Diaethyl-(2-oxo-cyclopentylmethyl)-phosphonat | 16965-94-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: Diaethyl-(2-oxo-cyclopentylmethyl)-phosphonat
• 英文别名: 2-(Diethoxyphosphorylmethyl)cyclopentan-1-one
• CAS: 16965-94-9
• 化学式: C₁₀H₁₉O₄P
• 分子量: 234.232
• InChiKey: PGHKLGSVLXDGBV-UHFFFAOYSA-N

物化性质

• 沸点：
  339.7±15.0 °C(Predicted)
• 密度：
  1.119±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Diaethyl-(2-oxo-cyclopentylmethyl)-phosphonat 在 吡啶 、 盐酸 、 ammonium hydroxide 、 氯化铵 作用下， 以 甲醇 为溶剂， 生成 (+/-)-cis-1-amino-2-(phosphonomethyl)-1-cyclopentanecarboxylic acid
  参考文献：
  名称：

  2,3-Ethylene- and 2,3-trimethylene-bridged analogues of the group III metabotropic glutamate receptor ligand 2-amino-4-phosphonobutanoic acid

  摘要：

  The estrogen receptor alpha (ER alpha) is understood to play an important role in the progression of breast cancer. Therefore, pure antiestrogens with a preference for this receptor form are of interest as new agents for the treatment of this malignancy. Several chemical structures with selective binding affinity for ER alpha have been identified and might be useful for the synthesis of ER alpha-selective pure antiestrogens. In this study we applied the 2,5-diphenyifuran system which is closely related to the triphenylfurans described by others. Various side chains with amino and/or sulfur functions were linked to C3 to convert the furans to estrogen antagonists without residual estrogenic activity. The degree of alpha-selectivity which ranges from 2.5- to 236-fold is strongly influenced by the alkyl group at C4. Antiestrogenic potency was determined in MCF-7/2a breast cancer cells stably transfected with a luciferase gene under the control of an ERE. The 2,5-bis(4-hydroxyphenyl)furan with an ethyl substituent and a 6-[N-methyl-N-(3-pentylthiopropyi)amino]hexyl side chain exerted the strongest antiestrogenic effect in this series with an IC50 value of 50 nM in cells stimulated with 1 nM estradiol. The RBA values of this derivative were 18% (ER alpha) and 3.4% (ER beta) of estradiol, respectively. It inhibited the growth of wild-type MCF-7 cells with an IC50 value of 22 nM. The data show that the 2,5-diphenylfuran system is appropriate for the development of pure antiestrogens with preference for ER alpha. (c) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2004.10.040
• 作为产物：
  描述：

  5-己烯酸 在 草酰氯 、 二乙基亚磷酸氢酯 、 过氧化苯甲酰 作用下， 以 1,4-二氧六环 、 二氯甲烷 为溶剂， 生成 Diaethyl-(2-oxo-cyclopentylmethyl)-phosphonat
  参考文献：
  名称：

  Radical Cyclizations of Alkenyl Acylphosphonate Derivatives under Thermal and Photochemical Conditions

  摘要：

  在热和光化学条件下，分别研究了烯丙基酰基膦酸酯和酰基膋氧化物衍生物作为受体在自由基环合反应中的应用。热条件下烯丙基酰基膦酸酯的环合反应在回流的二恶烷中顺利进行，以苯甲酰过氧化物为引发剂；加入亚磷酸二乙酯可提高化学产率。在300 nm光化学诱导下，烯丙基酰基二苯基膦氧化物的环合反应得到类似结果，尽管在一个案例中观察到了显著差异。在热和光化学条件下，S-丁-3-烯基膦硫酯的内环化反应提供了硫酯，而S-戊-4-烯基膦硫酯在类似条件下生成了四氢噻吩衍生物。

  DOI：

  10.1246/bcsj.78.1665

文献信息

• Verfahren zur Herstellung von 1-Alkoxyhexatrien-2-carbonsäureestern
  申请人：BAYER AG

  公开号：EP0453841A2

  公开（公告）日：1991-10-30

  >Verfahren zur Herstellung von 1-Alkoxyhexatrien-2-carbonsäureestern der allgemeinen Formel (I), welche als Antibiotica und Schädlingsbekämpfungsmittel bekannt sind, dadurch gekennzeichnet, daß man Oxophosphonsäureester der Formel (II), zunächst in einer ersten Stufe mit Alkoxycarbonylalkylphosphonester-Derivaten der Formel (III), in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart einer Base umsetzt, anschließend in einer zweiten Stufe die so erhältlichen Acrylesterderivate der Formel (IV), in welcher R¹, R² und R⁷ die oben angegebene Bedeutung haben, mit Ameisensäuremethylester in Gegenwart eines Verdünnungsmittels und in Gegenwart einer Base formyliert, dann entweder direkt in Anschluß daran in einem Reaktionsschritt oder auch in einer getrennten Reaktionsstufe mit einem Methylierungsmittel gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart einer Base methyliert und in einer letzten Stufe die so erhältlichen Alkoxymethylencarbonester der Formel (V), mit Ketonen oder Aldehyden der Formel (VI), gegebenenfalls in Gegenwart eines Verdünnungsmittels und in Gegenwart einer Base umsetzt.

  >通式(I)的 1-烷氧基己三烯-2-羧酸酯的制备方法、 作为抗生素和杀虫剂，其特征在于式（II）的氧化膦酸酯 首先在第一阶段与式（III）的烷氧基羰基烷基膦酸酯衍生物反应 在稀释剂存在下，可选择在碱存在下，然后在第二阶段，得到式（IV）的丙烯酸酯衍生物、 其中 R¹、R² 和 R⁷ 具有上述含义、 与甲酸甲酯在稀释剂和碱存在下进行甲酰化，然后在反应步骤中直接进行甲基化，或在单独的反应步骤中与甲基化剂（可选择在稀释剂和碱存在下进行）进行甲基化，最后得到式（V）的烷氧基亚甲基碳酯、 与式（VI）的酮或醛反应、 可选择在稀释剂和碱存在下进行。
• Reactions of Mannich bases with triethyl phosphite
  作者：B. E. Ivanov、V. F. Zheltukhin、T. G. Vavilova

  DOI：10.1007/bf00908280

  日期：1967.6
• Radical Cyclizations of Alkenyl Acylphosphonate Derivatives under Thermal and Photochemical Conditions
  作者：Chang Ho Cho、Sunggak Kim、Motoki Yamane、Hironori Miyauchi、Koichi Narasaka

  DOI：10.1246/bcsj.78.1665

  日期：2005.9

  The use of alkenyl acylphosphonate and acylphosphine oxide derivatives as acceptors in radical cyclizations was studied under thermal and photochemical conditions, respectively. The cyclizations of alkenyl acylphosphonates under thermal conditions occurred smoothly in refluxing dioxane using benzoyl peroxide as an initiator; the addition of diethyl phosphite increased the chemical yield. Photochemically induced cyclizations of alkenyl acyldiphenylphosphine oxides at 300 nm gave similar results, although a notable difference was observed in one case. The intramolecular cyclization of S-but-3-enyl phosphinothiolformates occurred under thermal and photochemical conditions, providing thiolactones, whereas S-pent-4-enyl phosphinothiolformate afforded the tetrahydrothiophene derivative under similar conditions.

  在热和光化学条件下，分别研究了烯丙基酰基膦酸酯和酰基膋氧化物衍生物作为受体在自由基环合反应中的应用。热条件下烯丙基酰基膦酸酯的环合反应在回流的二恶烷中顺利进行，以苯甲酰过氧化物为引发剂；加入亚磷酸二乙酯可提高化学产率。在300 nm光化学诱导下，烯丙基酰基二苯基膦氧化物的环合反应得到类似结果，尽管在一个案例中观察到了显著差异。在热和光化学条件下，S-丁-3-烯基膦硫酯的内环化反应提供了硫酯，而S-戊-4-烯基膦硫酯在类似条件下生成了四氢噻吩衍生物。
• 2,3-Ethylene- and 2,3-trimethylene-bridged analogues of the group III metabotropic glutamate receptor ligand 2-amino-4-phosphonobutanoic acid
  作者：Rodney L. Johnson、Kolluri S.S.P. Rao

  DOI：10.1016/j.bmcl.2004.10.040

  日期：2005.1

  The estrogen receptor alpha (ER alpha) is understood to play an important role in the progression of breast cancer. Therefore, pure antiestrogens with a preference for this receptor form are of interest as new agents for the treatment of this malignancy. Several chemical structures with selective binding affinity for ER alpha have been identified and might be useful for the synthesis of ER alpha-selective pure antiestrogens. In this study we applied the 2,5-diphenyifuran system which is closely related to the triphenylfurans described by others. Various side chains with amino and/or sulfur functions were linked to C3 to convert the furans to estrogen antagonists without residual estrogenic activity. The degree of alpha-selectivity which ranges from 2.5- to 236-fold is strongly influenced by the alkyl group at C4. Antiestrogenic potency was determined in MCF-7/2a breast cancer cells stably transfected with a luciferase gene under the control of an ERE. The 2,5-bis(4-hydroxyphenyl)furan with an ethyl substituent and a 6-[N-methyl-N-(3-pentylthiopropyi)amino]hexyl side chain exerted the strongest antiestrogenic effect in this series with an IC50 value of 50 nM in cells stimulated with 1 nM estradiol. The RBA values of this derivative were 18% (ER alpha) and 3.4% (ER beta) of estradiol, respectively. It inhibited the growth of wild-type MCF-7 cells with an IC50 value of 22 nM. The data show that the 2,5-diphenylfuran system is appropriate for the development of pure antiestrogens with preference for ER alpha. (c) 2004 Elsevier Ltd. All rights reserved.