1-氯-4,4-二甲氧基戊烷 | 56519-61-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 1-氯-4,4-二甲氧基戊烷
• 英文名称: 1-chloro-4,4-dimethoxypentane
• 英文别名: 5-chloro-2,2-dimethoxypentane；Pentane, 1-chloro-4,4-dimethoxy-
• CAS: 56519-61-0
• 化学式: C₇H₁₅ClO₂
• mdl: MFCD18973491
• 分子量: 166.648
• InChiKey: UBDRYQSBZIAAFH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  10
• 可旋转键数：
  5
• 环数：
  0.0
• 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：

  1-氯-4,4-二甲氧基戊烷 在 sodium azide 作用下， 以 二甲基亚砜 为溶剂， 以80%的产率得到5-azido-2,2-dimethoxypentane
  参考文献：
  名称：

  Synthesis of Novel Analogs of Acetyl Coenzyme A: Mimics of Enzyme Reaction Intermediates

  摘要：

  An improved method for the synthesis of analogs of coenzyme A (CoA) and its thioesters, which are modified in the thiol or thioester moiety, has been developed using a combination of chemical and enzymatic reactions, The enzymes catalyzing the last two steps of CoA biosynthesis were used to prepare a CoA analog (1c) in which an amide bond is replaced by a thioester bond and the thiol group is replaced by a methyl group. Reaction of 1c with a primary amine in aqueous solution results in aminolysis of the thioester linkage to form the desired CoA analog. Reaction with different amines permits the introduction of a variety of functional groups in place of the nor mal thiol or thioester group. This methodology has been used in the synthesis of five new analogs of acetyl-CoA in which the thioester sulfur is replaced by a methylene group and the acetyl group is replaced by carboxylate (14a), nitro (14b), carboxamide (14c), methyl sulfoxide (14d), and methyl sulfone (14e) groups. 14a-c were designed to mimic the possible enolate or enol intermediate in the reaction of citrate synthase and related enzymes. 14a and 14c are potent inhibitors of citrate synthase, with K-i values 1000- and 570-fold lower than the K-m for acetyl-CoA, respectively. CD titrations indicate that 14a and 14c have low affinity for citrate synthase in the absence of oxaloacetate, consistent with their recognition as enol or enolate analogs. 14b is a poor inhibitor of citrate synthase, with affinity slightly lower than that for acetyl-CoA. These results are consistent with generation of the enol form of acetyl-CoA as the nucleophilic intermediate in the reaction of citrate synthase. 14d and 14e were designed to mimic the tetrahedral intermediate or transition state in the reaction of chloramphenicol acetyltransferase and related acetyl-CoA-dependent acetyltransferases. Both compounds are poor inhibitors of chloramphenicol acetyltransferase, with affinities slightly lower than that of acetyl-CoA, indicating that these compounds are not good mimics of the enzyme-bound tetrahedral intermediate or transition state.

  DOI：

  10.1021/ja00090a014
• 作为产物：
  描述：

  5-氯-2-戊酮 、 原甲酸三甲酯 在 potassium carbonate 作用下， 反应 20.5h， 以84%的产率得到1-氯-4,4-二甲氧基戊烷
  参考文献：
  名称：

  β-Carotene autoxidation: oxygen copolymerization, non-vitamin A products, and immunological activity

  摘要：

  胡萝卜素据报道具有独立于维生素A活性的免疫效应。尽管抗氧化活性被认为是其作用的基础，但胡萝卜素能够自氧化为具有免疫活性的多种非维生素A产物的能力尚未被充分探索。我们进行了β-胡萝卜素自氧化的系统研究，并测试了产物混合物的免疫活性。自氧化主要通过氧共聚合进行，导致产生一个明确定义、可复制的产物，对应于几乎吸收了8摩尔当量的氧气。该产物被称为OxC-beta，经验式为C₄₀H₆₀O_{15>，与β-胡萝卜素的C40H56>相比，含氧量超过30%（重量百分比），β-胡萝卜素氧共聚物含量为85%（重量百分比），以及少量的许多C8-C18的非异戊二烯化合物。没有维生素A或更高分子量的异戊二烯化合物存在。以前尚未报道过聚合物的优势。这种聚合物似乎是孢子和花粉外壁中发现的生物聚合物孢粉素的较少聚合形式。番茄红素和辣胭脂素的自氧化显示出类似的聚合物优势。OxC-beta在PCR基因表达阵列中表现出免疫活性，表明胡萝卜素氧化产生了具有免疫调节潜力的非维生素A产物。}

  DOI：

  10.1139/cjc-2013-0494

文献信息

• Rearrangement of Hydroxylated Pinene Derivatives to Fenchone-Type Frameworks: Computational Evidence for Dynamically-Controlled Selectivity
  作者：Marcus Blümel、Shota Nagasawa、Katherine Blackford、Stephanie R. Hare、Dean J. Tantillo、Richmond Sarpong

  DOI：10.1021/jacs.8b05804

  日期：2018.7.25

  An acid-catalyzed Prins/semipinacol rearrangement cascade reaction of hydroxylated pinene derivatives that leads to tricyclic fenchone-type scaffolds in very high yields and diastereoselectivity has been developed. Quantum chemical analysis of the selectivity-determining step provides support for the existence of an extremely flat potential energy surface around the transition state structure. This

  已经开发出羟基化蒎烯衍生物的酸催化的 Prins/semipinacol 重排级联反应，该反应以非常高的产率和非对映选择性得到三环芘酮型支架。选择性决定步骤的量子化学分析为过渡态结构周围极其平坦的势能面的存在提供了支持。这种过渡态结构似乎是双峰的，即在通过过渡态分叉 (PTSB) 的动态控制下，fenchone 型三环支架优先于竞争性形成冰片（樟脑型）骨架。
• Synthesis and spectroscopic characterization of the doubly locked 9E,11Z retinal model systems 7E,13E-11,19-10,20-dimethanoretinal and its 13Z isomer
  作者：M. Groesbeek、G. W. Robijn、J. Lugtenburg

  DOI：10.1002/recl.19921110206

  日期：——

  7E,13E-11,19-10,20-dimethanoretinal (1) and its 13Z isomer 2 were prepared from β-ionone, using the novel synthon 2-(diethoxyphosphinyl)-5,5-dimethoxyhexanenitrile. This synthon was also used to prepare 7E,9E,13E-10,20-methanoretinal (3) and its 13Z isomer 4 in high yield, starting from β-ionone. Spectroscopic analysis (mass, 1H and 13C NMR and UV/Vis) of these compounds is discussed. The introduction

  使用新型合成子2-（二乙氧基膦基）-5,5-二甲氧基己腈，由β-紫罗兰酮制备了7E，13E -11,19-10,20-二甲基氨基视网膜（1）及其13 Z异构体2。该合成子还用于以β-紫罗兰酮为原料，以高收率制备7E，9E，13E -10,20-甲基视黄醛（3）及其13 Z异构体4。讨论了这些化合物的光谱分析（质量，1 H和13 C NMR和UV / Vis）。甲醇桥的引入导致最小的空间和电子变化。从1和2到达的光平稳态具有13 Z形式2为主要成分。这是极少数具有Z形作为光固定态主要成分的分子之一。1和2对13-C14-C双键的酸催化的异构化非常敏感。11,19-甲醇桥的存在是造成这种有效的ZE异构化的原因。
• Copper(I)-Catalyzed Ketone, Amine, and Alkyne Coupling for the Synthesis of 2-Alkynylpyrrolidines and -piperidines
  作者：Wim E. Van Beek、Joren Van Stappen、Philippe Franck、Kourosch Abbaspour Tehrani

  DOI：10.1021/acs.orglett.6b02127

  日期：2016.10.7

  A Cu(I)-catalyzed coupling of a ω-chloro ketone, a primary amine, and an alkyne is described. This protocol allows for the synthesis of α-quaternary carbons in 2-alkynyl-substituted N-heterocycles. The key step is the in situ generation of a cyclic ketiminium species, which has enhanced reactivity for alkynylation compared to acyclic ketiminium species.

  描述了Cu（I）催化的ω-氯酮，伯胺和炔烃的偶联。该方案允许在2-炔基取代的N-杂环中合成α-季碳。关键步骤是就地生成环状酮亚胺物种，与无环酮亚胺物种相比，它具有更高的烷基化反应活性。
• Rates of ionization of arylamino ketones possessing the potentiality for intramolecular imine formation and intramolecular proton abstraction
  作者：Sanford N. Gitel、C. David Gutsche

  DOI：10.1021/ja00847a005

  日期：1975.7
• Hydrolysis of the vinyl ether functional group in a model for prostacyclin in which the carboxyl group has been replaced by a pyridine ring
  作者：Nils Aake Bergman、Torbjoern Halvarsson

  DOI：10.1021/jo00270a023

  日期：1989.4