Whitby group

¹H NMR (400 MHz, CDCl₃): δ (ppm) = 7.547 – 7.496 (4H, m, H^{o-Ph major + minor}), 7.368 – 7.336 (6H, m, H^{m- + p-Ph major + minor}), 3.360 (3H, s, H^{1/2 minor}), 3.357 (3H, s, H^{1/2 minor}), 3.352 (3H, s, H^{1/2 major}), 3.344 (3H, s, H^{1/2 major}), 3.280 (1H, d, J = 8.8 Hz, H^{3/4 major}), 3.276 (1H, d, J = 8.8 Hz, H^{3/4 major}), 3.244 (1H, d, J = 8.8 Hz, H^{3/4 major}), 3.218 (1H, d, J = 8.8 Hz, H^{3/4 major}), 3.291 – 3.208 (4H, m, H^{3 + 4 minor}), 1.936 (1H, dddd, J = 12.0, 10.5, 8.3, 3.8 Hz, H^major), 1.790 (1H, m, H^major), 1.696 (1H, ddd, J = 11.3, 8.0, 5.5 Hz, H^major), 1.605 – 1.479 (12H, m, H^{major + minor}), 1.387 – 1.290 (2H, m, H^{major + minor}), 1.049 – 0.867 (5H, m, H^{major + minor}), 0.342 (3H, s, H^{13/13’ minor}), 0.340 (3H, s, H^{13/13’ minor}), 0.260 (3H, s, H^{13/13’ major}), 0.250 (3H, s, H^{13/13’ major}).

¹³C NMR (100.5 MHz, CDCl₃): δ (ppm) = 139.27 (2C^{Si-i-Ph major + minor}), 133.82 (4CH^{Si-p-Ph major + minor}), 128.69 (2CH^{Si-p-Ph major + minor}), 127.60 (4CH^{Si-m-Ph major + minor}), 78.02 (CH₂^{3/4 minor}), 78.02 (2CH₂^{3/4 major + minor}), 77.99 (CH₂^{3/4 major}), 59.20 (CH₃^{1/2 major}), 59.17 (CH₃^{1/2 major}), 58.06 (2CH₃^{1 + 2 minor}), 54.95 (C^{5 major}), 54.24 (C^{5 minor}), 53.49 (CH^{8/9 major}), 52.96 (CH^{8/9 major}), 52.53 (2CH^{8 + 9 minor}), 34.28 (CH₂^{6/7 major}), 33.97 (CH₂^{6/7 major}), 31.57 (2CH₂^{6 + 7 minor}), 29.35 (CH₂^{10/11 major}), 29.11 (2CH₂^{12 major + minor}), 27.27 (CH₂^{10/11 major}), 26.32 (2CH₂^{10 + 11 minor}), –3.12 (CH₃^{13/13’ minor}), –3.20 (CH₃^{13/13’ minor}), –4.56 (CH₃^{13/13’ major}),  –4.71 (CH₃^{13/13’ major}). 

HRMS (EI): Sample submitted for experiment. 

¹H NMR (400 MHz, BENZENE-D6): δ (ppm) = 7.311 – 7.249 (4H, m, H^o-Ph), 7.194 – 7.070 (14H, m, H^Ar), 5.211 (1H, d, J = 1.3 Hz, H^{10 major}), 5.146 (1H, d, J = 1.3 Hz, H^{10 minor}), 5.068 (1H, d, J = 1.3 Hz, H^{10 major}), 5.029 (1H, d, J = 1.3 Hz, H^{10 minor}), 2.952 (1H, td, J = 12.3, 5.8 Hz, H^{5b major}), 2.891 (1H, td, J = 11.8, 6.3 Hz, H^{5b minor}), 2.665 (1H, dd, J = 13.8, 5.8 Hz, H^{3a major}), 2.635 (1H, dd, J = 13.8, 5.8 Hz, H^{3a minor}), 2.550 (1H, dd, J = 12.3, 6.0 Hz, H^{7a major}), 2.329 (1H, ddt, J = 13.8, 11.5, 1.3 Hz, H^{3b major}), 2.316 (1H, t, J = 13.8 Hz, H^{3b minor}), 2.252 (1H, dd, J = 12.2, 5.7 Hz, H^{7a minor}), 2.157 – 1.940 (3H, m, 2H⁴ + H^{6 minor}), 1.885 (1H, t, J = 11.3 Hz, H^{6b major}), 1.753 – 1.622 (2H, m, H^{6 minor} + H), 1.740 (1H, dd, J = 11.3, 5.8 Hz, H^{6a major}), 1.538 – 1.129 (19H, m), 1.412 (1H, t, J = 12.3 Hz, H^{7b major}), 1.324 (1H, t, J = 12.2 Hz, H^{7b minor}), 0.897 (3H, t, J = 7.0 Hz, H^{16 minor}), 0.875 (3H, t, J = 7.0 Hz, H^{16 major}). 

¹³C NMR (100.5 MHz, CDCl₃): δ (ppm) = 158.49 (C^{9 major} ), 158.40 (C^{9 minor} ), 149.66 (C^{i-Ph, major}), 149.63 (C^{i-Ph, minor}), 145.60 (C^{1/2 major}), 145.56 (C^{1/2 minor}), 144.68 (C^{1/2 minor}), 144.63 (C^{1/2 major}), 128.99 (4CH^Ar), 128.68 (2CH^Ar), 128.40 (2CH^Ar), 127.30 (CH^Ar), 127.27 (CH^Ar), 126.73 (CH^Ar), 126.70 (CH^Ar), 126.44  (2CH^Ar), 125.65 (CH^Ar), 125.61 (CH^Ar), 122.93 (CH^Ar), 122.88 (CH^Ar), 114.10 (CH₂^{10 minor}), 113.99 (CH₂^{10 major}), 58.10 (C^{8 major}), 58.05 (C^{8 minor}), 56.97 (CH^{4/5 major}), 56.61 (CH^{4/5 minor}), 55.40 (CH^{4/5 minor}), 55.04  (CH^{4/5 major}), 43.40 (CH₂ ^major), 43.28 (CH₂ ^minor), 42.67 (CH₂ ^major), 41.24 (CH₂ ^minor), 39.54 (CH₂ ^minor),  38.09 (CH₂ ^major), 35.00 (2CH₂ ^{major + minor}), 32.54 (CH₂ ^minor), 32.49 (CH₂ ^major), 30.58 (CH₂ ^minor), 30.53 (CH₂ ^major),  25.74 (CH₂ ^minor), 25.63 (CH₂ ^major), 23.40 (2CH₂ ^{major + minor}), 14.67 (2CH₃^{16 major + minor}).

HRMS (EI): Found: [M]⁺, 344.2505. C₂₆H₃₂ requires: 344.2504. 

LRMS (CI): m/z: 345 ([M + H]^+·, 61%), 260 ([M – Hex + H]^+·, 14%), 130 (100%).

2D NMR 1H-1H COSY

IR (thin film): = 2933 (m), 2858 (m), 1622 (w), 1489 (w), 1459 (m), 900 (m), 775 (m), 741 (s), 699 (s) cm^–1. 

To a solution of Cp₂ZrCl₂ (0.293 g, 1.0 mmol) in dry THF (5 mL) cooled to  –78 °C was added n-BuLi (0.80 mL of a 2.5 M solution in hexanes, 2.0 mmol) dropwise over 3 minutes. After 25 min at the same temperature, a solution of 1-allyl-2-vinyllbenzene (0.144 g, 1.0 mmol) in dry THF (3 mL) was added dropwise. After 30 min at –78 °C the reaction mixture was allowed to warm to room temperature and stirred for 2 h. After cooling the reaction to –78 °C, a solution of 1,1-dibromoheptane (0.271 g, 1.05 mmol) in dry THF (1 mL) was added followed by dropwise addition of LDA (0.61 mL of a 1.8 M solution, 1.1 mmol). After stirring the reaction mixture for 15 min at –78 °C, lithium phenylacetylide was added dropwise, [prepared from phenylacetylene (0.33 mL, 3.0 mmol) in dry THF (3 mL) and n-BuLi (1.2 mL of a 2.5 M solution in hexanes, 3.0 mmol) at –5 ^oC over 15 min]. The stirring was continued for 1.5 h during which the reaction mixture was allowed to warm to –30 °C before addition of MeOH (5 mL) and a saturated aqueous solution of NaHCO₃ (6 mL). The whole mixture was allowed to warm to room temperature and left stirring overnight. The mixture then was poured onto H₂O (100 mL), the products extracted with Et₂O (3 × 50 mL). The combined organic phases were washed with H₂O (3 × 100 mL) and brine (100 mL), dried over MgSO₄, filtered and concentrated in vacuo to give the crude product as a yellow oil. Purification of the crude material by column chromatography on SiO₂ (230 – 400 mesh) with hexanes as the eluent gave the title compound as an inseparable mixture of isomers in NMR ratio of 1.4 : 1 and combined yield of 0.165g (48%, pale yellow oil). 

¹H NMR (400 MHz, BENZENE-D6); ¹³C NMR (100.5 MHz, CDCl₃); HRMS (EI); LRMS (CI); IR (thin film).

To a solution of Cp₂ZrCl₂ (0.293 g, 1.0 mmol) in dry THF (5 mL) cooled to –78 °C was added n-BuLi (0.80 mL of a 2.5 M solution in hexanes, 2.0 mmol) dropwise over 3 minutes. After 25 min at the same temperature, a solution of bis(methoxymethyl)hepta-1,6-diene (0.184 g, 1.0 mmol) in dry THF (3 mL) was added dropwise. After 30 min at –78 °C the reaction mixture was allowed to warm to room temperature and stirred for 2 h. After cooling the reaction mixture to –78 °C, a solution of (dichloromethyl)dimethyl(phenyl)silane (0.285 g, 1.3 mmol) in dry THF (1 mL) was added followed by dropwise addition of LDA (0.85 mL of a 1.8 M solution, 1.5 mmol). The reaction mixture was stirred for 0.5 h during which was allowed to warm to –60 °C before dropwise addition of lithium phenyl acetylide pre-mixed with HMPA. [Lithium phenyl acetylide was freshly prepared from phenylacetylene (0.33 mL, 3.0 mmol) in dry THF (3 mL) and n-BuLi (1.2 mL of a 2.5 M solution in hexanes, 3.0 mmol) at 0 ^oC over 10 min, then HMPA (0.52 mL, 3.0 mmol) was added and the stirring was continued at the same temperature for further 15 min]. The stirring was continued for 3 h during which time the reaction mixture was allowed to warm to –15 °C before addition of MeOH (5 mL) and a saturated aqueous solution of NaHCO₃ (6 mL). The whole mixture was allowed to warm to room temperature and left stirring overnight. The mixture then was poured onto H₂O (100 mL), the products extracted with Et₂O (3 × 75 mL). The combined organic phases were washed with H₂O (3 × 100 mL) and brine (100 mL), dried over MgSO₄, filtered and concentrated in vacuo to give the crude product as a red oil.

Purification of the crude material by column chromatography on Al₂O₃ (basic, grade III) with 5% of Et₂O in hexanes as the eluent gave the title compounds as a yellow oil in yield of0.072 g (22%). 

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Comments about the spectra, peak assignments, etc.

• 2D NMR 1H-13C Direct correlation
• 2D NMR 1H-13C Long-range correlation
• 2D NMR 1H-1H COSY
• 2D NMR 1H-1H Long-range correlation
• 2D NMR 1H-1H NOESY/ROESY
• APCl+ Mass Spectrum
• APCl- Mass Spectrum
• APPl+ Mass Spectrum
• APPl- Mass Spectrum
• Chemical Ionization +ve
• Chemical Ionization -ve
• CNMR
• Electron Impact
• ESI+ Mass Spectrum
• ESI- Mass Spectrum
• FNMR
• HNMR
• Infrared
• MALDI+ Mass Spectrum
• MALDI- Mass Spectrum
• Near Infrared
• PNMR
• Raman
• UV-Vis

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