Fate of 1-adamantyl carbene.  Evidence for the formation of the bridgehead olefin 3-homoadamantene

Farcasiu, M.; Fǎrcaşiu, D.; Conlin, Robert T.; Jones, Maitland; Schleyer, P. R.

doi:10.1021/ja00805a060

Cited by 39 publications

(15 citation statements)

References 5 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This molecule was selected with the goal of maximizing the cetane number through incorporation of a relatively long alkyl chain while keeping the viscosity and boiling point as low as possible. PA has previously been prepared from tosylhydrazone derived from 1-adamantanecarboxaldehyde , by reaction with n -BuLi and from 1-bromoadamantane by reaction with 1-pentylmagnesium bromide . To improve upon the poor atom economy of the tosylhydrazone route and the low yield obtained from 1-bromoadamantane, a new synthesis of PA was conceived, in which 1-adamantane carboxylic acid was converted to n -butyl-1-adamantanylketone, which was then reduced under Wolff–Kishner conditions to generate PA (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Molecular Design and Characterization of High-Cetane Alkyl Diamondoid Fuels

et al. 2016

View full text Add to dashboard Cite

Four alkyl diamondoids, 1-pentyladamantane (PA), 2-butyladamantane (BA), 2-propyladamantane (2-PrA), and 2-ethyladamantane (EA), were synthesized on a preparative scale, and key fuel properties, including density, net heat of combustion, low-temperature viscosity, and derived cetane number (DCN), were measured. The fuel molecules had densities up to 17% higher than conventional jet fuel and volumetric net heats of combustion comparable to or exceeding that of the synthetic missile fuel JP-10. Remarkably, the alkyl diamondoid fuels had DCNs in the range of 42–49, which should allow for their efficient combustion in diesel engines. PA, BA, and 2-PrA all had essentially the same DCN (∼49), while the short alkyl chain in EA lowered the value to 42.7. Bond dissociation energies for the formation of diradicals from 2-PrA and PA were calculated with density functional theory methods to gain a qualitative understanding of potential combustion mechanisms. Ring opening of the adamantane core during combustion is proposed to explain the high cetane number of these fuels. The alkyl diamondoids described in this report are the first examples of multicyclic hydrocarbons that combine extraordinary densities (>0.9 g/mL) with DCNs comparable to or exceeding that of conventional diesel fuel.

show abstract

Section: Resultsmentioning

confidence: 99%

Molecular Design and Characterization of High-Cetane Alkyl Diamondoid Fuels

et al. 2016

View full text Add to dashboard Cite

show abstract

“…Subsequent fragmentation of the ion at m/z 730 (MS 3 ) led to the sole formation of the ion at m/z 656. This may be rationalized as the sequential loss of neutral 1-adamantylcarbene fragment (or its isomer) [19] from both ends of the BIM scaffold to yield the doubly charged aggregate of the CB7 and BIM residue. This release of neutral AdCH fragments (exact mass of m/z 148) will be hereinafter referred to as the "148" fragmentation.…”

mentioning

confidence: 99%

Determination of Intrinsic Binding Modes by Mass Spectrometry: Gas‐Phase Behavior of Adamantylated Bisimidazolium Guests Complexed to Cucurbiturils

Černochová

Branná

Rouchal

et al. 2012

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Olefins 2 and 3 were transformed by ozonolysis to the known ketone, 4-protoadamantanone13 (5), and 3-noradam-Adams, Kovacic / Thermal Decomposition of 3-Homoadamantyl Acetate antanecarboxaldehyde (6). Reduction of the carbonyl-containing mixture with L1AIH4 provided a known derivative of the aldehyde, 3-noradamantylcarbinol14 (7), and the isomeric 4-hydroxyprotoadamantane15 (8).…”

Section: Resultsmentioning

confidence: 99%

“…4-Hydroxyprotoadamantane15 (8) and 3-Noradamantylcarbinol14 (7) . Treatment of the carbonyl mixture [5 (0.75 g, 5.0 mmol) and 6 (0.25 g, 1.69 mmol)] in 100 ml of anhydrous ether with LÍAIH4 (1.5 g) at room temperature for 2 hr resulted in conversion to the corresponding alcohols, 4-protoadamantanol (8) [exo (24% yield), mp 204-206°( lit.15 mp 204-206°); endo (41% yield), mp 215-217°( lit.15 mp 214-216°)] and 3-noradamantylcarbinol (7) (28% yield), mp 137-140°( lit.14 mp 142-144°).…”

Section: Methodsmentioning

confidence: 99%