Reactions of O,O'-dialkyl thiophosphoric acids with alkyl halides, in the presence of a base, provide a direct synthetic route to phosphorothioates via O,O'-dialkyl thiophosphate anion formation. Studies on the reaction of ambident nucleophile ammonium O,O'-diethyl thiophosphate with benzyl halides and tosylate in different solvents show that only S-alkylation is obtained. Reaction of this ambi...

Simple, secondary 2,4,6-triisopropyl benzoates (TIB esters) and secondary dialkyl N,N-diisopropyl carbamates have been reported to be resistant to deprotonation by strong bases. We have found that the combination of sBuLi (1.6 equiv) and TMEDA (6 equiv) in CPME at -60 °C enables deprotonation of unactivated secondary dialkyl TIB esters, but not the carbamates. These carbanions were reacted with...

The venom of the red imported fire ant, Solenopsis invicta, is dominated by trans stereoisomers of 2,6-dialkylpiperidines. cis Stereoisomers of alkaloids in the venom of S. invicta were separated from trans stereoisomers by using silica gel short column chromatography and identified by coupled gas chromatography mass spectrometry (GC-MS). Seven pairs of cis and trans sterecoisomers were identif...

Dibenzobarrelene derivatives, that are annelated with a pyrrolinium unit [N,N-dialkyl-3,4-(9',10'-dihydro-9',10'-anthraceno-3-pyrrolinium) derivatives], undergo a photo-induced di-π-methane rearrangement upon triplet sensitization to give the corresponding cationic dibenzosemibullvalene derivatives [N,N-dialkyl-3,4-{8c,8e-(4b,8b-dihydrodibenzo[a,f]cyclopropa[cd]pentaleno)}pyrrolidinium derivati...

Square planar dialkyl complexes of nickel, palladium and platinum exhibit intriguing difference in their reactivities. Thermolysis pathways of these dialkyls vary depending on the metal, ligands, alkyl groups, geometry as well as the presence or absence of added ligand. Kinetic studies on the thermolysis and trans-cis isomerizations of PdR,L2 (L = tertiary phosphine) complexes showed involvemen...

Protodeborylation of triorganoboranes, usually carried out under mild reaction conditions using an excess of acetic acid, affords 1,5-dialkyl-3,7-dimethyl-4,8,9-trioxa-2,6-dioxonia-1,5-diboratabicyclo [3.3.1]nona-2,6-dienes OB(R)OC(Me)OB(R)OC(Me)O [1 (R = Et), 2 (R = cyclooctyl)]. Acetoxy(dialkyl)boranes and di(acetoxy)alkylboranes were not formed in an appreciable amount. Compounds 1 and 2 wer...

the kinetics of the reactions between triphenylphosphine 1 and dialkyl acetylenedicarboxylates 2, in the presence of a nh-acid such as 5-nitroindazole 3,were studied. corresponding kinetic parameters to all reactions were evaluated, with the second order rate constant (k) values calculated. effects of solvent, temperature, and reactants (dialkyl acetylenedicarboxylates) structure and concentrat...

in order to investigate the effects of dimethylamino substituent at postion 2 of the dihydropyridine nucleus on its activity, dialkyl 1,4-dihydro-2-[2-(dimethy- lamino) ethyl]-6-methyl-4-(1-benzyl-2-alkylthio-5-imidazolyl)-3,5-pyrdinedicar- boxylates (6a-f) were synthesized. the synthesis was started from dialkyl 1,4- dihydro-2,6-dimethyl-4-(1-benzyl-2-alkylthio-5-imidazolyl)-3,5-pyridinedicar-...