4,4'-dimethoxytrityl cation | 14039-15-7

• 物质功能分类: 有机原料 - 烃类化合物及其衍生物 - 芳香烃
• 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: 4,4'-dimethoxytrityl cation
• 英文别名: [4-[(4-Methoxyphenyl)-phenylmethylidene]cyclohexa-2,5-dien-1-ylidene]-methyloxidanium
• CAS: 14039-15-7
• 化学式: C₂₁H₁₉O₂
• 分子量: 303.381
• InChiKey: JLRBVXBVFZQEHA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  10.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4,4'-dimethoxytrityl cation 在 ammonium hydroxide 作用下， 生成 胸苷酸
  参考文献：
  名称：

  A chemical 5′-phosphorylation of oligodeoxyribonucleotides that can be monitored by trityl cation release

  摘要：

  DOI：

  10.1016/s0040-4039(00)85043-1
• 作为产物：
  描述：

  Thiophosphoric acid O-[(2R,3S,5R)-2-[bis-(4-methoxy-phenyl)-phenyl-methoxymethyl]-5-(5-methyl-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-tetrahydro-furan-3-yl] ester O'-(2,4-dichloro-phenyl) ester S-methyl ester 在 甘油 作用下， 生成 4,4'-dimethoxytrityl cation
  参考文献：
  名称：

  Liguori, Angelo; Sindona, Giovanni; Uccella, Nicola, Journal of the Chemical Society. Perkin transactions II, 1988, p. 1661 - 1666

  摘要：

  DOI：

文献信息

• Reactivities of triarylmethyl and diarylmethyl cations with azide ion investigated by laser flash photolysis. Diffusion-controlled reactions
  作者：Robert A. McClelland、V. M. Kanagasabapathy、Narinder S. Banait、Steen Steenken

  DOI：10.1021/ja00003a040

  日期：1991.1

  By use of the technique of laser flash photolysis, rate constants k AZ and k S have been directly measured for the reactions at 20 o C in acetonitrile-water (AN-W) solutions of varying composition of 18 triarylmethyl and 10 diarylmethyl cations with azide and solvent. The cations have k S that depend on substituent and vary from ∼10 1 to ∼10 7 s −1 . For the more stable ions k AZ also varies, increasing

  通过使用激光闪光光解技术，已经直接测量了在 20 o C 下在 18 个三芳基甲基和 10 个二芳基甲基阳离子与叠氮化物的不同组成的乙腈-水 (AN-W) 溶液中反应的速率常数 k AZ 和 k S和溶剂。阳离子具有取决于取代基的k S 并且从～10 1 到～10 7 s -1 变化。对于更稳定的离子，k AZ 也发生变化，随着给电子量的减少而增加，并且随着乙腈含量的增加而增加多达10 3 。然而，对于不太稳定的阳离子，速率常数与取代基无关
• Oxidation Mechanism of NAD Dimer Model Compounds
  作者：Matthias Patz、Yoshihiro Kuwahara、Tomoyoshi Suenobu、Shunichi Fukuzumi

  DOI：10.1246/cl.1997.567

  日期：1997.6

  The oxidation of a dimeric N-benzyldihydronicotinamide with various oxidants such as quinones, triphenyl carbenium ions and a triplet exited tris(bipyridine) ruthenium(II) complex occurs via initial outer-sphere electron transfer followed by fast C–C bond cleavage and second electron transfer. The kinetic studies allow the determination of the oxidation potential of this compound.

  二聚 N-苄基二氢烟酰胺与各种氧化剂（如醌、三苯基碳鎓离子和三重态三（联吡啶）钌 (II) 络合物的氧化）通过初始外球电子转移随后快速 C-C 键断裂和第二电子发生转移。动力学研究可以确定该化合物的氧化电位。
• Reactivities of diarylmethyl and triarylmethyl cations with primary amines in aqueous acetonitrile solutions. The importance of amine hydration
  作者：Robert A. McClelland、V. M. Kanagasabapathy、Narinder S. Banait、Steen Steenken

  DOI：10.1021/ja00031a041

  日期：1992.2

  By use of the technique of laser flash photolysis, rate constants k(RNH 2 ) have been directly measured for the reactions of primary amines RCH 2 NH 2 (R=CH 3 CH 2 , CH 3 OCH 2 , NCCH 2 , CF 3 ) with diarylmethyl cations (D + ) in acetonitrile/water solutions

  利用激光闪光光解技术，直接测量了伯胺RCH 2 NH 2 (R=CH 3 CH 2 , CH 3 OCH 2 , NCCH 2 , CF 3 )反应的速率常数k(RNH 2 )乙腈/水溶液中的二芳基甲基阳离子 (D + )
• ¹H and¹³C NMR Detection of the Carbocations or Zwitterions from Rhodamine B Base, a Fluoran-Based Black Color Former, Trityl Benzoate, and Methoxy-Substituted Trityl Chlorides in the Presence of Alkali Metal or Alkaline Earth Metal Perchlorates in Acetonitrile Solution
  作者：Masashi Hojo、Tadaharu Ueda、Masanori Yamasaki、Akihiko Inoue、Sumio Tokita、Mitsuhiro Yanagita

  DOI：10.1246/bcsj.75.1569

  日期：2002.7

  The cleavage of C–O bonds in two fluoran-based dyes by the addition of alkali metal (M+ = Li+, Na+) and alkaline earth metal (M2+ = Mg2+, Ba2+) perchlorates in acetonitrile solution was examined by means of UV-visible absorption and 1H and 13C NMR spectroscopy at room temperature. Although the 1H NMR signals of the xanthene part of Rhodamine B base (3′,6′-bis(diethylamino)fluoran) were shifted toward lower fields, those of the isobenzofuran (or the benzoate) part were not shifted much upon the addition of M+ and M2+. The appearance of 13C signals at 163.6 and 162.4 ppm (vs TMS) in the presence of Li+ and Ba2+, respectively, confirmed the formation of the zwitterions from Rhodamine B base. The assignments of the 1H and 13C signals were performed by the HMBC method. The colored zwitterion of a practical black color former, 2′-anilino-6′-dibutylamino-3′-methylspiro[3H-isobenzofuran-1, 9′-(9H)xanthene]-3-one, was produced by the addition of M+ and M2+. The 13C NMR signals at 162.2 and 159.8 ppm in the presence of 2.0 mol dm-3 Mg(ClO4)2 and Ba(ClO4)2, respectively, gave conclusive evidence of the formation of the sp2-hybrid carbon center for the black color former. The interaction between the metal ions and the zwitterions from the fluoran-based dyes decreased as Mg2+ > Ba2+ > Li+ > Na+. The 1 : 1 complex formation constants with the metal ions for both dyes were evaluated based on the UV-visible absorption data. The smaller formation constants of the black color former, compared with those of Rhodamine B base, indicate some more difficulty in the cleavage of the γ-lactone ring, which is probably based on the asymmetric structure of the compound, i.e, only a single dibutylamono-group at the 3′- and 6′-positions. The evidence for the formation of both the trityl cation and the benzoate ion was obtained by the 1H NMR signals from trityl benzoate in the presence of Mg(ClO4)2 in CD3CN containing a small amount of CF3SO3D. The C–Cl bond cleavage of 4-methoxy, 4,4′-dimethoxy, and 4,4′,4′′-trimethoxytrityl chlorides, through the chemical interaction between Ba2+ and Cl- in acetonitrile soluition, was justified by our 13C NMR results.

  室温下，通过紫外-可见吸收以及 1H 和 13C NMR 光谱，研究了在乙腈溶液中加入碱金属（M+ = Li+、Na+）和碱土金属（M2+ = Mg2+、Ba2+）高氯酸盐对两种芴基染料中 C-O 键的裂解作用。虽然罗丹明 B 碱（3′,6′-双（二乙基氨基）荧烷）中的呫吨部分的 1H NMR 信号向低场移动，但在加入 M+ 和 M2+ 后，异苯并呋喃（或苯甲酸盐）部分的 1H NMR 信号移动不大。在 Li+ 和 Ba2+ 的存在下，分别在 163.6 和 162.4 ppm（相对于 TMS）出现的 13C 信号证实了罗丹明 B 碱形成了三元共轭物。1H 和 13C 信号的分配是通过 HMBC 方法进行的。通过添加 M+ 和 M2+，产生了实用黑色前体--2′-苯胺基-6′-二丁基氨基-3′-甲基螺[3H-异苯并呋喃-1，9′-(9H)氧杂蒽]-3-酮的有色齐聚物。在 2.0 mol dm-3 Mg(ClO4)2 和 Ba(ClO4)2 的存在下，13C NMR 信号分别为 162.2 和 159.8 ppm，这为黑色前体形成 sp2-杂化碳中心提供了确凿证据。金属离子与芴基染料中的齐聚物之间的相互作用按 Mg2+ > Ba2+ > Li+ > Na+ 的顺序递减。根据紫外可见吸收数据评估了两种染料与金属离子的 1 : 1 复合物形成常数。与罗丹明 B 碱的形成常数相比，黑色前者的形成常数较小，这表明γ-内酯环的裂解更为困难，这可能是基于化合物的不对称结构，即在 3′-和 6′-位置上只有一个二丁基氨基。在含有少量 CF3SO3D 的 CD3CN 中，苯甲酸三甲苯酯在 Mg(ClO4)2 的存在下产生的 1H NMR 信号证明了三甲苯酯阳离子和苯甲酸根离子的形成。13C NMR 结果证明，4-甲氧基、4,4′-二甲氧基和 4,4′,4′′-三甲氧基三苯甲基氯化物的 C-Cl 键是通过 Ba2+ 和 Cl- 在乙腈溶液中的化学作用裂解的。
• High yield detritylation of surface-attached nucleosides with photoacid generated in an overlying solid film: roles of translational diffusion and scavenging
  作者：Peter B. Garland、Pawel J. Serafinowski

  DOI：10.1039/b813319k

  日期：——

  Conventional solid-phase oligonucleotide synthesis overcomes the reversibility of acid-dependent detritylation by washing away the released dimethoxytrityl cations (DMT+) with acid. This option is unavailable if the acid is photogenerated in an overlying solid film, as in the photolithographic fabrication of oligonucleotide arrays on planar surfaces. To overcome the resulting reversibility problem we developed methods of achieving ≥98% detritylation of glass-attached 5′-O-DMT-thymidine, a model for 5′-O-DMT-protected oligonucleotides, by the photogeneration of trichloroacetic acid in a solid film. Enhanced intrafilm diffusion, insufficient to degrade the photolithographic resolution but enabling DMT+ to move from its plane of release into the overlying photoacid-generating film, increased detritylation from ≤30% to ≥98%. Inclusion of an intrafilm carbocation scavenger such as a triarylsilane hydride converted the detritylation into a time-dependent irreversible process proceeding to ≥99% detritylation within 60 s following brief photoacid generation. Light sensitivity is high, exceeding direct photodeprotection methods by 15–100 fold.

  传统的固相寡核苷酸合成方法是用酸洗掉释放出的二甲氧基三苯甲基阳离子（DMT+），从而克服了酸依赖性脱苯作用的可逆性。如果酸是在上覆固体薄膜中光照生成的，就无法使用这种方法，例如在平面上光刻制造寡核苷酸阵列。为了克服由此产生的可逆性问题，我们开发了一种方法，通过在固体薄膜中光生成三氯乙酸，实现玻璃附着的 5′-O-DMT 胸苷（5′-O-DMT 保护寡核苷酸的模型）≥98% 的脱苯甲基化。膜内扩散的增强不足以降低光刻分辨率，但却能使 DMT+ 从其释放平面移动到上覆的光酸生成膜中，从而将脱盐率从≤30%提高到≥98%。加入膜内碳位清除剂（如三芳基硅烷氢化物）后，在短暂的光酸生成后 60 秒内，脱苯甲酰化转化为与时间相关的不可逆过程，脱苯甲酰化率≥99%。光敏感性很高，比直接光防护方法高出 15-100 倍。