Oxalyl chloride → HCID 72971596, compound

HRID 1987371Notes

Reaction equation

HRID 1987371 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)[N:9]2[CH2:21][C:22]2[CH:30]=[CH:29][C:25]([C:26]([OH:28])=O)=[CH:24][CH:23]=2)=[N:4][CH:5]=[CH:6][CH:7]=1.C(Cl)(=O)C(Cl)=O.CCN(C(C)C)C(C)C.[NH2:46][OH:47].O>C(Cl)Cl.CN(C=O)C.[NH4+].[Cl-]>[CH3:20][C:19]1[C:14]([CH:10]2[CH2:11][CH2:12][CH2:13][CH:8]([C:3]3[C:2]([CH3:1])=[CH:7][CH:6]=[CH:5][N:4]=3)[N:9]2[CH2:21][C:22]2[CH:30]=[CH:29][C:25]([C:26]([NH:46][OH:47])=[O:28])=[CH:24][CH:23]=2)=[N:15][CH:16]=[CH:17][CH:18]=1

Participants

9

Reactant 4

HCID 65578Oxalyl chlorideHCID 81531DiisopropylethylamineHCID 22235265HCID 22235265, compoundHCID 67421363HCID 67421363, compound

Product 1

HCID 72971596HCID 72971596, compoundYield 16.3%

Reagents, catalysts & solvents 4

HCID 6228DimethylformamideCatalystHCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolventHCID 25517Ammonium ChlorideSolvent

Procedure

To a cold (0° C.) solution of 4-(3,3″-Dimethyl-3′,4′,5′,6′-tetrahydro-2′H-[2,2′;6′,2″]terpyridin-1′-ylmethyl)-benzoic acid (0.124 g,0.31 mmol) in CH2Cl2 (3 mL) and DMF (5 drops) was added oxalyl chloride (0.11 mL, 1.26 mmol). After 15 minutes, the mixture was concentrated and provided a beige solid. The solid was dissolved in DMF (3 mL) and treated with DIPEA (0.50 mL, 2.87 mmol) followed by NH2OH.H2O (72 mg, 1.04 mmol). The resultant mixture was stirred at room temperature overnight. The mixture was diluted with saturated aqueous NH4Cl (5 mL) and extracted with CH2Cl2 (5×10 mL). The combined organic extracts were dried (Na2SO4) and concentrated. Purification of the crude material by radial chromatography on silica gel (1 mm plate, 5:1:1 CH2ClN—CH3OH—NH4OH) provided 21 mg (16%) of COMPOUND 72 as a white solid. 1H NMR (CDCl3) δ 1.48-1.67 (m, 3H), 1.88-2.13 (m, 3H), 2.31 (s, 6H), 3.46 (s, 2H), 3.94 (d, 2H, J=10.5 Hz), 6.54 (d, 2H, J=6.9 Hz), 6.93 (dd, 2H, J=7.5, 4.5 Hz), 7.26-7.39 (m, 4H), 8.28 (d, 2H, J=3.3 Hz); ES-MS m/z 417 (M+H).

Workup

  1. concentrationthe mixture was concentrated
  2. customprovided a beige solid
  3. extractionextracted with CH2Cl2 (5×10 mL)
  4. dry with materialThe combined organic extracts were dried (Na2SO4)
  5. concentrationconcentrated
  6. customPurification of the crude material by radial chromatography on silica gel (1 mm plate, 5:1:1 CH2ClN—CH3OH—NH4OH)

Sources & evidence

ORD record
ord-18f91533bbfe4f6fb7ffb0767ce98313
Source dataset
uspto-grants-2009_06
Patent number
US07550484B2

Reaction notes

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