Meyers C Y, Tunnell J L, Robinson P D, Hua D H, Saha S
Department of Chemistry, Southern Illinois University, Carbondale 62901.
Acta Crystallogr C. 1992 Oct 15;48 ( Pt 10):1815-8. doi: 10.1107/s0108270192002014.
1-(9-Hydroxyfluoren-9-yl)-2,2-dimethyl-1-propanone, C18H18O2, M(r) = 266.34, orthorhombic, Pbcn, a = 18.917 (10), b = 11.843 (8), c = 13.177 (7) A, V = 2952 (5) A3, Z = 8, Dx = 1.198 g cm-3, lambda(Mo K alpha) = 0.71069 A, mu = 0.72 cm-1, F(000) = 1136, T = 296 K, R = 0.044 for 1042 unique observed reflections. Conversion of ap-9-pivaloylfluorene, ap-(I), into lithiated (I)-9-anion followed by the addition of MeOH, then H2O, led to unexpected hydroxylation to provide 20-40% of sp-9-hydroxy-9-pivaloyfluorene, sp-(II), and 60-80% recovery of ap-(I). The singular sp conformation of (II) in solution suggested by NMR was confirmed in the crystalline state by X-ray diffraction which showed the O(1)-C(9)-C(10)-O(2) torsion angle approximately 0 degrees and the C(10) = O(2)...H(9)-O(1) non-bonding distance 1.95 (4) A, suggesting strong intramolecular hydrogen bonding in this conformation.
1-（9-羟基芴-9-基）-2,2-二甲基-1-丙酮，C₁₈H₁₈O₂，M(r)=266.34，正交晶系，Pbcn空间群，a = 18.917(10)，b = 11.843(8)，c = 13.177(7) Å，V = 2952(5) ų，Z = 8，Dx = 1.198 g cm⁻³，λ(Mo Kα)=0.71069 Å，μ = 0.72 cm⁻¹，F(000)=1136，T = 296 K，对于1042个独立观测反射，R = 0.044。将对映体-9-新戊酰芴（ap-(I)）转化为锂化的(I)-9-阴离子，然后加入甲醇，再加入水，导致意外的羟基化反应，生成20 - 40%的螺-9-羟基-9-新戊酰芴（sp-(II)），且ap-(I)的回收率为60 - 80%。核磁共振表明溶液中(II)具有单一的螺构型，通过X射线衍射在晶体状态下得到证实，其显示O(1)-C(9)-C(10)-O(2)扭转角约为0°，C(10)=O(2)...H(9)-O(1)非键距离为1.95(4) Å，表明该构型中存在强分子内氢键。
