2-Oxopropyl 3-oxobutanoate | 137529-86-3

• 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: 2-Oxopropyl 3-oxobutanoate
• 英文别名: acetoacetic acid-(2-oxo-propyl ester)；Acetessigsaeure-(2-oxo-propylester)
• CAS: 137529-86-3
• 化学式: C₇H₁₀O₄
• 分子量: 158.154
• InChiKey: GQOFREXOMQUSHS-UHFFFAOYSA-N

物化性质

• 沸点：
  98-100 °C(Press: 0.2 Torr)
• 密度：
  1.115±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  60.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-Oxopropyl 3-oxobutanoate 在 三乙胺 、 甲烷磺酰基叠氮化物 作用下， 以 乙腈 为溶剂， 反应 3.0h， 以50%的产率得到2-Oxopropyl 2-diazo-3-oxobutanoate
  参考文献：
  名称：

  Stereo and electronic effects in the rhodium(II)-mediated synthesis of polycyclic lactones and lactams from .alpha.-diazo ester and amide precursors

  摘要：

  The rhodium(II) carboxylate catalyzed decomposition of several alpha-diazo esters and amides has been studied. A series of 5-keto-1-diazo acetates were prepared by acylation of alpha-hydroxy ketones using the (p-toluenesulfonyl)hydrazone of glyoxylic acid chloride. Treatment of these compounds with Rh(II) acetate afforded products derived from carbenoid insertion into solvent. When the hydrogen atom of the diazo carbon was replaced with an electron-withdrawing substituent, smooth cyclization occurred to produce a carbonyl ylide dipole which was subsequently trapped with different dipolarophiles. A series of N-alkyl-2-diazo-3-oxobutylamides, when treated with a catalytic quantity of rhodium(II) acetate, gave furo[3,4-c]furans in good yield. The reaction proceeds via addition of a rhodium-stabilized carbenoid onto the acetylenic pi-bond to give a vinyl carbenoid which subsequently cyclizes onto the neighboring carbonyl group to produce the furan ring. N-Alkynyl-substituted 2-diazoacetamides were also found to cyclize onto the tethered alkyne unit. The resulting rhodium carbenoid can undergo intramolecular and bimolecular cyclopropanation depending on both electronic and conformational factors. Rotamer population of the starting diazoamide was also found to influence product distribution.

  DOI：

  10.1021/jo00069a030
• 作为产物：
  描述：

  2-Methyl-2-propenyl-3-oxobutanoate 在 二甲基硫 、 臭氧 作用下， 生成 2-Oxopropyl 3-oxobutanoate
  参考文献：
  名称：

  Stereo and electronic effects in the rhodium(II)-mediated synthesis of polycyclic lactones and lactams from .alpha.-diazo ester and amide precursors

  摘要：

  The rhodium(II) carboxylate catalyzed decomposition of several alpha-diazo esters and amides has been studied. A series of 5-keto-1-diazo acetates were prepared by acylation of alpha-hydroxy ketones using the (p-toluenesulfonyl)hydrazone of glyoxylic acid chloride. Treatment of these compounds with Rh(II) acetate afforded products derived from carbenoid insertion into solvent. When the hydrogen atom of the diazo carbon was replaced with an electron-withdrawing substituent, smooth cyclization occurred to produce a carbonyl ylide dipole which was subsequently trapped with different dipolarophiles. A series of N-alkyl-2-diazo-3-oxobutylamides, when treated with a catalytic quantity of rhodium(II) acetate, gave furo[3,4-c]furans in good yield. The reaction proceeds via addition of a rhodium-stabilized carbenoid onto the acetylenic pi-bond to give a vinyl carbenoid which subsequently cyclizes onto the neighboring carbonyl group to produce the furan ring. N-Alkynyl-substituted 2-diazoacetamides were also found to cyclize onto the tethered alkyne unit. The resulting rhodium carbenoid can undergo intramolecular and bimolecular cyclopropanation depending on both electronic and conformational factors. Rotamer population of the starting diazoamide was also found to influence product distribution.

  DOI：

  10.1021/jo00069a030

文献信息

• PROCESS FOR PREPARING SODIUM SALTS OR POTASSIUM SALTS OF 4-HYDROXY-2-OXO-2,5-DIHYDROFURAN-3-CARBOXYLATE
  申请人：Funke Christian

  公开号：US20140148604A1

  公开（公告）日：2014-05-29

  Process for preparing sodium or potassium salts of 4-hydroxy-2-oxo-2,5-dihydrofuran-3-carboxylic esters, comprising the reaction of a malonic ester with potassium hydroxide to give the corresponding malonic ester potassium salt of the formula (III) which is then reacted further with a chloroacetic ester to give a compound of the formula (V) followed by a ring closure reaction in which the compound of the formula (V) is reacted with a sodium or potassium alkoxide of the formula ZOR 1 where R 1 , R 2 , R 3 and K are each as defined in the description.

  制备4-羟基-2-氧代-2,5-二氢呋喃-3-羧酸酯的钠盐或钾盐的过程，包括将丙二酸酯与氢氧化钾反应，得到相应的丙二酸酯钾盐（式III），然后进一步与氯乙酸酯反应，得到式（V）的化合物，随后进行环闭合反应，其中化合物（V）与式ZOR1的钠或钾烷氧化物反应，其中R1、R2、R3和K在描述中各自定义。
• MULTISTAGE PROCESS FOR PREPARING ALKALI METAL SALTS OF SPECIFIC 4-HYDROXY-2-OXO-2,5-DIHYDROFURAN-3-CARBOXYLIC ESTERS
  申请人：BAYER CROPSCIENCE AG

  公开号：US20150210662A1

  公开（公告）日：2015-07-30

  The present invention relates to a multi-stage method for preparing alkali metal salts of specific 4-hydroxy-2-oxo-2,5-dihydrofuran-3-carboxylic esters of the formula (I), in which M and R 1 are as defined in the description, which proceeds from malonic ester and does not require isolation of intermediates.

  本发明涉及一种多级方法，用于制备具有特定化学式(I)的4-羟基-2-氧代-2,5-二氢呋喃-3-羧酸酯的碱金属盐，其中M和R1如描述中定义，该方法从丙二酸酯开始，并且不需要分离中间体。
• An eight-step gram-scale synthesis of (−)-jiadifenolide
  作者：Hai-Hua Lu、Michael D. Martinez、Ryan A. Shenvi

  DOI：10.1038/nchem.2283

  日期：2015.7

  into a useful medicine requires continuous access to meaningful quantities of material. Although any chemical synthesis is broadly useful for its versatility, identification of a synthesis route that can be economically scaled represents a greater challenge. Here we report a concise synthesis of the neurotrophic trace metabolite (−)-jiadifenolide and its production on a gram-scale. The brevity of the

  将具有生物活性的次生代谢产物发展为有用的药物需要持续获取有意义数量的物质。尽管任何化学合成方法都具有广泛的用途，但要确定经济可行的合成方法仍是一个更大的挑战。在这里，我们报告了神经营养微量代谢物（-）-加地非诺利德的简明合成及其以克为单位的生产。途径和中间许多有效的密钥的结构相似的简洁八角萜使化学合成用于访问和修改这些潜在治疗剂的方法不容置疑。
• [EN] BUTENOLIDE ANTAGONISTS OF THE CGAS/STING PATHWAY<br/>[FR] ANTAGONISTES DU BUTÉNOLIDE DE LA VOIE CGAS/STING
  申请人：SCRIPPS RESEARCH INST

  公开号：WO2020118206A1

  公开（公告）日：2020-06-11

  A series of butenolide heterodimers were found to be inhibitors of the cGAS/STING pathway. They can be useful in therapies for treating a range of chronic interferon (IFN) associated autoimmune diseases and inflammation.

  一系列的丁内酯杂二聚体被发现可以抑制cGAS/STING通路。它们在治疗多种慢性干扰素(IFN)相关的自身免疫性疾病和炎症方面非常有用。
• Derivatives of acetoacetic acid. Part VIII. The synthesis of coumarins from aryl acetoacetates
  作者：R. N. Lacey

  DOI：10.1039/jr9540000854

  日期：——