methyl 4,6-dioxoheptanoate, keto-tautomer | 80480-42-8

• 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: methyl 4,6-dioxoheptanoate, keto-tautomer
• 英文别名: succinylacetone methyl ester；methyl 4,6-dioxoheptanoate；methyl-4,6-dioxoheptanoate
• CAS: 80480-42-8
• 化学式: C₈H₁₂O₄
• 分子量: 172.181
• InChiKey: RNKNGJNPKXTDJK-UHFFFAOYSA-N

物化性质

• 沸点：
  261.1±15.0 °C(Predicted)
• 密度：
  1.087±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  12
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  60.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 4,6-dioxoheptanoate, keto-tautomer 在 palladium on activated charcoal lead(IV) acetate 、 Montmorillonite clay K₁₀ 、 硫酸 、 氢溴酸 、 氢气 、 sodium acetate 、 potassium carbonate 、 溶剂黄146 、 三乙胺 、 三氟乙酸 、 copper dichloride 、 锌 作用下， 以 甲醇 、 二氯甲烷 、 溶剂黄146 、 丙酮 为溶剂， 25.0~90.0 ℃ 、275.79 kPa 条件下， 反应 27.25h， 生成 3,8,13,17-tetrakis<2-(methoxycarbonyl)ethyl>-7-<(methoxycarbonyl)methyl>-2,12,18-trimethylporphyrin
  参考文献：
  名称：

  Normal and Abnormal Heme Biosynthesis. 2.¹ Synthesis and Metabolism of Type-III Pentacarboxylic Porphyrinogens:  Further Experimental Evidence for the Enzymic Clockwise Decarboxylation of Uroporphyrinogen-III

  摘要：

  Uroporphyrinogen decarboxylase catalyses the sequential decarboxylation of uroporphyrinogen-III (1) to-give coproporphyrinogen-III (2), a precursor to the hemes and chlorophylls. This involves the decarboxylation of four nonequivalent acetate side chains to produce methyl units and in principle could take place by 24 different pathways involving up to 14 intermediary porphyrinogens. In the past, seemingly contradictory data have been presented that either support an ordered "clockwise" decarboxylation pathway or a random decarboxylation process. Four pentacarboxylate porphyrinogens might be involved immediately before the formation of 2, and these compounds have been synthesized as the corresponding porphyrin pentamethyl esters via tripyrrene and a,c-biladiene intermediates. Hydrolysis of the methyl esters and reduction with 3% sodium amalgam gave the required porphyrinogens, and these were incubated with crude enzyme preparations derived from chicken red cell hemolysates. One of these pentacarboxylate porphyrinogens (5dab) consistently proved to be a much better substrate than the other three, providing new support for the "clockwise" pathway for coproporphyrinogen-III formation.

  DOI：

  10.1021/jo9814748
• 作为产物：
  描述：

  在 对甲苯磺酸 作用下， 反应 1.0h， 以10.83 g的产率得到methyl 4,6-dioxoheptanoate, keto-tautomer
  参考文献：
  名称：

  Investigations regarding the utility of prodigiosenes to treat leukemia

  摘要：

  灵菌烯具有 4-甲氧基吡咯基二吡林骨架，以其抗癌活性而闻名。 C 环的结构修饰产生了一系列灵菌烯，在针对 NCI 60 癌细胞系组的体外分析中，这些灵菌烯显示出针对白血病细胞系的有希望的活性。使用斑马鱼模型对这些化合物进行的进一步体内研究表明，在人类 K562 慢性粒细胞白血病细胞中具有持久的抗白血病特性。

  DOI：

  10.1039/c2ob26535d

文献信息

• ALKALI-DEVELOPABLE PHOTOSENSITIVE RESIN COMPOSITION AND BETA-DIKETONE COMPOUND
  申请人：Yamada Takashi

  公开号：US20100129753A1

  公开（公告）日：2010-05-27

  An alkali developable photosensitive resin composition contains (J) a photopolymerizable unsaturated compound having a structure resulting from the addition reaction of (B) a compound having a β-diketone moiety or a compound having a β-ketoester group to the (meth)acryloyl group of (A) a compound having at least two (meth)acryloyl groups and a hydroxyl group and subsequent esterification of the hydroxyl group of the resulting addition product with (C) a polybasic acid anhydride. The compound having a β-diketone moiety is preferably a novel β-diketone compound represented by general formula (I): wherein R 1 is a C1-C20 alkyl group; R 2 represents R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 , or CN; R 11 , R 12 , and R 13 are each hydrogen, a C1-C20 alkyl group, etc.; a is 0 to 3; and b is 0 to 4.

  一种可由碱显影的光敏树脂组合物，含有（J）一种光聚合不饱和化合物，该化合物的结构是由（B）含β-二酮基团或含β-酮酯基团的化合物与（A）含至少两个(甲基)丙烯酰基团和一个羟基的化合物中的(甲基)丙烯酰基团发生加成反应，并随后将所得加成产物的羟基与（C）多元酸酐进行酯化反应得到的。含β-二酮基团的化合物最好是表示为通用公式（I）的一种新型β-二酮化合物：其中R1是C1-C20烷基团；R2代表R11、OR11、COR11、SR11、CONR12R13或CN；R11、R12和R13分别是氢、C1-C20烷基团等；a是0到3；b是0到4。
• Biosynthesis of porphyrins and related macrocycles. Part 16. Proof that the single intramolecular rearrangement leading to natural porphyrins (type-III) occurs at the tetrapyrrole level
  作者：Alan R. Battersby、Christopher J. R. Fookes、Mary J. Meegan、Edward McDonald、Hanns K. W. Wurziger

  DOI：10.1039/p19810002786

  日期：——

  established earlier is thus proved to take place at the tetrapyrole level. Synthesis of singly 13C-labelled bilane (2) followed by its enzymic conversion into uro'gen-III serves to register each of the pyrrole rings of the product relative to the initial bilane. Finally, methods for synthesis of the bilane are developed in two different doubly 13C-labelled forms to allow the following key points to be established

  未重排的氨基甲基胆烷（2）是通过合理的途径合成的，并被脱氨酶和辅酶合成，并协同作用转化为uro'gen-III（3）。因此证明了较早建立的单个重排步骤发生在四吡咯水平。单独合成13 C标记的胆烷（2），然后将其酶促转化为uro'gen-III，相对于初始胆烷来说，该产物的每个吡咯环均具有配准作用。最后，以两种不同的双13 C标记形式开发了合成胆烷的方法，从而可以通过13 C nmr光谱学在很大程度上确定以下关键点：（a）随着胆烷体系被转化为尿根-III，发生了末端环D的分子内重排，并且（b）线性四吡咯被完整地转化为尿根-III。
• Curable mixtures
  申请人：DAINIPPON INK AND CHEMICALS, INC.

  公开号：EP1323760A2

  公开（公告）日：2003-07-02

  A catalyst suitable for crosslinking reaction of a compound containing α,β-unsaturated carbonyl groups and a compound containing a CH-acidic methylene group is provided. A curable mixture comprises at least one compound containing at least two α,β-unsaturated carbonyl groups and at least one compound containing at least one CH-acidic methylene group and at least one trialkylphosphine.

  本发明提供了一种适用于含有α，β-不饱和羰基的化合物和含有 CH-酸性亚甲基的化合物进行交联反应的催化剂。可固化混合物包括至少一种含有至少两个 α，β-不饱和羰基的化合物和至少一种含有至少一个 CH-酸性亚甲基和至少一个三烷基膦的化合物。
• Photocurable composition, process for producing photocurable resin, and crosslinked product
  申请人：DAINIPPON INK AND CHEMICALS, INC.

  公开号：EP1342738A1

  公开（公告）日：2003-09-10

  A photocurable composition is provided which yields an excellent tack-free, hard cured product without any addition of photoinitiators. A photocurable composition which is excellent in storage stability is also provided. The photocurable composition contains a resin having an acryloyl group and a chemical structure element selected from the group consisting of β-diketone groups and β-ketoester groups, wherein the β-diketone group or the β-ketoester group has a tetra-substituted carbon atom between two carbonyl groups, which is capable of generating one or two free radicals under photoirradiation, and the photocurable composition does not increase more than 25% in viscosity when heated at 60°C for 5 days.

  本发明提供了一种光固化组合物，无需添加任何光引发剂，即可获得极佳的无粘性硬固化产品。此外，还提供了一种储存稳定性极佳的光固化组合物。这种光固化组合物含有一种具有丙烯酰基和化学结构元素的树脂，该化学结构元素选自 β-二酮基和 β-酮酯基组成的组，其中 β-二酮基或 β-酮酯基在两个羰基之间有一个四取代碳原子，在光照射下能产生一个或两个自由基，在 60°C 下加热 5 天，光固化组合物的粘度增加不超过 25%。
• Initiator-free crosslinkable oligomers and polymers
  申请人：DAINIPPON INK AND CHEMICALS, INC.

  公开号：EP1342737A1

  公开（公告）日：2003-09-10

  Acrylate group-containing oligomers and polymers that produce hard, tack-free and crosslinked products in the presence of air under UV light free from added photoinitiator, obtainable by reacting monomeric, oligomeric or polymeric β-ketoesters and β-diketones with monomeric, oligomeric or polymeric acrylic acid esters, wherein a) the acrylic acid esters that are used are at least difunctional b) the reaction is carried out in the presence of 0.3-5.0 wt.% of catalyst c) the reaction temperature is 60°-140°C d) the reaction temperature is maintained until the viscosity of the acrylate group-containing oligomers and polymers that are formed is constant e) the ratio of acrylic acid groups to β-dicarbonyl groups is 2.5:1 to 20:1. The acrylate group-containing oligomers and polymers are suitable for producing UV-hardenable coatings, printing inks, adhesives, sheets and moulding compositions.

  含丙烯酸酯基团的低聚物和聚合物，可通过使单体、低聚或聚合的 β-酮酯和β-二酮与单体、低聚或聚合的丙烯酸酯反应，在空气存在下，在不添加光引发剂的紫外光下生成坚硬、无粘性和交联的产品，其中 a) 所使用的丙烯酸酯至少具有双官能度 b) 反应在 0.3-5.0 重量百分比的催化剂存在下进行 c) 反应温度为 60°-140°C d) 反应温度保持恒定，直至形成的含丙烯酸酯基团的低聚物和聚合物的粘度不变 e) 丙烯酸基团与 β-二羰基基团的比例为 2.5:1 至 20:1。 含丙烯酸酯基团的低聚物和聚合物适用于生产紫外线硬化涂料、印刷油墨、粘合剂、板材和模塑组合物。