title: Conformational and spectroscopic study of xanthogen ethyl formates, ROC(S)SC(O)OCH₂CH₃. Isolation of CH₃CH₂OC(O)SH.
abstract: ROC(S)SC(O)OCH2CH3, with R=CH3-, (CH3)2CH- and CH3(CH2)2-, were obtained through the reaction between potassium xanthate salts, ROC(S)SK, and ethyl chloroformate, ClC(O)OCH2CH3. The liquid compounds were identified and characterized by (1)H and (13)C NMR and mass spectrometry. The conformations adopted by the molecules were studied by DFT methods. 6 conformers were theoretically predicted for R=CH3- and (CH3)2CH-, while the conformational flexibility of the n-propyl substituent increases the total number of feasible rotamers to 21. For the three molecules, the conformers can be associated in 3 groups, being the most stable the AS forms - the C=S double bond anti (A) with respect to the C-S single bond and the S-C single bond syn (S) with respect to the C=O double bond - followed by AA and SS conformers. The vibrational spectra were interpreted in terms of the predicted conformational equilibrium, presenting the ν(C=O) spectral region signals corresponding to the three groups of conformers. A moderated pre-resonance Raman enhancement of the ν(C=S) vibrational mode of CH3(CH2)2OC(S)SC(O)OCH2CH3 was detected, when the excitation radiation approaches the energy of a n→π∗ electronic transition associated with the C=S chromophore. UV-visible spectra in different solvents were measured and interpreted in terms of TD-DFT calculations. The unknown molecule CH3CH2OC(O)SH was isolated by the UV-visible photolysis of CH3OC(S)SC(O)OCH2CH3 isolated in Ar matrix, and also obtained as a side-product of the reaction between potassium xanthate salts, ROC(S)SK, and ethyl chloroformate, ClC(O)OCH2CH3.
authors.affiliation: CEQUINOR (CONICET-UNLP), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 47 esq. 115, (1900) La Plata, Argentina.
authors.forename: Luciana C
authors.initials: LC
authors.lastname: Juncal
authors.affiliation: CEQUINOR (CONICET-UNLP), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 47 esq. 115, (1900) La Plata, Argentina.
authors.forename: Melina V
authors.initials: MV
authors.lastname: Cozzarín
authors.affiliation: CEQUINOR (CONICET-UNLP), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 47 esq. 115, (1900) La Plata, Argentina. Electronic address: romano@quimica.unlp.edu.ar.
authors.forename: Rosana M
authors.initials: RM
authors.lastname: Romano
mesh_terms: D004220:Disulfides / Q000737:chemistry*; D004583:Electrons; D005563:Formic Acid Esters / Q000737:chemistry*; D013058:Mass Spectrometry; D008958:Models, Molecular; D008968:Molecular Conformation; D010782:Photolysis; D013056:Spectrophotometry, Ultraviolet; D017550:Spectroscopy, Fourier Transform Infrared; D013059:Spectrum Analysis, Raman; D013816:Thermodynamics; D014732:Vibration
chemical_list: D004220:Disulfides; D005563:Formic Acid Esters; C510888:ethyl formate
keywords: Conformations; Photochemistry; Vibrational spectroscopy