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546_project1 - Application of NMR Techniques to the...

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Application of NMR Techniques to the Structural Determination of Caryophyllene Oxide (Unknown #92) CH 2 O Me H H Me Me CH 2 O Me H H Me Me (Photo courtesy of Dr. Kazuo Yamasaki, Hiroshima University) Christopher J. Morten & Brian A. Sparling 5.46 Spring 2007
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C O CH 3 H H H 3 C H 3 C H E H Z H R H S H S H R H H S H R H S H R H S H R 1 2 3 4 13 6 7 8 9 14 11 12 5 10 Figure 1. Structure of (-)-caryophyllene oxide, or (1 R ,4 R ,6 R ,10 S )-4,12,12-trimethyl-9- methylene-5-oxatricyclo[8.2.0.0]4,6)]dodecane. Carbon Shift (ppm) 13 C Integration C1 C2 C3 C4 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 50.80 27.40 39.30 60.00 63.90 30.40 29.90 152.00 48.90 39.90 34.20 17.20 113.00 30.10 21.80 m s s w s s m w s s w s s s s Table 1 . Carbon signals of caryophyllene oxide.
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Proton Shift (ppm) & Int. Expected Mult. Observed Mult. J Values (Hz) Environment** d 3 d 2 H1 1.76 (1H) 10.1, 4.2 CH H2 pro-R 1.42 (1H) d 4 m 13.6, 4.2, 3.6 1.2 CH 2 H2 pro-S 1.65 (1H) d 4 m * CH 2 H3 pro-R 2.09 (1H) d 4 m 3.6* CH 2 H3 pro-S 0.96 (1H) d 3 ψ -d 3 13.2, 5.0 CH 2 H6 2.88 (1H) d 2 d 2 10.6, 4.2 CH H7 pro-R 1.32 (1H) d 4 ψ -d 4 10.6, 4.4, 3.7, 2.1 CH 2 H7 pro-S 2.25 (1H) d 4 ψ -d 4 4.4, 4.2, 3.7, 0.6 CH 2 H8 pro-R 2.34 (1H) d 3 ψ -d 3 4.4, 3.7, 4.5 CH 2 H8 pro-S 2.11 (1H) d 3 m 4.4* CH 2 H10 2.62 (1H) d 2 d 2 9.9, 8.5 CH H11 pro-R 1.68 (1H) d 2 d 2 * CH 2 H11 pro-S 1.61 (1H) d 2 d 2 * CH 2 H13 1.20 (3H) s s - CH 3 H14 pro-E 4.86 (1H) d d 1.2 CH 2 H14 pro-Z 4.97 (1H) d d 1.2 CH 2 H15 1.00 (3H) s s - CH 3 H16 0.98 (3H) s s - CH 3 Table 2. Proton signals and coupling of caryophyllene oxide. * Indicates that a full set of coupling constants could not be determined due to insufficient resolution on the 1D 1 H spectrum. ** CH = methine; CH 2 = diastereotopic methylenes (+ exo -methylene)
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Carbon Shift (ppm) Bonded Proton(s) Environment C-H Coupling* a 152.0 - C {A, B}, D, {E, G}, {F, N}, I, {J, L} b 113.0 A, B CH 2 D, {E, G} c 63.9 C CH {E, G}, {F, N}, {H, R}, O d 60.0 - C C, {F, N}, {H, R}, {K, M}, O e 50.8 I CH {B}, D, {H, R}, {J, L}, {K, M} f 48.9 D CH {A, B}, {E, G}, I, {J, L}, {K, M}, P, Q g 39.9 J, L CH 2 {A, B}, D, P, Q h 39.3 H, R CH 2 C, I, {K, M}, O i 34.2 - C D (weak), I, {J, L}, P, Q j 30.4 F, N CH 2 C, {E, G} k 30.1 Q CH 3 I, {J, L}, Q l 29.9 E, G CH 2 {A, B}, D, {F, N} m 27.4 K, M CH 2 D, {H, R}, I, J n 21.8 P CH 3 I, {J, L}, R o 17.2 O CH 3 {H, R} Table 3. HSQC and HMBC coupling data summary table for caryophyllene oxide. * Braces indicate that either coupling to both diastereotopic protons in a methylene pair is present or coupling to a single proton in one such pair is visible on HMBC.
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Methods of Analysis and Assignment: 1D NMR Methods 1. 1 H NMR (Appendix 1) a. 24 protons observed b. potential entry point: 2 doublets (H A , 4.97 ppm; H B , 4.86) with small coupling in alkene region - exo-methylene ? c.
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