di(tert-butyl)aluminium chloride | 22086-73-3

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: di(tert-butyl)aluminium chloride
• 英文别名: Ditert-butylalumanylium;chloride
• CAS: 22086-73-3
• 化学式: C₈H₁₈AlCl
• 分子量: 176.665
• InChiKey: RNGPIGJNRFZTPO-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  3.82
• 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：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  叔丁基肼 、 di(tert-butyl)aluminium chloride 以 甲苯 为溶剂， 以76%的产率得到di(tert-butyl)aluminium chloride t-butylhydrazine adduct
  参考文献：
  名称：

  酰肼铝。与四元 Al2N2 杂环形成二聚二（叔丁基）铝酰肼以及二烷基氯化铝与双（三甲基甲硅烷基）酰肼二锂反应

  摘要：

  The reaction of di(tert-butyl)aluminium chloride with tert-butylhydrazine yielded an adduct (1) which was isolated in a pure form and characterized by crystal structure determination. 1 reacted with n-butyllithium by deprotonation and salt elimination to give the corresponding di(tert-butyl)aluminium hydrazide (2), which is a dimer in solution and in the solid state and possesses a four-membered Al2N2 heterocycle with two exocyclic N-N bonds. The structure of 2 differs from that of other di(tert-butyl)aluminium hydrazides which have four- or five-membered heterocycles. Treatment of impure samples of 1 with n-butyllithium yielded by the cleavage of the N-N bonds a mixture of several un-known products, from which the dimeric, centrosymmetric aluminium amide [(Me3C)(2)AlN(H)CMe3](2) (3) was isolated. A similar product (4) was obtained in a low yield by the reaction of (Me3SiCH2)(2)AlCl with the dilithium hydrazide Li2N2(SiMe3)(2). An intact N-N bond was neither found in the second product isolated from this reaction. Instead a tricyclic compound was formed by C-H activation which has two five-membered AlNSiC2 heterocycles bridged by Al-N bonds.

  DOI：

  10.1002/1521-3749(200011)626:11<2284::aid-zaac2284>3.0.co;2-b

文献信息

• Structurally Engineered Deprotonation/Alumination of THF and THTP with Retention of Their Cycloanionic Structures
  作者：Elaine Crosbie、Pablo García-Álvarez、Alan R. Kennedy、Jan Klett、Robert E. Mulvey、Stuart D. Robertson

  DOI：10.1002/anie.201005119

  日期：2010.12.3

  Engagement ring: α‐Metalated by a lithium bisamido‐bisalkylaluminate base, the sensitive cycloanionic ring of THF or THTP remains intact by engaging with both metal centers of the base residue (see structure; X=O, S).

  订婚环：由双酰胺基双烷基铝酸锂碱金属构成的THF或THTP敏感的环阴离子环通过与碱残基的两个金属中心结合而保持完整（见结构； X = O，S）。
• Synthesis and characterization of the monomeric phosphinogallanes Bu^t₂GaPR′R″(R′, R″= bulky aryl or silyl groups) and related compounds
  作者：Mark A. Petrie、Philip P. Power

  DOI：10.1039/dt9930001737

  日期：——

  monoclinic, space group P21/c, a= 18.499(5), b= 10.028(4), c= 20.746(6)Å, β= 90.45(1)°, Z= 4, R= 0.043; 5, triclinic, space group P, a= 9.488(3), b= 11.416(5), c= 20.383(6)Å, α= 92.07(3), β= 96.80(2), γ= 103.17(3)°, Z= 2, R= 0.079; 6, triclinic, space group P, a= 12.219(3), b= 14.174(3), c= 21.831(5)Å, α= 92.95(2), β= 99.73(2), γ= 99.47(2)°, Z= 4, R= 0.053; 7, monoclinic, space group P21/c, a= 17.710(6)

  庞大的取代基的使用使得可以分离出其中镓和磷是三配位的几种单体膦基没花环的分离，光谱和结构表征。这些新的化合物具有下式卜吨2间隙（R）（SIPH 3）（R = C 6 H ^ 2卜吨3 -2,4,6- 1，C 6 H ^ 2镨我3 -2,4,6- 2， C 6 H 2 Me 3 -2,4,6 3或SiMe 3 4）。恒温11 H NMR研究表明，存在约20nm的旋转势垒。12.7千卡摩尔-1围绕在GA-P键1，其已经被归因于弱嘎-Pπ键合。合成和相关铝-磷物种的结构卜吨2的Al（ET 2 O）-P（C 6 H ^ 2镨我3 -2,4,6-）（SIPH 3）5和镓-砷物种卜吨还报道了2 GaAs [CH（SiMe 3）2 ]（SiPh 3）6。另外，变温1前体不对称膦（Ph 3 Si）P（R）H（R = C 6 H 2 Bu t 3 -2,4,6 7，C 6 H 2 Pr i 3 -2,4,6
• Reactivity of Carbonyl-Functionalized Phosphaalkenes RC(O)P=C(NMe2)2 (R =tBu, Ph) towards Electrophiles
  作者：Lothar Weber、Stefan Uthmann、Hans-Georg Stammler、Beate Neumann、Wolfgang W. Schoeller、Roland Boese、Dieter Bläser

  DOI：10.1002/(sici)1099-0682(199912)1999:12<2369::aid-ejic2369>3.0.co;2-s

  日期：1999.12

  [RC(OGaMe3)=P(GaMe3)C(NMe2)(2)] (10a,b). In contrast, one molecule of InMe3 was bound to the phosphorus center of the phosphorus compound. Reaction of the phosphaalkenes with [Ni(CO)(4)], [Fe-2(CO)(9)] or [(Z)-cyclooctene}Cr(CO)(5)] also took place at the pnictogen atom, resulting in complexes of the type [RC(O)PM(CO)(n)}C(NMe2)(2)] (R = tBu, Ph; M = Ni, n = 3; Fe, n = 4; Cr, n = 5). The chemical

  羰基官能化磷烯烃 RC(O)P=C(NMe2)(2) [R = tBu (2a), Ph (2b)] 与质子酸和烷基化试剂在二配位磷原子上发生反应，得到膦酰基取代的碳正离子 3a,b 和 4a,b。相反，用 Me3SiOSO2CF3 处理导致甲硅烷基对氧原子的攻击，并形成 [RC(OSiMe3)=PC(NMe2)(2)]SO3CF3 (5a,b)。类似地，路易斯酸 B(C6F5)(3)、Al(tBu)(2)Cl 和 AlMe3 与羰基的氧原子相连。将两当量的 GaMe3 添加到磷烯烃的氧和磷原子中以产生不耐热复合物 [RC(OGaMe3)=P(GaMe3)C(NMe2)(2)] (10a,b)。相比之下，一分子 InMe3 与磷化合物的磷中心结合。磷烯烃与 [Ni(CO)(4)] 的反应，[Fe-2(CO)(9)] 或 [(Z)-环辛烯}Cr(CO)(5)] 也发生在 pnictogen
• Terminally Dimetalated Tetramethylethylenediamine (TMEDA) Compounds
  作者：Xin Tian、Roland Fröhlich、Tania Pape、Norbert W. Mitzel

  DOI：10.1021/om0504405

  日期：2005.10.1

  tetramethylethylenediamine (TMEDA), LiCH2N(Me)CH2CH2N(Me)CH2Li (1), was prepared by transmetalation from Me3SnCH2N(Me)CH2CH2N(Me)CH2SnMe3 and n-BuLi. It was isolated as a highly air-sensitive white powder and was characterized by elemental analysis and by further transmetalation reactions. Compound 1 was used as a difunctional aminomethylating agent and reacted with R2MCl (R = Me, t-Bu; M = Al, Ga, In) to give the

  通过对Me 3 SnCH 2 N（Me）CH 2 CH 2 N（Me）CH进行重金属化制备了末端二锂化四甲基乙二胺（TMEDA）LiCH 2 N（Me）CH 2 CH 2 N（Me）CH 2 Li（1）2 SnMe 3和n -BuLi 。分离为高度对空气敏感的白色粉末，并通过元素分析和进一步的金属转移反应进行了表征。将化合物1用作双官能氨基甲基化剂，并与R 2 MCl（R = Me，t-Bu; M = Al，Ga，In）以选择性形成1,2,2,4,5,5-六甲基-1,4-二氮杂-2,5-二金属萘环[2.2.2]辛烷（M = Al（2），镓（3），在（4））和2,2,5,5-四-叔-丁基-1,4-二甲基-1,4-二氮杂-2,5- dimetallabicyclo [2.2.2]辛烷（M = Al（5），Ga（6））通过同时形成两个金属碳键和两个衍生金属氮键并伴随两个闭环而形成。化合物2 -
• Two Different Structural Motifs Observed for Dimeric Dialkylaluminum and Dialkylgallium Alkynides [R2E-C?C-C6H5]2
  作者：Werner Uhl、Frank Breher、Sima Haddadpour、Rainer Koch、Madhat Matar

  DOI：10.1002/zaac.200400150

  日期：2004.10

  interestingly, different types of molecular structures were observed depending on the steric demand of the substituents terminally attached to the aluminum or gallium atoms. The small methyl substituents gave structures in which the aluminum or gallium atoms seemed to be side-on coordinated by the C≡C triple bonds of almost linear E-C≡C groups. In contrast, the more bulky tert-butyl groups forced an arrangement

  二烷基铝和二烷基镓炔化物 [R2E-C≡CR']2 (R = Me, CMe3; E = Al, Ga; R' = Ph) 含有连接到其中心铝或镓原子的 C≡C 三键，很容易通过以下方法获得：二烷基元素氯化物与锂炔化物的反应或通过用二烷基铝或氢化二烷基镓处理相应的炔烃RC≡CH。第一个反应有利于 LiCl 的沉淀，第二个反应有利于形成元素氢。所有产物都形成二聚体，其中炔基的碳负离子碳原子采用桥接位置，但有趣的是，根据末端连接到铝或镓原子的取代基的空间需求，观察到不同类型的分子结构。小的甲基取代基给出的结构中铝或镓原子似乎是由几乎线性的 EC≡C 基团的 C≡C 三键配位的。相反，体积更大的叔丁基迫使C≡C三键垂直于分子的EE轴的排列。通过量子化学计算分析了不同的键合模式。Unterschiedliche Struktureinheiten in dimeren 二烷基铝-和二烷基镓烷基化物