8-Chloro-3,7-dimethyl-2,6-octadienyl Benzyl Ether | 52220-07-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 8-Chloro-3,7-dimethyl-2,6-octadienyl Benzyl Ether
• 英文别名: trans,trans-1-benzyloxy-8-chloro-3,7-dimethyl-2,6-octadiene；(E,E)-8-benzyloxy-1-chloro-2,6-dimethylocta-2,6-diene；[(2E,6E)-8-chloro-3,7-dimethylocta-2,6-dienoxy]methylbenzene
• CAS: 52220-07-2
• 化学式: C₁₇H₂₃ClO
• 分子量: 278.822
• InChiKey: LWOHFZLOQGNWEU-ZYHSJPTQSA-N

物化性质

• 沸点：
  382.6±42.0 °C(Predicted)
• 密度：
  1.012±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  19
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  8-Chloro-3,7-dimethyl-2,6-octadienyl Benzyl Ether 在 氨 、 lithium 作用下， 生成 (2E,6E,10E,14Z)-3,7,11-trimethyl-hexadeca-2,6,10,14-tetraen-1-ol
  参考文献：
  名称：

  Synthesis and carbon-13 nuclear magnetic resonance spectra of all-trans-geranylgeraniol and its nor analogs

  摘要：

  DOI：

  10.1021/jo00420a003
• 作为产物：
  描述：

  (3'E)-3-(5'-benzyloxy-3'-methylpent-3'-enyl)-2,2-dimethyloxirane 在 吡啶 、 氯化亚砜 、 高氯酸 作用下， 生成 8-Chloro-3,7-dimethyl-2,6-octadienyl Benzyl Ether
  参考文献：
  名称：

  Terao,S. et al., Journal of the Chemical Society. Perkin transactions I, 1978, p. 1101 - 1110

  摘要：

  DOI：

文献信息

• Muramyl Dipeptide Derivatives with Multiprenylacetyl Group. Synthesis and Immunological Activities
  作者：Tsunehiko Fukuda、Shigeru Kobayashi、Hidefumi Yukimasa、Shinji Terao、Masahiko Fujino、Tetsuo Shiba、Ikuo Saiki、Ichiro Azuma、Yuichi Yamamura

  DOI：10.1246/bcsj.54.3530

  日期：1981.11

  Several linear and branched all-trans-multiprenylacetic acids were synthesised, and introduced to the 6 position of the sugar moiety of muramyl dipeptide and its analog, via an amino acid as a linking unit. Compared with the saturated stearoyl derivative, all the compounds having a multiprenylacetyl group exhibited more potent adjuvant activity on the induction of delayed-type hypersensitivity to N-acetyl-3-(4-arsonophenylazo)-l-tyrosine. The derivatives with larger branched side chains tended to have increased activity.

  合成了几种线性和支链型全反式多萜酸，并通过氨基酸作为连接单元引入到穆拉酰二肽及其类似物的糖部分6位上。与饱和的硬脂酰衍生物相比，所有具有多萜乙酰基的化合物在诱导对N-乙酰-3-(4-砷苯基偶氮)-l-酪氨酸的延迟型超敏反应方面展现了更强的佐剂活性。具有较大支链侧链的衍生物往往表现出更强的活性。
• Synthesis of Methoxynor Polyisoprenoid Alcohols by Alkylation of (3-Methoxyallyl)lithium Reagents
  作者：Qingwu Jin、Robert M. Coates

  DOI：10.1135/cccc20020055

  日期：——

  A series of six methyl enol ether analogs 8-13 of geraniol, (E,E)-farnesol, and (E,E,E)-geranylgeraniol was synthesized from a group of three allylic methyl ethers and three allylic chlorides. Lithiation of the 1-methyl-, or 1-alkenylvinyl ethers with sec-butyllithium at -78 °C followed by alkylations of the resulting (Z)-(3-methoxyallyl)lithium reagents afforded the six possible Z-configured(trans) methoxynor polyprenyl benzyl ethers bearing the methoxy substituent at the internal and terminal double bonds with high Z/E ratios (5 : 1-31 : 1) and 47-80% yields. Reductive cleavage of the benzyl groups with lithium in liquid ammonia gave the corresponding methoxynor polyprenols. 11-Methoxy-18-nor and 7-methoxy-19-nor geranylgeraniols (13 and 12) were converted to the corresponding diphosphates, 7 and 32, by the Poulter displacement method. The stability of the enol ether in 7 in aqueous solution at pH 8 was verified by NMR analyses. The diphosphates of the methoxynor polyprenols may prove useful as substrate analogs for terpene synthases to capture transient intermediates in cyclization reactions catalyzed by these enzymes.

  一系列六种甲基烯醇醚类似物8-13，包括香叶醇、（E，E）-法尼醇和（E，E，E）-戊二烯醇的合成，从三种烯丙基甲基醚和三种烯丙基氯化物开始。在-78°C下用sec丁基锂对1-甲基或1-烯基乙烯醚进行锂化，然后通过烷基化反应得到（Z）-(3-甲氧基烯丙基)锂试剂，合成了可能的Z-构型（反式）甲氧基聚戊二烯苄醚，其在内部和末端双键处带有甲氧基取代基，Z/E比例高（5:1-31:1），产率为47-80%。在液氨中用锂对苄基进行还原解离，得到相应的甲氧基聚戊二烯醇。11-甲氧基-18-去和7-甲氧基-19-去戊二烯醇（13和12）通过Poulter位移法转化为相应的二磷酸酯7和32。通过NMR分析验证了在pH 8水溶液中7中烯醇醚的稳定性。这些甲氧基聚戊二烯醇的二磷酸酯可能作为萜类合酶的底物类似物，用于捕获这些酶催化的环化反应中的瞬态中间体。
• Regio- and Stereoselective Synthesis of 1,5-Dienes Using Allylic Barium Reagents
  作者：Akira Yanagisawa、Hiroaki Hibino、Shigeki Habaue、Yoshiyuki Hisada、Katsutaka Yasue、Hisashi Yamamoto

  DOI：10.1246/bcsj.68.1263

  日期：1995.5

  The highly α,α′ selective and stereocontrolled homocoupling reaction of allylic halides was achieved using barium reagent. The double-bond geometry of the starting allylic chloride was completely retained. The α,α′ cross-coupling products were also prepared stereospecifically and regioselectively by this method.

  使用钡试剂实现了烯丙基卤化物的高度α,α'选择性和立体控制的同偶联反应。完全保留了起始烯丙基氯的双键几何结构。α,α'交叉偶联产物也通过该方法立体定向和区域选择性制备。
• CYCLIZATION OF POLYENES XXVII. SYNTHESIS OF OXOCRINOL,<i>dl</i>-CAULERPOL, AND<i>dl</i>-CRINITOL
  作者：Tadahiro Kato、Hisao Takayanagi、Tadao Uyehara、Yoshio Kitahara

  DOI：10.1246/cl.1977.1009

  日期：1977.8.5

  Novel terpene alcohols, oxocrinol (1a), caulerpol (3a), and crinitol (2a), isolated from marine algae, were synthesized by the alkylation of lithium salt of benzenesulfonyl derivatives, 5, 6, and 11 (R = THP; X = SO2Ph) followed by reductive cleavage of SO2Ph and the protecting groups. The present study confirms unequivocally the proposed structures of oxocrinol, caulerpol, and crinitol, respectively.

  通过苯磺酰基衍生物 5、6 和 11（R = THP；X = SO2Ph）的锂盐烷基化，然后还原裂解 SO2Ph 和保护基，合成了从海洋藻类中分离出来的新型萜烯醇 oxocrinol (1a)、caulerpol (3a) 和 crinitol (2a)。本研究明确证实了所提出的oxocrinol、caulerpol 和 crinitol 的结构。
• PROCESS FOR THE PREPARATION OF VITAMIN K2
  申请人：KAPPA BIOSCIENCE AS

  公开号：US20150210620A1

  公开（公告）日：2015-07-30

  Using a combination of Kumada, Suzuki and Biellmann chemistry, various menaquinones can synthesised rapidly and with stereochemical integrity offering a new way of preparing these vitamin K2 components for the pharmaceutical market. In one embodiment a process for the preparation of a compound of formula (I) is defined including a step in which (i) a compound of formula (II) is reacted with a compound of formula (III) wherein R is an alkyl group; LG is a leaving group; m is an integer from 0 to 8; n is an integer of from 0 to 9; and X is hydrogen, halide, hydroxyl or protected hydroxyl; in the presence of a copper, nickel or palladium catalyst.

  利用 Kumada、Suzuki 和 Biellmann 化学的组合，可以快速合成各种 menaquinones，并保持立体化学完整性，为制备这些维生素 K2 成分提供了一种新的方法，以供制药市场使用。在一种实施例中，定义了一种制备化合物式（I）的过程，其中包括以下步骤：（i）将化合物式（II）与化合物式（III）反应，其中 R 是烷基；LG 是离去基团；m 是 0 到 8 的整数；n 是 0 到 9 的整数；X 是氢、卤素、羟基或受保护的羟基；在铜、镍或钯催化剂的存在下进行。