8,8-dimethyl-5,6,7,8-tetrahydronaphthalen-2-ol | 94250-82-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: 8,8-dimethyl-5,6,7,8-tetrahydronaphthalen-2-ol
• 英文别名: 8,8-dimethyl-5,6,7,8-tetrahydro-2-naphthol；4,4-dimethyl-6-tetralol；1,1-Dimethyl-tetralol-(7)；1,1-Dimethyl-7-tetralol；2-Naphthalenol, 5,6,7,8-tetrahydro-8,8-dimethyl-；8,8-dimethyl-6,7-dihydro-5H-naphthalen-2-ol
• CAS: 94250-82-5
• 化学式: C₁₂H₁₆O
• 分子量: 176.258
• InChiKey: ZXDFAXFEHLLRJQ-UHFFFAOYSA-N

物化性质

• 熔点：
  105.6 °C
• 沸点：
  283.8±29.0 °C(Predicted)
• 密度：
  1.018±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  8,8-dimethyl-5,6,7,8-tetrahydronaphthalen-2-ol 、 硫酸二甲酯 在 potassium carbonate 作用下， 以 丙酮 为溶剂， 反应 13.0h， 以76%的产率得到1,1-二甲基-7-甲氧基-1,2,3,4-四氢萘
  参考文献：
  名称：

  Annulation of .alpha.-formyl .alpha.,.beta.-unsaturated ketones by a Michael addition-cyclization sequence. A versatile synthesis of alicyclic six-membered rings

  摘要：

  DOI：

  10.1021/jo00204a003
• 作为产物：
  描述：

  4,4-二甲基环己酮 在 palladium on activated charcoal 硫酸 、 potassium tert-butylate 、 氢气 、 sodium hydride 、 对甲苯磺酸 、 pyridinium hydrobromide perbromide 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 吡啶 、 乙醇 、 乙酸乙酯 、 叔丁醇 为溶剂， 反应 49.16h， 生成 8,8-dimethyl-5,6,7,8-tetrahydronaphthalen-2-ol
  参考文献：
  名称：

  Annulation of .alpha.-formyl .alpha.,.beta.-unsaturated ketones by a Michael addition-cyclization sequence. A versatile synthesis of alicyclic six-membered rings

  摘要：

  DOI：

  10.1021/jo00204a003

文献信息

• Chiral Anion Phase-Transfer Catalysis Applied to the Direct Enantioselective Fluorinative Dearomatization of Phenols
  作者：Robert J. Phipps、F. Dean Toste

  DOI：10.1021/ja311798q

  日期：2013.1.30

  ambient reaction conditions with high enantioselectivity. The close relationship of the products with well-studied o-quinols provides numerous avenues for synthetic elaboration and exciting opportunities for bioisosteric replacement of hydroxyl with fluorine in natural products.

  手性阴离子相转移催化使由 BINOL 衍生的磷酸盐催化的苯酚直接和高度对映选择性氟化脱芳构化成为可能。该过程在环境反应条件下以高对映选择性有效地将简单、容易获得的酚类转化为带有反应性官能团的氟化手性小分子。产品与经过充分研究的邻羟基喹啉的密切关系为合成加工提供了许多途径，并为天然产物中的氟生物等排置换羟基提供了令人兴奋的机会。
• [EN] ASYMMETRIC ELECTROPHILIC FLUORINATION USING AN ANIONIC CHIRAL PHASE-TRANSFER CATALYST<br/>[FR] FLUORATION ÉLECTROPHILE ASYMÉTRIQUE UTILISANT UN CATALYSEUR DE TRANSFERT DE PHASE CHIRAL ANIONIQUE
  申请人：UNIV CALIFORNIA

  公开号：WO2013096971A1

  公开（公告）日：2013-06-27

  The discovery of distinct modes of asymmetric catalysis has the potential to rapidly advance chemists' ability to build enantioenriched molecules. As an example, the use of chiral cation salts as phase-transfer catalysts for anionic reagents has enabled a vast set of enantioselective transformations. A largely overlooked analogous mechanism wherein a chiral anionic catalyst brings a cationic species into solution is itself a powerful method. The concept is broadly applicable to a number of different reaction pathways, including to the enantioselective fluorocyclization of olefins, and dearomatization of aromatic systems with a cationic electrophile-transferring (e.g., fluorinating) agent and a chiral phosphate catalyst. The reactions proceed in high yield and stereoselectivity. The compounds and methods of the invention are of particular value, especially considering the scarcity of alternative approaches.

  发现不对称催化的不同模式具有潜力快速推动化学家构建手性富集分子的能力。例如，使用手性阳离子盐作为相转移催化剂用于阴离子试剂已经实现了大量手性选择性转化。一个被大多数人忽视的类似机制是手性阴离子催化剂将阳离子物种溶解到溶液中，这本身就是一种强大的方法。这一概念广泛适用于许多不同的反应途径，包括对烯烃进行手性选择性氟环化和用阳离子亲电试剂转移（例如，氟化）剂和手性磷酸盐催化剂进行芳香系统去芳构化。这些反应产率高，立体选择性好。该发明的化合物和方法具有特殊价值，尤其考虑到替代方法的稀缺性。
• 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。
• Novel 2,3,4,5-tetrahydro-1H-[1,4]diazepino[1,7-a]indole compounds
  申请人：——

  公开号：US20020002161A1

  公开（公告）日：2002-01-03

  Certain 2,3,4,5-tetrahydro-1H-[1,4]diazepino[1,7-a]indoles are 5-HT ligands and are useful for treating diseases wherein modulation of 5-HT activity is desired.

  某些2,3,4,5-四氢-1H-[1,4]二氮杂丁[1,7-a]吲哚化合物是5-HT受体配体，并且可用于治疗需要调节5-HT活性的疾病。
• 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。