Phosphoric Acid → HCID 25118843, compound

HRID 1894933Notes

Reaction equation

HRID 1894933 reaction equation
[NH2:1][C:2]1[N:7]=[C:6]([NH:8][CH2:9][C:10]2[C:15]([CH3:16])=[C:14]([CH2:17][NH:18][C:19]3[CH:24]=[CH:23][CH:22]=[C:21]([NH2:25])[N:20]=3)[C:13]([CH3:26])=[C:12]([CH2:27][NH:28][C:29]3[CH:34]=[CH:33][CH:32]=[C:31]([NH2:35])[N:30]=3)[C:11]=2[CH3:36])[CH:5]=[CH:4][CH:3]=1.CO[CH:39](OC)[CH2:40][C:41](=O)[CH3:42].OP(O)(O)=O>O>[CH3:39][C:40]1[N:35]=[C:31]2[C:32]([CH:33]=[CH:34][C:29]([NH:28][CH2:27][C:12]3[C:11]([CH3:36])=[C:10]([CH2:9][NH:8][C:6]4[CH:5]=[CH:4][C:3]5[C:2](=[N:1][C:4]([CH3:5])=[CH:3][CH:2]=5)[N:7]=4)[C:15]([CH3:16])=[C:14]([CH2:17][NH:18][C:19]4[CH:24]=[CH:23][C:22]5[C:21](=[N:25][C:11]([CH3:12])=[CH:10][CH:9]=5)[N:20]=4)[C:13]=3[CH3:26])=[N:30]2)=[CH:42][CH:41]=1

Participants

5

Reactant 3

HCID 1004Phosphoric AcidHCID 2285484,4-Dimethoxy-2-butanoneHCID 86641414HCID 86641414, compound

Product 1

HCID 25118843HCID 25118843, compoundYield 30%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

1,3,5-Tris[(6-amino-pyridin-2-yl)aminomethyl]-2,4,6-trimethylbenzene (2a) (2.0 g, 4.1 mmol), 4,4-dimethoxy-2-butanone (12.3 mmol), and H3PO4 (50 mL) were held at 90° for 4 h and then stirred at room temperature for 2 h. The reaction mixture was poured into water (200 mL), neutralized, and extracted several times with chloroform. The collected organic layers were dried over MgSO4 and the solvent was removed under reduced pressure. The crude product was purified several times by column chromatography (silica gel, CHCl3/CH3OH, 7:1 to 2:1 v/v). Yield 30%. M.p. 207-208° C. 1H-NMR (400 MHz, CDCl3): δ=2.34 (s, 9H), 2.61 (s, 9H), 4.71 (d, 6H, 3H, J=3.0 Hz), 5.12 (t, 3H, J=3.0 Hz), 6.60 (d, 3H, J=8.8 Hz), 6.98 (d, 3H, J=8.0 Hz), 7.65 (d, 3H, J=8.8 Hz), 7.74 (d, 3H, J=8.0 Hz). 13C NMR (100 MHz, CDCl3): δ=15.9, 25.0, 41.1, 112.4, 114.9, 115.9, 133.3, 136.0, 136.5, 137.2, 156.5, 158.7, 161.3. HR-MS calcd for C39H38N9: 632.3250; found: 632.3256. Rf=0.80 (CHCl3/CH3OH 2:1 v/v).

Workup

  1. extractionextracted several times with chloroform
  2. dry with materialThe collected organic layers were dried over MgSO4
  3. customthe solvent was removed under reduced pressure
  4. customThe crude product was purified several times by column chromatography (silica gel, CHCl3/CH3OH, 7:1 to 2:1 v/v)

Sources & evidence

ORD record
ord-936dc05ad3d44c04ada0d6a2cf5c58e8
Source dataset
uspto-grants-2013_08
Patent number
US08513420B2

Reaction notes

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