(Z)-1-chloro-5,5-diethoxy-1-penten-3-yne | 114534-23-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (Z)-1-chloro-5,5-diethoxy-1-penten-3-yne
• 英文别名: (Z)-1-chloro-5,5-diethoxyprop-1-en-3-yne；(Z)-5-chloro-1,1-diethoxypent-4-en-2-yne；(Z)-5-chloro-1,1-diethoxy-4-pentene-2-yne；(Z)-1-chloro-5,5-diethoxypent-1-en-3-yne
• CAS: 114534-23-5
• 化学式: C₉H₁₃ClO₂
• 分子量: 188.654
• InChiKey: PXVOVZJDORSBOT-VURMDHGXSA-N

物化性质

• 沸点：
  209.2±40.0 °C(Predicted)
• 密度：
  1.056±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 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：

  (Z)-1-chloro-5,5-diethoxy-1-penten-3-yne 在 硫酸 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 乙醇 、 水 为溶剂， 反应 22.0h， 生成 anti-2,4-pentadiynal tosylhydrazone
  参考文献：
  名称：

  Reactive Carbon-Chain Molecules:  Synthesis of 1-Diazo-2,4-pentadiyne and Spectroscopic Characterization of Triplet Pentadiynylidene (H−C⋮C−C̈−C⋮C−H)

  摘要：

  1-Diazo-2,4-pentadiyne (6a), along with both monodeuterio isotopomers; 6b and 6c, has been synthesized via a route that proceeds through diacetylene, 2,4-pentadiynal, and 2,4-pentadiynal tosylhydrazone. Photolysis of diazo compounds 6a-c (lambda > 444 nm; Ar or N-2, 10 K) generates triplet carbenes HC5H (1) and HC5D (1-d), which have been characterized by IR, EPR, and UV/vis spectroscopy. Although many resonance structures contribute to the resonance hybrid for this highly unsaturated carbon-chain molecule, experiment and theory reveal that the structure is best depicted in terms of the dominant resonance contributor of penta-1,4-diyn-3-ylidene (diethynylcarbene, H-C equivalent to C-C-C equivalent to C-H). Theory predicts an axially symmetric (D-h) structure and a triplet electronic ground state for 1 (CCSD(T)/ANO). Experimental IR frequencies and isotope shifts are in good agreement with computed values. The triplet EPR spectrum of 1 (vertical bar D/hc vertical bar = 0.6157 cm(-1), vertical bar E/hc vertical bar = 0.0006 cm(-1)) is consistent with an axially symmetric structure, and the Curie law behavior confirms that the triplet state is the ground state. The electronic absorption spectrum of 1 exhibits a weak transition near 400 nm with extensive vibronic coupling. Chemical trapping of triplet HC5H (1) in an O-2-cloped matrix affords the carbonyl oxide 16 derived exclusively from attack at the central carbon.

  DOI：

  10.1021/ja058252t
• 作为产物：
  描述：

  2,3-二溴-1,1-二乙氧基丙烷 在 copper(l) iodide 、 四(三苯基膦)钯 氨 、 sodium amide 、 正丁胺 作用下， 以 乙醚 、 苯 为溶剂， 反应 21.25h， 生成 (Z)-1-chloro-5,5-diethoxy-1-penten-3-yne
  参考文献：
  名称：

  Reactive Carbon-Chain Molecules:  Synthesis of 1-Diazo-2,4-pentadiyne and Spectroscopic Characterization of Triplet Pentadiynylidene (H−C⋮C−C̈−C⋮C−H)

  摘要：

  1-Diazo-2,4-pentadiyne (6a), along with both monodeuterio isotopomers; 6b and 6c, has been synthesized via a route that proceeds through diacetylene, 2,4-pentadiynal, and 2,4-pentadiynal tosylhydrazone. Photolysis of diazo compounds 6a-c (lambda > 444 nm; Ar or N-2, 10 K) generates triplet carbenes HC5H (1) and HC5D (1-d), which have been characterized by IR, EPR, and UV/vis spectroscopy. Although many resonance structures contribute to the resonance hybrid for this highly unsaturated carbon-chain molecule, experiment and theory reveal that the structure is best depicted in terms of the dominant resonance contributor of penta-1,4-diyn-3-ylidene (diethynylcarbene, H-C equivalent to C-C-C equivalent to C-H). Theory predicts an axially symmetric (D-h) structure and a triplet electronic ground state for 1 (CCSD(T)/ANO). Experimental IR frequencies and isotope shifts are in good agreement with computed values. The triplet EPR spectrum of 1 (vertical bar D/hc vertical bar = 0.6157 cm(-1), vertical bar E/hc vertical bar = 0.0006 cm(-1)) is consistent with an axially symmetric structure, and the Curie law behavior confirms that the triplet state is the ground state. The electronic absorption spectrum of 1 exhibits a weak transition near 400 nm with extensive vibronic coupling. Chemical trapping of triplet HC5H (1) in an O-2-cloped matrix affords the carbonyl oxide 16 derived exclusively from attack at the central carbon.

  DOI：

  10.1021/ja058252t

文献信息

• Pd-EnCat^TMTPP30 as a Catalyst for the Generation of Highly Functionalized Aryl- and Alkenyl-Substituted Acetylenes via Microwave-Assisted Sonogashira Type Reactions
  作者：Jörg Sedelmeier、Steven V. Ley、Heiko Lange、Ian R. Baxendale

  DOI：10.1002/ejoc.200900344

  日期：2009.9

  copper- and DMF-free conditions and does not require an inert atmosphere. Furthermore, the encapsulated catalyst can be recovered and recycled by a simple filtration of the reaction mixture. It can be reused in further reactions with only minor decrease in activity. Additionally, we were able to produce a variety of enyne derivatives under modified conditions employing the same Pd-EnCatTM source. (© Wiley-VCH

  我们报告了使用 Pd-EnCatTM TPP30 的芳基碘化物和溴化物与末端炔烃的快速微波辅助 Sonogashira 交叉偶联。在 100–120 °C 下，富电子和缺电子芳基卤化物在 MeCN 中与多种末端炔烃反应平稳。以良好至极好的收率和高纯度获得偶联产物。该反应可以在不含铜和 DMF 的条件下进行，不需要惰性气氛。此外，包封的催化剂可以通过反应混合物的简单过滤来回收和再循环。它可以重新用于进一步的反应，而活性只会略有下降。此外，我们能够在使用相同 Pd-EnCatTM 源的修改条件下生产各种烯炔衍生物。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
• Cytotoxic bicyclo[7.3.1]tridec-4-ene-2,6-diyne compounds and process for
  申请人：Bristol-Myers Squibb Company

  公开号：US05198560A1

  公开（公告）日：1993-03-30

  The present invention relates to a novel and efficient process for the preparation of 8-hydroxybicyclo[7.3.1]tridec-4-ene-2,6-diyne ring system which is part of the aglycone of esperemicin and to novel cytotoxic antitumor agents having said bicyclic ring system. The present invention also provides a method for treating mammalian malignant tumors by administering to an animal in need of such treatment an antitumor effective amount of a compound of the present invention.

  本发明涉及一种新颖高效的方法，用于制备8-羟基双环[7.3.1]十三烯-4-炔-2,6-二炔环系统，该环系统是埃斯佩雷霉素的无糖基部分，并且涉及具有该双环环系统的新型细胞毒抗肿瘤药物。本发明还提供了一种治疗哺乳动物恶性肿瘤的方法，即通过向需要此类治疗的动物投与本发明化合物的抗肿瘤有效量。
• Cytotoxic bicyclo [7.3.1.]tridec-4-ene-2,6-diyne compounds and process
  申请人：Bristol-Myers Squibb Company

  公开号：US05318989A1

  公开（公告）日：1994-06-07

  The present invention relates to a novel and efficient process for the preparation of 8-hydroxybicyclo[7.3.1]tridec-4-ene-2,6-diyne ring system which is part of the aglycone of esperemicin and to novel cytotoxic antitumor agents having said bicyclic ring system. The present invention also provides a method for treating mammalian malignant tumors by administering to an animal in need of such treatment an antitumor effective amount of a compound of the present invention.

  本发明涉及一种新的高效制备esperemicin中的8-羟基双环[7.3.1]十三烯-4-炔-2,6-二炔环系统的方法，并提供了具有该双环环系统的新型细胞毒性抗肿瘤药物。本发明还提供了一种通过向需要该治疗的动物施用本发明化合物的抗肿瘤有效量来治疗哺乳动物恶性肿瘤的方法。
• Cytotoxic bicyclo[7.3.1] tridec-4-ene-2,6-diyne compounds and process for the preparation thereof
  申请人：Bristol-Myers Squibb Company

  公开号：EP0454146A1

  公开（公告）日：1991-10-30

  The present invention relates to a novel and efficient process for the preparation of 8-hydroxy-bicyclo[7.3.1]-tridec-4-ene-2,6-diyne ring system which is part of the aglycone of esperemicin and to novel cytotoxic agents having said bicyclic ring system. The present invention also provides a method for treating animal malignant tumors by administering to an animal in need of such treatment an antitumor effective amount of a compound having the formula

  本发明涉及一种制备 8-羟基-双环[7.3.1]-十三烷-4-烯-2,6-二炔环系统的新型高效工艺，该环系是依斯瑞米星(esperemicin)苷元的一部分，本发明还涉及具有所述双环系统的新型细胞毒剂。本发明还提供了一种治疗动物恶性肿瘤的方法，即向需要治疗的动物施用抗肿瘤有效量的具有式
• Cytotoxic bicyclo (7.3.1)-tridec-4-ene-2,6-diyne compounds and process for the preparation thereof
  申请人：Bristol-Myers Squibb Company

  公开号：EP0538898A2

  公开（公告）日：1993-04-28

  The present invention relates to a novel and efficient process for the preparation of 8-hydroxy-bicycloÄ7.3.1Ütridec-4-ene-2,6-diyne ring system which is part of the aglycone of esperemicin and to novel cytotoxic antitumor agents having said bicyclic ring system. The present invention also provides a method for treating mammalian malignant tumors by administering to an animal in need of such treatment an antitumor effective amount of a compound of the present invention.

  本发明涉及一种制备8-羟基-双环Ä7.3.1Ütridec-4-烯-2,6-二炔环系统的新颖而有效的工艺，该环系统是依斯瑞米星(esperemicin)苷元的一部分，本发明还涉及具有所述双环系统的新型细胞毒性抗肿瘤药物。本发明还提供了一种治疗哺乳动物恶性肿瘤的方法，即向需要治疗的动物施用抗肿瘤有效量的本发明化合物。