Low Temperature Measurements of Carbon-Carbon Spin-Spin Couplings in s-cis and s-trans Rotamers of Enaminoketones; Comparison with DFT Computations

• Autorzy: Bugaj M. , Kamieńska-Trela K.
• Konferencja: 1st Symp. on NMR in Chemistry, Biology and Medicine; 8-10 Semptember, Warsaw, Poland. Issue dedicated to honour Prof. Witanowski
• Języki publikacji: EN

Abstrakty

EN

Low temperature 13C INADEQUATE spectra of 4-dimethylamino-but-3-en-2-one 1 and 4-methylamino-but-3-en-2-one 2 revealed J(CC) couplings across one, two and three bonds for the s-transand s-cis conformers of compound 1which exists solely in the trans form, and for the s-trans-s-cis and s-cis-s-cis conformers of the trans isomer of compound 2. A set of CC couplings was also obtained for the cis-s-cis-s-trans isomer of 2. The coupling constants obtained span a range of about 70 Hz, from about 2 Hz observed for the couplings across three bonds to 71 Hz measured for the couplings across the double bonds. Only a slight influence is exerted by the conformation on the couplings across one bond in trans-1 and trans-2. The most significant change is observed upon isomerization of compound 2 to the cis form. This outcome leads to internal hydrogen bond formation and to a decrease in both 1J(C2C3) and 1J(C3C4) coupling values, by 2.7 and 5.1 Hz, respectively. The couplings across two bonds are more sensitive towards changes in the conformation than are those across one bond; 2J(C1C3)'s in the s-trans conformers are significantly larger than those in the s-cis structures. Good agreement is observed between the experimental and B3LYP/6-311++G(2d,p)//B3LYP/6-311++G(2d,p) calculated couplings, and the corresponding linear regression is expressed by the following equation: J(CC)exptl. = [0.94(š 0.01) J(CC)calcd. + 0.62 (š0.71)] š 2.12 Hz.

Słowa kluczowe

EN

enaminoketones; carbon-carbon spin-spin coupling constants; low temperature measurements; calculations; DFT; conformation; hydrogen bond

• Wydawca: Polskie Towarzystwo Chemiczne
• Czasopismo: Polish Journal of Chemistry
• Rocznik: 2006
• Tom: Vol. 80, nr 7
• Strony: 1217--1231
• Opis fizyczny: Bibliogr. 26 poz., rys.

Twórcy

autor

Bugaj M.

autor

Kamieńska-Trela K.

• Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland

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