1-methoxy-1-methylspiro[2H-indene-3,4'-cyclohexa-2,5-diene]-1'-one | 115237-76-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: 1-methoxy-1-methylspiro[2H-indene-3,4'-cyclohexa-2,5-diene]-1'-one
• CAS: 115237-76-8
• 化学式: C₁₆H₁₆O₂
• 分子量: 240.302
• InChiKey: RFQLZEYTUDFYTP-UHFFFAOYSA-N

物化性质

• 沸点：
  381.4±42.0 °C(predicted)
• 密度：
  1.16±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-methoxy-1-methylspiro[2H-indene-3,4'-cyclohexa-2,5-diene]-1'-one 在 对甲苯磺酸 作用下， 以 氯仿 为溶剂， 反应 4.0h， 以86%的产率得到3'-methylspiro<2,5-cyclohexadiene-1,1'-inden>-4-one
  参考文献：
  名称：

  Intramolecular anodic carbon-carbon bond-forming reactions of oxidized phenol intermediates leading to spirodienones. Structural effects on reactivity and evidence for a phenoxonium ion intermediate

  摘要：

  Anodic oxidation of 4-phenylphenol in methanol leads to 4-methoxy-4-phenylcyclohexa-2,5-dienones whereas anodic oxidation of 4-(2-alkenylphenyl)-phenols leads to spirocyclic 2,5-cyclohexadienones in competition with methanol addition to the 4-position. Using 4-phenylphenol and (4-(2-propenylphenyl)phenol as model systems, the optimum conditions for solvent addition versus carbon-carbon bond formation have been studied. The yield of the anodic cyclization reaction shows a dramatic dependence on olefin structure. Whereas 4-(2-propenylphenyl)phenol gives the spirocyclic 2,5-cyclohexadienone in high yield, 4-(2-vinylphenyl)phenol affords the analogous product in only 16 % yield. This low yield of intramolecular carbon-carbon bond-forming reactions can be markedly improved if the vinyl substituent is forced closer to the 4-position of the phenol by the buttressing effect of a o-methyl group. Coloumetric studies as well as the oxidation chemistry of a (4-hydroxyphenyl)(2-propenylaryl)methane derivative support the involvement of a phenoxonium ion as the intermediate in these carbon-carbon bond-forming reactions. Finally, non-oxidative generation of a phenoxonium ion by reaction of 4-hydroxy-4-(2-propenylphenyl)2,5-cyclohexadieneone with methanesulfonyl chloride/triethylamine leads to spirodienones related to those isolated in the anodic oxidation chemistry. Although a slightly acidic media is critical for obtaining good yields of spirodienones for the propenyl system, anodic oxidation of the trimethylsilyl derivatives of the phenol allows this reaction to be performed in neutral or slightly basic media.

  DOI：

  10.1021/jo00064a017
• 作为产物：
  描述：

  4-(2-Prop-1-en-2-ylphenyl)phenol 在 吡啶 、 lithium perchlorate 作用下， 反应 2.23h， 生成 1-methoxy-1-methylspiro[2H-indene-3,4'-cyclohexa-2,5-diene]-1'-one
  参考文献：
  名称：

  Intramolecular anodic carbon-carbon bond-forming reactions of oxidized phenol intermediates leading to spirodienones. Structural effects on reactivity and evidence for a phenoxonium ion intermediate

  摘要：

  Anodic oxidation of 4-phenylphenol in methanol leads to 4-methoxy-4-phenylcyclohexa-2,5-dienones whereas anodic oxidation of 4-(2-alkenylphenyl)-phenols leads to spirocyclic 2,5-cyclohexadienones in competition with methanol addition to the 4-position. Using 4-phenylphenol and (4-(2-propenylphenyl)phenol as model systems, the optimum conditions for solvent addition versus carbon-carbon bond formation have been studied. The yield of the anodic cyclization reaction shows a dramatic dependence on olefin structure. Whereas 4-(2-propenylphenyl)phenol gives the spirocyclic 2,5-cyclohexadienone in high yield, 4-(2-vinylphenyl)phenol affords the analogous product in only 16 % yield. This low yield of intramolecular carbon-carbon bond-forming reactions can be markedly improved if the vinyl substituent is forced closer to the 4-position of the phenol by the buttressing effect of a o-methyl group. Coloumetric studies as well as the oxidation chemistry of a (4-hydroxyphenyl)(2-propenylaryl)methane derivative support the involvement of a phenoxonium ion as the intermediate in these carbon-carbon bond-forming reactions. Finally, non-oxidative generation of a phenoxonium ion by reaction of 4-hydroxy-4-(2-propenylphenyl)2,5-cyclohexadieneone with methanesulfonyl chloride/triethylamine leads to spirodienones related to those isolated in the anodic oxidation chemistry. Although a slightly acidic media is critical for obtaining good yields of spirodienones for the propenyl system, anodic oxidation of the trimethylsilyl derivatives of the phenol allows this reaction to be performed in neutral or slightly basic media.

  DOI：

  10.1021/jo00064a017

文献信息

• Spiro-annulated 2,5-cyclohexadienones via oxidation of 2′-alkenyl-p-phenyl phenols with iodobenzene diacetate
  作者：Andrew Callinan、Ying Chen、Gary W. Morrow、John S. Swenton

  DOI：10.1016/s0040-4039(00)97673-1

  日期：1990.1

  The oxidation of 2′-alkenyl-substituted p-phenyl phenols via iodobenzene diacetate gives spiro-annulated-2,5-cyclohexadienones.

  经由碘代苯二乙酸酯对2'-烯基取代的对苯基苯酚的氧化得到螺环化的2,5-环己二酮。
• Intramolecular cyclization of 2'-olepinic side-chains on anodically oxidized 4-phenylphenols. The effect of olefin substituents on carbon—carbon bond formation
  作者：Gary W. Morrow、Ving Chen、John S. Swenton

  DOI：10.1016/s0040-4020(01)87055-1

  日期：1991.1

  The anodic oxidation of 4-(2′-alkenyfphenyl)phenols in acetonitrile/methanol affords spirodienones arising from cyclization of the olefinic side-chain to the 4-position of the phenol and reaction of the resulting benzylic cation with methanoi. The efficiency of this carbon—carbon bond-forming reaction is dependent upon the olefinic substituents.

  在乙腈/甲醇中对4-（2'-链烯基苯基）苯酚进行阳极氧化可提供螺二烯酮，该螺二烯酮是由烯属侧链环化至苯酚的4-位以及所得苄基阳离子与甲烷反应而产生的。形成碳-碳键的反应的效率取决于烯烃取代基。
• Spiro-annulated cyclohexa-2,5-dienones via electrooxidation of p-aryl phenols a novel mode of anodic carbon-carbon bond formation
  作者：Gary W. Morrow、John S. Swenton

  DOI：10.1016/s0040-4039(00)96750-9

  日期：1987.1
• CALLINAN, ANDREW;YING, CHEN;MORROW, GARY W.;SWENTON, JOHN S., TETRAHEDRON LETT., 31,(1990) N2, C. 4551-4552
  作者：CALLINAN, ANDREW、YING, CHEN、MORROW, GARY W.、SWENTON, JOHN S.

  DOI：——

  日期：——