diphenyl [(triphenylphosphoranylidene)methyl]phosphonate | 22400-41-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: diphenyl [(triphenylphosphoranylidene)methyl]phosphonate
• 英文别名: diphenyl<(triphenylphosphoranylidene)methyl>phosphonate；[(diphenoxyphosphinyl)methylidene]triphenylphosphorane；Triphenyl-phosphoranylidenmethyl-phosphoransaeurediphenylester；Phosphonic acid, [(triphenylphosphoranylidene)methyl]-, diphenyl ester；diphenoxyphosphorylmethylidene(triphenyl)-λ5-phosphane
• CAS: 22400-41-5
• 化学式: C₃₁H₂₆O₃P₂
• 分子量: 508.493
• InChiKey: NOUUDSDXCIQGKJ-UHFFFAOYSA-N

物化性质

• 熔点：
  149-150 °C(Solv: ethyl acetate (141-78-6))
• 沸点：
  636.8±38.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  36
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  diphenyl [(triphenylphosphoranylidene)methyl]phosphonate 在 palladium on activated charcoal 吡啶 、 氢气 、 二甲基亚砜 、 N,N'-二环己基碳二亚胺 作用下， 以 甲醇 为溶剂， 反应 55.0h， 生成 2-<5',6'-dideoxy-2',3'-O-(1-methylethylidene)-6'-phosphono-β-D-ribo-hexofuranosyl>-4-thiazolecarboxamide, diphenyl ester
  参考文献：
  名称：

  Thiazole-4-carboxamide adenine dinucleotide (TAD). Analogs stable to phosphodiesterase hydrolysis

  摘要：

  Thiazole-4-carboxamide adenine dinucleotide (TAD), the active metabolite of the oncolytic C-nucleoside tiazofurin (TR), is susceptible to phosphodiesteratic breakdown by a unique phosphodiesterase present at high levels in TR-resistant tumors. Since accumulation of TAD, as regulated by its synthetic and degradative enzymes, appears to be an important determinant for sensitivity to the drug, a series of hydrolytically resistant phosphonate analogues of TAD were synthesized with the intent of producing more stable compounds with an ability to inhibit IMP dehydrogenase equivalent to TAD itself. Isosteric phosphonic acid analogues of TR and adenosine nucleotides were coupled with activated forms of AMP and TR monophosphate to give dinucleotides 2 and 4. Coupling of protected adenosine 5'-(alpha, beta-methylene)diphosphate with isopropylidene-TR in the presence of DCC afforded compound 3 after deprotection. These compounds are more resistant than TAD toward hydrolysis and still retain potent activity against IMP dehydrogenase in vitro. beta-Methylene-TAD (3), the most stable of the TAD phosphonate analogues, produced a depletion of guanine nucleotide pools in an experimentally induced TR-resistant P388 tumor variant that was superior to that obtained with TR in the corresponding sensitive line.

  DOI：

  10.1021/jm00159a027
• 作为产物：
  描述：

  methyl triphenylphosphonium bromide 、 氯磷酸二苯酯 在 正丁基锂 作用下， 生成 diphenyl [(triphenylphosphoranylidene)methyl]phosphonate
  参考文献：
  名称：

  Hollmann, Juergen; Schlimme, Eckhard, Liebigs Annalen der Chemie, 1984, # 1, p. 98 - 107

  摘要：

  DOI：

文献信息

• Novel acyclonucleotides: synthesis and antiviral activity of alkenylphosphonic acid derivatives of purines and a pyrimidine
  作者：Michael R. Harnden、Ann Parkin、Martin J. Parratt、Robert M. Perkins

  DOI：10.1021/jm00062a006

  日期：1993.5

  nitrogen-oxygen bond. The phosphonoalkenyl-substituted compounds 7a-c, 8a-c, 9, 10, and 12 were prepared either by Mitsunobu coupling of alcohols with purine or pyrimidine derivatives or by alternative alkylations of the heterocyclic bases. The (phosphonoalkenyl) oxy derivatives 7d-g, 8d-g, and 11 were synthesized by coupling of alcohols with 9-hydroxypurines or a 1-hydroxypyrimidine under Mitsunobu conditions

  合成了嘌呤和嘧啶的一系列膦酰基烯基和（膦酰基烯基）氧基衍生物。这些化合物是首先报道的无环核苷酸，其结合了α，β-不饱和膦酸部分作为磷酸酯模拟物，并且包括其中无环取代基被氮连接至嘌呤的N-9或嘧啶的N-1的化合物。 -碳或氮-氧键。膦酰基烯基取代的化合物7a-c，8a-c，9、10和12是通过醇与嘌呤或嘧啶衍生物的Mitsunobu偶联或通过杂环碱基的替代烷基化来制备的。（膦烯基）氧基衍生物7d-g，8d-g和11是通过在Mitsunobu条件下将醇与9-羟基嘌呤或1-羟基嘧啶偶联而合成的。测试了新型无环核苷酸对1型和2型单纯疱疹（HSV-1和HSV-2），水痘带状疱疹病毒（VZV），巨细胞病毒（CMV），维斯纳病毒和1型人类免疫缺陷病毒（HIV-1）的活性。鸟嘌呤衍生物具有中等至极强的细胞毒性，但腺嘌呤对细胞的毒性较小。在测试浓度下，直链系列中的（Z）异构体对疱疹病毒或HIV-1没有活性。
• Substituted aromatic phoshonic acid derivatives
  申请人：BASF Aktiengesellschaft

  公开号：US06175007B1

  公开（公告）日：2001-01-16

  Phosphonic acid compounds I wherein Eth is optionally substituted 1,2-ethynediyl, ethanediyl or ethene-1,2-diyl; Y1 is oxygen or sulfur; Y2 is oxygen, sulfur or —N(R6)—; Y3 is oxygen, sulfur or —N(R7)—; R1, R2, R6 and R7 are hydrogen or optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, phenyl or heterocyclyl, or R1 and R2, R1 and R6, R2 and R7 together are optionally substituted 1,2-ethanediyl, 1,3-propylene, tetramethylene, pentamethylene or ethyleneoxyethylene, or R1 and R2 together are optionally substituted 1,2-phenylene; R3 is cyano, halogen, alkyl, haloalkyl, alkoxy or haloalkoxy; R4 is hydrogen or halogen, and R5 is a heterocycle &PHgr;1 to &PHgr;22 as defined in the specification, their manufacture and intermediates therefore. The phosphonic acid compounds are effective against unwanted plants and act as desiccants and defoliants.

  磷酸化合物 I 其中 Eth 可选择地取代为 1,2-乙炔基、乙二基或乙烯-1,2-二基; Y1 为氧或硫; Y2 为氧、硫或—N(R6)—; Y3 为氧、硫或—N(R7)—; R1、R2、R6 和 R7 为氢或 可选择地取代的烷基、烯基、炔基、环烷基、苯基或杂环基，或 R1 和 R2、R1 和 R6、R2 和 R7 一起可选择地取代为 1,2-乙二基、1,3-丙二基、四亚甲基、五亚甲基或乙烯氧基乙烯，或 R1 和 R2 一起可选择地取代为 1,2-苯基; R3 为氰基、卤素、烷基、卤代烷基、烷氧基或卤代烷氧基; R4 为氢或卤素，且 R5 为规范中定义的杂环 &PHgr;1 至 &PHgr;22, 它们的制备及其中间体。这些磷酸化合物对不受欢迎的植物有效，并起到脱水剂和落叶剂的作用。
• Phosphorhaltige Kohlenhydrate, III. Darstellung von Zuckerphosphonaten durch <i>Wittig</i> ‐ und <i>Horner</i> ‐Reaktion
  作者：Hans Paulsen、Wilfried Bartsch、Joachim Thiem

  DOI：10.1002/cber.19711040823

  日期：1971.8

  [Triphenyl-phosphoranylidenmethan]-phosphonsäure-diphenylester nach Wittig oder mit Methan-bis-[phosphonsäure-diäthylester]-Natrium-Salz nach Horner zu trans-Olefin-Phosphonat-Zuckern (2, 4a, b), bei denen die Kette um ein C-Atom verlängert ist. Äthyliden-D-erythrose 5 ergibt nach Wittig ein cyclisches cis-Olefin-Phosphonat 6, nach Horner ein offenkettiges trans-Olefin-Phosphonat 7.

  开链醛糖保护（1，3）用游离的醛基与[三苯基phosphoranylidenemethane]反应-膦酸二苯酯按照维悌希或甲烷双- [膦酸二乙基酯]的钠盐根据霍纳以形成反式烯烃膦酸酯糖（2，图4a，b），其中，所述链被一个碳原子延长。根据维蒂希（Wittig）的观点，亚乙基-D-赤藓糖5给出了环状顺式-烯烃膦酸酯6，根据霍纳（Horner）的观点，开链反式-烯烃膦酸酯7。
• Synthesis and Stereochemical Elucidation of a 14-Membered Ring Phosphonate
  作者：Michael D. Pungente、Larry Weiler

  DOI：10.1021/ol006422v

  日期：2001.3.1

  [structure: see text]. We report the synthesis and stereochemical elucidation of a 14-membered ring phosphonate. The key step in the synthesis of the macrolide phosphonate was the cyclization of the acyclic precursor using the Mitsunobu reaction, a mild reaction for the preparation of mixed phosphonates.

  [结构：见文字]。我们报告的14元环膦酸酯的合成和立体化学阐明。合成大环内酯膦酸酯的关键步骤是使用Mitsunobu反应将无环前体环化，这是制备混合膦酸酯的温和反应。
• Synthesis of C-arabinofuranosyl compounds. Phosphonate and carboxylate isosteres of d-arabinose 1,5-bisphosphate
  作者：Bruce E. Maryanoff、Samuel O. Nortey、Ruth R. Inners、Susan A. Campbell、Allen B. Reitz、Dennis Liotta

  DOI：10.1016/s0008-6215(00)90891-7

  日期：1987.12

  key importance in the successful synthesis of a phosphonate analog of β- d -arabinose 1,5-bisphosphate ( 1 ), namely, 2,5-anhydro-1-deoxy-1-phosphono- d -glucitol 6-phosphate ( 4 ), whith high stereoselectivity. By contrast, condensation of the sodium salt of tetraethyl methylenediphosphonate and 2,3,5-tri- O -benzyl- d -arabinose ( 7 ) gave a phosphonate compound slightly enriched in the 2,5-anhydro-

  摘要用N-溴代琥珀酰亚胺对3,4,6-tri-O-苄基-1,2-二脱氧-d-阿拉伯糖-hex-1-烯醇进行亲电介导的环化反应主要产生2,5-脱水-3,4,6 -三-O-苄基-1-溴-1-脱氧-d-葡萄糖醇（10）。在成功合成β-d-阿拉伯糖1,5-双磷酸酯（1）的膦酸酯类似物（即2,5-脱水-1-脱氧1-膦酰基-d-）的成功合成中，这一显然由动力学控制的反应至关重要。具有高立体选择性的6-磷酸葡萄糖醇（4）。相反，将亚甲基二膦酸四乙酯的钠盐与2,3,5-三-O-苄基-d-阿拉伯糖（7）缩合，得到的膦酸酯化合物稍微富含2,5-脱水-d-甘露糖醇（α）。异构体。在稳定的phosphor烷与7的维蒂希-迈克尔反应中，α异构体占优势。由于甲基3,6-脱水-4,5的平衡，7-三-O-苄基-2-脱氧-d-甘油-d-半乳糖-（33）和-d-gulo-庚酸酯（34）（5：1）导致α：β比率为1：1 2,5