2-methylene-1-tetralone | 13203-73-1

• 物质功能分类: 化学试剂 - 有机试剂 - 多环化合物
• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: 2-methylene-1-tetralone
• 英文别名: 2-methylene-3,4-dihydronaphthalen-1(2H)-one；2-methylene-3,4-dihydro-2H-naphthalen-1-one；3,4-dihydro-2-methylene-1(2H)-naphthalenone；2-Methylenetetralin-1-one；2-methylidene-3,4-dihydronaphthalen-1-one
• CAS: 13203-73-1
• 化学式: C₁₁H₁₀O
• 分子量: 158.2
• InChiKey: VKRKOOOBSIIARV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-methylene-1-tetralone 以100%的产率得到spiro<2,3,5,6-tetrahydro-7,8-benzo-1-chroman-2,2'-(1',2',3',4'-tetrahydronaphthalen-1'-one)>
  参考文献：
  名称：

  N-Methylanilinium trifluoroacetate-promoted Prins reaction of α-methylene-α-tetralone dimers: generation of new molecular scaffolds

  摘要：

  alpha-Methylene-alpha-tetralone dimers (8-10) are shown to undergo a diastereoselective Prins reaction with paraformaldehyde in the presence of N-methylanilinium trifluoroacetate resulting in 2, 4, and 5. The structure of the new scaffold 2 was confirmed by X-ray crystallographic analysis. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2011.09.017
• 作为产物：
  描述：

  2-(piperidinomethyl)tetral-1-one hydrochloride 120.0~230.0 ℃ 、0.4 Pa 条件下， 生成 2-methylene-1-tetralone
  参考文献：
  名称：

  Muehlstaedt,M.; Gensrich,H.-J., Journal fur praktische Chemie (Leipzig 1954), 1966, vol. 34, p. 139 - 144

  摘要：

  DOI：

文献信息

• Efficient α-Methylenation of Carbonyl Compounds in Ionic Liquids at Room Temperature
  作者：J. Rodrigues、Juliana Vale、Daniel Zanchetta、Paulo Moran

  DOI：10.1055/s-0028-1087389

  日期：——

  The application of several 1-butyl-3-methylimidazolium (BMIM) salt ionic liquids as solvent in the α-methylenation of carbonyl compounds at room temperature is reported. The ionic liquid [BMIM][NTf2] gave a clean reaction in a short time and good yields of several α-methylene carbonyl compounds. This ionic liquid was reused without affecting the reaction rates or yields over seven runs.

  报道了几种1-丁基-3-甲基咪唑鎓（BMIM）盐离子液体在常温下对羰基化合物进行α-亚甲基化的溶剂应用。离子液体[BMIM][NTf2]在短时间内提供了干净的反应和多种α-亚甲基羰基化合物的高产率。这种离子液体在连续七次使用中重复使用，未影响反应速率或产率。
• Highly Enantioselective Construction of a Chiral Spirocyclic Structure by the [2 + 2 + 2] Cycloaddition of Diynes and <i>exo</i>-Methylene Cyclic Compounds
  作者：Kyoji Tsuchikama、Yusuke Kuwata、Takanori Shibata

  DOI：10.1021/ja064257u

  日期：2006.10.1

  The enantioselective [2 + 2 + 2] cycloaddition of 1,6-diynes with alpha-methylene lactones and cyclic ketones gave various chiral spirocyclic compounds. The reaction proceeded with high enantioselectivity when the rhodium-xylylBINAP complex was used as a chiral catalyst. Not only exo-methylene cyclic compounds but also exo-methylene acyclic compounds could be used as coupling partners for diynes. The

  1,6-二炔与α-亚甲基内酯和环酮的对映选择性[2+2+2]环加成得到各种手性螺环化合物。当铑-二甲苯基BINAP配合物用作手性催化剂时，反应以高对映选择性进行。不仅外型亚甲基环状化合物而且外型亚甲基无环化合物都可以用作二炔的偶联伙伴。本协议提供对具有四元碳中心（包括螺环系统）的新手性库的访问。
• Transition Metal-Free α-Csp³-H Methylenation of Ketones to Form C═C Bond Using Dimethyl Sulfoxide as Carbon Source
  作者：Yu-Feng Liu、Peng-Yi Ji、Jing-Wen Xu、Yu-Qun Hu、Qiang Liu、Wei-Ping Luo、Can-Cheng Guo

  DOI：10.1021/acs.joc.7b00619

  日期：2017.7.21

  metal-free reaction condition. Various aryl ketone derivatives react readily with DMSO, producing the α,β-unsaturated carbonyl compounds in yields of 42 to 90%. This method features a transition metal-free reaction condition, wide substrate scope and using DMSO as novel one-carbon source to form C═C bond, thus providing an efficient and expeditious approach to an important class of α,β-unsaturated carbonyl

  直接α-CSP 3 -H arylketones使用二甲亚砜作为单碳源过渡不含金属的反应条件下实现的，以形成C = C键的亚甲基化。各种芳基酮衍生物容易与DMSO反应，生成α，β-不饱和羰基化合物，产率为42％至90％。该方法具有无过渡金属的反应条件，较宽的底物范围以及使用DMSO作为新型一碳源形成C═C键的特点，从而为一种重要的α，β-不饱和羰基化合物提供了有效而快捷的方法。基于初步实验，揭示了这种转化的合理机制。
• Asymmetric Catalytic Epoxidation of Terminal Enones for the Synthesis of Triazole Antifungal Agents
  作者：Qianwen He、Dong Zhang、Fengcai Zhang、Xiaohua Liu、Xiaoming Feng

  DOI：10.1021/acs.orglett.1c02588

  日期：2021.9.3

  An enantioselective epoxidation of α-substituted vinyl ketones was realized to construct the key epoxide intermediates for the synthesis of various triazole antifungal agents. The reaction proceeded efficiently in high yields with good enantioselectivities by employing a chiral N,N′-dioxide/ScIII complex as the chiral catalyst and 35% aq. H2O2 as the oxidant. It enabled the facile transformation for

  实现了α-取代乙烯基酮的对映选择性环氧化，构建了合成各种三唑类抗真菌剂的关键环氧化物中间体。通过使用手性N,N'-二氧化物/Sc III配合物作为手性催化剂和 35% 的水溶液，该反应以高产率和良好的对映选择性有效进行。H 2 O 2作为氧化剂。它使光学活性艾沙康唑、依氟康唑和其他潜在的抗真菌剂的转化成为可能。
• Synthesis of 1,3-Aminoalcohols and Spirocyclic Azetidines via Tandem Hydroxymethylation and Aminomethylation Reaction of β-Keto Phosphonates with <i>N</i>-Nosyl-<i>O</i>-(2-bromoethyl)hydroxylamine
  作者：Binyu Wu、Hongbing Chen、Min Gao、Xiangnan Gong、Lin Hu

  DOI：10.1021/acs.orglett.1c01091

  日期：2021.6.4

  α-aminomethylation reaction of aromatic cyclic β-keto phosphonates with N-nosyl-O-(2-bromoethyl)hydroxylamine in the presence of DBU base has been developed, affording a range of 1,3-aminoalcohols in good yields. The resultant products could be flexibly transformed into the spirocyclic and bispirocyclic azetidines via one step of Mitsunobu reaction. Mechanistic study revealed that hydroxylamine in situ generated

  在 DBU 碱存在下，芳香环 β-酮膦酸酯与N - nosyl - O-（2-溴乙基）羟胺的前所未有的串联 α-羟甲基化和 α-氨基甲基化反应被开发出来，得到了一系列 1,3-氨基醇收益良好。所得产物可以通过Mitsunobu反应一步灵活地转化为螺环和双螺环氮杂环丁烷。机理研究表明，羟胺原位生成甲醛和诺磺酰胺，进而引发连续的 Horner-Wadsworth-Emmons、Michael 和 aldol 反应。