bis(trimethylsilyl)diazene | 13436-03-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: bis(trimethylsilyl)diazene
• 英文别名: Bis(trimethylsilyl)-diimin；Bis(trimethylsilyl)diazen；Bis-(trimethylsilyl)-diimin；Bis(trimethylsilyl)diimin；Bis-trimethylsilyl-diimin；Azotrimethylsilane
• CAS: 13436-03-8
• 化学式: C₆H₁₈N₂Si₂
• 分子量: 174.393
• InChiKey: MBINXQLYUAKLJA-UHFFFAOYSA-N

物化性质

• 沸点：
  146.2±23.0 °C(Predicted)
• 密度：
  0.82±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.11
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  bis(trimethylsilyl)diazene 在 bis(trimethylsilyl)diazene 作用下， 以 乙醚 为溶剂， 生成 Bis(trimethylsilyl)aminoisocyanid
  参考文献：
  名称：

  Wiberg,N.; Huebler,G., Zeitschrift fur Naturforschung, Teil B: Anorganische Chemie, Organische Chemie, 1976, vol. 31b, p. 1317 - 1321

  摘要：

  DOI：
• 作为产物：
  描述：

  N,N'-Bis(trimethylsilyl)-p-toluolsulfonohydrazid 生成 bis(trimethylsilyl)diazene
  参考文献：
  名称：

  Wiberg,N. et al., Chemische Berichte, 1976, vol. 109, p. 710 - 722

  摘要：

  DOI：
• 作为试剂：
  描述：

  bis(trimethylsilyl)diazene 在 bis(trimethylsilyl)diazene 作用下， 以 乙醚 为溶剂， 生成 Bis(trimethylsilyl)aminoisocyanid
  参考文献：
  名称：

  Wiberg,N.; Huebler,G., Zeitschrift fur Naturforschung, Teil B: Anorganische Chemie, Organische Chemie, 1976, vol. 31b, p. 1317 - 1321

  摘要：

  DOI：

文献信息

• Silyl-nitrogen compounds
  作者：Sham Kumar Vasisht、Mohini Sood、Nirupma Sood、Gursharan Singh

  DOI：10.1016/0022-328x(86)82052-6

  日期：1986.1

  Dilithium 1,2-bis(trimethylsilyl)hydrazine (1) reacts with CCl4, Me3SiCCl3 and CBr4 to form predominantly bis(trimethylsilyl)aminocarbonimidic dichloride, bis(trimethylsilyl)aminoisocyanide and bis(trimethylsilyl)diazene, whereas similar reactions with HCCl3, HCI3, H2CCl2 H2CI2, C2H4Cl2 or C2H2Cl4 lead to increasing amounts of bis(trimethylsilyl)hydrazine. In addition to the hydrazone, (Me3Si)2NNCH(Cl)

  1,2-双（三甲基甲硅烷基）肼二锂（1）与CCl 4，Me 3 SiCCl 3和CBr 4反应形成主要为双（三甲基甲硅烷基）氨基碳亚氨基二氯化物，双（三甲基甲硅烷基）氨基异氰酸酯和双（三甲基甲硅烷基）二氮杂。与HCCl 3，HCl 3，H 2 CCl 2 H 2 Cl 2，C 2 H 4 Cl 2或C 2 H 2 Cl 4的反应导致双（三甲基甲硅烷基）肼的量增加。除了the之外，3 Si）的2 NNCH（CL），反应1用CHCl 3形式少量triazasilacyclopentane的，（ME 3 Si）的2 NN森达3。相反，Me 2 SnCl 2与1反应生成四氮杂二氧杂环己烷[Me 2 SnNSiMe 3）2 ] 2，而SnCl 4，SnCl 2和PbCl 2主要充当氧化剂，Me 2 SiCl 2形成聚合物。1的反应的另一个乘积具有SnCl 2或PbCl 2的是LiN（SiMe
• Carbenoid entry into trifluoromethylated molecules: preparation of functionalized CF3-containing γ, δ -unsaturated carboxylic esters by rhodium-catalyzed reaction of ethyl 3,3,3-trifluoro-2-diazo-propionate with allylic sulfides and their further facile conversion to trifluoromethylated conjugated dienoic esters
  作者：Guoqiang Shi、Yuanyao Xu、Ming Xu

  DOI：10.1016/s0040-4020(01)96907-8

  日期：1991.1

  The [2,3]-sigmatropic rearrangement of sulfonium ylides derived from rhodium-catalyzed decomposition of ethyl 3,3,3-trifluoro-2-diazopropionate in the presence of allylic sulfides affords a variety of functionalized CF3-containing γ , δ-unsaturated carboxylic esters which have been further converted to synthetically useful trifluoromethylated dienoic esters via the dehydrosulfenylation sequence. For

  在烯丙基硫醚的存在下，铑在3,3,3-三氟-2-重氮丙酸乙酯催化下的铑分解反应生成of的[2,3]-σ重排，可提供多种功能化的含CF 3的γ，δ-不饱和羧酸酯，它们已经通过脱氢磺酰化顺序进一步转化为合成上有用的三氟甲基化的二烯酸酯。对于合成应用，合成了新型氟化类维生素A。
• An enantioselective approach to carbapenem antibiotics: formal synthesis of (+)-thienamycin
  作者：David J. Hart、Deok-Chan Ha

  DOI：10.1016/s0040-4039(01)80868-6

  日期：1985.1

  An enantioselective synthesis of intermediates in syntheses of thienamycin (15) and epithienamycin-C (16) is described.

  描述了在噻吩霉素（15）和上皮霉素-C（16）的合成中中间体的对映选择性合成。
• Silyl stabilized azanes: Reactions of mono- and dilithium bis(trimethylsilyl)hydrazide with dichloro- and tetrachlorostannane
  作者：J. Kataria、P. Mayer、S.K. Vasisht、P. Venugopalan

  DOI：10.1016/j.jorganchem.2009.03.004

  日期：2009.6

  SnCl4 acts primarily as an oxidant and oxidizes monolithium bis(trimethylsilyl) hydrazide 1 to mainly bis(trimethylsilyl)amine, BSA and tris(trimethylsilyl)hydrazine, TrSH and itself get reduced to SnCl2. Similarly, reaction of SnCl4 with dilithiumbis(trimethylsilyl) hydrazide 2, oxidizes it to lithium tris(trimethylsilyl)hydrazide, Li-TrSH. Reaction of dichlorostannane (reduction of oxidation state

  SnCl 4主要起氧化剂的作用，并且将单锂双（三甲基甲硅烷基）酰肼1氧化为主要的双（三甲基甲硅烷基）胺，BSA和三（三甲基甲硅烷基）肼，TrSH，并将其本身还原为SnCl 2。类似地，的SnCl反应4与dilithiumbis（三甲基甲硅烷基）酰肼2，它被氧化成锂，三（三甲基甲硅烷基）酰肼，锂TrSH。二氯锡烷与1的反应（锡的氧化态从+4还原为+2）与1的反应简单，得到浅黄色固体，即1,4-双（三甲基甲硅烷基）-1,2,4,5-四氮杂- 3,6-二萘环己烷，3b。而2与SnCl 2的反应中间stannimine [（ME 3 Si）的2 N-N的Sn]，tetramerizes和进一步失去四（三甲基硅烷基）四氮烯，TST，得到立方烷化合物〔（ME 3的Si）N-Sn系] 4，4。
• Functionalization Reactions Characteristic of a Robust Bicyclic Diphosphane Framework
  作者：Daniel Tofan、Manuel Temprado、Subhojit Majumdar、Carl D. Hoff、Christopher C. Cummins

  DOI：10.1021/ic401052a

  日期：2013.8.5

  The 3,4,8,9-tetramethy1-1,6-diphospha-bicyclo-[4.4.0]deca-3,8-diene (P-2(C6H10)(2)) framework containing a P-P bond has allowed for an unprecedented selectivity toward functionalization of a single phosphorus lone pair with reference to acyclic diphosphane molecules. Functionalization at the second phosphorus atom was found to proceed at a significantly slower rate, thus opening the pathway for obtaining mixed functional groups for a pair of P P bonded lambda(5)-phosphorus atoms. Reactivity with the chalcogen-atom donors MesCNO (Mes = 2,4,6-C6H2Me3) and SSIiPh(3) has allowed for the selective synthesis of the diphosphane chalcogenides OP2(C6H10)(2) (87%), O2P2(C6H10)(2) (94%), SP2(C6H10)(2) (56%), and S2P2(C6H10)(2) (87%). Computational studies indicate that the oxygen atom transfer reactions involve penta-coordinated phosphorus intermediates that have four membered PONC} cycles. The P E bond dissociation enthalpies in EP2(C6H10)(2) were measured via calorimetric studies to be 134.7 +/- 2.1 kcal/mol for P-O, and 93 +/- 3 kcal/mol for P-S, respectively, in good agreement with the computed values. Additional reactivity with breaking of the P P bond and formation of diphosphinate O3P2(C6H10)(2) was only observed to occur upon heating of dimethylsulfoxide solutions of the precursor. Reactivity of diphosphane P2(C6H10)2 with azides allowed the isolation of monoiminophosphoranes (RN)P-2(C6H10)(2)(R = Mes, CPh3, SiMe3), and treatment with additional MesN3 yielded symmetric and unsymmetric diiminodiphosphoranes (RN)(MesN)P-2(C6H10)(2) (91% for R = Mes). Metalation reactions with the bulky dihninodiphosphorane ligand (MesN)(2)P-2(C6H10)(2) (nppn) allowed for the isolation and characterization of (rippn)Mo(n(3)-C3H5)Cl(CO)(2) (91%), (nppn)NiCl2 (76%), and [(nppn)Ni(eta(3)-2-C3H4Me)][OTf] showing that these ligands provide an attractive preorganized binding pocket for both late and early transition metals.