(Z)-5-Cyclodecenone | 3468-78-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (Z)-5-Cyclodecenone
• 英文别名: 5Z-cyclodecen-1-one；cis-5-cyclodecenone；5-cyclodecen-1-one；Z-cyclodec-5-enone；cyclodec-5-enone；Cyclodec-5-enon；(5Z)-cyclodec-5-en-1-one
• CAS: 3468-78-8
• 化学式: C₁₀H₁₆O
• 分子量: 152.236
• InChiKey: FFARAHTUJVXTLB-UPHRSURJSA-N

物化性质

• 沸点：
  242.5±29.0 °C(Predicted)
• 密度：
  0.910±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 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：

  (Z)-5-Cyclodecenone 在 盐酸 、 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 16.0h， 生成 2,3,4,5,6,7,8,8a-octahydro-1H-naphthalen-4a-ol
  参考文献：
  名称：

  Electrophilic and radical transannular cyclizations of 5-cyclodecenone to give either hydronaphthalene or hydroazulene products

  摘要：

  The transannular cyclizations of the E and Z double-bond isomers of 5-cyclodecenone were investigated in order to determine the regio- and stereochemical preferences of the unsubstituted ring system. Electrophilic cyclization of the E isomer under either protic or Lewis acid conditions led to hydronaphthalenols with a preference for the trans ring fusion, while the Z led to only cis-fused hydronaphthalenols. Cyclization of the ketyl radical generated from the ketone led exclusively to a cis-fused hydroazulenol, regardless of double-bond geometry, although the E isomer was considerably more reactive than the Z isomer. The stereochemistry of the ring fusion in the products from (E)-5-cyclodecenone can be rationalized by cyclization through its lowest energy conformations in which the carbonyl oxygen is anti to the alkene hydrogen at C6, leading to the trans-fused hydronaphthalenol, and syn to the alkene hydrogen at C5, leading to the cis-fused hydroazulenol. For (Z)-5-cyclodecenone, molecular mechanics calculations found two low energy conformations, only one of which brings the alkene and the carbonyl groups close enough for their reaction with each other. In this conformation, the alkene hydrogens at C5 and C6 are syn to the oxygen of the ketone, leading to a cis ring fusion regardless of whether 1,5- or 1,6-cyclization is observed. The difference in regiochemistry in radical versus electrophilic cyclizations is explicable on the basis of the differences in mechanism for the two reaction pathways. The radical cyclizations are kinetic in nature with the ketyl radical adding to the proximate C5 alkene carbon in a very exothermic step, akin to the cyclization of 1-hexenyl radicals. The stereochemistry of the acid-induced cyclizations can be explained through the intermedicacy of either nonclassical or contact ion pairs, the regiochemistry reflecting the greater stability of the hydronaphthalene ring system over the hydroazulene. A system of nomenclature for unambiguously labeling each of the low energy conformations of (E)-5-cyclodecenones is also proposed.

  DOI：

  10.1021/jo00075a025
• 作为产物：
  描述：

  6-(toluene-4-sulfonyloxy)-cyclodecanone 在 N,N-二乙基苯胺 作用下， 生成 (Z)-5-Cyclodecenone
  参考文献：
  名称：

  Cyclic Polyolefins. VIII. Reactions of 6-Hydroxycyclodecanone and Cyclodecan-1,6-diol p-Toluenesulfonates

  摘要：

  DOI：

  10.1021/ja01163a072

文献信息

• Transposition oxy-cope assistee par le trifluoroacetate mercurique en quantite stoechiometrique et en quantite catalytique
  作者：Norbert Bluthe、Max Malacria、Jacques Gore

  DOI：10.1016/0040-4020(84)85011-5

  日期：1984.1

  Tertiary 1,5-hexadien-3-ols are transformed at room temperature into δ-ethylenic ketones in 35-90%, yields under two sets of conditions: treatment with one molar equivalent of mercuric trifluoroacetate followed by demercuration of the intermediate α-mercuro ketone with sodium borohydride; and treatment with 0.2 molar equivalent of t of lithium trifluoroacetate or trifluorométhansulfonate. The reactions

  在室温下，将1,5-己二烯-3-醇叔化成35-90％的δ-乙烯酮，在两种条件下收率：用一摩尔当量的三氟乙酸汞处理，然后使中间的α-水银脱汞酮与硼氢化钠；用0.2摩尔当量的三氟乙酸锂或三氟甲磺酸锂处理。反应是高度立体选择性的，酮的E异构体占产物的80-95％。在第二条件下观察到最高的选择性。
• A Facile Synthesis of 1,2-Divinylcycloalkanols and Their Behavior in the Oxy-Cope Rearrangement
  作者：Tetsuya Kato、Hisao Kondo、Masaki Nishino、Minoru Tanaka、Go Hata、Akihisa Miyake

  DOI：10.1246/bcsj.53.2958

  日期：1980.10

  2-chlorocycloalkanones with vinylmagnesium chloride gives 1,2-divinylcycloalkanols. Divinylation proceeds via a rearrangement of initially formed 2-chloro-1-vinylcycloalkanols to 2-vinylcycloalkanones followed by further vinylation of 2-vinylcycloalkanones. Thermal sigmatropic rearrangement of 1,2-divinylcycloalkanols gives 5-cycloalken-1-ones in good yields. The influence of the size of rings on the

  2-氯环烷酮与乙烯基氯化镁反应生成1,2-二乙烯基环烷醇。二乙烯基化通过最初形成的 2-氯-1-乙烯基环烷醇重排为 2-乙烯基环烷酮，然后 2-乙烯基环烷酮的进一步乙烯基化而进行。1,2-二乙烯基环烷醇的热sigmatropic重排以良好的产率得到5-环烯-1-酮。讨论了环的大小对反应途径的影响。
• Oxidation of unsaturated linear and cyclic hydrocarbons by molecular oxygen catalyzed by complexes of transition metals
  作者：G. A. Dzhemileva、V. N. Odinokov、U. M. Dzhemilev

  DOI：10.1007/bf00953862

  日期：1987.1
• Carbocyclic ring expansion reactiuon VIA radical chain processes
  作者：Jack E. Baldwin、Robert M. Adlington、Jeremy Robertson

  DOI：10.1016/0040-4020(89)80003-1

  日期：1989.1
• Hanack,M. et al., Chemische Berichte, 1972, vol. 105, p. 421 - 433
  作者：Hanack,M. et al.

  DOI：——

  日期：——