Diisopropylethylamine → 3,3''-Dimethyl-1'-[2-(2-methyl-[1,3]dioxolan-2-yl)-benzyl]-1',2',3',4',5',6'-hexahydro-[2,2'; 6',2'']terpyridine

HRID 1784204Notes

Reaction equation

HRID 1784204 reaction equation
[CH3:1][C:2]1[C:3]([CH:8]2[CH2:13][CH2:12][CH2:11][CH:10]([C:14]3[C:19]([CH3:20])=[CH:18][CH:17]=[CH:16][N:15]=3)[NH:9]2)=[N:4][CH:5]=[CH:6][CH:7]=1.Br[CH2:22][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][C:24]=1[C:29]1([CH3:34])[O:33][CH2:32][CH2:31][O:30]1.CCN(C(C)C)C(C)C>CN(C=O)C>[CH3:1][C:2]1[C:3]([CH:8]2[CH2:13][CH2:12][CH2:11][CH:10]([C:14]3[C:19]([CH3:20])=[CH:18][CH:17]=[CH:16][N:15]=3)[N:9]2[CH2:22][C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][C:24]=2[C:29]2([CH3:34])[O:30][CH2:31][CH2:32][O:33]2)=[N:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 81531DiisopropylethylamineHCID 109450651,3-Dioxolane, 2-[2-(bromomethyl)phenyl]-2-methyl-HCID 674211653,3''-Dimethyl-1',2',3',4',5',6'-hexahydro-[2,2'; 6',2'']terpyridine

Product 1

HCID 674235263,3''-Dimethyl-1'-[2-(2-methyl-[1,3]dioxolan-2-yl)-benzyl]-1',2',3',4',5',6'-hexahydro-[2,2'; 6',2'']terpyridineYield 90%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Using General Procedure A: A solution of 3,3″-dimethyl-1′,2′,3′,4′,5′,6′-hexahydro-[2,2′;6′,2″]terpyridine (0.547 g, 2.04 mmol), 2-(2-bromomethyl-phenyl)-2-methyl-[1,3]dioxolane (1.03 g, 3.99 mmol), KI (73 mg, 0.42 mmol), and DIPEA (0.70 mL, 4.02 mmol) in DMF (10 mL) was heated at 60° C. for 24 hours. Purification of the crude material by column chromatography on silica gel (40:1:1 CH2Cl2—CH3OH—NH4OH) provided 0.81 g (90%) of 3,3″-dimethyl-1′-[2-(2-methyl-[1,3]dioxolan-2-yl)-benzyl]-1′,2′,3′,4′,5′,6′-hexahydro-[2,2′;6′,2″]terpyridine as a white solid. 1H NMR (CDCl3) δ 1.46 (s, 3H), 1.60-1.83 (m, 3H), 2.15-2.20 (m, 1H), 2.47-2.57 (m, 8H), 3.26-3.31 (m, 2H), 3.82-3.87 (m, 2H), 4.01 (s, 2H), 4.44 (d, 2H, J=10.8 Hz), 6.72-6.82 (m, 4H), 7.05 (dd, 1H, J=7.2, 1.5 Hz), 7.21 (d, 2H, J=7.2 Hz), 7.46 (d, 1H, J=6.9 Hz), 8.19 (d, 2H, J=4.8 Hz); ES-MS m/z 444 (M+H).

Workup

  1. customPurification of the crude material by column chromatography on silica gel (40:1:1 CH2Cl2—CH3OH—NH4OH)

Sources & evidence

ORD record
ord-5a8d13c7819d4a7bbf64af0122245ff7
Source dataset
uspto-grants-2009_03
Patent number
US07501518B2

Reaction notes

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