aluminum(ethyl)(2,6-di-tert-butyl-4-methylphenoxy)2 | 61986-88-7

• 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: aluminum(ethyl)(2,6-di-tert-butyl-4-methylphenoxy)2
• 英文别名: ethylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide)；2,6-Ditert-butyl-4-methylphenolate;ethylaluminum(2+)
• CAS: 61986-88-7
• 化学式: C₃₂H₅₁AlO₂
• 分子量: 494.737
• InChiKey: NPUISZUNYPIASW-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  9.46
• 重原子数：
  35
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  aluminum(ethyl)(2,6-di-tert-butyl-4-methylphenoxy)2 在 benzophenone 作用下， 以 乙醚 、 正己烷 为溶剂， 生成
  参考文献：
  名称：

  铝的空间拥挤的芳氧基化合物：配位二苯甲酮的还原

  摘要：

  The interaction of AlEt(BHT)2 with benzophenone, O=CPh2, in pentane or benzene yields as the sole product Al(BHT)2(OCHPh2)(O=CPh2) (1). In diethyl ether, however, the Lewis acid-base complex AlEt(BHT)2(O=CPh2) (2) is isolated. Thermolysis of 2 yields Al(BHT)2(OCHPh2) (3), which reacts rapidly with Et2O, THF, or O=CPh2 to give the acid-base complexes Al(BHT)2(OCHPh2)(L) (L = Et2O (4), THF (5), O=CPh2 (1)). Interaction of AlEt2(BHT)(OEt2) with 1 equiv of benzophenone in diethyl ether produces the isolable complex AlEt2(BHT)(O=CPh2) (6). Solid-phase thermolysis of 6 yields the monomer AlEt(BHT)(OCHPh2) (7), which dimerizes upon dissolution in organic solvents to give [AlEt(BHT)(mu-OCHPh2)]2 (8). In the presence of excess benzophenone in benzene Solution, AlEt2(BHT)(OEt2) gives AlEt(BHT)(OCHPh2)(O=CPh2) (9), which rearranges when heated in hexane to the bridged dimer (BHT)(Et)Al(mu-OCHPh2)2Al(OCHPh2)(Et) (10). Thermolysis of 7 in the presence of excess benzophenone results in the reduction of a second ketone to give Al(BHT)(OCHPh2)2(O=CPh2) (11). Unlike the benzophenone derivatives, the reaction of acetophenone with AlEt(BHT)2 and AlEt2(BHT)(OEt2) does not result in ketone reduction but rather in the formation of the thermally stable Lewis acid-base adducts AlEt(BHT)2[O=C(Me)Ph] (12) and AlEt2(BHT)[O=C(Me)Ph] (13), respectively. The solvent-dependent formation of the benzophenone adducts 2 and 6 has been related to the solution equilibria and the relative metal-ligand bond dissociation energies (the BDE's) of the methyl compounds AlMe(BHT)2L(L = Et2O, THF, py, O=CPh2,O2N-C6H4-p-Me) and 1 which have been obtained from variable-temperature H-1 NMR data. The kinetics of the conversion of 2 to 1 and 9 to 11 have been investigated and the DELTA-H double dagger and DELTA-S double dagger values determined. Interaction of 2,6-diphenylphenol (DPP-H) with AlR3 in a 1:1 molar ratio allows for the isolation of the dimeric compounds [R2Al(mu-DPP)]2(R = Me (14), Et (15)). The reaction of 15 with O=CPh2 results after hydrolysis in the formation of approximately 1 equiv of HOCHPh2 per aluminum; however, no intermediate could be isolated.

  DOI：

  10.1021/om00041a017
• 作为产物：
  描述：

  2,6-二叔丁基-4-甲基苯酚 、 三乙基铝 以 正己烷 为溶剂， 生成 aluminum(ethyl)(2,6-di-tert-butyl-4-methylphenoxy)2
  参考文献：
  名称：

  立体位阻芳氧基取代的烷基铝化合物

  摘要：

  DOI：

  10.1021/om00092a026
• 作为试剂：
  描述：

  甲基锂 、 4-(二苄基氨基)环己酮 在 aluminum(ethyl)(2,6-di-tert-butyl-4-methylphenoxy)2 、 水 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 2.0h， 以76%的产率得到trans-4-(dibenzylamino)-1-methylcyclohexanol
  参考文献：
  名称：

  INDOLE DERIVATIVE

  摘要：

  公开号：

  EP2522657B1

文献信息

• Interaction of organic carbonyls with sterically crowded aryloxide compounds of aluminum
  作者：Michael B. Power、Simon G. Bott、David L. Clark、Jerry L. Atwood、Andrew R. Barron

  DOI：10.1021/om00162a021

  日期：1990.12
• Sterically crowded aryloxide compounds of aluminum: electronic and steric effects
  作者：Matthew D. Healy、Joseph W. Ziller、Andrew R. Barron

  DOI：10.1021/om00049a018

  日期：1991.3.27

  The mononuclear, four-coordinate aluminum compounds AlR2(BHT)L and AlR(BHT)2L [R = Me, Et; BHT = 2,6-di-tert-butyl-4-methylphenoxide; L = 2-Mepy, 4-Mepy, 2,6-Me2py, CH3CN, N(C2H4)3CH, HNEt2, HN(i)Bu2, H2N(t)Bu, H2N(n)Bu, NH3, py.O] are obtained when AlR3 is treated with the correct molar equivalent of BHT-H and the appropriate Lewis base. The aluminum-methyl C-13 NMR chemical shift for the monoaryloxide compounds AlMe2(BHT)L is dependent primarily on the steric bulk of the Lewis base. The reaction of AlMe3 with pentafluorophenol yields [Me2Al(mu-OC6F5)]2. Cleavage of the phenoxide-bridged dimer by N(C2H4)3CH leads to the formation of the Lewis acid-base complex. The molecular structures of AlMe2(BHT)(2,6-Me2py) (4), AlEt2(BHT)(H2N(t)Bu) (16), AlEt2(BHT)(py.O) (19), AlMe(BHT)2(py.O).1/2CH2Cl2 (20), and AlMe2(OC6F5)[N(C2H4)3CH] (23) have been determined by X-ray crystallography. The relationship between Al-O bond distances, Al-O-C bond angles, and the presence of Al-O pi-bonding is discussed. Crystal data for 4: monoclinic, P2(1)/n, a = 9.994 (2) angstrom, b = 21.647 (4) angstrom, c = 10.822 (2) angstrom, beta = 93.74 (2) degrees (198 K), Z = 4, R = 0.058, R(w) = 0.066. Crystal data for 16: monoclinic, P2(1)/n, a = 9.025 (2) angstrom, b = 13.862 (2) angstrom, c = 19.339 (4) angstrom, beta = 96.60 (1) degrees (183 K), Z = 4, R = 0.060, R(w) = 0.068. Crystal data for 19: monoclinic, P2(1)/n, a = 9.630 (2) angstrom, b = 18.232 (4) angstrom, c = 13.980 (3) angstrom, beta = 101.62 (2) degrees (173 K), Z = 4, R = 0.055, R(w) = 0.055. Crystal data for 20: monoclinic, C2/c, a = 25.025 (4) angstrom, b = 16.877 (3) angstrom, c = 19.261 (5) angstrom, beta = 117.59 (2) degrees (193 K), Z = 8, R = 0.073, R(w) = 0.077. Crystal data for 23: triclinic, P1BAR, a = 6.9822 (6) angstrom, b = 9.4896 (8) angstrom, c = 12.7230 (9) angstrom, alpha = 93.140 (6) degrees, beta = 94.650 (6) degrees, = 102.580 (7) degrees (183 K), Z = 2, R = 0.039, R(w) = 0.044.
• Sterically crowded aryloxide compounds of aluminium—reactivity of coordinated benzaldehyde
  作者：Michael B. Power、Andrew R. Barron

  DOI：10.1016/s0277-5387(00)80574-4

  日期：1990.1
• Power, Michael B.; Apblett, Allen W.; Bott, Simon G., Organometallics, 1990, vol. 9, # 9, p. 2529 - 2534
  作者：Power, Michael B.、Apblett, Allen W.、Bott, Simon G.、Atwood, Jerry L.、Barron, Andrew R.

  DOI：——

  日期：——
• Sterically crowded aryloxide compounds of aluminum: reactions with Main-Group chlorides
  作者：Matthew D. Healy、Joseph W. Ziller、Andrew R. Barron

  DOI：10.1021/om00045a018

  日期：1992.9

  The interaction of AlR(BHT)2 and AlR2(BHT)(OEt2) (R = Me, Et) with main-group chlorides Me3SnCl, SnCl2, BCl3, AlCl3, InCl3, and ZnCl2, in pentane, Et2O, or MeCN, leads to the formation of the aluminum chloride compounds AlCl(BHT)2 (1), AlCl(BHT)2(OEt2) (2), AlClMe(BHT)(OEt2) (3), AlClEt(BHT)(OEt2) (4), AlCl2(BHT)(OEt2) (5), [Al(mu-Cl)Me(BHT)]2 (6), and AlCl(BHT)2(NCMe) (8). In contrast, the reaction of AlMe(BHT)2 with AlCl3 in CH2Cl2 results in Friedel-Crafts alkylation by "CH2Cl" at the 4-position of BHT to give the substituted cyclohexadien-1-one 7. The kinetics of this reaction have been investigated. The reaction of AlMe(BHT)2 with 2 equiv of 2,6-Me2pyHCl yields the ionic complex [2,6-Me2pyH]-[AlCl2(BHT)2] (9). The molecular structures of 5, 6, and 9 have been determined by X-ray crystallography. Crystal data for 5: monoclinic, P2(1)/n, a = 10.796 (2) angstrom, b = 17.753 (3) angstrom, c = 11.343 (2) angstrom, beta = 97.36 (1)-degrees Z = 4, R = 0.067, R(w) = 0.078. Crystal data for 6: monoclinic, P2(1)/n, a = 10.410 (6) angstrom, b = 9.865 (3) angstrom, c = 16.42 (1) angstrom, beta = 97.20 (5)-degrees, Z = 2, R = 0.069, R(w) = 0.088. Crystal data for 9: triclinic, P1BAR, a = 9.3799 (8) angstrom, b = 13.898 (1) angstrom, c = 14.8255 (14) angstrom, alpha = 101.900 (8)-degrees, beta = 91.080 (7)-degrees, gamma = 98.050 (7)-degrees, Z = 2, R = 0.050, R(w) = 0.062.