Diisopropylethylamine → 3,3''-Dimethyl-1'-(2-pyridin-3-yl-ethyl)-1',2',3',4',5',6'-hexahydro-cis-[2,2':6',2'']terpyridine

HRID 1987377Notes

Reaction equation

HRID 1987377 reaction equation
[CH3:1][C:2]1[C:3]([C@H:8]2[CH2:13][CH2:12][CH2:11][C@@H: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.[N:21]1[CH:26]=[CH:25][CH:24]=[C:23]([CH2:27][CH2:28]OS(C)(=O)=O)[CH:22]=1.CCN(C(C)C)C(C)C>CN(C=O)C>[CH3:1][C:2]1[C:3]([C@H:8]2[CH2:13][CH2:12][CH2:11][C@@H:10]([C:14]3[C:19]([CH3:20])=[CH:18][CH:17]=[CH:16][N:15]=3)[N:9]2[CH2:28][CH2:27][C:23]2[CH:22]=[N:21][CH:26]=[CH:25][CH:24]=2)=[N:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 81531DiisopropylethylamineHCID 232850562-(Pyridin-3-yl)ethyl methanesulfonateHCID 575911373,3''-Dimethyl-1',2',3',4',5', 6'-hexahydro-cis-[2,2';6',2'']terpyridine

Product 1

HCID 575911473,3''-Dimethyl-1'-(2-pyridin-3-yl-ethyl)-1',2',3',4',5',6'-hexahydro-cis-[2,2':6',2'']terpyridineYield 63.2%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Using General Procedure A: A solution of 3,3″-Dimethyl-1′,2′,3′,4′,5′,6′-hexahydro-cis-[2,2′;6′,2″]terpyridine (0.219 g, 0.82 mmol), methanesulfonic acid 2-pyridin-3-yl-ethyl ester (approx. 3 mmol), KI (15 mg), and DIPEA (0.25 mL, 1.44 mmol) in DMF (3 mL was heated at 80° C. for 17 hours. Purification of the crude material by column chromatography on silica gel (CH2Cl2—CH3OH—NH4OH, 94:4:2) followed by radial chromatography on silica gel (1 mm plate, CH2Cl2—CH3OH—NH4OH, 50:1:1) provided 193 mg (63%) of COMPOUND 92 as a colorless oil. 1H NMR (CDCl3) δ 1.61-1.70 (m, 4H), 2.00-2.22 (m, 4H), 2.51 (s, 6H), 2.51-2.55 (m, 2H), 4.14-4.18 (m, 2H), 6.55-6.60 (m, 1H), 6.85 (dd, 1H, J=7.5, 4.8 Hz), 7.09-7.12 (m, 2H), 7.42 (d, 2H, J=6.9 Hz), 7.54-7.60 (m, 1H), 8.18 (dd, 1H, J=4.8, 1.5 Hz), 8.42-8.46 (m, 2H); 13C NMR (CDCl3) δ 17.59, 22.43, 24.32, 26.23, 28.85, 30.67, 47.26, 51.85, 63.52, 70.06, 121.05, 121.87, 131.24, 134.51, 137.16, 138.57, 145.34, 145.73, 148.78, 158.55; ES-MS m/z 373 (M+H). Anal. Calcd. for C24H28N4.0.3 H2O: C, 76.28; H, 7.63; N, 14.83. Found: C, 76.14; H, 7.78; N, 14.82.

Workup

  1. customPurification of the crude material by column chromatography on silica gel (CH2Cl2—CH3OH—NH4OH, 94:4:2)

Sources & evidence

ORD record
ord-2d0707b6f9dc4ed7bc95f54057a71018
Source dataset
uspto-grants-2009_06
Patent number
US07550484B2

Reaction notes

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