79996-96-6Relevant academic research and scientific papers
Fluorescent chemosensor for chloroalkanes
Lee, Jung-Jae,Noll, Bruce C.,Smith, Bradley D.
, p. 1735 - 1738 (2008)
Two structurally related macrocyclic amines with naphthalene groups are shown to act as fluorescent dosimeters for reactive chloroalkanes, including the common Industrial solvent dichloromethane. The macrocyclic structures contain two NH residues which greatly accelerate N-alkylation by activating the chloride leaving group. The chemical reaction increases fluorescence Intensity by promoting excimer emission and attenuating the quenching Induced by photoinduced electron transfer (PET).
Study of Reactions Leading to Sulfine Formation. 3. Competition of Reaction Pathways in the Reaction of Methoxide Ion with Methyl 1-Naphthylmethanesulfinates
Kice, John L.,Lotey, Harvinder
, p. 3596 - 3602 (2007/10/02)
In CD3O1-/CD3OD methyl 1-naphthylmethanesulfinates, NpCH2S(O)OCH3 (2), undergo both exchange of CH3O by CD3O by substitution at the sulfinyl group and elimination to form the sulfine, NpCH=S=O.With use of methyl (2-methoxy-1-naphthyl)methanesulfinate (2a) it has been shown that formation of the sulfine takes place by an (E1cB)irrev mechanism.The rates of substitution (ks) and elimination (ke) of a series of 2 have been determined in CD3O1-/CD3OD by 1H NMR spectroscopy, and the effect of several reaction variables on the competition between substitution and elimination has been examined.Salient results are as follows: (1) the rate of elimination is markedly increased by the presence of electron-withdrawing substituents on the aromatic ring, but the rate of substitution is increased only modestly by the same substituents; (2) substituents at the 2-position of the naphthyl group cause a large decrease in ks (steric hindrance to substitution at S=O) but have little effect on ke (elimination rate not sensitive to steric requirements of ortho substituents); (3) the activation energy for elimination is almost 9 kcal/mol greater than the activation energy for substitution.This large difference in activation energy contrasts with the 1-2 kcal/mol difference for elimination vs substitution found14 with alkyl halides.
