6,6-Dimethyl-2-(3,3-dimethylbutynyl)-2-cyclohexen-1-one | 157952-81-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6,6-Dimethyl-2-(3,3-dimethylbutynyl)-2-cyclohexen-1-one
• 英文别名: 2-(3,3-Dimethylbut-1-ynyl)-6,6-dimethylcyclohex-2-en-1-one
• CAS: 157952-81-3
• 化学式: C₁₄H₂₀O
• 分子量: 204.312
• InChiKey: NURBQTUUTGXKFK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 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：

  6,6-Dimethyl-2-(3,3-dimethylbutynyl)-2-cyclohexen-1-one 在 sodium hydroxide 、 双氧水 作用下， 以 甲醇 为溶剂， 以82%的产率得到3,3-dimethyl-1-(3,3-dimethylbut-1-ynyl)-7-oxabicyclo[4.1.0]heptan-2-one
  参考文献：
  名称：

  通过1-炔基-7-氧杂双环[4.1.0]庚烷-2-酮从2-炔基环己二-2-烯酮中制得2-炔基环戊-2-烯醇

  摘要：

  2-炔基环己-2-烯酮1a–c和2a–c与MeOH中的H 2 O 2 / NaOH反应，得到1-炔基-7-氧杂双环[4.1.0]庚-2-酮3a–c和4a–c， 分别。3-未取代的双环环氧酮3a，3b和4a，4b与H 2 O 2 / NaOH进一步反应，经历环收缩和（正式）脱羰基反应，生成2-炔基-环-2-戊烯基化合物5a，5b和6a ，6b分别。在环己酮1的辐射（λ= 350 nm）下，在中性条件下也可获得环氧酮3在空气饱和的苯溶液中。同样，在中性条件下氧代cycloalkenecarbonitriles 8反应（热）用H 2 ö 2在MeCN，得到oxabicyclic腈9。

  DOI：

  10.1002/hlca.19960790515
• 作为产物：
  描述：

  6,6-二甲基-2-环己烯-1-酮 在 四(三苯基膦)钯 作用下， 以 四氢呋喃 、 吡啶 、 四氯化碳 为溶剂， 生成 6,6-Dimethyl-2-(3,3-dimethylbutynyl)-2-cyclohexen-1-one
  参考文献：
  名称：

  Furans from Novel [3 + 2] Photocycloaddition of Alkenes to 2-(1-Alkynyl)cyclohexenones

  摘要：

  Photocycloaddition of 2-alkynyl-substituted cyclohexenones 8c-11c with isobutylene (2) and tetramethylethylene (3a) leads to tricyclic furans 15a-18a and 15b-17b; respectively, in gas chromatographic yields of similar to 90%. A suggested mechanism for this novel-process is shown in eq 2. Tetramethoxyethylene (3b) gives only oxetanes 22 and 23, and the 3-methyl-substituted ketone 12c fails to react with 2 and 3a,b. tert-Butylethylene gives [2 + 2] adduct 24 with 10c.

  DOI：

  10.1021/jo00097a049

文献信息

• ——
  作者：Birgit Witte、Lars Meyer、Paul Margaretha

  DOI：10.1002/(sici)1522-2675(20000315)83:3<554::aid-hlca554>3.0.co;2-i

  日期：2000.3.15

  Irradiation (350 nm) of 2-alkynylcyclohex-2-enones 1 in benzene in the presence of an excess of 2-methylbut-1-en-3-yne (2) affords in each case a mixture of a cis-fused 3,4,4a,5,6,8a-hexahydronaphthalen-1(2H)-one 3 and a bicyclo[4.2.0]octan-2-one 4 (Scheme 2), the former being formed as main product via 1,6-cyclization of the common biradical intermediate. The (parent) cyclohex-2-enone and other alkylcyclohex-2-enones 7 also give naphthalenones 8, albeit in lower yields, the major products being bicyclo[4.2.0]octan-2-ones (Scheme 4). No product derived from such a 1,6-cyclization is observed in the irradiation of 3-alkynylcyclohexenone 9 in the presence of 2 (Scheme 4). Irradiation of the 2-cyano-substituted cyclohexenone 12 under these conditions again affords only traces of naphthalenone 13, the main product now being the substituted bicyclo[4.2.0]oct-7-ene 16 (Scheme 5), resulting from [2 + 2] cycloaddition of the acetylenic C-C bond of 2 to excited 12.
• Furans from Novel [3 + 2] Photocycloaddition of Alkenes to 2-(1-Alkynyl)cyclohexenones
  作者：Paul Margaretha、William C. Agosta、Stefan Reichow

  DOI：10.1021/jo00097a049

  日期：1994.9

  Photocycloaddition of 2-alkynyl-substituted cyclohexenones 8c-11c with isobutylene (2) and tetramethylethylene (3a) leads to tricyclic furans 15a-18a and 15b-17b; respectively, in gas chromatographic yields of similar to 90%. A suggested mechanism for this novel-process is shown in eq 2. Tetramethoxyethylene (3b) gives only oxetanes 22 and 23, and the 3-methyl-substituted ketone 12c fails to react with 2 and 3a,b. tert-Butylethylene gives [2 + 2] adduct 24 with 10c.
• 2-Alkynylcyclopent-2-enols from 2-Alkynylcyclohex-2-enonesvia 1-Alkynyl-7-oxabicyclo[4.1.0]heptan-2-ones
  作者：Birgit Sander、Sven Andresen、Stefan Reichow、Katia Dubois、William C. Agosta、Paul Margaretha

  DOI：10.1002/hlca.19960790515

  日期：1996.8.7

  1-alkynyl-7-oxabicyclo[4.1.0]heptan-2-ones 3a–c and 4a–c, respectively. The 3-unsubstituted bicyclic epoxy ketones 3a, 3b, and 4a, 4b react further with H2O2/NaOH, undergoing ring contraction and (formal) decarbonylation to give 2-alkynylcy-clopent-2-enols 5a, 5b, and 6a, 6b, respectively. Epoxy ketones 3 are also obtained under neutral conditions on irradiation (λ = 350 nm) of cyclohexenones 1 in air-saturated

  2-炔基环己-2-烯酮1a–c和2a–c与MeOH中的H 2 O 2 / NaOH反应，得到1-炔基-7-氧杂双环[4.1.0]庚-2-酮3a–c和4a–c， 分别。3-未取代的双环环氧酮3a，3b和4a，4b与H 2 O 2 / NaOH进一步反应，经历环收缩和（正式）脱羰基反应，生成2-炔基-环-2-戊烯基化合物5a，5b和6a ，6b分别。在环己酮1的辐射（λ= 350 nm）下，在中性条件下也可获得环氧酮3在空气饱和的苯溶液中。同样，在中性条件下氧代cycloalkenecarbonitriles 8反应（热）用H 2 ö 2在MeCN，得到oxabicyclic腈9。