010-02-26 | Arkema France | Dimethyldisulfure issu au moins partiellement de matieres renouvellables |
JP2012229329A (ja) * | 2011-04-26 | 2012-11-22 | Institute Of National Colleges Of Technology Japan | ジスルフィドポリマーの製造方法及びジスルフィドコポリマー |
CN110229086A (zh) * | 2019-06-24 | 2019-09-13 | 扬州市职业大学(扬州市广播电视大学) | 一种二甲基二硫醚合成废气处理工艺 |
CN111072539A (zh) * | 2019-12-27 | 2020-04-28 | 北京工商大学 | 一种简便的硫代甲磺酸甲酯的制备方法 |
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Patent Citations (7)
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GB825347A (en) * | 1957-05-06 | 1959-12-16 | Rech S Et Propagande Scient | Improvements in the production of bis-chloromethyl bisulphide |
CN1188759A (zh) * | 1998-02-24 | 1998-07-29 | 北京轻工业学院 | 一种甲基烃基二硫醚的制备方法 |
JP2007238517A (ja) * | 2006-03-09 | 2007-09-20 | Hamamatsu Kagaku Gijutsu Kenkyu Shinkokai | ジスルフィド化合物の製造方法 |
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CN111072539A (zh) * | 2019-12-27 | 2020-04-28 | 北京工商大学 | 一种简便的硫代甲磺酸甲酯的制备方法 |
Non-Patent Citations (1)
Title |
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