2,2,4,4-tetramethyl-3-oxopentanedioic acid dimethyl ester | 10472-32-9

• 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: 2,2,4,4-tetramethyl-3-oxopentanedioic acid dimethyl ester
• 英文别名: dimethyl 2,2,4,4-tetramethyl-3-oxopentanedioate；2,2,4,4-tetramethyl-3-oxo-glutaric acid dimethyl ester；2,2,4,4-Tetramethyl-3-oxo-glutarsaeure-dimethylester；dimethyl 1,1,3,3-tetramethyl-2-oxo-1,3-propanedicarboxylate；3-Oxo-2,2,4,4-tetramethyl-glutarsaeure-dimethylester；Dimethyl-2,2,4,4-tetramethyl-3-pentanondiacid
• CAS: 10472-32-9
• 化学式: C₁₁H₁₈O₅
• 分子量: 230.261
• InChiKey: RHIKDGISMTUGTE-UHFFFAOYSA-N

物化性质

• 沸点：
  132-133 °C(Press: 20 Torr)
• 密度：
  1.074±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 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：

  2,2,4,4-tetramethyl-3-oxopentanedioic acid dimethyl ester 在 吡啶 、 盐酸 、 lithium aluminium tetrahydride 、 水 、 4-甲基苯磺酸吡啶 、 sodium hydride 、 pyridinium chlorochromate 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 16.0h， 生成 rac-(2S,3R)-3-hydroxy-3-(2-hydroxy-1,1-dimethylethyl)-2-(3-methoxyphenyl)-4,4-dimethyl-2,3,4,5-tetrahydrofuran
  参考文献：
  名称：

  Synthesis of bicyclic dioxetanes tethering a fluororescer through an ω-carbamoyl-substituted linker and their high-performance chemiluminescence in an aqueous system

  摘要：

  Bicyclic dioxetanes 3 and 4 tethering a fluorescein or 4-(benzothiazol-2-yl)-3-hydroxyphenyl moiety through a linker were synthesized by the use of dihydrofuran-intermediate 5 or its advanced intermediate 6. These dioxetanes underwent base-induced decomposition to effectively give light due to intramolecular energy-transfer from an excited oxidobenzoate to a tethered fluorophore. Although the chemiluminescence efficiency Phi(CL) values for 3 and 4 were only ca. 2-fold greater than that for parent 2 in a TBAF/acetonitrile system, these values were 30-550-fold greater than that for 2 in a NaOH/H2O system. Such marked increase of Phi(CL) was hardly observed by the simple addition of 25 or 26 as a model of a tethered fluorescer. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.04.078
• 作为产物：
  描述：

  1,3-丙酮二羧酸二甲酯 、 碘甲烷 在 sodium hydride 作用下， 生成 2,2,4,4-tetramethyl-3-oxopentanedioic acid dimethyl ester
  参考文献：
  名称：

  Synthesis of bicyclic dioxetanes tethering a fluororescer through an ω-carbamoyl-substituted linker and their high-performance chemiluminescence in an aqueous system

  摘要：

  Bicyclic dioxetanes 3 and 4 tethering a fluorescein or 4-(benzothiazol-2-yl)-3-hydroxyphenyl moiety through a linker were synthesized by the use of dihydrofuran-intermediate 5 or its advanced intermediate 6. These dioxetanes underwent base-induced decomposition to effectively give light due to intramolecular energy-transfer from an excited oxidobenzoate to a tethered fluorophore. Although the chemiluminescence efficiency Phi(CL) values for 3 and 4 were only ca. 2-fold greater than that for parent 2 in a TBAF/acetonitrile system, these values were 30-550-fold greater than that for 2 in a NaOH/H2O system. Such marked increase of Phi(CL) was hardly observed by the simple addition of 25 or 26 as a model of a tethered fluorescer. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.04.078

文献信息

• 1, 2-Dioxetane derivatives and reagents employing them
  申请人：TOSOH CORPORATION

  公开号：US20030207329A1

  公开（公告）日：2003-11-06

  A 1,2-dioxetane derivative of the formula (I): 1 wherein Ar is an aryl group which may have an alkyl group, an aryl group, a halogen atom, an alkoxyl group, a carboxyl group, a formyl group, an alkyl ester, an aryl ester, an alkylketone, an arylketone or a hetero ring bonded thereto, X is a substituent capable of labeling an organic compound or a biological molecule, or an ester, Y is a hydrogen atom, an acyl group or a group of the formula —Si(R 4 R 5 R 6 ) (wherein each of R 4 , R 5 and R 6 which are independent of one another, is an alkyl group or an aryl group), Z is an alkyl group, an aryl group, an oxygen atom, a sulfur atom, a carbonyl group, —(CO)—O—, —O—(CO)—, —NH—, —NH—CO—, —CO—NH—, —OSi(R 7 R 8 )— (wherein each of R 7 and R 8 which are independent of each other, is an alkyl group or aryl group) or a group of the formula —(R 9 R 10 )SiO— (wherein each of R 9 and R 10 which are independent of each other, is an alkyl group or an aryl group), each of R 1 and R 2 is an alkyl group or an aryl group, and R 3 is a spacer.

  Ar是一个可能带有烷基，芳香基，卤素原子，烷氧基，羧基，甲酰基，烷基酯，芳基酯，烷基酮，芳基酮或异环与之结合的芳基，X是能够标记有机化合物或生物分子的取代基，或酯，Y是氢原子，酰基或式—Si(R4R5R6)的基团（其中R4、R5和R6各自独立，是烷基或芳基），Z是烷基，芳基，氧原子，硫原子，羰基，—(CO)—O—，—O—(CO)—，—NH—，—NH—CO—，—CO—NH—，—OSi(R7R8)—（其中R7和R8各自独立，是烷基或芳基）或式—(R9R10)SiO—（其中R9和R10各自独立，是烷基或芳基），R1和R2各自是烷基或芳基，R3是一个间隔物。
• 1, 2-dioxetane derivatives and reagents employing them
  申请人：Matsumoto Masakatsu

  公开号：US20050153365A1

  公开（公告）日：2005-07-14

  A 1,2-dioxetane derivative of the formula (I): wherein Ar is an aryl group which may have an alkyl group, an aryl group, a halogen atom, an alkoxyl group, a carboxyl group, a formyl group, an alkyl ester, an aryl ester, an alkylketone, an arylketone or a hetero ring bonded thereto, X is a substituent capable of labeling an organic compound or a biological molecule, or an ester, Y is a hydrogen atom, an acyl group or a group of the formula —Si(R 4 R 5 R 6 ) (wherein each of R 4 , R 5 and R 6 which are independent of one another, is an alkyl group or an aryl group), Z is an alkyl group, an aryl group, an oxygen atom, a sulfur atom, a carbonyl group, —(CO)—O—, —O—(CO)—, —NH—, —NH—CO—, —CO—NH—, —OSi(R 7 R 8 )— (wherein each of R 7 and R 8 which are independent of each other, is an alkyl group or aryl group) or a group of the formula —(R 9 R 10 )SiO— (wherein each of R 9 and R 10 which are independent of each other, is an alkyl group or an aryl group), each of R 1 and R 2 is an alkyl group or an aryl group, and R 3 is a spacer.

  化合物的化学式为(I)的1,2-二氧杂环丙烷衍生物，其中Ar是一个芳基基团，可以带有一个烷基，一个芳基，一个卤素原子，一个烷氧基，一个羧基，一个甲酰基，一个烷基酯，一个芳基酯，一个烷基酮，一个芳基酮或与之结合的杂环，X是一个能够标记有机化合物或生物分子的取代基或酯基，Y是氢原子，酰基或公式—Si(R4R5R6)的基团（其中R4，R5和R6各自独立地是烷基或芳基），Z是烷基，芳基，氧原子，硫原子，羰基，—(CO)—O—，—O—(CO)—，—NH—，—NH—CO—，—CO—NH—，—OSi(R7R8)—（其中R7和R8各自独立地是烷基或芳基）或公式—(R9R10)SiO—的基团（其中R9和R10各自独立地是烷基或芳基），R1和R2各自是烷基或芳基，而R3是一个间隔基团。
• 1,2-dioxetane derivates and reagents employing them
  申请人：Tosoh Corporation

  公开号：EP1342724A1

  公开（公告）日：2003-09-10

  A 1,2-dioxetane derivative of the formula (I): wherein Ar is an aryl group which may have an alkyl group, an aryl group, a halogen atom, an alkoxyl group, a carboxyl group, a formyl group, an alkyl ester, an aryl ester, an alkylketone, an arylketone or a hetero ring bonded thereto, X is a substituent capable of labeling an organic compound or a biological molecule, or an ester, Y is a hydrogen atom, an acyl group or a group of the formula -Si(R4R5R6) (wherein each of R4, R5 and R6 which are independent of one another, is an alkyl group or an aryl group), Z is an alkyl group, an aryl group, an oxygen atom, a sulfur atom, a carbonyl group, -(CO)-O-, -O-(CO)-, -NH-, -NH-CO-, -CO-NH-, -OSi(R7R8)- (wherein each of R7 and R8 which are independent of each other, is an alkyl group or aryl group) or a group of the formula -(R9R10) SiO- (wherein each of R9 and R10 which are independent of each other, is an alkyl group or an aryl group), each of R1 and R2 is an alkyl group or an aryl group, and R3 is a spacer.

  式(I)的 1,2-二氧杂环丁烷衍生物： 其中 Ar 是芳基，可具有烷基、芳基、卤素原子、烷氧基、羧基、甲酰基、烷基酯、芳基酯、烷基酮、芳基酮或以其键合的杂环、Y 是氢原子、酰基或式 -Si(R4R5R6)的基团（其中 R4、R5 和 R6 各自独立、是烷基或芳基），Z 是烷基、芳基、氧原子、硫原子、羰基、-(CO)-O-、-O-(CO)-、-NH-、-NH-CO-、-CO-NH-、-OSi(R7R8)-（其中 R7 和 R8 各自独立、或式 -(R9R10) SiO- 的基团（其中 R9 和 R10 彼此独立，各自为烷基或芳基），R1 和 R2 各自为烷基或芳基，R3 为间隔物。
• Murin et al., Chemische Berichte, 1959, vol. 92, p. 2033,2037
  作者：Murin et al.

  DOI：——

  日期：——
• Synthesis and characterization of permethylated 1,3,5-tri- and 1,3,5,7-tetracarbonyl compounds
  作者：Silke Erfle、Thomas Rahn、Franziska Bendrath、Wolfgang Baumann、Dirk Michalik、Haijun Jiao、Anke Spannenberg、Armin Börner、Peter Langer

  DOI：10.1016/j.tet.2011.08.065

  日期：2011.11

  Permethylated 1,3,5-tri- and 1,3,5,7-tetracarbonyl compounds were prepared and structurally characterized. 2,2,4,4-Tetramethyl-3,5-dioxoesters were prepared by condensation of 1,3-bis(trimethylsilyloxy)-1,3-butadienes with acid chlorides and subsequent reaction with methyl iodide. 2,2,4,4,6,6-Hexa-substituted 3,5-dioxopimelates were prepared by condensation of 1,3-bis(trimethylsilyloxy)-1,3-butadienes with methyl 3-chloro-3-oxopropanoate and subsequent methylation. The use of caesium carbonate as the base for the methylation proved to be important to achieve good yields. The conformation of the products was studied by experimental and theoretical methods (DFT calculations). (C) 2011 Elsevier Ltd. All rights reserved.