Sodium Bicarbonate → 3,3''-Dimethyl-1',2',3',4',5', 6'-hexahydro-cis-[2,2';6',2'']terpyridine

HRID 1987316Notes

Reaction equation

HRID 1987316 reaction equation
C([N:4]1[C@H:9]([C:10]2[C:15]([CH3:16])=[CH:14][CH:13]=[CH:12][N:11]=2)[CH2:8][CH2:7][CH2:6][C@@H:5]1[C:17]1[C:22]([CH3:23])=[CH:21][CH:20]=[CH:19][N:18]=1)C=C.C([O-])(O)=O.[Na+]>C(Cl)Cl.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:16][C:15]1[C:10]([C@H:9]2[CH2:8][CH2:7][CH2:6][C@@H:5]([C:17]3[C:22]([CH3:23])=[CH:21][CH:20]=[CH:19][N:18]=3)[NH:4]2)=[N:11][CH:12]=[CH:13][CH:14]=1

Participants

5

Reactant 2

HCID 516892Sodium BicarbonateHCID 674222901'-Allyl-3,3''-dimethyl-1',2',3',4',5',6'-hexahydro-cis-[2,2'; 6',2'']terpyridine

Product 1

HCID 575911373,3''-Dimethyl-1',2',3',4',5', 6'-hexahydro-cis-[2,2';6',2'']terpyridineYield 85%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 6344DichloromethaneSolvent

Procedure

To a solution of 1′-allyl-3,3″-dimethyl-1′,2′,3′,4′,5′,6′-hexahydro-cis-[2,2′;6′,2″]terpyridine (142 mg, 0.462 mmol) in CH2Cl2 was added 1,3-dimethylbarbaturic acid (361 mg, 2.31 mmol) and Pd(PPh3)4 (53 mg, 0.046 mmol) and the reaction mixture was stirred for 20 h. Saturated solution of NaHCO3 (10 mL) was added and the mixture was extracted with CH2Cl2 (3 times 20 mL). The organic extracts were dried (MgSO4), filtered and concentrated. The crude material was purified by flash column chromatography on silica gel (9:1:0.2 CH2Cl2-MeOH—NH4OH) to provide 105 mg (85%) of the 3,3″-dimethyl-1′,2′,3′,4′,5′, 6′-hexahydro-cis-[2,2′;6′,2″]terpyridine as a clear oil. 1H NMR(CDCl3) δ 1.51-1.63 (m, 2H), 1.76-1.85 (m, 3H), 2.11-2.15 (m, 1H), 2.37 (s, 6H), 3.10-3.30 (m, 1H), 4.22 (d, 2H, J=10.8 Hz), 7.02 (dd, 2H, J=7.5, 4.5 Hz), 7.38 (d, 2H, J=7.5 Hz), 8.45 (d, 2H, J=4.5 Hz); 13C NMR (CDCl3) δ 18.68, 25.84, 32.28, 57.60, 121.96, 129.73, 138.04, 147.31, 160.94; ES-MS m/z 269.1 (M+H). Anal. Calcd. for C17H21N3.0.1CH2Cl2: C, 74.45; H, 7.75; N, 15.23. Found: C, 74.70; H, 7.80; N, 15.18.

Workup

  1. extractionthe mixture was extracted with CH2Cl2 (3 times 20 mL)
  2. dry with materialThe organic extracts were dried (MgSO4)
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe crude material was purified by flash column chromatography on silica gel (9:1:0.2 CH2Cl2-MeOH—NH4OH)

Sources & evidence

ORD record
ord-bb81ad8e1fbd414a8c17891a7401612a
Source dataset
uspto-grants-2009_06
Patent number
US07550484B2

Reaction notes

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