4-benzyloxyacetoacetic acid isopropyl ester | 85525-24-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-benzyloxyacetoacetic acid isopropyl ester
• 英文别名: propan-2-yl 3-oxo-4-phenylmethoxybutanoate
• CAS: 85525-24-2
• 化学式: C₁₄H₁₈O₄
• 分子量: 250.295
• InChiKey: YORRWYJZJNWMJS-UHFFFAOYSA-N

物化性质

• 沸点：
  356.0±22.0 °C(Predicted)
• 密度：
  1.094±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  18
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  4-benzyloxyacetoacetic acid isopropyl ester 在 正丁基锂 、 (R)-RuCl₂(2,2'-bis(di(tolylphosphanyl)-1,1'-binaphthyl) 、 氢气 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 异丙醇 为溶剂， 反应 26.5h， 生成 propan-2-yl (2R,3R)-3-hydroxy-2-methyl-4-phenylmethoxybutanoate
  参考文献：
  名称：

  An efficient protocol for the stereoselective dihydroxylation of ene-ester systems

  摘要：

  Dihydroxylation of ene ester systems was achieved in good yield and diastereoselectivity under classical catalytic OsO4 and NMO conditions using the intrinsic diastereoselectivity in alpha-methyl beta-OTBS systems. This intrinsic diastereoselection can be reversed using 'super' AD-mix to give the opposite diastereomer also in good selectivity. The regioselection of dihydroxylation in diene esters using a modified 'super' AD-mix was poor. This methodology can be applied towards the synthesis of part structures of the marine macrolide Altohyrtin A. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(98)00800-x
• 作为产物：
  描述：

  sodium benzoate 以 四氢呋喃 为溶剂， 生成 4-benzyloxyacetoacetic acid isopropyl ester
  参考文献：
  名称：

  Process for the production of tetronic acid

  摘要：

  从4-卤代乙酰乙酸酯制备四酮酸的过程，首先将4-卤代乙酰乙酸酯转化为相应的4-苄氧乙酰乙酸酯。然后将4-苄基酯氢解成中间产物。通过酸处理将4-羟基乙酰乙酸酯转化为四酮酸。在转化之前可以分离出4-羟基乙酰乙酸酯。可以通过将4-卤代乙酰乙酸酯与苄醇的金属盐转化来制备4-苄氧乙酰乙酸酯。氢解反应可以在酸的存在下进行，从而在现场形成的4-羟基乙酰乙酸酯直接重排成四酮酸。氢解反应可以在加压的情况下在氢化催化剂的存在下进行。

  公开号：

  US04421922A1

文献信息

• Process for producing optically active gamma-butyrolactone
  申请人：——

  公开号：US20030105341A1

  公开（公告）日：2003-06-05

  This invention provides a novel process for producing optically active 3-hydroxy-&ggr;-butyrolactone in a short step, which is superior economically and in efficiency and industrially suitable by using a starting material which is inexpensive and easily available and reagents easy to handle. This invention relates to a process for producing optically active 3-hydroxy-&ggr;-butyrolactone represented by formula I: 1 wherein the symbol * means an asymmetric carbon atom, which comprises hydrogenating an optically active 4-substituted oxy-3-hydroxybutyrate represented by formula II: 2 wherein R 1 represents a C 1-4 lower alkyl group, R 2 represents a protective group for a hydroxyl group deprotected by hydrogenation with a heterogeneous hydrogenation catalyst, and the symbol * has the same meaning as defined above, in the presence of a heterogeneous hydrogenation catalyst and an acidic substance followed by deprotection and simultaneous ring closure thereof.

  本发明提供了一种新的生产光学活性3-羟基-γ-丁内酯的工艺，该工艺步骤短，经济高效，适合工业应用，使用的起始材料廉价易得，试剂易于处理。本发明涉及一种生产光学活性3-羟基-γ-丁内酯的工艺，其化学式为I:1，其中符号*表示不对称碳原子，包括在异质催化剂和酸性物质的存在下，氢化化合式II:2所代表的光学活性4-取代氧基-3-羟基丁酸酯，其中R1表示C1-4较低烷基基团，R2表示羟基的保护基，通过脱保护和同时环闭反应。
• [EN] PROCESS FOR THE PREPARATION OF TIPIRACIL HYDROCHLORIDE<br/>[FR] PROCÉDÉ DE PRÉPARATION DE TIPIRACIL CHLORHYDRATE
  申请人：AMNEAL PHARMACEUTICALS COMPANY GMBH

  公开号：WO2019002407A1

  公开（公告）日：2019-01-03

  The present invention relates to a process for preparation of tipiracil of formula (I) or salt thereof.

  本发明涉及制备式(I)的替匹拉酚或其盐的过程。
• Pyrrolopyridazinone Compound
  申请人：Hagihara Masahiko

  公开号：US20090036453A1

  公开（公告）日：2009-02-05

  The present invention discloses a pyrrolopyridazinone compound represented by the formula (1): wherein R 1 represents C 1 -C 2 alkyl group or halogeno C 1 -C 2 alkyl group, R 2 repersents C 3 -C 5 cycloalkyl group, (C 3 -C 5 cycloalkyl)C 1 -C 2 alkyl group or C 1 -C 3 alkyl group, R 3 represents hydrogen atom, or methylene group or cis-vinylene group for forming substituted oxygen-containing hetero ring in combination with group —O—R 2 , R 4 represents hydrogen atom, halogen atom, C 1 -C 8 alkyl group, C 2 -C 6 alkenyl group, C 2 -C 6 alkynyl group, hydroxy C 3 -C 6 alkenyl group, hydroxy C 3 -C 6 alkynyl group, C 1 -C 6 alkyl group substituted by substituent(s) selected from Substituent group (a), C 3 -C 6 cycloalkyl group which may be substituted by substituent(s) selected from Substituent group (b), “C 1 -C 3 alkyl group which is substituted by C 3 -C 6 cycloalkyl group which may be substituted by substituent(s) selected from Substituent group (b), and which may be substituted by a hydroxy group”, an aromatic ring group or heteroaromatic ring group each of which may be substituted by a substituent(s) selected from Substituent group (c) or “C 1 -C 2 alkyl group which is substituted by aromatic ring group or heteroaromatic ring group each of which may be substituted by group(s) selected from Substituent group (c), and which may be substituted by a hydroxy group”, Substituent group (a) represents a halogen atom, hydroxy group, cyano group, carboxy group, C 1 -C 5 alkoxy group, halogeno C 1 -C 4 alkoxy group, C 3 -C 6 cycloalkoxy group, (C 3 -C 6 cycloalkyl)C 1 -C 2 alkoxy group, C 1 -C 4 alkoxycarbonyl group, C 2 -C 4 alkanoyl group, C 2 -C 4 alkanoyloxy group or C 1 -C 4 alkyl-substituted amino group, Substituent group (b) represents a hydroxy group or a halogen atom, Substituent group (c) represents a halogen atom, a hydroxy group, a cyano group, a nitro group, a carboxy group, C 1 -C 5 alkoxy group, C 1 -C 4 alkoxycarbonyl group, C 2 -C 4 alkanoyloxy group, C 1 -C 4 alkyl-substituted amino group or a C 1 -C 4 alkyl group which may be substituted by a substituent(s) selected from the group consisting of (a halogen atom, a hydroxy group and a carboxy group), or a pharmaceutically acceptable salt thereof.

  本发明公开了一种由式（1）表示的吡咯吡啶二酮化合物：其中，R1代表C1-C2烷基或卤代C1-C2烷基，R2代表C3-C5环烷基、（C3-C5环烷基）C1-C2烷基或C1-C3烷基，R3代表氢原子，或与基团-O-R2结合形成取代含氧杂环的亚甲基或顺式乙烯基，R4代表氢原子、卤素原子、C1-C8烷基、C2-C6烯基、C2-C6炔基、羟基C3-C6烯基、羟基C3-C6炔基、由从取代基团（a）中选择的取代基团取代的C1-C6烷基，可由从取代基团（b）中选择的取代基团取代的C3-C6环烷基，可由从取代基团（b）中选择的取代基团取代的C1-C3烷基，且可由羟基取代，芳香环基或杂芳香环基，每个都可由从取代基团（c）中选择的取代基团取代或由取代基团（c）选择的基团取代的C1-C2烷基，且可由羟基取代，取代基团（a）表示卤素原子、羟基、氰基、羧基、C1-C5烷氧基、卤代C1-C4烷氧基、C3-C6环烷氧基、（C3-C6环烷基）C1-C2烷氧基、C1-C4烷氧羰基、C2-C4酰基、C2-C4酰氧基或C1-C4烷基取代的氨基基团，取代基团（b）表示羟基或卤素原子，取代基团（c）表示卤素原子、羟基、氰基、硝基、羧基、C1-C5烷氧基、C1-C4烷氧羰基、C2-C4酰氧基、C1-C4烷基取代的氨基基团或可由从由卤素原子、羟基和羧基组成的基团中选择的取代基团取代的C1-C4烷基，或其药学上可接受的盐。
• Process for producing optically active y-Butyrolactone
  申请人：Takasago International Corporation

  公开号：EP1277748A1

  公开（公告）日：2003-01-22

  A novel process for producing optically active 3-hydroxy-γ-butyrolactone in a short step, which is superior economically and in efficiency and industrially suitable by using a starting material which is inexpensive and easily available and reagents easy to handle. This invention relates to a process for producing optically active 3-hydroxy-γ-butyrolactone represented by formula I: wherein the symbol * means an asymmetric carbon atom, which comprises hydrogenating an optically active 4-substituted oxy-3-hydroxybutyrate represented by formula II: wherein R1 represents a C1-4 lower alkyl group, R2 represents a protective group for a hydroxyl group deprotected by hydrogenation with a heterogeneous hydrogenation catalyst, and the symbol * has the same meaning as defined above, in the presence of a heterogeneous hydrogenation catalyst and an acidic substance followed by deprotection and simultaneous ring closure thereof.

  一种在短步骤内生产光学活性 3-羟基-γ-丁内酯的新工艺，该工艺通过使用廉价易得的起始原料和易于处理的试剂，在经济性和效率方面具有优越性，并适用于工业。本发明涉及一种生产光学活性 3-羟基-γ-丁内酯的工艺，由式 I 表示： 其中符号 * 表示不对称碳原子，该工艺包括氢化由式 II 代表的具有光学活性的 4-取代氧基-3-羟基丁酸酯： 其中 R1 代表 C1-4 低级烷基，R2 代表通过异相氢化催化剂氢化脱保护羟基的保护基团，符号 * 的含义与上述定义相同，在异相氢化催化剂和酸性物质存在下，然后脱保护并同时闭环。
• Process for producing optically active alpha butyrolactone
  申请人：Takasago International Corporation

  公开号：EP1403262A1

  公开（公告）日：2004-03-31

  A novel process for producing optically active 3-hydroxy-γ-butyrolactone in a short step, which is superior economically and in efficiency and industrially suitable by using a starting material which is inexpensive and easily available and reagents easy to handle. This invention relates to a process for producing optically active 3-hydroxy-γ-butyrolactone represented by formula I: wherein the symbol * means an asymmetric carbon atom, which comprises hydrogenating an optically active 4-substituted oxy-3-hydroxybutyrate represented by formula II: wherein R1 represents a C1-4 lower alkyl group, R2 represents a protective group for a hydroxyl group deprotected by hydrogenation with a heterogeneous hydrogenation catalyst, and the symbol * has the same meaning as defined above, in the presence of a heterogeneous hydrogenation catalyst and an acidic substance followed by deprotection and simultaneous ring closure thereof.

  一种在短步骤内生产光学活性 3-羟基-γ-丁内酯的新工艺，该工艺通过使用廉价易得的起始原料和易于处理的试剂，在经济性和效率方面具有优越性，并适用于工业。本发明涉及一种生产光学活性 3-羟基-γ-丁内酯的工艺，由式 I 表示： 其中符号 * 表示不对称碳原子，该工艺包括氢化由式 II 代表的具有光学活性的 4-取代氧基-3-羟基丁酸酯： 其中 R1 代表 C1-4 低级烷基，R2 代表通过异相氢化催化剂氢化脱保护羟基的保护基团，符号 * 的含义与上述定义相同，在异相氢化催化剂和酸性物质存在下，然后脱保护并同时闭环。