dimethyl 1-allyl-1,3-acetonedicarboxylate | 78755-53-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: dimethyl 1-allyl-1,3-acetonedicarboxylate
• 英文别名: dimethyl 2-allyl-3-oxopentanedioate；dimethyl 2-allyl-3-oxoglutarate；2-allyl-3-oxo-glutaric acid dimethyl ester；2-Allyl-3-oxo-glutarsaeure-dimethylester；Dimethyl 3-oxo-2-prop-2-enylpentanedioate
• CAS: 78755-53-0
• 化学式: C₁₀H₁₄O₅
• 分子量: 214.218
• InChiKey: XYSDJFLGLFRWER-UHFFFAOYSA-N

物化性质

• 沸点：
  93-98 °C(Press: 0.5-0.75 Torr)
• 密度：
  1.109±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  15
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  dimethyl 1-allyl-1,3-acetonedicarboxylate 在 氢氧化钾 作用下， 生成 3-hydroxy-8-nonene-2,5-dione
  参考文献：
  名称：

  Process for manufacture of 2, 5 diketo-8-nonen-3-ol

  摘要：

  该发明涉及一种单烯丙基丙酮二羧酸二酯、其自由酸及其碱金属和碱土金属盐。该酯可通过在无水条件下，在碱性缩合剂和惰性有机溶剂的存在下，将丙酮羧酸二酯与烯丙基卤化物反应而制备得到。反应可在升高的温度下进行，如果需要，还可在压力下进行。用作试剂的酯最好是碳原子数最多为5的酯，如甲基、乙基和丙基酯，而缩合剂适宜为碱金属醇盐。当使用烯丙基氯化物作为试剂时，最好过量使用。得到的烯丙基丙酮羧酸酯可用碱性碳酸钠或碱性地球金属化合物的水溶液皂化，例如氢氧化钠、碳酸钠或碳酸锂，以得到相应的烯丙基-丙酮二羧酸盐，可通过加入低级脂肪醇等方式进行分离。盐的水溶液可酸化以释放自由酸，然后通过丙酮萃取等方式进行回收。或者，盐的水溶液可在pH值为6.5至9.5的条件下与丙酮醛反应，形成相应的1-烯丙基-2,5-二酮-4-羟基庚酸盐，可通过与非溶剂如甲醇沉淀或在真空下冷冻状态下干燥溶液来分离。自由酸可通过将盐的水溶液冷却至接近其冰点，加入稀酸并搅拌，然后通过冷冻干燥酸化溶液来获得。自由酸在室温下脱羧成为非-8-烯-2,5-二酮-3-醇，可通过与稀碱环化为烯丙内酮。通过将庚酸金属盐的水溶液酸化至pH值约为1.0-2.5，然后在中性水溶性溶剂的存在下，用水不相溶的溶剂进行萃取，即可直接得到无环酮醇。在实例中：（1）烯丙基溴在甲醇溶液中与丙酮羧酸二甲酯和甲醇钠在回流下反应，得到单烯丙基二甲基丙酮二羧酸酯；然后将酯皂化为氢氧化钾，用硫酸中和产物，加入丙酮醛，将pH值调整为7.5-8.0，在室温下搅拌混合物；得到的1-烯丙基-2,5-二酮-4-羟基庚酸钠盐水溶液用HCl酸化至pH2，放出CO2；得到非-8-烯-2,5-二酮-3-醇。 （2）烯丙基氯（3摩尔比例）在甲醇溶液中与丙酮羧酸二甲酯和甲醇钠反应，如（1）所述，以得到二甲基单烯丙基丙酮二羧酸酯。

  公开号：

  US02768967A1
• 作为产物：
  描述：

  1,3-丙酮二羧酸二甲酯 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 生成 dimethyl 1-allyl-1,3-acetonedicarboxylate
  参考文献：
  名称：

  通过插入-片段化-Dieckman-芳构化级联反应，用二甲基丙酮二羧酸酯对芳烃进行苯环环化：迅速进入萘二酚和邻苯二酚间苯二酚

  摘要：

  芳烃插入带有1,3,5-三羰基的二甲基丙酮二甲酸二甲酯（DMAD）中的过程通过4步级联过程进行，最终完成了多功能的一锅合成的功能修饰的间苯二酚。已经探索了这些实体上的官能团扩增和转化，目的是将其应用于天然产物合成和访问其他有趣的支架。

  DOI：

  10.1016/j.tet.2019.04.020

文献信息

• SYNTHESIS OF 6-ALLYL-7-HYDROXY-5-METHOXY-4-METHYLPHTHALIDE, A KEY INTERMEDIATE IN THE SYNTHESIS OF MYCOPHENOLIC ACID
  作者：Adrián Covarrubias-Zúnniga、José Diaz-Dominguez、José S. Olguín-Uribe

  DOI：10.1081/scc-100104047

  日期：2001.1

  followed by a regiocontrolled Dieckmann-type cyclization over the adequate methyl ester group, has been applied to an efficient formal synthesis of the antitumor antibiotic, mycophenolic acid 1. This tandem annulation reaction generates the fully substituted aromatic intermediate 12, which was transformed by a simple six-step sequence to 2, and even to 1 by the methodology of Birch et al.[15]

  基于 1-烯丙基-1,3-丙酮二羧酸二甲酯阴离子 8 与 4-新戊酰氧基-2-丁缩醛 9 的迈克尔加成的收敛芳香环化策略，然后在足够的甲基酯基团上进行区域控制的 Dieckmann 型环化，具有已应用于抗肿瘤抗生素霉酚酸 1 的有效形式合成。 这种串联环化反应生成完全取代的芳香族中间体 12，通过简单的六步序列将其转化为 2，甚至通过 Birch 的方法转化为 1等[15]
• Alkylation of Dimethyl 1,3-Acetonedicarboxylate
  作者：Adrián Covarrubias-Zúñiga、Laura San Germán-Sanchez、José G. Avila-Zárraga

  DOI：10.1081/scc-120023437

  日期：2003.9

  A reliable, reproducible, general, and detailed procedure for the alkylation of dimethyl-1,3-acetonedicarboxylate is described.
• Reduction of 2-substituted 3-oxoglutarates mediated by baker's yeast. Variation in enantioselectivity without corresponding variation in diastereoselectivity
  作者：Tuncer Arslan、Steven A. Benner

  DOI：10.1021/jo00060a048

  日期：1993.4

  The reduction of 2-substituted 3-oxoglutarates by yeast yields a new class of chiral building blocks, 2-allyl- and 2-propargyl-3-hydroxyglutarates. These are useful as starting points for the synthesis of, inter alia, branched chain analogs of sugars and nucleosides. When allyl is the side chain, the principal product has the absolute configuration (2S,3S), proven by correlation with a compound whose absolute configuration was established by crystallography. Several features of this yeast-mediated reduction are noteworthy. First, its diastereoselectivity is higher than its enantioselectivity, especially with the propargyl side chain. Further, with all substrates, variation in enantioselectivity is not manifested by a variation in diastereoselectivity. This example therefore serves as a warning for those using yeast-mediated reactions that diastereoselectivity cannot be accepted as a substitute for direct measurements of enantioselectivity, even with analogous substrates and similar reaction conditions. Finally, an unexpected metabolism of impurities in the starting material by the yeast made the overall transformation preparatively useful.
• Benzannulation of arynes with dimethylacetonedicarboxylates via an insertion-fragmentation-Dieckman-aromatization cascade: Expeditious entry to naphthoresorcinols and binaphthoresorcinols
  作者：Shweta Singh、Ramesh Samineni、Srihari Pabbaraja、Goverdhan Mehta

  DOI：10.1016/j.tet.2019.04.020

  日期：2019.5

  dimethylacetonedicarboxylate (DMAD) proceeds through a 4-step cascade process to eventuate in a versatile one pot synthesis of functionally embellished naphthoresorcinols. Functional group amplifications and transformations on these entities have been explored with the intent to apply them for natural products syntheses and to access other interesting scaffolds.

  芳烃插入带有1,3,5-三羰基的二甲基丙酮二甲酸二甲酯（DMAD）中的过程通过4步级联过程进行，最终完成了多功能的一锅合成的功能修饰的间苯二酚。已经探索了这些实体上的官能团扩增和转化，目的是将其应用于天然产物合成和访问其他有趣的支架。
• Process for manufacture of 2, 5 diketo-8-nonen-3-ol
  申请人：PFIZER &

  公开号：US02768967A1

  公开（公告）日：1956-10-30

  The invention comprises di-esters of monoallyl acetone dicarboxylic acid, the free acid and its alkali-metal and alkaline-earth metal salts. The esters may be prepared by reacting a diester of acetone carboxylic acid with an allyl halide in the presence of an alkaline condensing agent and an inert organic solvent, under anhydrous conditions. Reaction may be effected at raised temperature and if desired under pressure. The esters used as reagents are preferably those having up to 5 carbon atoms, such as the methyl, ethyl and propyl esters, and the condensing agent is suitably an alkali metal alcoholate. When allyl chloride is used as reagent it is preferably present in excess. The resulting allyl acetone carboxylic acid esters may be saponified with an aqueous solution of a basic alkali metal or alkaline earth metal compound, e.g. sodium or lithium carbonate or an hydroxide of sodium, potassium, lithium or barium to give the corresponding salts of allyl-acetone dicarboxylic acid which may be isolated, e.g. by addition of a lower aliphatic alcohol. Aqueous solutions of the salts may be acidified to liberate the free acid which is then recoverable, e.g. by acetone extraction. Alternatively the aqueous solutions of the salts may be reacted with pyruvaldehyde at a pH from about 6.5 to 9.5 to form the corresponding salts of 1-allyl-2,5-diketo-4-hydroxyheptanoic acid which may be isolated by precipitation with a non-solvent, e.g. methanol or by drying the solution in the frozen state under vacuum. The free acid may be obtained by cooling an aqueous solution of the salt to near its freezing point, adding dilute acid with agitation and freeze drying the acidified solution. The free acid decarboxylates at room temperature to nona-8-ene - 2,5 - dione - 3 - ol, which may be cyclized with dilute alkali to allethrolone. The acyclic ketonic alcohol may be obtained direct by acidifying the aqueous solution of the metal salt of the heptanoic acid to a pH of about 1.0-2.5 with a mineral acid, followed by extraction with a water-immiscible solvent, preferably in the presence of a neutral water-soluble solvent. In examples: (1) allyl bromide is reacted with a methanolic solution of dimethyl acetone dicarboxylate and sodium methoxide under reflux and the resulting mono-allyl dimethyl acetone dicarboxylate is isolated; the ester is then saponified with aqueous KOH, the product neutralized with sulphuric acid, pyruvaldehyde is added, the pH adjusted to 7.5-8.0 and the mixture stirred at room temperature; the resulting aqueous solution of 1-allyl-2,5-diketo-4-hydroxy heptanoic acid sodium salt is acidified with HCl to pH 2 with evolution of CO2; the resulting nona-8-ene-2,5-dione-3-ol is isolated. (2) Allyl chloride (3 molar proportions) is reacted with dimethyl acetone dicarboxylate and sodium methoxide as in (1) to give dimethyl mono-allyl acetone dicarboxylate.

  该发明涉及一种单烯丙基丙酮二羧酸二酯、其自由酸及其碱金属和碱土金属盐。该酯可通过在无水条件下，在碱性缩合剂和惰性有机溶剂的存在下，将丙酮羧酸二酯与烯丙基卤化物反应而制备得到。反应可在升高的温度下进行，如果需要，还可在压力下进行。用作试剂的酯最好是碳原子数最多为5的酯，如甲基、乙基和丙基酯，而缩合剂适宜为碱金属醇盐。当使用烯丙基氯化物作为试剂时，最好过量使用。得到的烯丙基丙酮羧酸酯可用碱性碳酸钠或碱性地球金属化合物的水溶液皂化，例如氢氧化钠、碳酸钠或碳酸锂，以得到相应的烯丙基-丙酮二羧酸盐，可通过加入低级脂肪醇等方式进行分离。盐的水溶液可酸化以释放自由酸，然后通过丙酮萃取等方式进行回收。或者，盐的水溶液可在pH值为6.5至9.5的条件下与丙酮醛反应，形成相应的1-烯丙基-2,5-二酮-4-羟基庚酸盐，可通过与非溶剂如甲醇沉淀或在真空下冷冻状态下干燥溶液来分离。自由酸可通过将盐的水溶液冷却至接近其冰点，加入稀酸并搅拌，然后通过冷冻干燥酸化溶液来获得。自由酸在室温下脱羧成为非-8-烯-2,5-二酮-3-醇，可通过与稀碱环化为烯丙内酮。通过将庚酸金属盐的水溶液酸化至pH值约为1.0-2.5，然后在中性水溶性溶剂的存在下，用水不相溶的溶剂进行萃取，即可直接得到无环酮醇。在实例中：（1）烯丙基溴在甲醇溶液中与丙酮羧酸二甲酯和甲醇钠在回流下反应，得到单烯丙基二甲基丙酮二羧酸酯；然后将酯皂化为氢氧化钾，用硫酸中和产物，加入丙酮醛，将pH值调整为7.5-8.0，在室温下搅拌混合物；得到的1-烯丙基-2,5-二酮-4-羟基庚酸钠盐水溶液用HCl酸化至pH2，放出CO2；得到非-8-烯-2,5-二酮-3-醇。 （2）烯丙基氯（3摩尔比例）在甲醇溶液中与丙酮羧酸二甲酯和甲醇钠反应，如（1）所述，以得到二甲基单烯丙基丙酮二羧酸酯。