Terephthalaldehyde → HCID 53792269, compound

HRID 351154Notes

Reaction equation

HRID 351154 reaction equation
[CH:1]1[C:6]([CH:7]=[O:8])=[CH:5][CH:4]=[C:3]([CH:9]=O)[CH:2]=1.[H][H].[NH2:13][CH2:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][N:16]=1>[Pd].CO.NCC1C=CC=CN=1>[N:16]1[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=1[CH2:14][NH:13][CH2:9][C:3]1[CH:2]=[CH:1][C:6]([CH2:7][OH:8])=[CH:5][CH:4]=1

Participants

7

Reactant 3

HCID 12173TerephthalaldehydeHCID 195092-PyridinemethanamineHCID 178418361HCID 178418361, compound2×

Product 1

HCID 53792269HCID 53792269, compoundYield 108.6%

Reagents, catalysts & solvents 3

HCID 195092-PyridinemethanamineCatalystHCID 23938PalladiumCatalyst2×HCID 887MethanolSolvent2×

Procedure

Terephthaldicarboxaldehyde (40.75 g, 0.304 mol), methanol (250 mL), palladium on activated carbon, (10%, 4.24 g) and 2-(aminomethyl)pyridine (3.1 mL, 0.003 mol, 0.01 mol equiv) were combined in a hydrogenation vessel and the reaction mixture was shaken on a Parr hydrogenator for 3.5 hours at 38 psi of hydrogen. The mixture was filtered through celite and the cake was washed with methanol. The solution was dried over Na2SO4, filtered, then reduced in volume to ˜200 mL under reduced pressure. To this stirred solution is then added a solution of 2-(aminomethyl)pyridine (28 mL, 0.272 mol, 0.9 mol. Equiv.) in methanol (50 mL) over 15 minutes. This was allowed to stir overnight at room temperature. The solution was transferred to a hydrogenation flask and palladium on activated carbon (10%, 2.60 g, 0.06) was added and the flask was shaken on a Parr hydrogenator for 4 hours at 39 psi of hydrogen. The mixture was filtered through celite and the cake was washed with methanol. The filtrates were then evaporated and the crude material was filtered through silica gel (180 g, 9:1 CH2Cl2:CH3OH) to provide the title compound (67.45 g, 93%) as a yellow oil. 1H NMR (CDCl3) δ 2.28 (br, 2H), 3.82 (s, 2H), 3.90 (s, 2H), 4.65 (s, 2H), 7.16 (br t, 1 H, J=6.0 Hz), 7.26–7.35 (m, 5H), 7.64 (td, 1H, J=7.7, 1.7 Hz), 8.54 (br d, 1H, J=4.5 Hz).

Workup

  1. filtrationThe mixture was filtered through celite
  2. washthe cake was washed with methanol
  3. dry with materialThe solution was dried over Na2SO4
  4. filtrationfiltered
  5. customThe solution was transferred to a hydrogenation flask
  6. filtrationThe mixture was filtered through celite
  7. washthe cake was washed with methanol
  8. customThe filtrates were then evaporated
  9. filtrationthe crude material was filtered through silica gel (180 g, 9:1 CH2Cl2:CH3OH)

Sources & evidence

ORD record
ord-2a31b7664de247c592abd61ec5d1668d
Source dataset
uspto-grants-2007_02
Patent number
US07183273B2

Reaction notes

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