housane | 172745-90-3

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 环丁烷木脂素
• 英文名称: housane
• 英文别名: anti-3,3-dimethyl-2,4-diphenyl-tricyclo[3.3.0.0^2,4]octane；(1S,2R,4S,5R)-3,3-dimethyl-2,4-diphenyltricyclo[3.3.0.02,4]octane
• CAS: 172745-90-3
• 化学式: C₂₂H₂₄
• 分子量: 288.433
• InChiKey: JVFPPAIAEBXMEF-ZIEJVCCYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  housane 在 氯丁烷 作用下， 以 various solvent(s) 为溶剂， 生成
  参考文献：
  名称：

  通过脉冲辐射分解检测源自环戊基和乌唑型偶氮烷烃的苯基取代自由基阳离子：杂原子取代对自由基阳离子反应性的影响

  摘要：

  环戊烷和尿唑退火的偶氮烷烃和 housanes 的自由基阳离子是通过脉冲辐射分解产生的，瞬态通过时间分辨光学监测在光谱和动力学上表征。对于环戊烷退火的偶氮烷 1 和 housane 2 的桥头取代二苯基衍生物，仅观察到相应的近似 1,2 自由基阳离子物种，由最初形成且寿命太短 (<1 μs) 的不饱和 1,3 自由基产生阳离子通过 1,2-甲基迁移。相比之下，对于相应的 urazole-annelated 偶氮烷烃 4，检测到初始的 1,3 自由基阳离子 5•+，其中甲基取代的 5b•+ 去质子化为自由基 5b•。

  DOI：

  10.1021/ja970647s
• 作为产物：
  描述：

  (1α,4α,4aα,7aα)-4,4a,5,6,7,7a-Hexahydro-8,8-dimethyl-1,4-diphenyl-1,4-methano-1H-cyclopenta[d]pyridazin 以 二氯甲烷 为溶剂， 以100%的产率得到housane
  参考文献：
  名称：

  Diastereo- and Regioselective Synthesis of Diquinanes and Related Systems from Tricyclo[3.3.0.02,4]octanes by Chemical Electron Transfer (CET)

  摘要：

  提供了一种通过三环[3.3.0.02,4]辛烷的单电子氧化和随后的立体控制重排合成二喹烷的新合成方法。后者化合物可通过酸催化异吡唑环加成，随后氢化和分子氮的光排出方便地获得。三环辛烷的氧化重排催化且清洁地进行，区域和立体选择性地得到相应的二喹烷。

  DOI：

  10.1055/s-1995-4072

文献信息

• 1,3-Diradicals Embedded in Curved Paraphenylene Units: Singlet versus Triplet State and In-Plane Aromaticity
  作者：Yuki Miyazawa、Zhe Wang、Misaki Matsumoto、Sayaka Hatano、Ivana Antol、Eiichi Kayahara、Shigeru Yamago、Manabu Abe

  DOI：10.1021/jacs.1c01329

  日期：2021.5.19

  interactions and singlet versus triplet state, as well as their unique characteristics such as in-plane aromaticity. A triplet ground state was predicted for the larger 1,3-diradicals, such as the seven- and eight-paraphenylene-unit-containing diradicals DR-7CPP (n = 4) and DR-8CPP (n = 5), by quantum chemical calculations. The smaller-sized diradicals DR-(n+3)CPPs (n = 0–3) were found to possess singlet ground

  从基础化学以及材料科学的角度来看，弯曲的π共轭分子和开壳结构引起了人们的极大关注。在这项研究中，研究了嵌入弯曲的环对亚苯基（CPP s）结构DR-（n +3）CPP s（n = 0-5）中的1,3-二基（DR s）的化学性质，以了解自旋-自旋相互作用，单重态与三重态的曲率和系统大小，以及它们的独特特征，例如平面内的芳香性。预测较大的1,3-双基自由基为三重态基态，例如含七和八对亚苯基单元的双基自由基DR - 7CPP（n = 4）和DR - 8CPP（n = 5），通过量子化学计算。发现较小的双基自由基DR-（n +3）CPP s（n = 0-3）具有单重态基态。因此，基态自旋多重性由对亚苯基环的大小控制。DR - 6CPP在其含偶氮的前驱体（AZ - 6CPP）的光化学脱氮中的实验生成证实了其对基态自旋多重性的尺寸效应。）。有趣的是，在较小尺寸的单重态（例如S- DR - 4CPP（n =
• The <i>D</i> Parameter (EPR Zero-Field Splitting) of Localized 1,3-Cyclopentanediyl Triplet Diradicals as a Measure of Electronic Substituent Effects on the Spin Densities in <i>Para</i>-Substituted Benzyl-Type Radicals
  作者：Waldemar Adam、Fumio Kita、Heinrich M. Harrer、Werner M. Nau、Rainer Zipf

  DOI：10.1021/jo960396q

  日期：1996.1.1

  parameter of the triplet diradical species. A theoretical analysis shows that the D parameter is a measure of the spin density rho at the benzylic positions and the inter-radical distance d in localized diradicals. A good correlation exists between the D parameter of these triplet diradicals (constant inter-radical distance d) and the EPR hyperfine coupling constants of the corresponding benzyl-type monoradicals

  这种可加性使我们能够将这些三重态双自由基看作是两个单独的单自由基组分的复合物，并使我们能够从三重态双自由基种类的D参数评估苄基型单自由基的有价值的电子性能。理论分析表明，D参数是对苄基位置的自旋密度rho和局部双基自由基的径向间距d的度量。这些三重双自由基的D参数（恒定的自由基间距d）与相应的苄基单自由基的EPR超精细偶合常数之间存在良好的相关性，这表明所观察到的电子取代基效应反映了C原子上自旋密度的变化。激进的网站。
• Preferred Formation ofanti-Housane (Retention) in the Sensitized Photodenitrogenation of Cyclopentane-Annellated DBH-Type Azoalkanes through Long-Range Steric Effects in the Cyclization of the Triplet Cyclopentane-1,3-diyl Diradicals
  作者：Waldemar Adam、Manfred Diedering、Vicente Martí

  DOI：10.1002/ejoc.200390098

  日期：2003.2

  The photolysis of the cyclopentene- and cyclopentane-annellated DBH-type azoalkanes 1a and 1b affords under singlet conditions (high-temperature direct photolysis) predominantly the inverted housanes syn-2 in similar amounts for both derivatives 2a and 2b. Under triplet conditions (low-temperature direct or benzophenone-sensitized photolysis), the photolysis leads to the retained housane anti-2 as

  环戊烯和环戊烷退火的 DBH 型偶氮烷烃 1a 和 1b 的光解在单线态条件下（高温直接光解）主要提供了衍生物 2a 和 2b 数量相似的反向 housanes syn-2。在三重态条件下（低温直接或二苯甲酮敏化光解），光解导致保留的 housane anti-2 作为主要的非对映异构体，但 2a 的顺/反 housane 比率存在显着差异（38:62）对于 2b (6:94)。三线态途径的抗立体选择性的这种显着差异在环戊烷-1,3-二基三线态双自由基 3DR 环化过程中，环化环和嵴二甲基取代的亚甲基桥之间的长程空间相互作用在机械上合理化在 ISC 之后。相比之下，对于单线态过程，中间二氮烯基双自由基 1DZ 沿 SH2 途径（反转）的脱氮对这些远程空间效应非常不敏感。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany,
• 1,3-Cyclopentanediyl Diradicals:  Substituent and Temperature Dependence of Triplet−Singlet Intersystem Crossing
  作者：Fumio Kita、Waldemar Adam、Paul Jordan、Werner M. Nau、Jakob Wirz

  DOI：10.1021/ja991362d

  日期：1999.10.1

  prediction by the model, push−pull substitution does not enhance the ionic contribution. Arrhenius parameters, Ea = 2−6 kcal mol-1 and A = 107−1010 s-1, were determined from the temperature dependences of the decay rate constants. A sensitive statistical test is used to establish that the Arrhenius parameters exhibit enthalpy−entropy compensation, ...

  33 1,3-二芳基-1,3-环戊二基三线态双自由基的寿命由相应偶氮烷前体的激光闪光光解确定。在 294 K 的脱气溶液中，一阶衰减率常数的范围为 0.8 到 16.7 × 105 s-1，并且表现出对布朗 σ+ 取代基常数的系统但非线性的依赖性。根据双轨道中的双电子模型对自旋轨道耦合的分析表明，电子对系统间交叉率的影响是通过影响双自由基最低单线态波函数中离子贡献的权重来实现的。与直觉相反，但与模型的预测一致，推挽取代不会增强离子贡献。Arrhenius 参数，Ea = 2−6 kcal mol-1 和 A = 107−1010 s-1，由衰减率常数的温度依赖性确定。使用敏感的统计测试来确定 Arrhenius 参数表现出焓-熵补偿，...
• Wavelength-Selective Photodenitrogenation of Azoalkanes to High-Spin Polyradicals with Cyclopentane-1,3-diyl Spin-Carrying Units and Their Photobleaching:  EPR/UV Spectroscopy and Product Studies of the Matrix-Isolated Species
  作者：Waldemar Adam、Wiebke Maas、Werner M. Nau

  DOI：10.1021/jo0013960

  日期：2000.12.1

  The photolysis of the mono-, bis-, and trisazoalkanes 1, 2, and 3 in a toluene matrix at 77 K has been studied by EPR and UV spectroscopy. The purpose was to find the optimal conditions for the generation of the corresponding organic high-spin polyradicals (the triplet diradicals D-1, D-2, and D-3, the tetraradicals T-2 and T-3, and the hexaradical H-3) all with localized cyclopentane-1,3-diyl spin-carrying units, connected by m-phenylene (except D-1) as ferromagnetic coupler. Irradiation of these azoalkanes at 333, 351, or 364 nm gave different polyradical compositions. This observed wavelength dependence is due to the secondary photoreaction (photobleaching) of the polyradical intermediate. The photobleaching process has been examined in detail for the triplet diradical D-1, for which pi,pi* excitation affords the cyclopentenes 5 instead of the housane 4 (the usual product of the diradical D-1 on warm-up of the matrix). The pi,pi*,-excited diradical D-1 fragments into a pair of allyl and methyl radicals (the latter was observed by EPR spectroscopy of a photobleached sample), and recombination affords the cyclopentene. Similar photochemical events are proposed for the photobleaching of the tetraradical T-2 and hexaradicaI H-3, derived from the respective azoalkanes 2 and 3. Thus, photobleaching of the polyradicals competes effectively with their photogeneration from the azoalkane. This unavoidable event is the consequence of spectral overlap between the cumyl-radical pi,pi* chromophore of the polyradical and the n,pi*: chromophore of the azoalkane at the wavelength (364 MI), at which the latter is photoactive for the required extrusion of molecular nitrogen.