methyl (2,2,2-trichloroethyl) carbonate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机碳酸及其衍生物
• 英文名称: methyl (2,2,2-trichloroethyl) carbonate
• 英文别名: Methyl 2,2,2-trichloroethyl carbonate
• 化学式: C₄H₅Cl₃O₃
• 分子量: 207.441
• InChiKey: HYBCSYUDJOFGEO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  9,10-dihydrolysergic acid methyl ester 、 氯甲酸-2,2,2-三氯乙酯 在 potassium hydrogencarbonate 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 生成 2,2,2-三氯乙醇 、 氯乙双酯 、 methyl (2,2,2-trichloroethyl) carbonate 、 6-nor-6-(2,2,2-trichloroethoxycarbonyl)-9,10-dihydrolysergic acid methyl ester
  参考文献：
  名称：

  A DMAP-Catalyzed Approach to the Industrial-Scale Preparation ofN-6-Demethylated 9,10-Dihydrolysergic Acid Methyl Ester: A Key Cabergoline and Pergolide Precursor

  摘要：

  A scalable new approach for the preparation of N-6-demethylated 9,10-dihydrolysergic acid methyl ester using 2,2,2-trichloroethyl chloroformate was developed. A key discovery that enabled the efficient and industrial-scalable process is linked to the rigorous extrusion of water in the reaction system and application of an organic catalyst such as 4-(N,N-dimethylamino)pyridine (DMAP) instead of the alkali metal bicarbonate additives. Namely, in the previously known process, the concomitant presence of bicarbonates and traces of water triggers side reaction cycles that produce and accumulate hydrochloric acid and water. The former slows down the reaction. Moreover, these cycles cause the formation of multiple carbonate and alcohol-type side products to a significant extent that provide a low-quality N-6-demethylated product. All of these shortcomings are circumvented by the application of DMAP as a catalyst and the use of a reaction medium free of water. This approach allows operation on an industrial scale (51 kg batch) with higher yields, shorter reaction times, and improved product quality.

  DOI：

  10.1021/op500394f

文献信息

• Preparation of N-6 demethylated, 9,10-dihydrolysergic acid alkyl esters
  申请人：LEK Pharmaceuticals d.d.

  公开号：EP2113504A1

  公开（公告）日：2009-11-04

  A process for producing N-6 demethylated 9,10-dihydrolysergic acid alkyl ester is described, which comprises a step of N-6 demethylation of 9,10-dihydrolysergic acid alkyl esters with chloroformate and wherein the N-6 demethylation step is performed in the presence of an organic catalyst. Further, a process for converting a compound of formula I (DHLSAIkyI) into a compound of formula II (DHLSAIkyI-F) comprises the steps of: providing (and maintaining) a reaction medium free of water and/or HCI, and reacting DHLSAIkyI with chloroformate in said reaction medium free of water and/or HCI, to obtain the compound of formula II (DHLSAIkyI-F).

  本发明涉及一种制备N-6去甲基化9,10-二氢麦角酸烷基酯的方法，包括使用氯甲酸酯对9,10-二氢麦角酸烷基酯进行N-6去甲基化步骤，其中在有机催化剂的存在下进行N-6去甲基化步骤。此外，本发明还涉及一种将式I化合物（DHLSAIkyI）转化为式II化合物（DHLSAIkyI-F）的方法，包括以下步骤：提供（并维持）一个不含水和/或HCl的反应介质，并在该不含水和/或HCl的反应介质中使用氯甲酸酯对DHLSAIkyI进行反应，以获得式II化合物（DHLSAIkyI-F）。
• NONAQUEOUS ELECTROLYTE SOLUTION, NONAQUEOUS ELECTROLYTE SECONDARY CELL, AND CARBONATE COMPOUNDS
  申请人：Shima Noriko

  公开号：US20090253048A1

  公开（公告）日：2009-10-08

  The present invention provides a nonaqueous electrolytic solution which can give excellent cycle characteristics. The nonaqueous electrolytic solution contains a linear carbonate represented by the formula (1): wherein, in the formula (1), X a represents each independently hydrogen or any group; R a represents optionally substituted alkyl; and n represents an integer of zero or more.

  本发明提供了一种非水电解质溶液，可以提供优异的循环特性。该非水电解质溶液包含由式（1）表示的线性碳酸酯：其中，在式（1）中，X分别表示氢或任何基团；R表示可选取代的烷基；n表示零或更多的整数。
• 1-Sulfo-2-oxoazetidine derivatives, their production and use
  申请人：Takeda Chemical Industries, Ltd.

  公开号：EP0053816A1

  公开（公告）日：1982-06-16

  A 1-sulfo-2-oxoazetidine derivative of formula wherein R is a residue derived from an organic compound by removal of one hydrogen atom attached to a carbon atom thereof; R' is an amino group which may optionally be , acylated or protected; X is hydrogen or methoxy, and methods of producing said compound (I) which may be written as follows or wherein the symbols have the same meanings as respectively defined above. The compound (I) has improved antimicrobial and β-lactamase-inhibitory activities and is of value as drugs for human beings and domesticated animals.

  一种 1-磺基-2-氧代氮杂环丁烷衍生物，其式中，R 是有机化合物的残基，通过去除连接到其碳原子上的一个氢原子而得到；R'是氨基，可任选被酰化或保护；X 是氢或甲氧基，以及生产所述化合物 (I) 的方法，其可如下写法或其中的符号分别具有与上述定义相同的含义。 该化合物 (I) 具有更好的抗菌活性和β-内酰胺酶抑制活性，具有作为人类和驯养动物药物的价值。
• 1-Sulfo-2-azetidinone derivatives, their production and use
  申请人：Takeda Chemical Industries, Ltd.

  公开号：EP0093376A2

  公开（公告）日：1983-11-09

  A 1-sulfo-2-oxoazetidine derivative of the formula wherein R8 is -COQ° (Q° is an amino group which may optionally be protected or substituted), -COQ5 (Q5 is a hydroxyl group which may optionally be protected), -(CH2)na- R4a (na is an integer of 1 to 3: R4a is a hydrogen atom or a carbamoylamino, N-sulfocarbamoylamino, carbamoyl, carbamoyloxy, N-sulfocarbamoyloxy, haloalkylcarbonylcarbamoyloxy, alkylsulfonyloxy, pyridinio, alkoxy, alkylsulfinyl, alkylsulfonyl, halogenoalkylcarbonyloxy, hydroxyl, alkoxycarbonyl, acyloxy, 1-alkoxyiminoalkyl, alkylcarbonyl or acylamino group) or a nitrogen-containing heterocyclic group; R' is an amino group which may optionally be acylated or protected; and X is a hydrogen atom or a methoxy group, or a salt or ester thereof, and methods of producing said compound (Ia) which may be shown as follows wherein the symbols have the same meanings as respectively defined above, and intermediates for preparing the compound (Ia) and methods of producing them. The compound (Ia) has improved antimicrobial and β-lactamase- inhibitory activities and is of value as drugs for human beings and domesticated animals.

  式中的 1-磺基-2-氧氮杂环丁烷衍生物 其中 R8 为-COQ°（Q°为氨基，可任选被保护或取代）、-COQ5（Q5 为羟基，可任选被保护）、-(CH2)na- R4a（na 为 1 至 3 的整数：R4a 是氢原子或氨基甲酰氨基、N-硫代氨基甲酰氨基、氨基甲酰基、氨基甲酰氧基、N-硫代氨基甲酰氧基、卤代烷基羰基氨基甲酰氧基、烷基磺酰氧基、吡啶基、烷氧基、烷基亚磺酰基、烷基磺酰基、卤代烷基羰基氧基、羟基、烷氧基羰基、酰氧基、1-烷氧基亚氨基烷基、烷基羰基或酰氨基）或含氮杂环基团；R'是可选择酰化或保护的氨基；X是氢原子或甲氧基，或其盐或酯，以及生产所述化合物（Ia）的方法，可如下所示 其中符号的含义分别与上述定义相同，以及制备化合物（Ia）的中间体及其生产方法。化合物（Ia）具有更好的抗菌和抑制β-内酰胺酶的活性，具有作为人类和驯养动物药物的价值。
• Novel carbonate compounds, non-aqueous electrolytic solutions and batteries comprising nonaqueous electrolytic solutions
  申请人：MITSUI PETROCHEMICAL INDUSTRIES, LTD.

  公开号：EP0599534A1

  公开（公告）日：1994-06-01

  A carbonate compound of formula (I):         R¹CH₂-O-CO-O-CH₂R²   (I) wherein: R¹ is a hydrogen atom, an alkyl group or an alkyl group substituted with one or more halogen atoms; and R² is an alkyl group having no hydrogen atom at the α-position thereof or an alkyl group substituted with one or more halogen atoms and having no hydrogen atom at the α-position thereof; with the proviso that R¹ is not identical to R².

  式 (I) 的碳酸盐化合物： R¹CH₂-o-Co-CH₂R² (I) 其中 R¹ 是氢原子、烷基或被一个或多个卤素原子取代的烷基；及 R² 是α 位无氢原子的烷基或被一个或多个卤素原子取代且α 位无氢原子的烷基； 但 R¹ 与 R² 不完全相同。