title: Structure of sp-9-hydroxy-9-pivaloylfluorene, product of base-catalyzed autoxidation of ap-9-pivaloylfluorene.
abstract: 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.
authors.affiliation: Department of Chemistry, Southern Illinois University, Carbondale 62901.
authors.forename: C Y
authors.initials: CY
authors.lastname: Meyers
authors.forename: J L
authors.initials: JL
authors.lastname: Tunnell
authors.forename: P D
authors.initials: PD
authors.lastname: Robinson
authors.forename: D H
authors.initials: DH
authors.lastname: Hua
authors.forename: S
authors.initials: S
authors.lastname: Saha
mesh_terms: D055598:Chemical Phenomena; D002627:Chemistry, Physical; D003460:Crystallization; D005449:Fluorenes / Q000737:chemistry*; D006860:Hydrogen Bonding; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D015394:Molecular Structure; D010084:Oxidation-Reduction; D014961:X-Ray Diffraction
chemical_list: D005449:Fluorenes; C078298:9-hydroxy-9-pivaloylfluorene