Methyl 3,3-dimethyl-2-oxocyclohexanecarboxylate | 101327-97-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl 3,3-dimethyl-2-oxocyclohexanecarboxylate
• 英文别名: 2-methoxycarbonyl-6,6-dimethylcyclohexanone；methyl 3,3-dimethyl-2-oxocyclohexane-1-carboxylate
• CAS: 101327-97-3
• 化学式: C₁₀H₁₆O₃
• 分子量: 184.235
• InChiKey: VHSWOYCDHVZSOU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Methyl 3,3-dimethyl-2-oxocyclohexanecarboxylate 在 sodium hydride 、 magnesium chloride 作用下， 以 四氢呋喃 、 二甲基亚砜 、 N,N-二甲基甲酰胺 为溶剂， 反应 30.25h， 生成 Ethyl 4-(3,3-dimethyl-2-oxocyclohexyl)butyrate
  参考文献：
  名称：

  Retinoids and Related Compounds. 17. Conformational Study of Retinochrome Chromophore: Synthesis of 8,18-Ethanoretinal and a New Retinochrome Analog

  摘要：

  In order to investigate the chromophore conformation around the trimethylcyclohexene ring in retinochrome, (all-E)-8,18-ethanoretinal (2), in which C-8 and C-18 positions of retinal 1 was connected by an ethylene group, was synthesized via the Dieckmann condensation of diester 6 from 2,2-dimethylcyclohexanone 7. This analog 2 was incorporated into aporetinochrome, forming a pigment with lambda(max) at 498 nm. Its opsin shift (2200 cm(-1)) is of the same order of magnitude as that of native retinochrome (2400 cm(-1)), suggesting that the conformations of both chromophores are fairly similar in the protein. In addition, MMX calculations indicate that the torsional angle around the 6-7 single bond in retinochrome might correspond to the allowable torsional angle in 8,18-ethanoretinal (2).

  DOI：

  10.1021/jo00102a015
• 作为产物：
  描述：

  2-甲基环己酮 在 sodium hydride 作用下， 生成 Methyl 3,3-dimethyl-2-oxocyclohexanecarboxylate
  参考文献：
  名称：

  β-二羰基化合物的α-羟基化

  摘要：

  各种β-二羰基化合物可以被-氯过苯甲酸（MCPBA）羟基化为它们的甲硅烷基烯醇醚。

  DOI：

  10.1016/s0040-4039(00)89191-1

文献信息

• An Improved Synthesis of Benzocycloalkanone Derivatives
  作者：Akimori Wada、Kyoko Sawada、Naomi Ono、Masayoshi Ito

  DOI：10.1248/cpb.52.132

  日期：——

  A convenient and improved annulation method for the synthesis of bicyclic ketones was developed. A 2,2-dimethyl-6-(2-phenylsulfonyl)ethylcyclohexanone was converted into a sulfonylester by the addition of ethyl acetate and subsequent dehydration. A Dieckmann type condensation of the sulfonylester followed by desulfonylation afforded the 8,8-dimethyl-1,2,3,4,5,6,7,8-octahydronaphthalene-2-one in good

  开发了一种方便且改进的合成双环酮的方法。通过加入乙酸乙酯并随后脱水，将2，2-二甲基-6-（2-苯基磺酰基）乙基环己酮转化为磺酰基酯。磺酰基酯的狄克曼型缩合，然后进行磺酰化以良好的产率得到8,8-二甲基-1,2,3,4,5,6,7,8-八氢萘-2-酮。该环状方法也适用于苯并环辛酮衍生物的合成。
• Carlactone-type strigolactones and their synthetic analogues as inducers of hyphal branching in arbuscular mycorrhizal fungi
  作者：Narumi Mori、Kenta Nishiuma、Takuya Sugiyama、Hideo Hayashi、Kohki Akiyama

  DOI：10.1016/j.phytochem.2016.05.012

  日期：2016.10

  chemically and evaluated for hyphal branching-inducing activity in germinating spores of the arbuscular mycorrhizal fungus Gigaspora margarita. Hyphal branching activity was found to correlate with the degree of oxidation at C-19 methyl. Carlactone was only weakly active (100 ng/disc), whereas carlactonoic acid showed comparable activity to the natural canonical strigolactones such as strigol and sorgomol

  宿主根部附近的菌丝分枝是丛枝菌根真菌的宿主识别反应。这种形态事件是由独脚金内酯引起的。独脚金内酯是类胡萝卜素衍生的萜类化合物，由卡拉内酯及其氧化衍生物合成。为了测试卡拉内酯及其氧化衍生物在丛枝菌根共生体中作为宿主来源的预定植信号的可能性，化学合成了卡拉内酯、卡拉内酯酸和卡拉内酯以及单羟基卡拉内酯、4-、18-和 19-羟基卡拉内酯并评估了丛枝菌根真菌 Gigaspora margarita 的萌发孢子中的菌丝分枝诱导活性。发现菌丝支化活性与 C-19 甲基的氧化程度相关。卡拉内酯只有微弱的活性 (100 ng/盘)，而卡拉内酯酸显示出与天然经典独脚金内酯如独脚金和山梨醇 (100 pg/盘) 相当的活性。C-4 或 C-18 的羟基化对活性没有显着影响。通过将甲酰基 Meldrum 酸与苄基、环己基甲基和环香叶醇（A 环部分）反应，然后偶联所得甲酰乙酸酯的烯醇钾，合成了一系列内酯类似物，命名为
• [EN] HETEROBICYCLIC COMPOUNDS AS HISTAMINE H4-RECEPTOR ANTAGONISTS<br/>[FR] COMPOSÉS HÉTÉROBICYCLIQUES UTILES COMME ANTAGONISTES DU RÉCEPTEUR H4 DE L'HISTAMINE
  申请人：UCB PHARMA SA

  公开号：WO2009047255A1

  公开（公告）日：2009-04-16

  The present invention concerns heterobicyclic compounds of formula (I) processes for preparing them, pharmaceutical compositions containing them and their use as pharmaceuticals.

  本发明涉及公式（I）的杂双环化合物，制备它们的方法，含有它们的药物组合物以及它们作为药物的用途。
• Retinoids and related compounds. Part 26. Synthesis of (11Z)-8,18-propano- and methano-retinals and conformational study of the rhodopsin chromophore†
  作者：Akimori Wada、Masako Tsutsumi、Yuka Inatomi、Hiroo Imai、Yoshinori Shichida、Masayoshi Ito

  DOI：10.1039/b104394n

  日期：——

  In order to clarify the conformation of the chromophore in rhodopsin, especially the effect of the torsional angle around the C6–C7 single bond on the CD spectrum, 8,18-propano- and methano-retinal 4 and 5 were prepared via the palladium-catalyzed coupling reaction of vinyl triflates derived from bicyclic ketones 10 and 27 with methyl (E)-3-(trimethylstannyl)but-2-enoate. In a binding experiment with bovine opsin, retinal analogs 4 and 5 afforded the new rhodopsin analogs. Although the opsin shifts of these pigments were similar to that of the native rhodopsin, CD spectra exhibited the characteristic feature owing to the locked structures of retinal analogs. This fact strongly indicates that the CD spectra were significantly influenced by the torsional angles around the 6–7 and 8–9 single bonds of the chromophore in the protein.

  为了弄清视网膜素中发色团的构象，特别是围绕 C6-C7 单键的扭转角对 CD 光谱的影响，我们通过钯催化双环酮 10 和 27 衍生的乙烯基三甲酸酯与 (E)-3-(trimethylstannyl)but-2-enoate 甲酯的偶联反应，制备了 8,18-丙基和甲基视网膜素 4 和 5。在与牛视网膜蛋白的结合实验中，视网膜类似物 4 和 5 得到了新的视网膜蛋白类似物。虽然这些色素的视紫红质偏移与原生视紫红质相似，但由于视网膜类似物的锁定结构，它们的 CD 光谱呈现出特有的特征。这一事实有力地表明，CD 光谱受到蛋白质中发色团 6-7 和 8-9 单键周围扭转角的显著影响。
• HETEROBICYCLIC COMPOUNDS AS HISTAMINE H4-RECEPTOR ANTAGONISTS
  申请人：Raphy Gilles

  公开号：US20100298289A1

  公开（公告）日：2010-11-25

  The present invention concerns heterobicyclic compounds of formula (I) processes for preparing them, pharmaceutical compositions containing them and their use as pharmaceuticals.

  本发明涉及式（I）的杂双环化合物，其制备过程，含有它们的制药组合物以及它们作为药物的用途。