Philip B. Shevlin

Reversible addition of hydroxide to the fullerenes

Abstract Heating a highly colored solution of C60/C70 in toluene in the presence of excess solid KOH under vacuum results in decolorization of the solution with the formation of a precipitate. Addition of oxygen to the resultant cooled mixture regenerates the C60/C70 in 76% yield. An examination of the electronic spectrum as the reaction proceeds indicates that C60 reacts slower than C70. Addition of hydroxide ions to the fullerene cages to generate oxygenated potassium fullerides is postulated.

The phenylcarbene rearrangement as a source of real carbenes

Abstract The phonylcarbene rearrangement is used to produce carbenes that are compared to the intermediates formed on photolysis and pyrolysis of diazo compounds.

Formation of benzo[ghi]fluoranthenes by palladium catalyzed intramolecular coupling

Abstract A novel synthesis of benzo[ ghi ]fluoranthenes by palladium mediated coupling is reported. The high yields, mild reaction conditions and functional group tolerance are an advantage of this method.

A Short Synthesis of 1-Vinyluracil and 1-Vinylthymine

Abstract 1-Vinyluracil and 1-vinylthymine, monomers for nucleic acid bases attached functional polymers, were synthesized for the first time from uracil and thymine in 3 steps in 54% and 50% overall yields using the Mitsunobu reactions of 2a and 2b with 2-chloroethanol as a key step.

Convenient synthesis of 6,5 open and 6,6 closed cycloalkylidenefullerenes

Abstract A number of cycloalkylidenefullerenes have been prepared by reaction of C 60 with tosylhydrazone lithium salts in refluxing toluene. Short reaction times lead to high yields of 6,5 open methanofullerenes which subsequently rearrange to the 6,6 closed isomers.

An experimental and theoretical evaluation of the mechanism of hydrocyanic acid formation in the reaction between atomic carbon and ammonia

On montre que HCN est genere par elimination de H 2 a partir du complexe C − NH 3 + , suivie par une transposition de HNC en HCN

6-isobutyrylaminopurine: A convenient building block for the synthesis of carbocyclic adenosine analogs

Abstract Readily available 6-isobutyrylaminopurine can replace either a primary or secondary OH group under Mitsunobu conditions and provide an efficient synthesis of carbocyclic analogs of adenosine. X-ray data indicates that only the desired N9 - substituted derivatives of adenine are formed.

The electronics structures of small strained rings. An investigation of the interaction between the oxygen and the π orbitals in 3-methyleneoxetane and 3-oxetanone

Abstract The ultraviolet photoelectron spectra of 3-methyleneoxetane (I), 3-oxetanone (II) and β-propiol-octane (III) have been investigated for the purpose of studying the interaction processes between the endocyclic oxygen and the methylene or carbonyl groups of I and II, respectively. Molecular orbital calculations at the MINDO/3, MNDO, and STO-3G/431-G levels have been performed to aid analyses of the data. The interaction process occurs primarily through the pseudo-π-CH 2 orbitals for I and II. Substantial stabilizing inductive effects are noted for the lone-pair and π orbitals for these molecules.

Trapping of a cycloheptatetraene in the reaction of atomic carbon with phenol

Reaction of atomic carbon with phenol generates tropone in a reaction postulated to proceed via the hydroxycycloheptatetraenes, which rearrange to tropone. When the hydroxyphenylcarbenes are generated by the C atom deoxygenation of the corresponding aldehydes, the meta and para isomers produce tropone; the ortho isomer does not.

The formation of amino acid precursors in the reaction of atomic carbon with water and ammonia at 77 K.

When atomic carbon is condensed on a surface at 77 K containing ammonia and water, glycine, N-methylglycine, alanine, β-alanine, aspartic acid and serine are generated. It is postulated that these reactions may mimic those which occur when an extraterrestrial carbon atom condenses on a frozen surface coated with water and ammonia and may provide a route to extraterrestrial amino acids. Experiments designed to elucidate the mechanisms of amino acid formation under these conditions have been carried out.