dimethyl (acetoxymethylene)malonate | 88456-30-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: dimethyl (acetoxymethylene)malonate
• 英文别名: Dimethyl acetoxymethylenemalonate；Propanedioic acid, [(acetyloxy)methylene]-, dimethyl ester；dimethyl 2-(acetyloxymethylidene)propanedioate
• CAS: 88456-30-8
• 化学式: C₈H₁₀O₆
• 分子量: 202.164
• InChiKey: ILZMALAQUFATGO-UHFFFAOYSA-N

物化性质

• 沸点：
  210.7±30.0 °C(Predicted)
• 密度：
  1.229±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  dimethyl (acetoxymethylene)malonate 在 potassium tert-butylate 作用下， 以 四氢呋喃 、 甲苯 为溶剂， -78.0~25.0 ℃ 、1000.0 MPa 条件下， 生成 exo-dimethyl 2-<3,3-bis(methoxycarbonyl)bicyclo<2.2.1>hept-5-en-2-yl>malonate
  参考文献：
  名称：

  2-{3,3-双(甲氧基羰基)双环[2.2.1]庚-5-烯-2-基}丙二酸二甲酯。合成和碱催化的 C-C 键裂解反应

  摘要：

  环戊二烯与 1,1,3,3-四（甲氧基羰基）丙烯反应生成二甲基 2-{3,3-双（甲氧基羰基）双环-[2.2.1]hept-5-en-的内型和外型混合物2-基}丙二酸，通过碱介导的逆迈克尔反应，立体选择性地生成 2-{4-[2,2-双(甲氧羰基)乙烯基]环戊-2-烯-1-基}丙二酸二甲酯的顺式异构体.

  DOI：

  10.1246/cl.1994.1285
• 作为产物：
  描述：

  dimethyl (hydroxymethylene)malonate 生成 dimethyl (acetoxymethylene)malonate
  参考文献：
  名称：

  KATAGIRI, NOBUYA;AKATSUKA, HIDENORI;HANEDA, TORU;KANEKO, CHIKARA;SERA, AK+, J. ORG. CHEM., 53,(1988) N 23, C. 5464-5470

  摘要：

  DOI：

文献信息

• Diels–Alder Reaction of Dimethyl Acetoxymethylenemalonate with 3,4-Dialkoxyfurans and the Utility of Its Adducts in the Stereospecific Synthesis of Lyxopyranosyl C-Glycosides
  作者：Nobuya Katagiri、Hidenori Akatsuka、Toru Haneda、Chikara Kaneko

  DOI：10.1246/cl.1987.2257

  日期：1987.11.5

  Dimethyl lyxopyranosylmalonates were synthesized in stereospecific manner from the adducts obtained from Diels–Alder reaction of 3,4-dialkoxyfurans and dimethyl acetoxymethylenemalonate, through retrograde aldol C–C bond fission under reductive condition as a key step.

  二甲基吡喃糖基丙二酸酯是由 3,4-二烷氧基呋喃和乙酰氧基亚甲基丙二酸二甲酯的 Diels-Alder 反应得到的加合物以立体定向的方式合成的，关键步骤是在还原条件下通过逆行醛醇 C-C 键裂变。
• Synthesis of nucleosides and related compounds. XIV. Diels-Alder reaction of di-l-menthyl acetoxymethylenemalonate with cyclopentadiene: Effects of high-pressure and catalysts upon asymmetric induction.
  作者：Nobuya KATAGRI、Nobuhisa WATANABE、Chikara KANEKO

  DOI：10.1248/cpb.38.69

  日期：——

  Asymmetric Diels-Alder reaction of di-l-menthyl acetoxymethylenemalonate with cyclopentadiene under high pressure was examined. The yield, proportion of exo isomer, and diastereomeric excess (d.e.) of the adduct increased with increase of pressure when the reactions were carried out without any catalyst. The absolute structure of the major diastereoisomer of the endo adduct corresponded to the natural configuration, which could be transformed to a precursor of aristeromycin, while the exo adduct had the unnatural configuration. The same diastereoselectivity was also observed when diethylaluminum chloride (capable of chelating with only one carbonyl group of the dienophile) was used as the catalyst. On the contrary, both endo and exo isomers obtaiend from the high-pressure-mediated Diels-Alder reaction in the presence of zinc chloride or tris(6, 6, 7, 7, 8, 8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionato)ytterbium (capable of chelating with the two carbonyl groups of the dienophile at the same time) had the natural configuration. Possible mechanisms of these selectivities are proposed.

  研究了乙酰氧亚甲基丙二酸二对甲苯酯与环戊二烯在高压下的不对称 Diels-Alder 反应。在不使用任何催化剂的情况下进行反应时，加合物的产率、外异构体比例和非对映过量（d.e.）随压力的增加而增加。内向加合物的主要非对映异构体的绝对结构符合自然构型，可转化为阿里斯霉素的前体，而外向加合物则具有非自然构型。当使用二乙基氯化铝（只能与亲二烯的一个羰基螯合）作为催化剂时，也观察到了相同的非对映选择性。相反，在氯化锌或三(6, 6, 7, 7, 8, 8, 8-七氟-2, 2-二甲基-3, 5-辛二酮酸)镱（能同时与亲二烯的两个羰基螯合）存在下，高压介导的 Diels-Alder 反应所产生的内向和外向异构体都具有天然构型。提出了这些选择性的可能机制。
• Synthesis of Nucleosides and Related Compounds. XXVI. The Difference in Efects between High Pressure and LiClO4 for the Diels-Alder Reaction of Cyclopentadiene with Methylenemalonates or O-Acetylisonitrosomalonates.
  作者：Nobuya KATAGIRI、Ayumu KURIMOTO、Chikara KANEKO

  DOI：10.1248/cpb.40.1737

  日期：——

  Diels-Alder reactions of cyclopentadiene with methylenemalonates or O-acetylisonitrosomalonates in the presence of LiClO4 as the catalyst were examined and the results were compared with those obtained under high pressure without the catalyst. Diels-Alder reaction of cyclopentadiene with dimethyl acetoxymethylenemalonate (1) in the presence of LiClO4 afforded the [4+2] adduct (2) as a mixture of endo- and exo-isomers, whose ratio was 2.0, irrespective of the solvent or the concentration of LiClO4. Asymmetric Diels-Alder reaction of cyclopentadiene with di-l-methyl acetoxymethylenemalonate (3) was accelerated remarkably by LiClO4. The configurations of both endo and exo adducts corresponded to the natural form (D-form). These results suggested strongly that LiClO4 would behave as a bidentate Lewis acid catalyst just like titanium tetrachloride. the hetero Diels-Alder reaction of cyclopentadiene with O-acetylisonitrosomalonate in LiClO4-ether produced the adduct (5) in a higher yield than the reaction performed under high pressure.

  以 LiClO4 为催化剂，研究了环戊二烯与亚甲基丙二酸二甲酯或 O-乙酰基异亚硝基丙二酸二甲酯的 Diels-Alder 反应，并将结果与不使用催化剂在高压下得到的结果进行了比较。环戊二烯与乙酰氧基甲叉丙二酸二甲酯（1）在 LiClO4 存在下发生的 Diels-Alder 反应得到的 [4+2] 加合物（2）是内异构体和外异构体的混合物，其比例为 2.0，与溶剂或 LiClO4 的浓度无关。环戊二烯与二-l-甲基乙酰氧亚甲基丙二酸二酯（3）的不对称 Diels-Alder 反应在 LiClO4 的作用下明显加快。内向加合物和外向加合物的构型都与天然形式（D-form）一致。这些结果有力地表明，LiClO4 与四氯化钛一样，是一种双齿路易斯酸催化剂。环戊二烯与 O-乙酰基异硝基丙二酸酯在 LiClO4-ether 中的杂 Diels-Alder 反应生成的加合物（5）的产率比在高压下进行的反应更高。
• Katagiri, Nobuya; Haneda, Toru; Kaneko, Chikara, Chemical and pharmaceutical bulletin, 1986, vol. 34, # 11, p. 4875 - 4878
  作者：Katagiri, Nobuya、Haneda, Toru、Kaneko, Chikara

  DOI：——

  日期：——
• High pressure mediated Diels-Alder reaction of furan with dialkyl (acetoxymethylene)malonate
  作者：Akira Sera、Meguru Ohara、Toshiaki Kubo、Kuniaki Itoh、Hiroaki Yamada、Yuji Mikata、Chikara Kaneko、Nobuya Katagiri

  DOI：10.1021/jo00258a012

  日期：1988.11