4-chlorobicyclo[5.4.1]dodeca-1,3,6,8,10-pentaen-5-one | 37765-19-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-chlorobicyclo[5.4.1]dodeca-1,3,6,8,10-pentaen-5-one
• 英文别名: 11-chloro-3,8-methano[11]annulenone
• CAS: 37765-19-8
• 化学式: C₁₂H₉ClO
• 分子量: 204.656
• InChiKey: FLGBUZKPBVYMIF-WKRCBEILSA-N

物化性质

• 沸点：
  450.7±34.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.06
• 重原子数：
  14.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  4-chlorobicyclo[5.4.1]dodeca-1,3,6,8,10-pentaen-5-one 在 sodium tetrahydroborate 、 溶剂黄146 作用下， 以 氘代甲醇 为溶剂， 反应 25.08h， 生成
  参考文献：
  名称：

  1,6-Methanocyclooundeca [ b ] pyrimido [5,4- d ]吡咯-12,14-dione衍生物的新颖合成和性质：一些胺和醇的自动循环氧化

  摘要：

  通过烯胺烷基化和11-脱水缩合反应，合成了新型的1,6-甲基环戊烯[ b ]嘧啶基[5,4 - d ]吡咯-12,14-二酮衍生物6a，b和7a - c。含6-氨基-3-取代的尿嘧啶衍生物的氯3,8-甲醇[11]环烯酮（8），随后消除HCl。的1 1 H NMR谱澄清，化合物6A，b和图7a - Ç芳烃分子是具有变径π系统的芳族分子，这是由桥亚甲基质子和周围质子的化学位移暗示的。与环庚[ b ]嘧啶基[5,4- d ]吡咯衍生物的乙烯基化合物相比，电化学还原显示出更大的正还原电位。在寻找6a，b和7a - c的氧化功能时，化合物6a和7b已证明在好氧和光辐照条件下，氧化苄胺，环己胺和苄醇以超过100％的收率得到相应的羰基化合物，而在好氧和热条件下，在100°C，只有苄胺被氧化。因此，化合物6a和7b在自循环过程中氧化胺和醇，并且与热过程相比，光照射下的效率更高，这表明氧化反应可能是通过电子

  DOI：

  10.1021/jo035336g
• 作为产物：
  描述：

  (1α,3α,5α,7α)-4,4-dichlorotricyclo<5.4.1.0^3,5>dodeca-7,9,11-triene 在 吡啶 、 manganese(IV) oxide 、 silver nitrate 作用下， 以 乙二醇二甲醚 为溶剂， 生成 4-chlorobicyclo[5.4.1]dodeca-1,3,6,8,10-pentaen-5-one
  参考文献：
  名称：

  Reisdorff,J.; Vogel,E., Angewandte Chemie, 1972, vol. 84, # 5, p. 208 - 210

  摘要：

  DOI：

文献信息

• New Synthesis, Properties, and Oxidizing Ability of 1,3-Dimethyl-5,10-methanocycloundeca[4,5]furo[2,3-<i>d</i>]pyrimidin- 2,4(1,3<i>H</i>)-dionylium Tetrafluoroborate
  作者：Shin-ichi Naya、Masato Warita、Yuhki Mitsumoto、Makoto Nitta

  DOI：10.1021/jo048575s

  日期：2004.12.1

  A novel synthesis of 1,3-dimethyl-5,10-methanocycloundeca[4,5]furo[2,3-d]pyrimidin-2,4(1,3H)-dionylium tetrafluoroborate (10+·BF4-) was accomplished by the reaction of 3,8-methano[11]annulenone with dimethylbarbituric acid and following acidic cyclization, albeit in low yield. Remarkable structural characteristics were suggested on inspection of the spectral data and MO calculation, and it was clarified

  1,3-二甲基-5,10- methanocycloundeca的一种新颖的合成[4,5]呋喃并[2,3- d ]嘧啶-2,4（1,3 ħ）-dionylium四氟硼酸盐（10 + ·BF 4 - ）通过3，8-甲基[11]环戊烯酮与二甲基巴比妥酸的反应并在酸性环化后进行反应，尽管收率低。在检查光谱数据和MO计算时，提出了显着的结构特征，并明确了正电荷主要集中在C11处。阳离子10 +的p K R +值经分光光度法测定为4.6，比1,3，二甲基-7,12-methanocycloundeca [4,5] furo [2,3 - d ]嘧啶-2,4（1， 3 H）-二氟四氟硼酸二钾（p K R +＝ 8.7）。该值也比母体1,6-甲基[11]环戊烯鎓离子的值小1.6 pH单位（p K R + = 6.2）。该特征是基于源自母体阳离子的键固定的扰动而合理化的。循环伏安法（CV）时，电化学还原10
• On the reaction of prop-2-enylidenetriphenylphosphorane derivatives. Novel synthesis of 4,9-methanocyclopentacycloundecene derivatives and their spectroscopic and chemical properties
  作者：Tohru Takayasu、Makoto Nitta

  DOI：10.1039/a703314a

  日期：——

  Novel 3-ethoxycarbonyl-2-ethoxy- and 2-ethoxy-4,9-methanocyclopentacycloundecenes 12 and 13 are synthesized by the reaction of 9-chloro-1,6-methano[11]annulen-8-one 8, a 10π-electron vinylogue of 2-chlorotropone, with 2-ethoxy-3-(ethoxycarbonyl)prop-2-enylidene- and 2-ethoxyprop-2-enylidenetriphenylphosphorane, 7a and 7b, respectively. The reaction pathways involve a Michael-type addition of phosphoranes 7a,b onto ketone 8, subsequent proton migration regenerating the phosphorane moiety, which undergoes intramolecular Wittig reaction, and aromatization, eliminating HCl. The 1H NMR spectra show that compounds 12 and 13 are aromatic molecules having a diatropic 14-electron cyclic π system. The UV–visible absorption spectra of compounds 12 and 13 exhibit extended cyclic conjugation of the aromatic perimeter according to a bathochromic shift of the longest absorption maxima as compared to those of the related azulene derivatives having the same substituents. In addition, the first example of an aromatic substitution reaction of the methanocyclopentacycloundecene ring system has been studied, and shows that the compounds 12 and 13, like azulene, undergo trifluoroacetylation under exceptionally mild conditions and exhibit the same site-selectivity as does azulene. The electrochemical properties of compounds 12 and 13 as well as the related azulene derivatives are also analyzed and discussed on the basis of MNDO calculations.

  新型3-乙氧基羰基-2-乙氧基-和2-乙氧基-4,9-亚甲基环五环十一碳烯12和13是通过9-氯-1,6-亚甲基[11]annulen-8-one 8、10π- 2-氯代酮与2-乙氧基-3-(乙氧基羰基)丙-2-烯叉基-和2-乙氧基丙-2-烯叉基三苯基膦的电子乙烯系，分别为7a和7b。反应途径包括将正膦 7a,b 迈克尔型加成到酮 8 上，随后质子迁移再生正膦部分，该部分经历分子内 Wittig 反应，以及芳构化，消除 HCl。 1H NMR谱表明化合物12和13是具有双异性14电子环状π体系的芳香族分子。与具有相同取代基的相关甘菊环衍生物相比，化合物 12 和 13 的紫外-可见吸收光谱根据最长吸收最大值的红移表现出芳香族周长的扩展循环共轭。此外，还研究了亚甲基环五环十一碳烯环系的芳香族取代反应的第一个实例，结果表明化合物12和13与甘菊环一样，在极其温和的条件下进行三氟乙酰化，并表现出与甘菊环相同的位点选择性。基于MNDO计算，对化合物12和13以及相关甘菊环衍生物的电化学性质进行了分析和讨论。
• On the reaction of (vinylimino)phosphorane and related compounds. 22. Syntheses and structural studies of methanocycloundeca[b]pyrrole ring systems
  作者：Nobuhiro Kanomata、Kenichi Kamae、Yukio Iino、Makoto Nitta

  DOI：10.1021/jo00046a010

  日期：1992.9

  Novel 2-phenyl-6,11- and 2-phenyl-4,9-methanocycloundeca[b]pyrroles (15a and 16a) were synthesized in moderate yields by the reaction of 3,8-methano[11]annulenone (3), a 10pi-electron vinylogue of tropone, with [(l-phenylvinyl)imino]triphenylphosphorane (8a) and subsequent dehydrogenation. Similarly, the reaction of the annulenone 3 with (inden-3-ylimino)tributylphosphorane (8c) and subsequent aromatization afforded 7,12- and 9,14-methano-15H-cycloundeca[b]indeno[2,3-d]pyrroles (15c and 16c), which also have methanocycloundeca[b]pyrrole ring systems. Preparation of 2-phenyl-5,10-methanocycloundeca[b]pyrrole (17), an isomer of both 15a and 16a, was also accomplished in low yield by the reaction of 4,9-methano[ll]annulenone (5) with an excess of [(1-phenylvinyl)imino]tributylphosphorane (8d). The reactivity of annulenone 5 with (vinylimino)phosphoranes was found to be quite low as compared to the higher reactivity of annulenone 3 and tropone. Compounds 15a,c, 16a,c, and 17 are the first nitrogen analogues of cyclopentacycloundecene ring systems which have vinylogous structures of 1-azaazulene. Structures of the products obtained were examined by H-1 NMR spectra and UV spectra. The H-1 NMR spectra clarified that the compounds 15a,c, 16a,c, and 17 are aromatic molecules having a diatropic 14pi-electron system, and 5,10-methano derivative 17 has a more diatropic nature than the compounds 15a,c and 16a,c. The UV spectra of 15a,c, 16a,c, and 17 exhibited increased cyclic conjugation of the aromatic perimeter according to a bathochromic shift of the longest absorption maxima as compared to the corresponding 1-azaazulene derivatives.
• Generation and properties of 4,9- and 3,8-methano[11]annulenylidenes
  作者：W. M. Jones、R. A. LaBar、U. H. Brinker、P. H. Gebert

  DOI：10.1021/ja00461a034

  日期：1977.9
• Novel Synthesis and Properties of 1,6-Methanocycloundeca[<i>b</i>]pyrimido[5,4-<i>d</i>]pyrrole-12,14-dione Derivatives:  Autorecycling Oxidation of Some Amines and Alcohols
  作者：Yuhki Mitsumoto、Makoto Nitta

  DOI：10.1021/jo035336g

  日期：2004.2.1

  compounds of cyclohepta[b]pyrimido[5,4-d]pyrrole derivatives. In a search for the oxidizing function of 6a,b and 7a−c, compounds 6a and 7b were demonstrated to oxidize benzylamines, cyclohexylamine, and benzyl alcohol to give the corresponding carbonyl compounds in more than 100% yield under aerobic and photoirradiation conditions, while only benzylamine was oxidized under aerobic and thermal conditions

  通过烯胺烷基化和11-脱水缩合反应，合成了新型的1,6-甲基环戊烯[ b ]嘧啶基[5,4 - d ]吡咯-12,14-二酮衍生物6a，b和7a - c。含6-氨基-3-取代的尿嘧啶衍生物的氯3,8-甲醇[11]环烯酮（8），随后消除HCl。的1 1 H NMR谱澄清，化合物6A，b和图7a - Ç芳烃分子是具有变径π系统的芳族分子，这是由桥亚甲基质子和周围质子的化学位移暗示的。与环庚[ b ]嘧啶基[5,4- d ]吡咯衍生物的乙烯基化合物相比，电化学还原显示出更大的正还原电位。在寻找6a，b和7a - c的氧化功能时，化合物6a和7b已证明在好氧和光辐照条件下，氧化苄胺，环己胺和苄醇以超过100％的收率得到相应的羰基化合物，而在好氧和热条件下，在100°C，只有苄胺被氧化。因此，化合物6a和7b在自循环过程中氧化胺和醇，并且与热过程相比，光照射下的效率更高，这表明氧化反应可能是通过电子