Solving Unknown Structures Using NMR - University of Aberdeen利用核磁共振-阿伯丁大学求解未知结构.ppt

Solving Unknown Structures Using NMR Six Simple Steps for Successful Structure Solution Get molecular formula. Use combustion analysis, mass spectrum and/or 13C NMR spectrum. Calculate double bond equivalents. Determine functional groups from IR, 1H and 13C NMR Compare 1H integrals to number of H’s in the MF. Determine coupling constants (J’s) for all multiplets. Use information from 3. and 4. to construct spin systems (substructures) Assemble substructures in all possible ways, taking account of dbe and functional groups. Make sure the integrals and coupling patterns agree with the proposed structure. * Organic Structure Analysis, Crews, Rodriguez and Jaspars Organic Structure Analysis, Crews, Rodriguez and Jaspars ? Organic Structure Analysis, Crews, Rodriguez and Jaspars USING 1H NMR DATA UNKNOWN B A compound shows an M+. in the EIMS at 154 m/z Further fragments are at 121, 93, 71, 55 and 39 m/z The IR shows bands at 3400 cm-1 (broad) 1450 cm-1 Use the 1H and 13C data to determine the structure of the compound Organic Structure Analysis, Crews, Rodriguez and Jaspars d s d t s t q q t q 13C NMR DATA UNKNOWN B A B C D E F GHI J Organic Structure Analysis, Crews, Rodriguez and Jaspars MOLECULAR FORMULA DETERMINATION UNKNOWN B (C)2 + (CH)2 + (CH2)3 + (CH3)3 = C10H17 s d t q B E A C D F I G H J = 137 Da The M+. appears at 154 m/z, so there is a mass difference of 17 Da (= OH) Therefore molecular formula = C10H18O (2 dbe) Organic Structure Analysis, Crews, Rodriguez and Jaspars 1H NMR DATA UNKNOWN B Integrals: H 3H 2H 3H 3H 5H ONLY 17 H! Organic Structure Analysis, Crews, Rodriguez and Jaspars SUBSTRUCTURES UNKNOWN B dC 125 d, 132 s dH 5.05 t Me groups at dH 1.5 dC 112 t, 146 d dH 5.00 dd, 5.15 dd, 5.85 dd dC 73 s dH 1.05 s MF = C10H18O ! Organic Structure Analysis, Crews, Rodriguez and Jaspars WORKING STRUCTURES UNKNOWN B A – Ha should be ddt B – Ha should be ddt C – Ha should