1,4-bis-(diazobenzyl)benzene | 18344-70-2

• 分子结构分类: 有机化合物 - 碳氢化合物衍生物 - 醌二甲烷类
• 英文名称: 1,4-bis-(diazobenzyl)benzene
• 英文别名: 1,4-bis(diazobenzyl)benzene；1,4-C6H4(C(Ph)N2)2；1,4-Bis-<α-diazo-benzyl>-benzol；1,4-Bis-(α-diazobenzyl)-benzol；1,4-Bis-(α-diazobenzyl)benzol；1,4-Bis(α-diazobenzyl)benzol；Agn-PC-00dgdp；[[4-[diazonio(phenyl)methylidene]cyclohexa-2,5-dien-1-ylidene]-phenylmethyl]iminoazanide
• CAS: 18344-70-2
• 化学式: C₂₀H₁₄N₄
• 分子量: 310.358
• InChiKey: BVPLGHIKVDESFL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  41.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,4-bis-(diazobenzyl)benzene 以 乙醚 为溶剂， 生成 dimethyl 3-[4-[2,3-bis(methoxycarbonyl)-1-phenylcycloprop-2-en-1-yl]phenyl]-3-phenylcyclopropene-1,2-dicarboxylate
  参考文献：
  名称：

  Duerr, Heinz; Schommer, Charles; Muenzmay, Thomas, Angewandte Chemie, 1986, vol. 98, # 6, p. 565 - 567

  摘要：

  DOI：
• 作为产物：
  描述：

  1,4-dibenzoylbenzene dihydrazone 在 sodium methylate 、 potassium iodide 作用下， 以 甲醇 为溶剂， 以81%的产率得到1,4-bis-(diazobenzyl)benzene
  参考文献：
  名称：

  Okimoto; Numata; Takahashi, Polish Journal of Chemistry, 2005, vol. 79, # 9, p. 1477 - 1482

  摘要：

  DOI：

文献信息

• Quintet carbenes
  作者：S.-I. Murahashi、Y. Yoshimura、Y. Yamamoto、I. Moritani

  DOI：10.1016/0040-4020(72)88031-1

  日期：1972.1

  m-phenylenebis(phenylmethylene) (1) and m-phenylenebis(methylene) (2) has been studied. Dicarbene 1 adds to 1,1-diphenylethylene (84%) and strongly abstracts an H atom, Dicarbene 1 has a triplet-like character. Photolysis of 1,3-bis(α-diazomethyl)-benzene (6) in cis-2-butene results in nearly stereospecific cyclopropanation (98% cis-cis adducts, 20–22), accompanied by 2% trans-cis adducts (24–25). Dilution of

  五重峰卡宾的化学反应性，米-phenylenebis（苯基亚甲基）（1）和米-phenylenebis（亚甲基）（2）进行了研究。碳二烯1加成1,1-二苯乙烯（84％）并强烈抽象出H原子，碳二烯1具有三重态特征。1,3-双（α-重氮甲基）-苯（6）在顺式-2-丁烯中的光解作用导致几乎立体定向的环丙烷化（98％的顺式-顺式加合物，20-22），伴随着2％的反式-顺式加合物（24-25）。用环己烷稀释顺-2-丁烯可得到反式-反式加合物（23）。的五重峰米-phenylenebis（亚甲基）可能是在nonstereospecific除了在稀释实验的关键中间体，该反式-反加合物（23）产生通过在五重峰卡宾。
• Synthesis, Molecular Structure, and Reactivity of Rhodium(I) Complexes with Diazoalkanes and Related Substrates as Ligands
  作者：Helmut Werner、Norbert Mahr、Justin Wolf、Arno Fries、Matthias Laubender、Elke Bleuel、Raquel Garde、Pascual Lahuerta

  DOI：10.1021/om0302037

  日期：2003.8.1

  A series of (diazoalkane)rhodium(I) compounds of the general composition trans-[RhCl(N2CRR‘)(PiPr3)2] with R = R‘ = Ph, p-C6H4Me, p-C6H4Cl and R = Ph, R‘ = p-C6H4Me, o-C6H4Me, CH3, CH2Ph, CF3 has been prepared from the dimer [RhCl(PiPr3)2]2 (1) and the diazoalkane. This preparative route has also been extended to complexes in which the N2C unit(s) of 1,4-C6H4C(Ph)N2}2, 9-diazofluorene, 9,10-anthraquinone-9-diazide

  一般组成的一系列（重氮烷）铑（I）化合物反式-[RhCl（N 2 CRR'）（P i Pr 3）2 ]，R = R'= Ph，p -C 6 H 4 Me，p -C 6 H 4 Cl和R = Ph，R'= p -C 6 H 4 Me，o -C 6 H 4 Me，CH 3，CH 2 Ph，CF 3由二聚体[RhCl（P i Pr 3）2 ]2（1）和重氮烷。该制备途径也已扩展到其中1,4-C 6 H 4 C（Ph）N 2 } 2的N 2 C单元，9-重氮芴，9,10-蒽醌-9-的配合物。二叠氮化物和3-甲基-1,4-萘醌-1-二叠氮与14电子[RhCl（P i Pr 3）2 ]片段连接。C（CO 2 Et）2 N 2的行为与预期相同，用1处理后即可得到复杂的反式-[RhCl N 2 C（CO 2 Et）2 }（Pi Pr 3）2），CH（CO 2 Et）N 2与相同的原料反应，生成二氮衍生物反式-[RhCl（N
• Komplexchemie reaktiver organischer verbindungen
  作者：Wolfgang A. Herrmann、Johann Plank、Gangolf W. Kriechbaum、Manfred L. Ziegler、Heike Pfisterer、Jerry L. Atwood、Robin D. Rogers

  DOI：10.1016/0022-328x(84)85079-2

  日期：1984.3

  The diazoalkane route has been used for the clean incorporation of diarylcarbene ligands into the organomanganese complexes of composition (η5-C5H4R)Mn(CO)2− thf (1, R = H; 2, R = CH3; thf = tetrahydrofuran), whose precursors are labile to substitution. The structure of the complex 4b derived from diazosuberon (3b) and exhibiting a seven-membered carbocyclic carbene ligand has been established by virtue

  重氮烷路线已被用于diarylcarbene配体的清洁掺入的组合物（η的organomanganese络合物5 -C 5 H ^ 4 R）的Mn（CO）2- THF（1，R = H; 2，R = CH 3 ; thf =四氢呋喃），其前体对取代敏感。该复合物的结构图4b从diazosuberon（派生3B），并且表现出七元碳碳烯配体，已凭借单晶X射线衍射研究的（建立单斜，空间群Ç 2H 5 - P 2 / N;一个1045.6（4），b 789.9（4），c 2153.6（4）pm；β101.56（3）°; Z = 4；R = 0.075，R w = 0.059）。使用相同的合成方法，可以从1，4-双（重氮苄基）苯（3d）开始以52％的产率获得含有ω，ω'-双卡宾桥的双核化合物4d。对于η的合成方法上简单的程序2个-ketene络合物从金属卡宾的高压羰基化出现4b中和5b中。所述benzannelated
• Acetylacetonato, pentachlorophenolato and carboxylato rhodium(I) complexes and their reactivity in the C–C coupling reaction of olefins and diazoalkanes
  作者：Helmut Werner、Norbert Mahr、Michael E. Schneider、Marco Bosch、Justin Wolf

  DOI：10.1016/j.poly.2004.06.009

  日期：2004.11

  The acetylacetonato complexes [Rh(kappa(2)-O-O)(C2H4)(PiPr(3))] (O-O=acac 5, acac-f(3) 6, acac-f(6) 7) and [Rh(kappa(2)-O-O)(PiPr(3))(2)] (O-O=acac 10, acac-f(6) 11) were prepared from either [Rh(kappa(2)-O-O)(C2H4)(2)] (2-4), [Rh(eta(3)-C3H5)(PiPr(3))(2)] (8) or [RhCl(PiPr(3))(2)](2) (9) as the starting materials. While attempts to obtain the diazoalkane derivatives [Rh(kappa(2)-O-O)(N2CR2)(PiPr(3))] (R=Ph, p-Tol) failed, treatment of 5-7 with N2CC4Cl4 gave the corresponding substitution products [Rh(kappa(2)-O-O)(N2CC4Cl4)(PiPr(3))] (12-14) in good yields. The reaction of 8 with C6Cl5OH afforded the square-planar complex [Rh(kappa(2)-OC6Cl5)(PiPr(3))(2)] (15), in which the pentachlorophenolato ligand is coordinated in a chelating fashion. From 15 and C2H4, O-2 and N2CPh2 the 1:1 adducts trans-[Rh(kappa(1)-OC6Cl5)(L)(PiPr(3))(2)] (16-18) were prepared. Compound 15 catalyzes the reaction of ethene with diaryldiazomethanes to give, instead of 1, 1 -diarylcyclopropanes, the isomeric olefins R2C=CHCH3 (R = C6H5 1b, p-C6H4Me 19, p-C(6)H(4)Cl20) as the main products. The carboxylato, complexes [Rh(kappa(2)-O2CMe)(PiPr(3))(2)] (21) and [Rh(kappa(2)-O2CCF3)(PiPr(3))(2)] (25) react with N2CRR' (R = R'= C4Cl4; R=R'=Ph; R=H, Ph, R'=C(O)Ph) by opening the chelate bond to give the four-coordinate 1:1 adducts trans-[Rh(kappa(1)-O2CMe)(N2CRR')(PiPr(3))(2)] (22-24) and trans-[Rh(kappa(1)-O2CCF3)(N2CRR')(PiPr(3))(2)](26-28), respectively. Treatment of 25 with PhCHN2 produced the dinitrogen complex trans- [Rh (kappa(1)-O2CCF3)(N-2)(PiPr(3))(2)] (29). In contrast to the trifluoracetato compound 25, which catalyzes the reaction of ethene and diaryldiazomethanes N2CRR' to give mainly the trisubstituted olefins R'RC=CHCH3, the corresponding reaction of C2H4 and N2CRR' with acetato complex 21 as the catalyst affords the isomeric ethene derivatives CH2=CHCHRR' as the major products. A mechanism for this unexpected C-C coupling reaction is discussed. (C) 2004 Elsevier Ltd. All rights reserved.
• Herrmann, Wolfgang A.; Plank, Johann; Hubbard, John L., Zeitschrift fur Naturforschung, Teil B: Anorganische Chemie, Organische Chemie, 1983, vol. 38, # 11, p. 1392 - 1398
  作者：Herrmann, Wolfgang A.、Plank, Johann、Hubbard, John L.、Kriechbaum, Gangolf W.、Kalcher, Willibald、et al.

  DOI：——

  日期：——