C[O:2][C:3]1[CH:4]=[C:5]([C:9]23[CH2:18][C:17]4[CH:19]=[CH:20][CH:21]=[CH:22][C:16]=4[CH2:15][C:14]2([CH3:23])[CH2:13][N:12]([CH3:24])[CH2:11][CH2:10]3)[CH:6]=[CH:7][CH:8]=1.Br.[OH-].[Na+].C([O-])(O)=O.[Na+]>C(O)(=O)C>[OH:2][C:3]1[CH:4]=[C:5]([C:9]23[CH2:18][C:17]4[CH:19]=[CH:20][CH:21]=[CH:22][C:16]=4[CH2:15][C:14]2([CH3:23])[CH2:13][N:12]([CH3:24])[CH2:11][CH2:10]3)[CH:6]=[CH:7][CH:8]=1To a 10 mL single-necked flask was added 100 mg (0.31 mmol) of (±)-1,2,3,4,4a,5,10,10a-octahydro-4a-(3-methoxyphenyl)-2, 10a-dimethylbenzo[g]isoquinoline (10) and 0.8 mL of glacial acetic acid and 0.8 mL of 48% HBr. This mixture was heated under reflux for 18 h and then cooled to room temperature. The pH was then adjusted to 10 with cooling starting with 50% NaOH and finishing with saturated NaHCO3. This was extracted 2 times with CHCl3 and 2 times with 3:1 n-butanol:toluene. Both extracts were dried over K2CO3, and then the solvent was removed. The material from both extracts was examined by 1H NMR and was shown to contain the desired product. The material from the CHCl3 layer was chromatographed on silica gel eluting with 25 % CMA-80 in CHCl3. This gave 27 mg of the desired product (7) (28% yield). The residue was dissolved in MeOH, and to this was added 3 equivalents of 1N HCl in dry ethyl ether. The solvents were removed, and the residue crystallized from ether/MeOH. The butanol extracts contained 45 mg of the desired material giving an overall yield of 74.6 %. MP ° C 270-275 (dec). Anal. Calcd for C21H26NOCl.0.25H2O: C, 65.54; H, 7.20; N, 3.64. Found: C, 65.86; H, 7.15; N, 3.42. 1H NMR (DMSO) δ1.014 (s, 3H); 1.587 (d, 1H, J=14.3 Hz); 2.072 (s, 3H); 2.358 (d, 1H, J=17.4. Hz); 2.498 (d, 1H, J=17.4 Hz); 2.734 (s, 3H); 2.924-2.792 (m, 3H); 3.113 (d, 1H, J=13.1 Hz); 3.602 (d, 1H, J=18.78 Hz); 6.562 (d, 1H, J=8.0 Hz); 6.611(m, 2H); 6.993 (t, 1H, 3=7.5 Hz); 7.081 (d, 1H, J=7.5 Hz); 7.148 (t, 1H, J=7.8 Hz); 7.269-7.193 (m, 2H); 9.30 (s, 1H); 9.898 (bs, 1H). 13C NMR (DMSO) δ156.7, 146.4, 135.5, 133.3, 128.5, 128.4, 128.2, 126.2, 125.7, 117.6, 114.3, 113.5, 59.2, 49.4, 38.6, 35.4, 35.2, 31.0, 28.7, 22.8.
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