2-(10-bromodecyl)-1,3-dioxolane | 154839-51-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧戊环
• 英文名称: 2-(10-bromodecyl)-1,3-dioxolane
• CAS: 154839-51-7
• 化学式: C₁₃H₂₅BrO₂
• 分子量: 293.244
• InChiKey: GWWVIJNJELSFMR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  16
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(10-bromodecyl)-1,3-dioxolane 在 盐酸 、 cesium hydroxide 作用下， 以 1,4-二氧六环 为溶剂， 反应 7.5h， 生成 5'-(11-oxoundecylthio)-4,4',5-tris(methylthio)tetrathiafulvalene
  参考文献：
  名称：

  Long-lived photoproduced radical ions in tetrathiafulvalenes covalently tethered to C60

  摘要：

  C-60 or [60]fullerene, a reversible one- to six-electron acceptor with moderate first electron. affinity, was covalently linked, via a 1,3-dipolar addition reaction using azomethine ylides and two flexible insulating sigma-chains of different lengths, to a tetrathioalkyltetrathiafulvalene, a reversible one- to two-electron donor with low first ionization potential, yielding molecules 1 and 2. The electrochemical oxidation and reduction waves are the same as those of the separate components; UV-VIS spectra indicate no appreciable charge transfer in the ground state between the donor and acceptor moieties of these D-sigma-A systems 1 and 2: there is only a weak shoulder at 800 nm (epsilon approximate to 200 L mol(-1) cm(-1)), which could be the intervalence transfer band.These same molecules, as well as their donor and acceptor components taken separately, were electrochemically oxidized/reduced in liquid solutions, and also irradiated with laser light in low-temperature glasses. The electron paramagnetic resonance (EPR) spectra revealed photoexcited electron transfer at 77 K, with resulting S = 1/2 radical cation and radical anion states. In a glass at 77 K these radical signals survive a long time (up to several days) after the end of light irradiation. This may be separately solvated pairs of long-lived radicals D.+-sigma-A and D-sigma-A(.-) or, less likely, a long-lived excited-state zwitterionic biradical D.+-sigma-A(.-) with increasing temperature and the onset of diffusional motion, the EPR signals disappear.

  DOI：

  10.1039/a803737j
• 作为产物：
  描述：

  11-溴-1-十一醇 在 草酰氯 、 对甲苯磺酸 、 二甲基亚砜 、 三乙胺 作用下， 以 甲苯 为溶剂， 反应 16.0h， 生成 2-(10-bromodecyl)-1,3-dioxolane
  参考文献：
  名称：

  Efficient Synthesis of (2S,12′R)-2-(12′-Aminotridecyl)pyrrolidine: A Defense Alkaloid of the Mexican Bean Beetle

  摘要：

  本文描述了从(R)-脯氨酸开始合成墨西哥豆甲虫 Epilachna varivestis 的防御生物碱 (2S,12′R)-2-(12′-aminotridecyl)pyrrolidine [(S,R)-8] 的过程。第二个立体中心是通过甲基锂与醛-SAMP-腙的亲核 1,2-加成，然后进行还原性 N-N 键裂解生成的。该产品收率高，对映异构体和非对映异构体纯度高。

  DOI：

  10.1055/s-2000-6379

文献信息

• Synthesis and absolute configuration of 2-(12′-aminotridecyl)-pyrrolidine, a defensive alkaloid from the Mexican bean beetle, Epilachna varivestis
  作者：Xiongwei Shi、Athula B. Attygalle、Shang-Cheng Xu、Viqar U. Ahmad、Jerrold Meinwald

  DOI：10.1016/0040-4020(96)00326-2

  日期：1996.5

  The synthesis of 2-(12′-aminotridecyl)-pyrrolidine (1), a defensive alkaloid recently isolated from the Mexican bean beetle, Epilachna varivestis, is described. The (2S,12′R) configuration is assigned to this alkaloid by comparing the 1H NMR spectrum of its (S)-MTPA derivative with that of (R)- and (S)-MTPA [α-methoxy-α-(trifluoromethyl)phenylacetyl] derivatives of the synthetic sample. These results

  描述了2-（12'-氨基十三烷基）-吡咯烷（1）的合成，该化合物是最近从墨西哥甲虫Epilachna varivestis中分离出的一种防御性生物碱。（2小号，12' - [R ）配置由所述比较分配给该生物碱1其（的H NMR谱小号）-MTPA衍生物与（的[R和（ - ）小号）-MTPA [α甲氧基α-合成样品的（（三氟甲基）苯基乙酰基]衍生物。这些结果表明1的17个碳骨架是乙酸盐而不是脯氨酸衍生的。
• Synthesis and Photocyclization of .alpha.-Methylene-.gamma.-butyrolactone-Thymine Heterodimers
  作者：Elena Gimenez-Arnau、Stephane Mabic、Jean-Pierre Lepoittevin

  DOI：10.1021/tx00043a002

  日期：1995.1

  ne--thymine heterodimers 6 and 7 with 5 and 10 carbon alkyl chains, respectively, were prepared to study the photoreactivity of lactone rings toward thymine and the influence of spacer length on photoadduct geometry. Deoxygenated solutions (10(-3) M) of heterodimers 6 and 7 were irradiated at 365 nm in acetone. Irradiation of compound 6 (5 carbons alkyl chain) gave a single photoadduct 8 (70% yield)

  分别制备了两个具有5和10个碳烷基链的α-亚甲基-γ-丁内酯-胸腺嘧啶异二聚体6和7，以研究内酯环对胸腺嘧啶的光反应性以及间隔基长度对光加合物几何形状的影响。异二聚体6和7的脱氧溶液（10（-3）M）在丙酮中于365 nm照射。辐照化合物6（5个碳原子的烷基链）得到一个光加合物8（70％收率），而辐照化合物7（10个碳原子的烷基链）则以3/2的比例得到两个光加合物9a和9b（95％收率）。化合物8被鉴定为涉及胸腺嘧啶部分的5“，6”双键和内酯的3,6外亚甲基基团的顺式-内-内分子内[2 + 2]光加合物。化合物9a被鉴定为顺式-syn-exo分子内[2 + 2]光加合物，涉及5“，6”
• Boronic Acids:  New Coupling Partners in Room-Temperature Suzuki Reactions of Alkyl Bromides. Crystallographic Characterization of an Oxidative-Addition Adduct Generated under Remarkably Mild Conditions
  作者：Jan H. Kirchhoff、Matthew R. Netherton、Ivory D. Hills、Gregory C. Fu

  DOI：10.1021/ja0283899

  日期：2002.11.1

  The Suzuki reaction is an exceptionally useful cross-coupling process that has been widely applied in synthetic chemistry, and boronic acids are, by far, the most commonly employed coupling partner. To date, however, no versatile method has been developed for cross-coupling boronic acids with unactivated alkyl (as opposed to aryl or vinyl) electrophiles. This report describes a catalyst system that

  Suzuki 反应是一种非常有用的交叉偶联过程，已广泛应用于合成化学中，而硼酸是迄今为止最常用的偶联伙伴。然而，迄今为止，尚未开发出将硼酸与未活化的烷基（与芳基或乙烯基相反）亲电试剂交叉偶联的通用方法。本报告描述了在室温下实现这一目标的催化剂系统。在机械方面，这项研究表明 Pd(P(t-Bu)2Me)2 在令人惊讶的温和条件下（0 摄氏度）发生氧化加成。所得加合物对β-氢化物消除足够稳定，因此可以对其进行结构表征，并且它是交叉偶联过程中具有化学活性的中间体。
• Synthesis and Photoreaction of a-Methylene-γ-Butyrolactone-Psoralen Heterodimers
  作者：Elena Giménez-Arnau、Cécile Bussey、Jean-Pierre Lepoittevin

  DOI：10.1111/j.1751-1097.1997.tb08564.x

  日期：1997.2

  Three double‐headed molecules were synthesized by linking a photoreactive linear (1, 2) or angular (3) furocou‐marin via a linear 10‐ or 5‐carbon chain to an electro‐philic α‐methylene‐γ‐butyrolactone. The photochemical behavior of these molecules was investigated in ethanol at 365 nm and the photocycloadducts obtained from each compound were isolated and characterized. In all cases, the photoreactivity

  通过将光反应性线性 (1, 2) 或角形 (3) 呋喃香豆素通过线性 10 或 5 碳链与亲电的 α-亚甲基-γ-丁内酯连接，合成了三个双头分子。在乙醇中在 365 nm 处研究这些分子的光化学行为，并对从每种化合物中获得的光环加合物进行分离和表征。在所有情况下，光反应性结果表明补骨脂素的 3,4-吡喃酮双键（线性或角形）是最具反应性的，3,4-吡喃酮和外亚甲基双键之间的 [2 + 2] 分子内光环加合物是获得。化合物1和2得到了两种分子内光环加合物，顺式-外型衍生物的产率分别为46%和36%，反式-syn-exo衍生物的产率分别为14%和18%。对于化合物 3，
• Efficient Synthesis of (2S,12′R)-2-(12′-Aminotridecyl)pyrrolidine: A Defense Alkaloid of the Mexican Bean Beetle
  作者：Dieter Enders、Christoph Thiebes

  DOI：10.1055/s-2000-6379

  日期：——

  The synthesis of (2S,12′R)-2-(12′-aminotridecyl)pyrrolidine [(S,R)-8], a defense alkaloid of the Mexican bean beetle Epilachna varivestis starting from (R)-proline is described. The second stereogenic center is generated by nucleophilic 1,2-addition of methyllithium to an aldehyde-SAMP-hydrazone, followed by reductive N-N bond cleavage. The product is obtained in good yield and high enantiomeric and diastereomeric purity.

  本文描述了从(R)-脯氨酸开始合成墨西哥豆甲虫 Epilachna varivestis 的防御生物碱 (2S,12′R)-2-(12′-aminotridecyl)pyrrolidine [(S,R)-8] 的过程。第二个立体中心是通过甲基锂与醛-SAMP-腙的亲核 1,2-加成，然后进行还原性 N-N 键裂解生成的。该产品收率高，对映异构体和非对映异构体纯度高。