diethyl 2-methylbutylidenemalonate | 185320-54-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: diethyl 2-methylbutylidenemalonate
• 英文别名: Diethyl 2-(2-methylbutylidene)propanedioate
• CAS: 185320-54-1
• 化学式: C₁₂H₂₀O₄
• 分子量: 228.288
• InChiKey: JDVMLQDSFQHZSV-UHFFFAOYSA-N

物化性质

• 沸点：
  253.5±13.0 °C(Predicted)
• 密度：
  1.003±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  16
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  diethyl 2-methylbutylidenemalonate 在 三乙胺 、 三氟乙酸 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 (+/-)-trans-2-ethyl-3-hydroxy-2,8-dimethyl-2,3-dihydro-4H-furo[2,3-d]pyrido[1,2-a]pyrimidin-4-one
  参考文献：
  名称：

  Electro-organic Reactions. Part 49. The Synthesis and Stereoselective Electrochemical Hydroxylation of 2,3-Dihydro-4H-furo[2,3-d]pyrido[1,2-a]pyrimidin-4-ones.

  摘要：

  Attempted electrochemical (anodic) hydroxylation of pyridopyrimidine derivatives in the pyridine ring, using trifluoroacetate as nucleophile, fails because enol forms predominate which undergo anodic C-O coupling. Substitution, aimed at precluding enolisation, led to an alternative tautomerisation to 8-methyl-3-alkylmethylene-4H-pyrido [1,2-a]pyrimidine-2,4-diones which in acidic solution are converted into the title compounds. The 8-methyl-2,3-dihydro-4H-furo[2,3-d]pyrido[1,2-a]pyrimidine-4-ones are novel and have been fully characterised by spectroscopy and X-ray crystallography. They are electroactive and are oxidised anodically in trifluoroacetic acid-dichloromethane-triethylammonium trifluoroacetate solutions to give the corresponding 3-hydroxy derivatives in good yield. Several examples of this allylic substitution reaction are presented; for cases disubstituted at the 2-position (R-1,R-2) diastereoselective hydroxylation with d.e. ca. 50% (3:1) is observed in which preferential nucleophilic attack on the stabilised intermediate allylic cation occurs at the least hindered face. The stereochemistry of the 3-hydroxy derivatives was assigned by NOE experiments.

  DOI：

  10.3891/acta.chem.scand.53-0901
• 作为产物：
  描述：

  2-甲基丁醛 、 丙二酸二乙酯 在 哌啶乙酸盐 作用下， 以 苯 为溶剂， 以90%的产率得到diethyl 2-methylbutylidenemalonate
  参考文献：
  名称：

  Electro-organic Reactions. Part 49. The Synthesis and Stereoselective Electrochemical Hydroxylation of 2,3-Dihydro-4H-furo[2,3-d]pyrido[1,2-a]pyrimidin-4-ones.

  摘要：

  Attempted electrochemical (anodic) hydroxylation of pyridopyrimidine derivatives in the pyridine ring, using trifluoroacetate as nucleophile, fails because enol forms predominate which undergo anodic C-O coupling. Substitution, aimed at precluding enolisation, led to an alternative tautomerisation to 8-methyl-3-alkylmethylene-4H-pyrido [1,2-a]pyrimidine-2,4-diones which in acidic solution are converted into the title compounds. The 8-methyl-2,3-dihydro-4H-furo[2,3-d]pyrido[1,2-a]pyrimidine-4-ones are novel and have been fully characterised by spectroscopy and X-ray crystallography. They are electroactive and are oxidised anodically in trifluoroacetic acid-dichloromethane-triethylammonium trifluoroacetate solutions to give the corresponding 3-hydroxy derivatives in good yield. Several examples of this allylic substitution reaction are presented; for cases disubstituted at the 2-position (R-1,R-2) diastereoselective hydroxylation with d.e. ca. 50% (3:1) is observed in which preferential nucleophilic attack on the stabilised intermediate allylic cation occurs at the least hindered face. The stereochemistry of the 3-hydroxy derivatives was assigned by NOE experiments.

  DOI：

  10.3891/acta.chem.scand.53-0901

文献信息

• METHOD OF PRODUCING A BISBENZODITHIOL COMPOUND
  申请人：Motoki Masuji

  公开号：US20090240067A1

  公开（公告）日：2009-09-24

  A method of producing a compound represented by formula (1), including: allowing 1,4-benzoquinone or 1,2-benzoquinone to react with a dithiocarbamate compound represented by formula (2) in a polar solvent: wherein R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R 1 and R 2 may be the same or different and may be combined with each other to form a ring, X represents an ion necessary to neutralize the charge of the molecule, m represents an integer of 1 to 2, n represents an integer of 1 to 2, M represents a hydrogen atom, a metal atom or a conjugate acid of a base, p represents an integer of 1 to 4, and q represents an integer of 1 to 4.

  一种生产由化学式（1）表示的化合物的方法，包括：允许1,4-苯醌或1,2-苯醌在极性溶剂中与由化学式（2）表示的二硫代氨基甲酸盐化合物发生反应：其中R1和R2各自独立地表示氢原子、烷基、芳基或杂环基，R1和R2可以相同也可以不同，并且可以结合在一起形成环，X表示中性化分子电荷所需的离子，m表示1至2的整数，n表示1至2的整数，M表示氢原子、金属原子或碱的共轭酸，p表示1至4的整数，q表示1至4的整数。
• Synthesis of [1.1.1]Propellanes by Bridging of Bicyclo[1.1.0]butanes
  作者：Markus Werner、David S. Stephenson、Günter Szeimies

  DOI：10.1002/jlac.199619961103

  日期：1996.11

  Several [1.1.1]propellanes were synthesized by bridging the 1,3-positions of the corresponding bicyclo[1.1.0]butane. The synthesis of 1-bromo-3-(chloromethyl)bicyclobutanes and the bridging were carried out in a one-pot reaction by addition of 2.0 equiv. of MeLi to 1,1-dibromo-2,2-bis(chlormethyl)-cyclopropanes 10. Three routes to 10 were investigated: Firstly, the Wittig reaction of 1,3-dichloroacetone

  通过桥接相应的双环[1.1.0]丁烷的1,3-位，合成了几种[1.1.1]丙炔。1-溴-3-（氯甲基）双环丁烷的合成和桥连通过添加2.0当量的一锅法进行。MeLi合成1,1-二溴-2,2-双（氯甲基）-环丙烷10。研究了10种方法的三种途径：首先，除6m外，1,3-二氯丙酮的Wittig反应成功生成（氯甲基）烯丙基氯6，仅用衍生自伯烷基卤化物的Wittig试剂成功，其次，还原二乙基与苯中的LiAlH 4的亚烷基丙二酸酯，得到甲醇12，将其转化为6通过与N-氯代琥珀酰亚胺/二甲基硫醚反应。的环丙烷化6至10是通过相转移催化的条件下与溴仿/ NaOH调节反应来实现的。最后，根据顺序11 13 14 10，从亚烷基丙二酸二乙酯开始，还原和环丙烷化的顺序可以互换。丙烷5b和3用LiAlH 4还原为双环[1.1.1]戊烷15b和e。5d和5p的二维INADEQUATE NMR光谱表明耦合常数J（13
• SOLID CATALYST COMPONENT FOR OLEFIN POLYMERIZATION, CATALYST FOR OLEFIN POLYMERIZATION, AND METHOD FOR PRODUCING OLEFIN POLYMER
  申请人：Uozumi Toshiya

  公开号：US20140221583A1

  公开（公告）日：2014-08-07

  An olefin polymer that is obtained using an olefin polymerization catalyst that includes a solid catalyst component for olefin polymerization that includes titanium, magnesium, a halogen, and an ester compound (A) represented by the following formula (1): R 1 R 2 C═C(COOR 3 )(COOR 4 ), an organoaluminum compound, and an optional external electron donor compound, exhibits primary properties (e.g., molecular weight distribution and stereoregularity) similar to those of an olefin polymer obtained using a solid catalyst component that includes a phthalic ester as an electron donor.

  使用一种包括钛、镁、卤素和酯化合物(A)的固体催化剂组分（式子1：R1R2C═C(COOR3)(COOR4)）进行烯烃聚合得到的烯烃聚合物，加上有机铝化合物和可选的外部电子给体化合物，表现出与包括邻苯二甲酸酯作为电子给体的固体催化剂组分得到的烯烃聚合物相似的主要性质（如分子量分布和立构规则性）。
• Method for producing solid catalyst component for olefin polymerization, catalyst for olefin polymerization and a process for propylene polymerization
  申请人：TOHO TITANIUM CO., LTD.

  公开号：US10246530B2

  公开（公告）日：2019-04-02

  A method for producing a solid catalyst for olefin (co)polymerization includes bringing into contact with each other a magnesium compound, a tetravalent titanium halide compound, an organic compound represented the following general formula (1) R1k(C6H4-k)(COOR2)(COOR3)  (1) and an organic compound represented the following general formula (2) R4R5C═C (COOR6)(COOR7)  (2) wherein R1 is a halogen atom or an alkyl group, R2 and R3 are a linear alkyl group, R4 and R5 are independently an atom or group selected from a hydrogen atom, halogen, a linear alkyl group, a branched alkyl group a vinyl group, a linear or branched alkenyl group, a cycloalkenyl group, an aromatic hydrocarbon group, and R6 and R7 are independently a linear alkyl group, a branched alkyl group, a vinyl group, a linear or branched alkenyl group a cycloalkyl group, a cycloalkenyl group, or an aromatic hydrocarbon group.

  一种生产烯烃（共）聚合用固体催化剂的方法，包括使镁化合物、四价卤化钛化合物、下 列通式（1）代表的有机化合物相互接触 R1k(C6H4-k)(COOR2)(COOR3) (1) 和 代表以下通式(2)的有机化合物 R4R5C═C (COOR6)(COOR7) (2) 其中 R1 是卤素原子或烷基，R2 和 R3 是直链烷基，R4 和 R5 独立地是选自氢原子、卤素、直链烷基、支链烷基、乙烯基、直链或支链烯基、环烯基、芳香烃基的原子或基团，R6 和 R7 独立地是直链烷基、支链烷基、乙烯基、直链或支链烯基、环烷基、环烯基或芳香烃基。
• METHOD FOR PRODUCING SOLID CATALYST COMPONENT FOR OLEFIN POLYMERIZATION, CATALYST FOR OLEFIN POLYMERIZATION AND A PROCESS FOR PROPYLENE POLYMERIZATION
  申请人：Toho Titanium Co., Ltd.

  公开号：EP3645586A1

  公开（公告）日：2020-05-06