2-(3,3-dimethyl-but-1-ynyl)-5,5-dimethylcyclohex-2-enone | 142672-76-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(3,3-dimethyl-but-1-ynyl)-5,5-dimethylcyclohex-2-enone
• 英文别名: 5,5-Dimethyl-2-(3,3-dimethylbut-1-ynyl)cyclohex2-enone；2-(3,3-dimethylbut-1-ynyl)-5,5-dimethylcyclohex-2-en-1-one
• CAS: 142672-76-2
• 化学式: C₁₄H₂₀O
• 分子量: 204.312
• InChiKey: JILCZAAKOVNQOR-UHFFFAOYSA-N

物化性质

• 沸点：
  299.7±30.0 °C(Predicted)
• 密度：
  0.94±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 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：

  2-(3,3-dimethyl-but-1-ynyl)-5,5-dimethylcyclohex-2-enone 在 sodium hydroxide 、 双氧水 作用下， 以 甲醇 为溶剂， 以74%的产率得到4,4-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：

  三丁基(3,3-二甲基丁-1-炔基)锡烷 、 2-iodo-5,5-dimethylcyclohex-2-enone 在 四(三苯基膦)钯 作用下， 以 四氢呋喃 为溶剂， 以42%的产率得到2-(3,3-dimethyl-but-1-ynyl)-5,5-dimethylcyclohex-2-enone
  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

• Photocycloaddition of cyclohex-2-enones to acrylonitrile
  作者：Lars Meyer、Nacira Alouane、Kerstin Schmidt、Paul Margaretha

  DOI：10.1139/v03-016

  日期：2003.6.1

  The photocycloaddition of cyclohex-2-enones 1a, 1b, and 5a–5c to acrylonitrile (2) in benzene has been studied. The reactions proceed with moderate regioselectivity and with preferential formation of diastereomeric mixtures of endo- and exo-5-oxobicyclo[4.2.0]octane-7-carbonitriles 3, 4, and 6–8. Very similar relative rates of conversion to products are observed in the photocycloadditions of 1b, 5a

  已经研究了环己-2-烯酮 1a、1b 和 5a??5c 与苯中的丙烯腈 (2) 的光环加成反应。该反应以中等区域选择性进行，优先形成内-和外-5-氧代双环[4.2.0]辛烷-7-腈3、4和6--8的非对映异构混合物。在 1b、5a 和 5b 分别与 2 和甲基丙烯腈 (9) 的光环加成反应中观察到非常相似的相对转化率。相比之下，5,5-二甲基环己-2-烯酮 (1b) 与 2,3-二甲基丁-2-烯 (12) 形成环加合物的效率与不饱和腈一样，但 2,5,5-三烷基环己-2-烯酮 5a 和 5b 不以可测量的转化率与该烯烃反应。
• Tetrasubstituted furans from photocycloaddition of alkenes to 2-(1-alkynyl)cyclohexenones
  作者：Paul Margaretha、Stefan Reichow、William C. Agosta

  DOI：10.1039/c39920000797

  日期：——

  Photocycloaddition of 2-(1-alkynyl)cyclohexenones 1 and 2 with alkenes 3 and 4 furnishes tetrasubstituted furans 5–8 as the only isolated products; a suggested mechanism leads from the alkyl propynyl biradical 12 to carbene 13, which then closes to the furan.

  2-（1-炔基）的光致环己烯酮1和2与烯烃3和4种配料四取代呋喃5 - 8作为唯一的分离产品; 一种建议的机理是从烷基丙炔基双自由基12到达卡宾13，然后卡宾13靠近呋喃。
• Photocycloaddition of Cyclohex-2-enones to 2-Alkylprop-2-enenitriles
  作者：Lars Meyer、Bruno Elsholz、Ingo Reulecke、Kerstin Schmidt、Paul Margaretha、Pablo Wessig

  DOI：10.1002/1522-2675(200207)85:7<2065::aid-hlca2065>3.0.co;2-s

  日期：2002.7

  The outcome of the photocycloaddition of cyclohex-2-enones to 2-alkylprop-2-enenitriles differs basically from that of the corresponding 2-alkylbut-1-en-3-ynes. While the latter afford mainly products resulting from 1,6-cyclization of the intermediate triplet alkyl-(prop-2-ynyl) 1,4-biradical, the former give only cyclobutane-carbonitriles resulting from 1,4-cyclization of the singlet alkyl-cyanoalkyl 1,4-biradical.
• ——
  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.
• Photochemical Formation of 3,4,4a,5,6,8a-Hexahydro-2<i>H</i>-naphthalen-1-ones from Cyclohex-2-enones and 2-Methylbut-1-en-3-yne
  作者：Birgit Witte、Paul Margaretha

  DOI：10.1021/ol990003k

  日期：1999.7.1

  Irradiation of 2-alkynylcyclohex-2-enones 1a and 1b in the presence of 2-methylbut-1-en-3-yne in benzene affords 6-methylenehexahydronaph-thalen-1-ones 2 as main products while photolysis in methanol gives predominantly 1:1 diastereomeric mixtures of 6-methoxy-6-methylnaphthalenones 4 and 5, respectively, The key step in this stepwise [4 + 2]-cycloaddition is the 1,6-cyclization of biradical 6 to 1,2-cyclohexadiene 7.