Potassium Carbonate → 3,3''-Dimethyl-1'-(2-pyrdin-2-yl-ethyl)-1',2',3',4',5',6'-hexahydro-cis-[2,2';6',2'']terpyridine

HRID 1987378Notes

Reaction equation

HRID 1987378 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]=[CH:23][C:22]=1[CH2:27][CH2:28]OS(C)(=O)=O.C([O-])([O-])=O.[K+].[K+]>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:22]2[CH:23]=[CH:24][CH:25]=[CH:26][N:21]=2)=[N:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 226370342-(Pyridin-2-yl)ethyl methanesulfonateHCID 575911373,3''-Dimethyl-1',2',3',4',5', 6'-hexahydro-cis-[2,2';6',2'']terpyridine

Product 1

HCID 575911273,3''-Dimethyl-1'-(2-pyrdin-2-yl-ethyl)-1',2',3',4',5',6'-hexahydro-cis-[2,2';6',2'']terpyridineYield 43.4%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
85 °C

Procedure

Using General Procedure A: A suspension of 3,3″-dimethyl-1′,2′,3′,4′,5′,6′-hexahydro-cis-[2,2′;6′,2″]terpyridine (252 mg, 0.94 mmol), methanesulfonic acid 2-pyridin-2-yl-ethyl ester (approx. 4.9 mmol) and K2CO3 (1.30 g, 9.42 mmol) in DMF (5 mL) was heated at 85° C. for 2.5 d. Purification of the crude material by column chromatography on silica gel (CH2Cl2—CH3OH—NH4OH, 96:4:0 then 94:4:2) followed by radial chromatography on silica gel (1 mm plate, CH2Cl2—CH3OH—NH4OH, 25:1:1) provided 152 mg (43%) of COMPOUND 97 as a pale yellow oil. 1H NMR (CDCl3) δ 1.60-1.72 (m, 3H), 1.96-2.23 (m, 5H), 2.51 (s, 6H), 2.61-2.66 (m, 2H), 4.15 (d, 2H, J=12 Hz), 6.33-6.38 (m, 1H), 6.85 (dd, 1H, J=7.2, 5.1 Hz), 7.07 (dd, 2H, J=7.5, 4.8 Hz), 7.27 (dt, 1H, J=7.5, 1.5 Hz), 7.40 (d, 2H, J=7.5 Hz), 8.19 (d, 1H, J=4.8 hz), 8.42-8.47 (m, 2H); 13C NMR (CDCl3) δ 19.18, 25.52, 30.76, 34.77, 49.87, 63.61, 120.80, 122.22, 122.76, 131.72, 136.15, 138.83, 147.10, 149.18, 160.47, 161.42; ES-MS m/z 373 (M+H). Anal. Calcd. for C24H28N4.1.6 H2O: C, 71.83; H, 7.84; N, 13.96. Found: C, 71.84; H, 7.53; N, 13.65.

Workup

  1. customPurification of the crude material by column chromatography on silica gel (CH2Cl2—CH3OH—NH4OH, 96:4:0

Sources & evidence

ORD record
ord-df9679eafa354316ae550390f636f757
Source dataset
uspto-grants-2009_06
Patent number
US07550484B2

Reaction notes

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