bis(chlorotriazine) | 201288-39-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: bis(chlorotriazine)
• 英文别名: 2-N-[17-[(4-amino-6-chloro-1,3,5-triazin-2-yl)amino]-25,26,27,28-tetrapropoxy-5-pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9(27),10,12,15(26),16,18,21,23-dodecaenyl]-6-chloro-1,3,5-triazine-2,4-diamine
• CAS: 201288-39-3
• 化学式: C₄₆H₅₂Cl₂N₁₀O₄
• 分子量: 879.889
• InChiKey: NPSLIFJJSNRFQF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.2
• 重原子数：
  62
• 可旋转键数：
  16
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  190
• 氢给体数：
  4
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  bis(chlorotriazine) 在 1-(3-二甲基氨基丙基)-3-乙基碳二亚胺 、 N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate 作用下， 以 二氯甲烷 为溶剂， 生成 tert-butyl N-[2-[[3-[[4-amino-6-[[17-[[4-amino-6-[[2,2-dimethyl-3-[[2-[(2-methylpropan-2-yl)oxycarbonylamino]acetyl]amino]propyl]amino]-1,3,5-triazin-2-yl]amino]-25,26,27,28-tetrapropoxy-5-pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9(27),10,12,15(26),16,18,21,23-dodecaenyl]amino]-1,3,5-triazin-2-yl]amino]-2,2-dimethylpropyl]amino]-2-oxoethyl]carbamate
  参考文献：
  名称：

  Self-Assembly of Polar Functionalities Using Noncovalent Platforms

  摘要：

  [GRAPHICS]Small peptide fragments functionalized with dimelamine units spontaneously form well-defined assemblies. The hydrogen-bond donating and accepting sites in the peptide units are perfectly compatible with the hydrogen-bond assembly motif and slightly stabilize the assembly via additional hydrogen bond formation.

  DOI：

  10.1021/ol000244o
• 作为产物：
  描述：

  5,17-diamino-25,26,27,28-tetrakis(propyloxy)calix[4]arene 在 氨 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 生成 bis(chlorotriazine)
  参考文献：
  名称：

  Noncovalent Assembly of Functional Groups on Calix[4]Arene Molecular Boxes

  摘要：

  AbstractCalix[4]arenes diametrically substituted at the upper rim with two melamine units spontaneously form well‐defined box‐like assemblies in the presence of two equivalents of 5,5‐diethylbarbituric acid. These assemblies, consisting of nine different components, are held together by 36 hydrogen bonds and are stable in apolar solvents at concentrations of up to 10−4M. This paper reports the first X‐ray crystal structure, and the MALDI TOF mass spectra together with the complete 1H NMR spectroscopic characterization of these hydrogen‐bonded assemblies. The crystal structure clearly shows that the assemblies are stereogenic, as a result of the antiparallel orientation of the two rosette motifs. Furthermore, the synthesis of twelve new 1,3‐bis(melamine)calix[4]arenes carrying different numbers and types of functionalities at the upper rim is described. Detailed 1H NMR spectroscopic studies on the assembly behavior of these functionalized calix[4]arenes shows that 1) polar substituents (e.g. nitro, cyano) hardly affect the stability of the hydrogen‐bonded assembly; 2) hydrogen bond donating or accepting groups, like amino and acetamido, can disturb assembly of the boxes under certain conditions by destabilizing the calix[4]arene pinched cone conformation as a result of intramolecular hydrogen bond formation; and 3) sterically bulky groups (e.g. tBu) can significantly inhibit the formation of the hydrogen‐bonded assembly, but this effect very much depends on the exact positions of the groups.

  DOI：

  10.1002/chem.19970031115

文献信息

• Covalent Linkage of Melamine and Cyanurate Improves the Thermodynamic Stability of Hydrogen-Bonded Double Rosettes in Polar Solvents
  作者：Olivier Félix、Mercedes Crego-Calama、Ingrid Luyten、Peter Timmerman、David N. Reinhoudt

  DOI：10.1002/ejoc.200390205

  日期：2003.4

  form well-defined double rosette assemblies. DMSO titration experiments illustrate that the covalent linkage between the cyanurate and dimelamine moieties produces a significant increase in the thermodynamic stabilities of these conjugates. The relative stability of the assemblies seems to be primarily governed by the structure of the component connecting the melamine and cyanurate units. The highest

  本文描述了对八种不同杯[4]芳烃二(三聚氰胺-氰尿酸盐)或二(三聚氰胺-巴比妥酸盐)偶联物的合成、自组装行为和热力学稳定性的研究。成功的合成策略包括通过酰胺键形成反应制备氨基-n-烷基官能化杯[4]芳烃二三聚氰胺与羧基官能化氰脲酸酯或巴比妥酸酯。1H NMR 实验表明，八个缀合物中的三个形成明确定义的双花环组件。DMSO 滴定实验表明，氰尿酸盐和二三聚氰胺部分之间的共价键显着提高了这些缀合物的热力学稳定性。组件的相对稳定性似乎主要由连接三聚氰胺和氰尿酸酯单元的组件结构决定。对于二（三聚氰胺-氰尿酸酯）组装件观察到最高稳定性（χDMSO = 70%），其中组件通过正庚基酰胺甲基接头连接。将接头尺寸从正庚酰胺甲基增加到正癸酰胺甲基会略微降低相应双花环组件的热力学稳定性（ΔχDMSO ≈ 10%）。然而，在甲基羰基的α位引入取代基后，双花环结构的热力学稳定性急剧下降。使用苄基取代基（基于 D-苯
• Thermodynamic Stability of Hydrogen-Bonded Nanostructures: A Calorimetric Study
  作者：Mattijs G. J. ten Cate、Jurriaan Huskens、Mercedes Crego-Calama、David N. Reinhoudt

  DOI：10.1002/chem.200400085

  日期：2004.8.6

  whereas for double rosettes 2 a(3).(BuCYA)(6) and 2 b(3).(BuCYA) (2=calix[4]arene-dimelamine) it is 0.7 and 7.1 microM, respectively. DeltaG degrees, DeltaH degrees, and TDeltaS degrees values indicate that the thermodynamics of double rosettes reflect the independent assembly of two individual single rosette structures or two rosettes reinforced by additional stabilizing interactions. In more polar solvents

  通过量热法研究了不同极性的溶剂混合物中氢键结合的聚集体（玫瑰红）的自组装。C（50）参数（当组件中包含50％的组件时的浓度）用于比较具有不同化学计量的组件。单玫瑰花结1（3）的C（50）。（1,2-二氯乙烷中的（BuCYA）（3）（1 = N，N-二（4-叔丁基苯基）三聚氰胺; BuCYA =正丁基氰尿酸）为25 microM，而对于双玫瑰花结2 a（3）。（BuCYA）（6）和2 b（3）。（BuCYA）（2 = calix [4] arene-dimelamine），分别为0.7和7.1 microM。DeltaG度，DeltaH度和TDeltaS度值表明双玫瑰花结的热力学反映了两个单独的单个玫瑰花结结构或通过附加稳定相互作用增强的两个玫瑰花结的独立组装。在极性更大的溶剂中，双玫瑰花结的稳定性降低。根据DeltaG度与溶剂极性的相关性，可以预测在甲醇或水中组装双玫瑰花结应该是可能的。通过（1）H
• Diastereoselective Noncovalent Synthesis of Hydrogen-Bonded Double-Rosette Assemblies
  作者：Leonard J. Prins、Ron Hulst、Peter Timmerman、David N. Reinhoudt

  DOI：10.1002/1521-3765(20020517)8:10<2288::aid-chem2288>3.0.co;2-3

  日期：2002.5.17

  or M) in the corresponding hydrogen-bonded assemblies 1(3).(CA)(6) (de>98 %). The high degree of chiral induction results from the presence of six chiral centers in close proximity (C(alpha)) to the core of the assembly. A much lower level of chiral induction is observed for assemblies with chiral centers that are more remote (C(beta)). All diastereomerically pure assemblies 1(3).(CA)(6) exhibit very

  杯[4]芳烃1的二蜜胺组分中或氰尿酸酯组分CA中存在的手性中心在相应的氢键键合组件1（3）。（CA）（6）（de）中定量诱导一种惯性（P或M）。 > 98％）。高度的手性诱导是由于六个手性中心（Cα）与装配体的核心非常接近。对于具有更远的手性中心（Cβ）的装配体，观察到了更低的手性诱导水平。所有非对映体纯组装1（3）。（CA）（6）都显示出非常高的CD活性（deltavarepsilon（max）约100 L mol（-1）cm（-1）），与低CD活性（deltavarepsilon （最大）
• Self-assembly and stability of double rosette nanostructures with biological functionalities
  作者：Mattijs G. J. ten Cate、Merdan Omerović、Gennady V. Oshovsky、Mercedes Crego-Calama、David N. Reinhoudt

  DOI：10.1039/b508449k

  日期：——

  The syntheses of calix[4]arene dimelamines that are functionalized with alkyl, aminoalkyl, ureido, pyridyl, carbohydrate, amino acid and peptide functionalities, and their self-assembly with barbituric acid or cyanuric acid derivatives into well-defined hydrogen-bonded nanostructures are described. The thermodynamic stability of these hydrogen-bonded assemblies was studied by CD spectroscopy in mixtures of CHCl3 and MeOH. The stability of the assemblies depends on several steric factors and the polarity of the functional groups connected to the assembly components.

  用烷基、氨基烷基、脲基、吡啶基、碳水化合物、氨基酸和肽官能团官能化的杯[4]芳烃二三聚氰胺的合成，以及它们与巴比妥酸或氰尿酸衍生物的自组装成明确的氢键纳米结构描述的。通过 CD 光谱在 CHCl3 和 MeOH 混合物中研究了这些氢键组装体的热力学稳定性。组件的稳定性取决于几个空间因素以及连接到组件组件的官能团的极性。
• Enantioselective Formation of a Dynamic Hydrogen-Bonded Assembly Based on the Chiral Memory Concept
  作者：Tsutomu Ishi-i、Mercedes Crego-Calama、Peter Timmerman、David N. Reinhoudt、Seiji Shinkai

  DOI：10.1021/ja0207302

  日期：2002.12.1

  In this paper, we report the enantioselective formation of a dynamic noncovalent double rosette assembly 1a(3).(CYA)(6) composed of three 2-pyridylcalix[4]arene dimelamines (1a) and six butylcyanuric acid molecules (BuCYA). The six 2-pyridyl functionalities of the assembly interact stereoselectively with chiral dicarboxylic acids 3a-e via two-point hydrogen-bonding interactions. One of the two enantiomeric assemblies (P- or M-) 1a(3).(CYA)(6) is formed in excess as the result of the complexation of the chiral diacids, resulting in formation of optically active assemblies. The complexations with dibenzoly tartaric acids D-3a and L-3a (3 equivalent), respectively, leading to the formation of diastereomeric assemblies (P)-1a(3).(BuCYA)(6).(D-3a)(3) and (M)-1a(3).(BuCYA)(6).(L-3a)(3) with 90% diastereomeric excess. The diastereomeric excess in (M)-1a(3).(BuCYA)(6).(L-3a)(3) is "memorized" when L-3a is removed by precipitation with ethlylenediamine (EDA). The assembly (M)-1a(3).(BuCYA)(6) is still optically active (90% enantiomeric excess), although none of its individual components are chiral. (M)-1a(3).(BuCYA)(6) has a high kinetic stability toward racemization (E-a = 119 kJ mol(-1), half-life of (M)-1a(3).(BuCYA)(6) is ca. 1 week at 20degreesC).