4-(Tetrahydro-4H-thiopyran-4-ylidene)cyclohexanone | 169822-63-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻烷
• 英文名称: 4-(Tetrahydro-4H-thiopyran-4-ylidene)cyclohexanone
• 英文别名: 4-(Thian-4-ylidene)cyclohexan-1-one
• CAS: 169822-63-3
• 化学式: C₁₁H₁₆OS
• 分子量: 196.313
• InChiKey: ZXPPVUYOVZUVKZ-UHFFFAOYSA-N

物化性质

• 熔点：
  182 °C
• 沸点：
  335.8±42.0 °C(Predicted)
• 密度：
  1.142±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-(Tetrahydro-4H-thiopyran-4-ylidene)cyclohexanone 在 N,N-二甲基甲酰胺二新戊基乙缩醛 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 生成 4-(tetrahydro-4H-thiopyran-4-cyclohexylidene-4'-ylidene)tetrahydro-4H-thiopyran
  参考文献：
  名称：

  在四氢4H-硫代吡喃末端封端的寡聚（环己基）中的长距离spi-pi相互作用。光电子能谱，从头算起SCF MO计算和自然键轨道分析

  摘要：

  通过He（I）光电子能谱（PES）和从头算RHF / 6-31G *计算，确定了在四氢4H-硫代吡喃末端封端的寡核苷酸（环己叉基）中的远距离sigma-pi相互作用。使用Koopmans定理（Iv，j = -epsilonj）并通过与相关参考化合物的电离作用相关联，分配最高占据分子轨道（MO's）的垂直电离能Ivj。实验（PES）和理论（RHF / 6-31G *）结果吻合良好。对于含有两个非共轭π键分裂δIv的三环己叉基衍生物，π带的j在约0.5至0.7eV的范围内（δε约0.6至0.9eV）。对于在其α和ω末端位置包含两个硫原子的双环和亚环己基化合物，pi型硫孤对带[Lppi（S）]的相差约为0.3-0.4 eV，δ-ε约为0.3-0.4 eV。 0.4 eV），即s距离上的sigma-pi相互作用。分别出现8和12A。相互作用的大小和观察到的分裂与寡（环己叉）烃骨架的反构象和同构象无关。RHF

  DOI：

  10.1021/jo000199y
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 4-(Tetrahydro-4H-thiopyran-4-ylidene)cyclohexanone
  参考文献：
  名称：

  Oligo(cyclohexylidenes): Parent Compounds and End-Functionalized Derivatives

  摘要：

  Parent oligo(cyclohexylidenes) 1(n) (n = 1-4) were synthesized using a modified Barton-Kellogg olefin synthesis. Surprisingly, the crude compounds 1(2) and 1(4) contained small amounts of the 1(n-1) and 1(n+1) homologues. As evidenced by a close examination of mass spectral data of selectively deuterated tercyclohexylidenes 1(2)d(4)d(4) and 1(2)-d(8), their formation can be attributed to scrambling of the intermediate azines. With increasing n, a marked decrease in solubility as well as an increase in thermal stability was found. Powder diffraction measurements indicate that the parent compounds 1(n), irrespective of n, pack in a similar fashion in the solid state. The theoretically (MMX, AM1, and ab initio) predicted rodlike structure of the oligo(cyclohexylidenes) was confirmed by single-crystal X-ray structures of 1(1) and three derivatives (12(1), 13(1), and 30(2)). In line with the powder diffraction data in the series 1(n), a similar packing motif was found for the derivatives. To circumvent side product formation due to azine scrambling, a different synthetic approach was used for the preparation of end-functionalized oligo(cyclohexylidenes), i.e. decarboxylation and dehydration of beta-hydroxy acids.

  DOI：

  10.1021/jo00119a014

文献信息

• Through-Bond Orbital Coupling in End-Functionalized Bicyclohexylidenes − Photoelectron Spectroscopy and Ab initio SCF−MO Calculations
  作者：Albert W. Marsman、Remco W. A. Havenith、Sabine Bethke、Leonardus W. Jenneskens、Rolf Gleiter、Joop H. van Lenthe

  DOI：10.1002/1099-0690(200007)2000:14<2629::aid-ejoc2629>3.0.co;2-6

  日期：2000.7

  between the functional groups and the hydrocarbon skeleton in a series of end-functionalized oligo(cyclohexylidenes) 1−12, their HeI photoelectron (PE) spectra were measured and analyzed. Vertical ionization energies, Ivj, of the highest occupied molecular orbitals (MOs) of 1−12 were assigned using ab initio RHF/6−31G* MO energies (−εj) in combination with Koopmans’ theorem. Excellent to good agreement was

  为了确定在一系列末端官能化的低聚（亚环己基）1-12 中的官能团和烃骨架之间是否发生通过键（TB）轨道相互作用，测量并分析了它们的 HeI 光电子（PE）光谱。使用 ab initio RHF/6-31G* MO 能量 (-εj) 结合 Koopmans 定理分配了 1-12 的最高占据分子轨道 (MO) 的垂直电离能 Ivj。在 PES 和 RHF/6-31G* 结果之间发现了极好的一致性。此外，Ivj，作业进一步证实了-
• 4-(Tetrahydro-4H-thiopyran-1-oxide-4-ylidene)-cyclohexanone oxime in the solid-state. A two-dimensional network of enantiomorphous chains interconnected by weak hydrogen bonds
  作者：Albert W. Marsman、Bart L. A. van Poecke、Leonardus W. Jenneskens、Anthony L. Spek、Egbertus T. G. Lutz、Joop H. van der Maas

  DOI：10.1039/b500527b

  日期：——

  From a saturated C6H6 solution of racemic 4-(tetrahydro-4H-thiopyran-1-oxide-4-ylidene)-cyclohexanone oxime [1 (1-R/1-S)] the co-crystal (1)4444·C6666H6666 is crystallized. Single crystal X-ray analysis showed that (1)4444·C6666H6666 (P space group) in the solid-state consists of enantiomorphous, non-covalent polymer-like chains that contain, in an alternating fashion, the crystallographically independent enantiomers 1-R and 1-R′ or 1-S and 1-S′, respectively. Within each chain the enantiomers are linked by ‘head-to-tail’ intermolecular oxime–sulfoxide hydrogen bonding [D(2) motif]. Neighbouring chains consist of enantiomers with opposite configuration and possess opposite molecular ‘head-to-tail’ alignments. The enantiomorphous chains are interconnected by weak intermolecular C–H⋯O hydrogen bonds involving centrosymmetric C–H⋯oxime [R22(12)] and C–H⋯sulfoxide [R22(8)] motifs between the 1-R and 1-S molecules in neighbouring chains; a nearly planar two-dimensional hydrogen bonding network motif is obtained. In the crystallographic direction [1 0 0] the layers stack in such a fashion that chains occupying successive layers with an identical ‘head-to-tail’ alignment are positioned on top of each other. Concomitantly, channels with areas of ca. 25 Å2 are obtained, which are occupied by C6H6 solvent molecules. A comparison of the IR and Raman spectra of (1)4444·C6666H6666 with those obtained for native 1 that does not contain C6H6, indicates that intermolecular oxime–sulfoxide hydrogen bonding [D(2) motif] also occurs for native 1 in the solid-state.

  从外消旋 4-(四氢-4H-噻喃-1-氧化物-4-亚基)-环己酮肟[1 (1-R/1-S)]的饱和 C6H6 溶液中结晶出共晶体 (1)4444-C6666H6666。单晶 X 射线分析表明，(1)4444-C6666H6666（P 空间群）在固态下由对映体、非共价聚合物状链组成，这些链以交替的方式分别包含晶体学上独立的对映体 1-R 和 1-R′ 或 1-S 和 1-S′。在每条链中，对映体通过分子间 "头对尾 "的肟-亚砜氢键连接[D(2)图案]。相邻的链由构型相反的对映体组成，具有相反的分子 "头尾 "排列。对映体链之间通过微弱的分子间 C-H⋯O 氢键相互连接，相邻链中的 1-R 分子和 1-S 分子之间涉及中心对称的 C-H⋯肟 [R22(12)] 和 C-H⋯sulfoxide [R22(8)] 主题；从而形成了一个近乎平面的二维氢键网络结构。在晶体学方向[1 0 0]上，各层以这样一种方式堆叠，即占据连续层的链以相同的 "头尾 "排列方式相互叠加。同时，获得了面积约为 25 Å2 的通道，这些通道被 C6H6 溶剂分子占据。将 (1)4444-C6666H6666 的红外光谱和拉曼光谱与不含 C6H6 的原生 1 的红外光谱和拉曼光谱进行比较，结果表明原生 1 在固态中也存在分子间的肟-亚砜氢键[D(2) 主题]。
• Oligo(cyclohexylidenes): Parent Compounds and End-Functionalized Derivatives
  作者：Frans J. Hoogesteger、Remco W. A. Havenith、Jan W. Zwikker、Leonardus W. Jenneskens、Huub Kooijman、Nora Veldman、Anthony L. Spek

  DOI：10.1021/jo00119a014

  日期：1995.7

  Parent oligo(cyclohexylidenes) 1(n) (n = 1-4) were synthesized using a modified Barton-Kellogg olefin synthesis. Surprisingly, the crude compounds 1(2) and 1(4) contained small amounts of the 1(n-1) and 1(n+1) homologues. As evidenced by a close examination of mass spectral data of selectively deuterated tercyclohexylidenes 1(2)d(4)d(4) and 1(2)-d(8), their formation can be attributed to scrambling of the intermediate azines. With increasing n, a marked decrease in solubility as well as an increase in thermal stability was found. Powder diffraction measurements indicate that the parent compounds 1(n), irrespective of n, pack in a similar fashion in the solid state. The theoretically (MMX, AM1, and ab initio) predicted rodlike structure of the oligo(cyclohexylidenes) was confirmed by single-crystal X-ray structures of 1(1) and three derivatives (12(1), 13(1), and 30(2)). In line with the powder diffraction data in the series 1(n), a similar packing motif was found for the derivatives. To circumvent side product formation due to azine scrambling, a different synthetic approach was used for the preparation of end-functionalized oligo(cyclohexylidenes), i.e. decarboxylation and dehydration of beta-hydroxy acids.
• Long-Range σ−π Interactions in Tetrahydro-<i>4H</i>-thiopyran End-Capped Oligo(cyclohexylidenes). Photo-Electron Spectroscopy, ab Initio SCF MO Calculations, and Natural Bond Orbital Analyses
  作者：Albert W. Marsman、Remco W. A. Havenith、Sabine Bethke、Leonardus W. Jenneskens、Rolf Gleiter、Joop H. van Lenthe、Martin Lutz、Anthony L. Spek

  DOI：10.1021/jo000199y

  日期：2000.7.1

  alpha- and omega-end positions the pi-type sulfur lone pair bands [Lppi(S)] split significantly by deltaIvj approximately 0.3 to 0.4 eV (delta-epsilonj approximately 0.3 to 0.4 eV), i.e. sigma-pi interactions over distances of ca. 8 and 12 A, respectively, occur. The magnitude of the interactions and the observed splittings are independent of the anti and syn conformations of the oligo(cyclohexylidene) hydrocarbon

  通过He（I）光电子能谱（PES）和从头算RHF / 6-31G *计算，确定了在四氢4H-硫代吡喃末端封端的寡核苷酸（环己叉基）中的远距离sigma-pi相互作用。使用Koopmans定理（Iv，j = -epsilonj）并通过与相关参考化合物的电离作用相关联，分配最高占据分子轨道（MO's）的垂直电离能Ivj。实验（PES）和理论（RHF / 6-31G *）结果吻合良好。对于含有两个非共轭π键分裂δIv的三环己叉基衍生物，π带的j在约0.5至0.7eV的范围内（δε约0.6至0.9eV）。对于在其α和ω末端位置包含两个硫原子的双环和亚环己基化合物，pi型硫孤对带[Lppi（S）]的相差约为0.3-0.4 eV，δ-ε约为0.3-0.4 eV。 0.4 eV），即s距离上的sigma-pi相互作用。分别出现8和12A。相互作用的大小和观察到的分裂与寡（环己叉）烃骨架的反构象和同构象无关。RHF