3,3-二甲基-1,5-二氧杂螺[5.5]十一烷-9-羧酸 | 169822-66-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 3,3-二甲基-1,5-二氧杂螺[5.5]十一烷-9-羧酸
• 英文名称: 3,3-dimethyl-1,5-dioxaspiro[5.5]undecane-9-carboxylic acid
• 英文别名: 3,3-Dimethyl-1,5-dioxaspiro[5.5]undecane-9-carboxylic acid
• CAS: 169822-66-6
• 化学式: C₁₂H₂₀O₄
• 分子量: 228.288
• InChiKey: SJJHVUGBGCVKPB-UHFFFAOYSA-N

物化性质

• 沸点：
  359.3±42.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,3-二甲基-1,5-二氧杂螺[5.5]十一烷-9-羧酸 在 palladium on activated charcoal 氢气 、 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 、 正己烷 、 乙腈 为溶剂， 生成 4-(3,3-Dimethyl-1,5-dioxa-spiro[5.5]undec-9-yl)-cyclohexanecarboxylic acid 2,2-dimethyl-propyl ester
  参考文献：
  名称：

  Oligo(Cyclohexylidene)s and Oligo(Cyclohexyl)s as Bridges for Photoinduced Intramolecular Charge Separation and Recombination

  摘要：

  A series of semirigid donor-bridge-acceptor (D-B-A) molecules was synthesized to study the effect of the position and number of nonconjugated olefinic bonds in the bridge on the photoinduced charge-separation and charge-recombination kinetics. The molecules consist of a phenylpiperidine electron donor, an oligo(cyclohexylidene) or oligo(cyclohexyl) bridge, and a dicyanovinyl acceptor. Partly saturated ter(cyclohexylidene) bridges were used as well. The edge-to-edge donor-acceptor separation of the compounds under study varies between 2.89 and 15.4 Angstrom. The replacement of a C-C single bond by an olefinic bond increases the rate of charge separation with a factor of 3.0 +/- 0.8 per replaced bond. For all D-B-A compounds the extended fully charge-separated state folds to a compact charge-transfer (CCT) conformer. The rate of charge recombination (CR) of the CCT state increases with solvent polarity for those compounds having an olefinic bond located three sigma bonds from the acceptor. Thus, while in cyclohexane the CR rate is equal for all compounds, in benzene the CR rate in compounds with an olefinic bond near the acceptor is 10 times larger than in compounds with a single bond instead. It is believed that a (virtual) charge-transfer state involving the radical cation of the olefinic bond and the radical anion of the acceptor (D-B.+-A(.-)) is responsible for the enhanced CR process.

  DOI：

  10.1021/jp0271716
• 作为产物：
  描述：

  2,2-dimethylpropane-1,3-diyl bis(3,3-dimethyl-1,5-dioxaspiro[5.5]undecane-9-carboxylate) 在 sodium hydroxide 作用下， 以 甲醇 为溶剂， 生成 3,3-二甲基-1,5-二氧杂螺[5.5]十一烷-9-羧酸
  参考文献：
  名称：

  Oligo(Cyclohexylidene)s and Oligo(Cyclohexyl)s as Bridges for Photoinduced Intramolecular Charge Separation and Recombination

  摘要：

  A series of semirigid donor-bridge-acceptor (D-B-A) molecules was synthesized to study the effect of the position and number of nonconjugated olefinic bonds in the bridge on the photoinduced charge-separation and charge-recombination kinetics. The molecules consist of a phenylpiperidine electron donor, an oligo(cyclohexylidene) or oligo(cyclohexyl) bridge, and a dicyanovinyl acceptor. Partly saturated ter(cyclohexylidene) bridges were used as well. The edge-to-edge donor-acceptor separation of the compounds under study varies between 2.89 and 15.4 Angstrom. The replacement of a C-C single bond by an olefinic bond increases the rate of charge separation with a factor of 3.0 +/- 0.8 per replaced bond. For all D-B-A compounds the extended fully charge-separated state folds to a compact charge-transfer (CCT) conformer. The rate of charge recombination (CR) of the CCT state increases with solvent polarity for those compounds having an olefinic bond located three sigma bonds from the acceptor. Thus, while in cyclohexane the CR rate is equal for all compounds, in benzene the CR rate in compounds with an olefinic bond near the acceptor is 10 times larger than in compounds with a single bond instead. It is believed that a (virtual) charge-transfer state involving the radical cation of the olefinic bond and the radical anion of the acceptor (D-B.+-A(.-)) is responsible for the enhanced CR process.

  DOI：

  10.1021/jp0271716

文献信息

• Oligo(cyclohexylidene) oximes and derivatives as probe molecules for long-range substituent effects on 13C NMR chemical shifts
  作者：Frans J. Hoogesteger、David M. Grove、Leonardus W. Jenneskens、Theodorus J. M. de Bruin、Bart A. J. Jansen

  DOI：10.1039/p29960002327

  日期：——

  aliphatic oximes (1–4) the influence of the oxime substituent on the 13C NMR chemical shifts has been studied. Various 2D NMR techniques were applied for the unequivocal assignment of their 1H and 13C resonances. For bicyclohexylidene oximes 1–2 long-range substituent effects on the 13C NMR chemical shifts of aliphatic carbon atoms of the six-membered rings due to the presence of the oxime group are

  对于一系列棒状脂肪族肟（1-4），已经研究了肟取代基对13 C NMR化学位移的影响。将各种2D NMR技术应用于其1 H和13 C共振的明确分配。对于双环己基肟，由于存在肟基，在六元环的脂肪族碳原子的13 C NMR化学位移上有1–2个远程取代基作用，直至远离亚氨基的6个碳碳键为止碳！在13从双环己基肟3-4获得的C NMR数据表明，在该系列反应中，作用仅限于与亚胺基碳有5个键的碳原子。观察到的两个系列之间的差异归因于存在于1-2中的烯烃双键，该双键被肟取代基的电场极化。
• Scalable Electrochemical Decarboxylative Olefination Driven by Alternating Polarity**
  作者：Alberto F. Garrido‐Castro、Yuta Hioki、Yoshifumi Kusumoto、Kyohei Hayashi、Jeremy Griffin、Kaid C. Harper、Yu Kawamata、Phil S. Baran

  DOI：10.1002/anie.202309157

  日期：2023.10.16

  The electrochemical conversion of unactivated carboxylic acids to olefins under alternating polarity is reported. By modulating electrode surface quality and local acidity, chemoselective Hofer-Moest reactivity is realized on conventionally difficult substrates, including primary and secondary unactivated carboxylic acids. This simple protocol is exceptionally scalable (1 kg) and cost-effective.

  报道了在交替极性下未活化的羧酸向烯烃的电化学转化。通过调节电极表面质量和局部酸度，在传统的困难底物（包括未活化的初级和次级羧酸）上实现了化学选择性 Hofer-Moest 反应性。这个简单的协议具有出色的可扩展性（1 kg）且具有成本效益。
• Stepwise versus Direct Long-Range Charge Separation in Molecular Triads
  作者：R. J. Willemse、J. J. Piet、J. M. Warman、F. Hartl、J. W. Verhoeven、A. M. Brouwer

  DOI：10.1021/ja983716r

  日期：2000.4.1

  Trifunctional electron donor-donor-acceptor molecules are described in which photoinduced charge separation, D-2-D-1-A* --> D-2-D-1(+)-A(-), is followed by a charge migration step D-2-D-1(+)-A(-) (CS1) --> D-2(+)-D-1-A- (CS2), leading to a relatively long-lived charge-separated state. The rate of the charge migration process could be determined in a range of solvents of low polarity. In benzene and dioxane, reversibility of the process allowed the determination of the free energy difference between CS1 and CS2. The relative energy of the CS2 state is much lower than expected from simple electrostatic models. An increase of the charge migration rate was found with increasing solvent polarity within a series of alkyl ethers or alkyl acetates. However, an apparent preferential stabilization of the CS1 state in acetates relative to ethers leads to discontinuities in the solvatochromic shift behavior of the CT fluorescence from the CS1 state, and in the increase of the charge migration rate as a function of dielectric constant. In a reference compound lacking the intermediate redox unit, direct long-range charge separation yielding a D-2(+)-bridge-A(-) charge-separated state can occur, but the yield is significantly lower than in the triads.
• Photoinduced Intramolecular Charge Separation in Donor/Acceptor-Substituted Bicyclohexylidene and Bicyclohexyl
  作者：Frans J. Hoogesteger、Cornelis A. van Walree、Leonardus W. Jenneskens、Martin R. Roest、Jan W. Verhoeven、Wouter Schuddeboom、Jacob J. Piet、John M. Warman

  DOI：10.1002/1521-3765(20000818)6:16<2948::aid-chem2948>3.0.co;2-0

  日期：2000.8.18

  The photophysical properties of a bicyclohexylidene (1DA) and a bicyclohexyl (2DA) substituted with an anilino electron donor and a dicyanoethylene electron acceptor have been studied. Quenching of local donor emission is observed for these compounds as well as quenching of the "pseudo-local" acceptor emission. Transient absorption spectra show dialkylanilino-type radical-cation and dicyanoethylene-type radical-anion absorptions. These results show that intramolecular charge separation takes place in 1DA and 2DA. This was corroborated by time-resolved microwave conductivity measurements from which large excited-state dipole moments were found for both 1DA and 2DA. Time-resolved fluorescence spectroscopy revealed that in the charge-separated state in cyclohexane for 2DA, molecular folding takes place on a nanosecond timescale. For 1DA in cyclohexane, either charge separation takes place in a (fully) folded conformation or very rapid (subnanosecond timescale) folding takes place subsequent to charge separation. In addition to this difference in conformational behavior, the presence of the exocyclic double bond between the cyclohexyl-type rings results in efficient quenching of the anilino donor triplet state and acceleration of the charge recombination rate by a factor of 20.
• Oligo(Cyclohexylidene)s and Oligo(Cyclohexyl)s as Bridges for Photoinduced Intramolecular Charge Separation and Recombination
  作者：Wibren D. Oosterbaan、Carola Koper、Thijs W. Braam、Frans J. Hoogesteger、Jacob J. Piet、Bart A. J. Jansen、Cornelis A. van Walree、H. Johan van Ramesdonk、Marijn Goes、Jan W. Verhoeven、Wouter Schuddeboom、John M. Warman、Leonardus W. Jenneskens

  DOI：10.1021/jp0271716

  日期：2003.5.1

  A series of semirigid donor-bridge-acceptor (D-B-A) molecules was synthesized to study the effect of the position and number of nonconjugated olefinic bonds in the bridge on the photoinduced charge-separation and charge-recombination kinetics. The molecules consist of a phenylpiperidine electron donor, an oligo(cyclohexylidene) or oligo(cyclohexyl) bridge, and a dicyanovinyl acceptor. Partly saturated ter(cyclohexylidene) bridges were used as well. The edge-to-edge donor-acceptor separation of the compounds under study varies between 2.89 and 15.4 Angstrom. The replacement of a C-C single bond by an olefinic bond increases the rate of charge separation with a factor of 3.0 +/- 0.8 per replaced bond. For all D-B-A compounds the extended fully charge-separated state folds to a compact charge-transfer (CCT) conformer. The rate of charge recombination (CR) of the CCT state increases with solvent polarity for those compounds having an olefinic bond located three sigma bonds from the acceptor. Thus, while in cyclohexane the CR rate is equal for all compounds, in benzene the CR rate in compounds with an olefinic bond near the acceptor is 10 times larger than in compounds with a single bond instead. It is believed that a (virtual) charge-transfer state involving the radical cation of the olefinic bond and the radical anion of the acceptor (D-B.+-A(.-)) is responsible for the enhanced CR process.