5-bromo-1,3-phenylenebis(N-tert-butyl-N-hydroxyamine) | 151799-65-4

• 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: 5-bromo-1,3-phenylenebis(N-tert-butyl-N-hydroxyamine)
• 英文别名: 1-bromo-3,5-bis(N-tert-butylhydroxylamino)benzene；3,5-bis(N-tert-butylhydroxylamino)bromobenzene；N-[3-bromo-5-[tert-butyl(hydroxy)amino]phenyl]-N-tert-butylhydroxylamine
• CAS: 151799-65-4
• 化学式: C₁₄H₂₃BrN₂O₂
• 分子量: 331.253
• InChiKey: INMMYTHQSXEJES-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  46.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5-bromo-1,3-phenylenebis(N-tert-butyl-N-hydroxyamine) 在 咪唑 、 亚硝基叔丁烷 作用下， 以 乙醚 、 N,N-二甲基甲酰胺 为溶剂， 反应 10.0h， 生成 5-(N-tert-butyl-N-hydroxyamino)-1,3-phenylenebis(N-tert-butyl-N-(tert-butyldimethylsilyloxy)amine)
  参考文献：
  名称：

  Persistent 1,3,5-benzenetriyltris(N-tert-butyl nitroxide) and its analogs with quartet ground states. Intramolecular triangular exchange coupling among three nitroxide radical centers

  摘要：

  1,3,5-Benzenetriyltris(N-tert-butyl nitroxide (3), its 2-methoxy derivative (4), and 1,3,5-tris{ip-(N-oxy-N-tert-butylamino)phenyl}benzene (5) were prepared and studied by EPR and magnetic susceptibility/magnetization measurements. Trinitroxides 3 and 4 showed EPR fine structures characteristic of quartet states: 3: g = 2.0062, \D/hc\ = 0.009 32 cm-1 and \E/hc\ = 0.000 15 cm-1; 4: g = 2.0063, \D/hc\ = 0.009 66 cm-1 and \E/hc\ = 0.000 32 cm-1. The changes in the signal intensity vs reciprocal temperature obeyed Curie's law in the range 10-100 K, suggesting that the quartets are their ground states. Magnetization data for 3 and 4 at 1.8, 3.0, and 4.0 K in the field range 0-7 T obeyed the Brillouin function in which S = 3/2. The effective magnetic moment of a crystalline sample of 4 obtained on a SQUID susceptometer was 3.21 mu(B) at 240 K, increased gradually, reached a maximum (mu(eff)/mu(B) = 3.73) at 32 K, and decreased steeply as the temperature was decreased. The results were interpreted in terms of an isosceles-triangular exchange interaction among the three nitroxide radicals within a molecule (J1/k(B) = 68.4 and J2/k(B) = 5.0 K) and antiferromagnetic intermolecular interaction (theta = -1.7 K). A methoxy group on the m-phenylene ring was found to weaken the through-ring exchange coupling among the attached nitroxide radicals by an order of magnitude. An X-ray structure analysis of a clear red block cubic single crystal of 5, Pa3BAR (No. 205), a = 18.786(2) angstrom, V = 6631(2) angstrom3, Z = 8, D(calc) = 1.301 g cm-3, revealed the molecular structure with three nitroxide groups 37.5-degrees out of the peripheral p-phenylene rings which am tilted out of the central benzenetriyl unit by 19.5-degrees in a propeller conformation. Temperature dependences of the mu(eff) values observed for crystalline and matrix-isolated 5 in the range 5-300 K gave J/k(B) values of +6.8 K (theta = -2.1 K) and +5.3 K, respectively, when analyzed in terms of a regular-triangular exchange coupling model. Lower spin polarization on the 1,3,5-triphenylbenzene chromophore is concluded to be responsible for the reduced J value in 5.

  DOI：

  10.1021/j100152a034
• 作为产物：
  描述：

  1,3,5-三溴苯 、 叔丁基锂 在 亚硝基叔丁烷 作用下， 以 乙醚 为溶剂， 以71.4%的产率得到5-bromo-1,3-phenylenebis(N-tert-butyl-N-hydroxyamine)
  参考文献：
  名称：

  Persistent 1,3,5-benzenetriyltris(N-tert-butyl nitroxide) and its analogs with quartet ground states. Intramolecular triangular exchange coupling among three nitroxide radical centers

  摘要：

  1,3,5-Benzenetriyltris(N-tert-butyl nitroxide (3), its 2-methoxy derivative (4), and 1,3,5-tris{ip-(N-oxy-N-tert-butylamino)phenyl}benzene (5) were prepared and studied by EPR and magnetic susceptibility/magnetization measurements. Trinitroxides 3 and 4 showed EPR fine structures characteristic of quartet states: 3: g = 2.0062, \D/hc\ = 0.009 32 cm-1 and \E/hc\ = 0.000 15 cm-1; 4: g = 2.0063, \D/hc\ = 0.009 66 cm-1 and \E/hc\ = 0.000 32 cm-1. The changes in the signal intensity vs reciprocal temperature obeyed Curie's law in the range 10-100 K, suggesting that the quartets are their ground states. Magnetization data for 3 and 4 at 1.8, 3.0, and 4.0 K in the field range 0-7 T obeyed the Brillouin function in which S = 3/2. The effective magnetic moment of a crystalline sample of 4 obtained on a SQUID susceptometer was 3.21 mu(B) at 240 K, increased gradually, reached a maximum (mu(eff)/mu(B) = 3.73) at 32 K, and decreased steeply as the temperature was decreased. The results were interpreted in terms of an isosceles-triangular exchange interaction among the three nitroxide radicals within a molecule (J1/k(B) = 68.4 and J2/k(B) = 5.0 K) and antiferromagnetic intermolecular interaction (theta = -1.7 K). A methoxy group on the m-phenylene ring was found to weaken the through-ring exchange coupling among the attached nitroxide radicals by an order of magnitude. An X-ray structure analysis of a clear red block cubic single crystal of 5, Pa3BAR (No. 205), a = 18.786(2) angstrom, V = 6631(2) angstrom3, Z = 8, D(calc) = 1.301 g cm-3, revealed the molecular structure with three nitroxide groups 37.5-degrees out of the peripheral p-phenylene rings which am tilted out of the central benzenetriyl unit by 19.5-degrees in a propeller conformation. Temperature dependences of the mu(eff) values observed for crystalline and matrix-isolated 5 in the range 5-300 K gave J/k(B) values of +6.8 K (theta = -2.1 K) and +5.3 K, respectively, when analyzed in terms of a regular-triangular exchange coupling model. Lower spin polarization on the 1,3,5-triphenylbenzene chromophore is concluded to be responsible for the reduced J value in 5.

  DOI：

  10.1021/j100152a034

文献信息

• Intermediate-paramagnetic phases with a half and a quarter spin entities in fluorinated biphenyl-3,5-diyl bis(tert-butyl nitroxides)
  作者：Takuya Konno、Hiroki Kudo、Takayuki Ishida

  DOI：10.1039/c5tc00668f

  日期：——

  biradical, 2′,5′-difluorobiphenyl-3,5-diyl bis(tert-butyl nitroxide), showed spin-transition-like behaviour at TC↑ = 182 K and TC↓ = 181 K. This compound had a quarter of the nominal amount of paramagnetic spins in the low-temperature phase and a half in the high-temperature phase. Another new 3′-monofluoro derivative maintained a half amount of the spins as a single solid phase, which is isomorphous

  一种新的三重态双自由基，2'，5'-二氟联苯-3,5-二基双（叔丁基氮氧化物），在T C↑ = 182 K和T C↓时表现出自旋跃迁状的行为＝ 181K。该化合物在低温相中具有标称量的顺磁性自旋量的四分之一，而在高温相中具有一半的标称量。另一种新的3'-单氟衍生物将一半的自旋保持为单个固相，与二氟类似物的高温相同构。在自旋转变过程中，氮和氧原子之间的可逆键形成以分子间方式发生在相邻的氮氧化物基团上。这些中间状态在多步自旋跃迁过程中从设计的非对称双基出现。
• Ferromagnetic 2p-2p and 4f-2p Couplings in a Macrocycle from Two Biradicals and Two Gadolinium(III) Ions
  作者：Saki Ito、Toru Yoshitake、Takayuki Ishida

  DOI：10.3390/molecules27154930

  日期：——

  characterized by means of room-temperature ESR spectroscopy displaying a zero-field splitting pattern together with a half-field signal. Complex formation with gadolinium(III) 1,1,1,5,5,5-hexafluoropentane-2,4-dionate (hfac) afforded a macrocycle [Gd(hfac)3(m-iPr3BPBN)}2]. As the X-ray crystallographic analysis clarified, the biradical serves as a bridging ligand, giving a 16-membered ring, where each nitroxide

  制备了一种新的地面三重态双自由基 2',4',6'-三异丙基联苯-3,5-二基双（叔丁基硝基氧）( iPr 3 BPBN )，并通过显示零场的室温 ESR 光谱表征分裂模式连同半场信号。与钆 (III) 1,1,1,5,5,5-六氟戊烷-2,4-二酮酸盐 (hfac) 形成络合物，得到大环 [Gd(hfac) 3 (m- iPr 3 BPBN )} 2 ]。正如 X 射线晶体学分析所阐明的那样，双自由基充当桥接配体，形成一个 16 元环，其中每个氮氧自由基氧原子直接与 Gd 3+离子键合。磁性研究表明iPr 3 BPBN桥实际上表现为三线态双自由基，并且 Gd 3+ -自由基磁耦合是弱铁磁的。在H = −2 J S 1 • S 2约定中，交换参数估计为 2 j rad-rad / k B > 300 K 和 2 J Gd-rad / k B = 1.2 K。基于原子坐标的DFT计算阐明了无金属iPr