四氢呋喃-2-基甲基3-氧代丁酸酯 | 7249-93-6

• 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
• 中文名称: 四氢呋喃-2-基甲基3-氧代丁酸酯
• 英文名称: (tetrahydrofuran-2-yl)methyl 3-oxobutanoate
• 英文别名: tetrahydrofurfuryl acetoacetate；Tetrahydrofuran-2-ylmethyl 3-oxobutanoate；oxolan-2-ylmethyl 3-oxobutanoate
• CAS: 7249-93-6
• 化学式: C₉H₁₄O₄
• 分子量: 186.208
• InChiKey: GDOYYMOEBDFFIQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  四氢呋喃-2-基甲基3-氧代丁酸酯 在 lithium hydroxide 、 三乙胺 、 甲烷磺酰基叠氮化物 作用下， 生成 Tetrahydrofuran-2-ylmethyl diazoacetate
  参考文献：
  名称：

  Spirolactones from Dirhodium(II)-Catalyzed Diazo Decomposition with Regioselective Carbon-Hydrogen Insertion

  摘要：

  Dirhodium(II) caprolactamate, Rh-2(cap)(4), catalyzes diazo decomposition of cycloalkylmethyl diazoacetates which form spirolactones in moderate to high yield by insertion into a tertiary carbon-hydrogen bond. Similar results are obtained with diazoacetates derived from tetrahydropyran-2-methanol and tetrahydrofurfuryl alcohol but not from cyclopropylmethanol. With tetrahydrofuran-3-ylmethyl diazoacetate, Rh-2(cap)(4) catalysis promotes delta-lactone formation via insertion into the oxygen-activated secondary C-H bond instead of gamma-lactone formation by carbene insertion into the unactivated tertiary C-H bond. However, when both 1,5- and 1,6-positions are activated for insertion by adjacent oxygen atoms, as in (2,2-dimethyl-1,3-dioxolan-4-yl)methyl diazoacetate, five-membered ring formation occurs exclusively in Rh-2(cap)(4)-catalyzed reactions, whereas use of dirhodium(II) acetate leads to both insertion products.

  DOI：

  10.1021/jo00115a018
• 作为产物：
  描述：

  四氢糠醇 、 双乙烯酮 在 4-二甲氨基吡啶 作用下， 以 四氢呋喃 为溶剂， 反应 0.08h， 以80%的产率得到四氢呋喃-2-基甲基3-氧代丁酸酯
  参考文献：
  名称：

  Acetoacetylation with Diketene Catalyzed by 4-Dimethylaminopyridine

  摘要：

  报道了一种有效的方法，将醇1与双酮烯酮2进行乙酰乙酰化反应，生成乙酰乙酸酯3。

  DOI：

  10.1055/s-1989-27260

文献信息

• 1-benzyl-3,5-dimethyl-4-piperdyl ester of a Hantzsch dihydropyridine
  申请人：Kyowa Hakko Kogyo Co., Ltd.

  公开号：US04639522A1

  公开（公告）日：1987-01-27

  The compound of the formula ##STR1## is disclosed to have a less rapid decrease in blood pressure in its use as an antihypertensive.

  公式##STR1##的化合物在作为降压药使用时，被披露为血压下降速度较慢。
• BF₃·OEt₂: An Efficient Catalyst for Transesterification of <font>β</font>-Ketoesters
  作者：Jinhui Yang、Congbin Ji、Yanmin Zhao、Yunfeng Li、Shizhi Jiang、Zhiwei Zhang、Yongqiang Ji、Wanyi Liu

  DOI：10.1080/00397910903029842

  日期：2010.3.12

  A facile and selective transesterification of β-ketoesters using BF3·OEt2 as catalyst is described. The emphasis has been placed on the reaction of methyl acetoacetate with a series of alcohols of different structures, leading in all cases to good to excellent yields.

  描述了使用 BF3·OEt2 作为催化剂的 β-酮酯的简便和选择性酯交换。重点放在乙酰乙酸甲酯与一系列不同结构的醇的反应上，在所有情况下都产生良好的收率。
• Spirolactone syntheses through a rhodium-catalyzed intramolecular C–H insertion reaction: model studies towards the synthesis of syringolides
  作者：Mauricio Navarro Villalobos、John L. Wood

  DOI：10.1016/j.tetlet.2009.08.126

  日期：2009.11

  Model studies towards the total synthesis of syringolides using a rhodium-catalyzed intramolecular C–H insertion reaction as the key step are described. A highly stereospecific synthesis of spirolactones is achieved employing this methodology.

  描述了使用铑催化的分子内C–H插入反应作为关键步骤对丁香酚全合成的模型研究。使用这种方法可以实现螺内酯的高度立体特异性合成。
• 1,4-Dihydropyridine derivatives
  申请人：KYOWA HAKKO KOGYO CO., LTD.

  公开号：EP0106276A2

  公开（公告）日：1984-04-25

  A 1,4-dihydropyridine derivative having hypotensive activity is represented by the formula (I): in which one of R, and R2 represents an alkyl group or a group of the formula (II): in which R5 represents an alkoxy group or a substituted or unsubstituted heterocyclic group and n represents 0 or an integer of 1 - 3, and the other of R, and R2 represents a group of the formula (III): in which R6 represents a substituted or unsubstituted aralkyl group and R7, R8, R9, R10, R11 and R12 are the same or different groups and each represertts hydrogen or an alkyl group, and two alkyl groups may be attached to one carbon atom on the piperidine ring. When R, is an alkyl group and Ra is an unsubstituted aralkyl group, at least one of R7, Rs, Rs, R10, R11 and R12 represents an alkyl group. Also disclosed are pharmaceutically acceptable acid addition salts of compound (I).

  具有降血压活性的 1,4-二氢吡啶衍生物由式（I）表示： 其中 R 和 R2 中的一个代表烷基或式（II）中的一个基团： 其中 R5 代表烷氧基或取代或未取代的杂环基团，n 代表 0 或 1 - 3 的整数，R 和 R2 中的另一个代表式（III）的基团： 其中 R6 代表取代或未取代的芳烷基，R7、R8、R9、R10、R11 和 R12 为相同或不同的基团，各自代表氢或烷基，两个烷基可连接到哌啶环上的一个碳原子上。当 R 是烷基而 Ra 是未取代的芳烷基时，R7、Rs、Rs、R10、R11 和 R12 中至少有一个代表烷基。还公开了化合物（I）的药学上可接受的酸加成盐。
• Selective Catalytic Transesterification, Transthiolesterification, and Protection of Carbonyl Compounds over Natural Kaolinitic Clay
  作者：Datta E. Ponde、Vishnu H. Deshpande、Vivek J. Bulbule、Arumugam Sudalai、Anil S.Gajare

  DOI：10.1021/jo971404l

  日期：1998.2.1

  Transesterification and transthiolesterification of beta-keto esters with variety of alcohols and thiols and selective protection of carbonyl functions with various protecting groups catalyzed by natural kaolinitic clay are described. The clay has been found to be an efficient catalyst in transesterifying long chain alcohols, unsaturated alcohols, and phenols to give their corresponding beta-keto esters in high yields. For the first time, transthiolesterification of beta-keto esters with a variety of thiols has been achieved under catalytic conditions. Clay also catalyzes selective transesterification of beta-keto esters by primary alcohols in the presence of secondary and tertiary alcohols giving corresponding beta-keto esters. A systematic study involving the reactivity of different nucleophiles (alcohols, amines, and thiols) toward beta-keto esters is also described. Sterically hindered carbonyl groups as well as alpha,beta-unsaturated carbonyl groups underwent protection without the deconjugation of the double bond. Chemoselective protection of aldehydes in the presence of ketones has also been achieved over natural kaolinitic clay.