Aerosol direct fluorination. Synthesis of perfluoroadamantane, the penultimate step

Abstract

Unclassified Is. OECL ASSI FICATION/DOWNGRADING SCHEDULE IS. DISTRIBUTION STATEMENT (of this Report)Thts document has been approved for public release and sale; its distribution is unlimited. The aerosol direct fluorination technique has been successfully employed to convert adamantane to perfluoroadamantane in 28% overall yields based on input. Although physical losses in the reactor reduced yields the major (74.4%) product collected was perfluoroadamantane. Fragmentation and ring-opening proved to be insignificant as was the proportion of 1-hydrylpentadecafluoroadamantane. DO

Preparation, Structure, and Properties of Symmetrically 1,3-Difunctionalized Penta- and Hexafluorobicyclo[1.1.1]pentanes

“…Direct Fluorination. Successful direct fluorination of various polycyclic hydrocarbons (norbornane, bicyclo[2.2.2]octane, adamantane, diamantane, and bisnoradamantane 7 ) has been reported. However, according to a preliminary report 7 ring opening was observed during attempted direct fluorination of [1.1.1]propellane and cubane, presumably because of their highly strained nature.…”

Perfluorinated Stellanes: The Synthesis of Perfluorinated Bisnoradamantane. Long-Range 19F NMR Virtual Coupling

“…Later it was also used to explain fluorine−fluorine long-range coupling in perfluorinated chain compounds . In the 19 F NMR spectrum of the highly symmetric F -adamantane, long-range fluorine−fluorine virtual coupling resulted in symmetrical splitting patterns; the simpler and highly symmetric F -bisnoradamantane produces results which are better resolved and more easily interpretable (Figure ). This simplicity of interpretation is rarely seen even in other only slightly less symmetrical perfluorinated compounds, e.g., F -adamantane-2,6-dione (Figure ).…”

“…In recent years, our interest in the syntheses of perfluorinated cage compounds has led to the syntheses of perfluorinated adamantane, diamantane, [2.2.2]bicyclooctane, etc. These three molecules are notable in that the smallest ring in each system is a six-membered ring.…”

Synthesis of the chiral 4-substituted 1-phenylcyclohexene PD137789 via intramolecular Wittig reaction

“…The solid was recrystallized from ethyl acetate (10 mD-EtgO (50 mL) with cooling to 0 °C to afford pure 6 as colorless crystals (4.75 g, 56% yield), mp 80-83 °C: [a]D -22.4°( c 2.9, CHClg); NMR (300 MHz, CDClg) 7.93 (d, 2 H, J = 7.3 Hz), 7.57 (t, 1 H, J = 7.3 Hz), 7.46 (t, 2 H, J = 7.3 Hz), 4.42 (m, 1 H), 4.25 (td, 1 H, J = 11.0, 3.4 Hz), 3.02 (t, 2 H, J = 7.3 Hz), 2.73 (dd, 1 H, J = 16, 4 Hz), 2.19 (dd, 1 H ,J= 17,10 Hz), 2.02 (m, 2 ), 1.84 (m, 2 ), 1.57 (m, 1 H); 13C NMR (CDClg) 199.1,170.9,136. (Ji)-<-Oxo-j9-t2-(triphenylphosphoranyI)ethyl]benzenehexanoic Acid Bromide (8). The lactone 6 (4.65 g, 20 mmol) and triphenylphosphonium hydrobromide (7.10 g, 20 mmol) were stirred together and heated in an oil bath at 160 °C for 2 h. Upon cooling the phosphonium salt 8 was obtained as a glassy solid (11.7 g) which was used directly in the following reaction: NMR (200 MHz) 1.9-1.2 (m, 20 H), 3.74 (m, 1 H) 3.5 (m, 1 H), 2.9 (m, 3 ), 2.60 (m, 1 H) 2.38 (m, 1 ), 1.75 (m, 4 H); 13C NMR (CDClg) 199.9, 173.9, 136.5, 135.2 (3 C), 133.5 (d, 6 C, «/C-p = 10 Hz), 133.15, 130.5 (d, 6 C, =7C-p = 12 Hz), 128.6 (2 C), 128.0 (2 C), 117.8 (d, 3 C, Jc-p = 86 Hz), 39.4, 35.9, 35.7, 27.2, 25.9,19.0 (d, 1 C, Jc-p = 51 Hz).…”