aluminum hydride diethyl etherate | 16905-68-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: aluminum hydride diethyl etherate
• 英文别名: alane-ether complex
• CAS: 16905-68-3；855944-56-8
• 化学式: C₄H₁₃AlO
• 分子量: 104.128
• InChiKey: CTEFTLJKOHSCMA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.14
• 重原子数：
  6.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  aluminum hydride diethyl etherate 在 盐酸 作用下， 以 甲苯 、 水 为溶剂， 反应 1.0h， 生成 aluminium hydride
  参考文献：
  名称：

  METHOD FOR THE PRODUCTION OF ALPHA-ALANE

  摘要：

  一种制备α-氢化铝的方法。该方法包括将三氯化铝和碱金属氢化物反应以形成氢化铝-醚络合物溶液。可以向氢化铝-醚络合物溶液中加入水醚溶液，以形成部分水解的醚/氢化铝-醚络合物溶液。将结晶添加剂溶液加入氢化铝-醚络合物溶液或水醚/氢化铝-醚络合物溶液中，以形成结晶溶液。所述结晶添加剂选择自以下组合物：角鲨烯、环十二烯、诺博美烯、诺博二烯、苯基端基聚丁二烯、2,4-二甲基苯醚、3,5-二甲基苯醚、2,6-二甲基苯醚、聚二甲基硅氧烷及其混合物。从结晶溶液中去除醚以结晶α-氢化铝。

  公开号：

  US20050222445A1
• 作为产物：
  描述：

  在 LiAlH₄ 作用下， 以 乙醚 、 正戊烷 为溶剂， 生成 aluminum hydride diethyl etherate 、 、
  参考文献：
  名称：

  Homo- and heteronuclear hydrido lutetiecene complexes with bulky 1,3-di(tert-butyl)cyclopentadienyl (C5H3tBu2) ligands. The molecular structure of [(tBu2C5H3)LuH]4[AlH4·Et2O]2[AlH4]2

  摘要：

  Reactions occurring in the system (Cp"2LuCl)2-MAlH4-L-solvent have been studied. It has been shown that the aluminohydride complexes (Cp"2LnAlH4.L)2 formed are unstable and decompose, depending on reaction conditions, along three pathways: (a) desolvation, (b) dissociation of solvated aluminium hydride and (c) destruction of the cene moiety to produce the polynuclear monocyclopentadienyl hydridoaluminohydridic complex [(tBu2C5H3)LuH]4[AlH4.Et2O]2[AlH4]2 (XII). Similar reaction of the departure of one of the cyclopentadienyl ligands is observed in (Cp"2LuCl)2 when it dissolved in aromatic solvents. Crystals of XII are triclinic: a = 11.616(2), b = 14.822(2), c = 24.236(5) angstrom, alpha = 87.51(1), beta = 100.59(1), gamma = 75.83(1)-degrees, space group P1BAR, Z = 2. XII is characterized by the previously unknown tetrahedral metal core made of Lu atoms bound by bridging hydrogens and tri- (AlH4) and tetra-dentate (AlH4.Et2O) groups.

  DOI：

  10.1016/0022-328x(91)80244-e
• 作为试剂：
  描述：

  3-bromo-2-chloro-5-pyridinecarbonyl chloride 在 sodium hydroxide 、 dibutyltin diacetate 、 aluminum hydride diethyl etherate 、 乙酸酐 、 碳酸氢钠 作用下， 以 四氢呋喃 、 丙酮 为溶剂， 反应 52.0h， 生成 2,3-dihydro-5-(2-chloro-3-bromopyridin-5-yl)-6,7-bis(hydroxymethyl)-1H-pyrrolizine bis(N-2-propylcarbamate)
  参考文献：
  名称：

  Vinylogous carbinolamine tumor inhibitors. 24. Synthesis, chemistry, and antineoplastic activity of .alpha.-halopyridinium salts: potential pyridone prodrugs of acylated vinylogous carbinolamine tumor inhibitors.

  摘要：

  A series of 4- and 5-[2,3-dihydro-6,7-bis[[(N-alkylcarbamoyl)oxy]methyl]-1H-pyrrol izin-5- yl]-2-halopyridinium iodides were synthesized. The rates of hydrolysis of the alpha-halopyridinium salts to the corresponding pyridones, and the reactivities of the carbamate moieties were studied as a function of pH, buffer composition, and ionic strength. The 4- and 5-pyrrolizinyl-2-halopyridinium iodides and the corresponding pyridones were evaluated against P388 lymphocytic leukemia in vivo. The alpha-fluoropyridinium compounds were active but the alpha-chloro compounds were not. This activity was correlated with the rates of hydrolysis of the alpha-halopyridinium compounds to the active pyridone. Compounds that were active in the P388 screen were evaluated in L1210 leukemia, M5076 carcinoma, and MX-1 mammary xenograft assays in mice.

  DOI：

  10.1021/jm00168a021

文献信息

• Dithiocarbamate complexes of trivalent aluminium and gallium via metal hydrides
  作者：Philip C. Andrews、Stacey M. Lawrence、Colin L. Raston、Brian W. Skelton、Vicki-Anne Tolhurst、Allan H. White

  DOI：10.1016/s0020-1693(99)00480-6

  日期：2000.4

  Reaction of the thiurams [R2NC(S)S]2 (R=Me, Et, Bz) with the trimethylamine complexes of alane (AlH3) and gallane (GaH3) results in the high yield production of the tris-dithiocarbamate complexes [M(S2CNR2)3] (M=Al, Ga) formed via the reductive cleavage of the SS bond. Transmetallation reactions of [(Et2O)k·AlH3]n with [M′(S2CNEt2)n] (M′=As, Sb, n=3, M′=Se, n=2) also result in the synthesis of [Al(S2CNEt2)3]

  秋兰姆[R 2 NC（S）S] 2（R = Me，Et，Bz）与烷烃（AlH 3）和没食子烷（GaH 3）的三甲胺络合物反应，可高产率地产生tris-二硫代氨基甲酸酯配合物[M（S 2 CNR 2）3 ]（M ＝ Al，Ga）通过SS键的还原性裂解形成。[[Et 2 O）k ·AlH 3 ] n与[M'（S 2 CNEt 2）n ]（M'= As，Sb，n = 3，M'= Se，n = 2）的金属转移反应也发生在[Al（S 2CNEt 2）3 ]高收率。这些复合物中的许多已经在结构上表征：[Al（S 2 CNEt 2）3 ]（1），与它的铬（III）类似物同构，属于单斜晶系P 2 1 / n，Z = 4，其形式为[M（S 2 CNEt 2）3 ]家族；AlS为2.377（6）–2.390（6）Å，类似于先前为[Al（S 2 CNMe 2）3 ]·CH 2 Cl 2建立的值，该结构与其Ga类似物是同构的，3，（三斜线P，Z
• Lewis base complexes of AlH3: prediction of preferred structure and stoichiometry
  作者：Terry D. Humphries、Keelie T. Munroe、Andreas Decken、G. Sean McGrady

  DOI：10.1039/c3dt00047h

  日期：——

  The structures adopted by a range of complexes AlH3·nL, (n = 1 or 2), have been explored in detail to identify the factors that determine the value of n, and whether a monomeric or dimeric arrangement is preferred for the 1 : 1 complexes. Single-crystal X-ray diffraction, vibrational and NMR spectroscopies, and thermal analysis data have been collected, DFT calculations have been performed for AlH3·nL species, and pKa values have been collated for a series of amine and phosphine ligands L. The pKa of the ligand L exerts an important influence on the type of complex formed: as the basicity of L increases, a monomeric structure is favoured over a dimeric arrangement. Dimeric amine complexes form if pKa < 9.76, while monomeric complexes are preferred when pKa > 9.99. The steric requirements of L also influence the structural preference: bulky ligands with large cone angles (>163°) tend to favour formation of monomers, while smaller cone angles (<125°) encourage the formation of dimeric or 1 : 2 adducts. The steric bulk of the ligand appears to be more important for phosphine complexes, with smaller phosphines being unable to stabilise the complex at ambient temperatures even through dimerisation. Raman spectroscopy and DFT calculations have been particularly helpful in elucidating the stoichiometric preferences of complexes that have been contentious; these include AlH3·NMe2Et, AlH3·NMe3 and AlH3·nEt2O.

  一系列复合物 AlH3·nL （n = 1 或 2）采用的结构已被详细研究，以识别决定 n 值的因素，以及 1:1 复合物是偏向单体还是二聚体排列。研究收集了单晶 X 射线衍射、振动和 NMR 光谱以及热分析数据，并对 ·nL 物种进行了 DFT 计算。同时，还整理了一系列胺和磷烷配体 L 的 pKa 值。配体 L 的 pKa 对形成的复杂类型产生重要影响：随着 L 的碱性增加，单体结构相较于二聚体结构更受青睐。当 pKa < 9.76 时，形成二聚胺复合物，而当 pKa > 9.99 时，单体复合物更为优选。配体 L 的空间要求也会影响结构偏好：大锥角（>163°）的体积大配体倾向于形成单体，而小锥角（<125°）则鼓励形成二聚体或 1:2 加合物。对于磷烷复合物而言，配体的空间体积似乎更加重要，较小的磷烷在常温下即使通过二聚化也无法稳定复合物。拉曼光谱和 DFT 计算在阐明某些存在争议的复合物的计量偏好方面特别有帮助，这些复合物包括 ·NMe2Et、 ·NMe3 和 ·nEt2O。
• Secondary Amine Stabilized Aluminum Hydrides Derived from <i>N</i>,<i>N</i>‘-Di-<i>tert</i>-butylethylenediamines
  作者：Michael G. Gardiner、Stacey M. Lawrence、Colin L. Raston

  DOI：10.1021/ic950978a

  日期：1996.1.1

  various aluminum hydride sources has been investigated. HN(t-Bu)CH(t-Bu)CH(2)N(H)(t-Bu) forms a dimeric lithium chelated adduct of LiAlH(4), [[HN(t-Bu)CH(t-Bu)CH(2)N(H)(t-Bu)]Li(&mgr;-H)(2)AlH(2)}(2)], 4, which thermally decomposes to yield the tetrameric lithium diamidoaluminum hydride [Li[N(t-Bu)CH(t-Bu)CH(2)N(t-Bu)]AlH(2)}(4)], 5. The same diamine reacts with AlH(3).NMe(3) or AlH(3) diethyl etherate

  已经研究了各种氢化铝源对取代的N，N'-二叔丁基乙二胺的金属化作用。HN（t-Bu）CH（t-Bu）CH（2）N（H）（t-Bu）形成LiAlH（4）的二聚锂螯合加合物，[[HN（t-Bu）CH（t- Bu）CH（2）N（H）（t-Bu）] Li（＆mgr; -H）（2）AlH（2）}（2）]，4，发生热分解，生成四聚二氨基氢化铝锂[ Li [N（t-Bu）CH（t-Bu）CH（2）N（t-Bu）] AlH（2）}（4）]，5。相同的二胺与AlH（3）.NMe（3）反应）或AlH（3）二乙基醚化物得到仲胺稳定的氨基铝氢化物[[HN（t-Bu）CH（t-Bu）CH（2）N（t-Bu）} AlH（2）]，2。同样，相同的氢化铝源与二胺rac-HN（t-Bu）CH（Me）CH（Me）N（H）（t-Bu）反应生成[rac-HN（t-Bu）CH（ Me）CH（Me）N（t-Bu）} AlH（2）]。3
• [EN] PROCESS FOR THE GENERATION OF METAL-CONTAINING FILMS<br/>[FR] PROCÉDÉ DE PRODUCTION DE FILMS CONTENANT DU MÉTAL
  申请人：BASF SE

  公开号：WO2019120743A1

  公开（公告）日：2019-06-27

  The present invention is in the field of processes for preparing inorganic metal-containing films. The process for preparing inorganic metal-containing films comprising bringing a solid substrate in contact with a compound of general formula (I) or (II) in the gaseous state, formula (I), formula (II), wherein A is NR2 or OR with R being an alkyl group, an alkenyl group, an aryl group, or a silyl group, E is NR or O, n is 1, 2 or 3, and R' is hydrogen, an alkyl group, an alkenyl group, an aryl group, or a silyl group, wherein if n is 2 and E is NR or A is OR, at least one R in NR or OR bears no hydrogen atom in the 1-position.

  本发明涉及制备无机金属含膜的工艺领域。制备无机金属含膜的工艺包括将固体基底与通式(I)或(II)的化合物在气态下接触，其中通式(I)、通式(II)中，A为NR2或OR，R为烷基、烯基、芳基或硅基，E为NR或O，n为1、2或3，R'为氢、烷基、烯基、芳基或硅基，若n为2且E为NR或A为OR，则NR或OR中至少有一个R在1-位置不带氢原子。
• Molecular Structures of Dimeric and Trimeric Dineopentylaluminum Hydride and Trimeric Diphenylaluminum Hydride
  作者：Werner Uhl、Christian Appelt、Jana Backs、Hans Klöcker、Andrej Vinogradov、Hauke Westenberg

  DOI：10.1002/zaac.201300484

  日期：2014.1

  determined the crystal structure of this important starting material and found different ring sizes with dimeric versus trimeric formula units. The molecular shape depends on the polarity of the solvent used for recrystallization (n-pentane or 1,2-difluorobenzene). The synthesis of diphenylaluminum hydride, which is also long known in the literature, was optimized. It has a trimeric structure in the solid

  自 1988 年以来，二新戊基氢化铝 H-Al(CH2CMe3)2 的合成在文献中就已为人所知。我们确定了这一重要起始材料的晶体结构，并发现了具有二聚体与三聚体式单元的不同环大小。分子形状取决于用于重结晶的溶剂（正戊烷或 1,2-二氟苯）的极性。对文献中长期已知的二苯基氢化铝的合成进行了优化。它在固态时具有三聚体结构，带有一个 Al3H3 杂环。