Veratroyl chloride → HCID 135470462, compound

HRID 1531675Notes

Reaction equation

HRID 1531675 reaction equation
C([O:4][S:5]([C:8]1[C:17]([N:18]=[N:19][C:20]2[CH:25]=[CH:24][C:23]([O:26][CH3:27])=[CH:22][CH:21]=2)=[C:16]([OH:28])[C:15]2[C:10](=[CH:11][C:12]([NH2:29])=[CH:13][CH:14]=2)[CH:9]=1)(=[O:7])=[O:6])(C)C.C(N(C(C)C)CC)(C)C.[CH3:39][O:40][C:41]1[CH:42]=[C:43]([CH:47]=[CH:48][C:49]=1[O:50][CH3:51])[C:44](Cl)=[O:45]>ClCCl>[CH3:39][O:40][C:41]1[CH:42]=[C:43]([CH:47]=[CH:48][C:49]=1[O:50][CH3:51])[C:44]([NH:29][C:12]1[CH:11]=[C:10]2[C:15]([C:16]([OH:28])=[C:17]([N:18]=[N:19][C:20]3[CH:21]=[CH:22][C:23]([O:26][CH3:27])=[CH:24][CH:25]=3)[C:8]([S:5]([OH:4])(=[O:7])=[O:6])=[CH:9]2)=[CH:14][CH:13]=1)=[O:45]

Participants

5

Reactant 3

HCID 77070Veratroyl chlorideHCID 81531DiisopropylethylamineHCID 135494401HCID 135494401, compound

Product 1

HCID 135470462HCID 135470462, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

7-Amino-4-hydroxy-3-(4-methoxy-phenylazo-napthalene-2-sulfonic acid isopropyl ester (Example 6, 100 mg, 0.24 mmol ) was dissolved in dichloromethane (15 mL) and diisopropylethylamine (84 μL, 62 mg, 0.48 mmol). 3,4-Dimethoxybenzoyl chloride (56 mg, 0.28 mmol) was added under nitrogen and the reaction mixture was allowed to stir for 16 h. The solution was washed with water, 1N HCl, and saturated sodium bicarbonate solution. The organic layer was dried with MgSO4 and concentrated. This concentrate was purified by chromatography (silica gel, eluent: 50% ethyl acetate/hexane) to provide the sulfonic acid, isopropyl ester (27 mg, 0.047 mmole, 17%). This ester (16 mg, 0.028 mmole) was suspended in 2-butanone (0.5 mL) and sodium iodide (6 mg, 0.041 mmole) was added. The resulting suspension was heated with stirring to 60° C. for 72 h. The solvent was removed under a stream of nitrogen. The remaining solid was suspended in acetone and filtered to provide the title compound (9 mg, 0.016 mmole, 67%, calculated from the isopropyl ester) as a red solid: NMR (DMSO-d6): δ 16.30 (s, 1H), 10.39 (s, 1H), 8.26 (d, J=9 Hz, 1H), 8.17 (s, 1H), 7.96 (d, J=8 Hz, 1H), 7.90 (d, J=8 Hz, 2H), 7.68 (d, J=9 Hz, 1H), 7.58 (s, 1H), 7.50 (s, 1H), 7.10 (m, 3H), 3.95 (m, 9H): Analytical HPLC: 82% pure: MS (ES-NEG): [M−H] 536.

Workup

  1. washThe solution was washed with water, 1N HCl, and saturated sodium bicarbonate solution
  2. dry with materialThe organic layer was dried with MgSO4
  3. concentrationconcentrated
  4. customThis concentrate was purified by chromatography (silica gel, eluent: 50% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-4fb584d0bf6648b9a5836e4877302b8f
Source dataset
uspto-grants-2001_03
Patent number
US06200963B1

Reaction notes

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