Triethylamine → HCID 22629022, compound

HRID 277582Notes

Reaction equation

HRID 277582 reaction equation
C(Cl)(=O)C(Cl)=O.[CH3:7][S:8]([C:11]1[CH:19]=[CH:18][C:14]([C:15]([OH:17])=O)=[CH:13][CH:12]=1)(=[O:10])=[O:9].[NH2:20][C:21]1[CH:22]=[CH:23][C:24](/[CH:31]=[CH:32]/[C:33]2[CH:38]=[CH:37][C:36]([NH:39][C:40](=[O:52])[C:41]3[CH:46]=[CH:45][C:44]([O:47][CH2:48][CH2:49][O:50][CH3:51])=[CH:43][CH:42]=3)=[CH:35][C:34]=2[S:53]([OH:56])(=[O:55])=[O:54])=[C:25]([S:27]([OH:30])(=[O:29])=[O:28])[CH:26]=1.C(N(CC)CC)C>CN(C=O)C.ClCCl.O>[CH3:51][O:50][CH2:49][CH2:48][O:47][C:44]1[CH:43]=[CH:42][C:41]([C:40]([NH:39][C:36]2[CH:37]=[CH:38][C:33](/[CH:32]=[CH:31]/[C:24]3[CH:23]=[CH:22][C:21]([NH:20][C:15](=[O:17])[C:14]4[CH:13]=[CH:12][C:11]([S:8]([CH3:7])(=[O:9])=[O:10])=[CH:19][CH:18]=4)=[CH:26][C:25]=3[S:27]([OH:30])(=[O:29])=[O:28])=[C:34]([S:53]([OH:56])(=[O:55])=[O:54])[CH:35]=2)=[O:52])=[CH:46][CH:45]=1

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 77670p-(Methylsulphonyl)benzoic acidHCID 22628992HCID 22628992, compound

Product 1

HCID 22629022HCID 22629022, compoundYield 76.6%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

Oxalyl chloride (0.5 mL) and DMF (1 drop) were added to a 0° C., stirred solution of commercially available 4-(methylsulfonyl)-benzoic acid (97 mg, 0.5 mmol) dichloromethane (10 mL). Concentration in vacuum afforded an off white powder. A solution of this powder in dichloromethane (5 mL) was added to a 0° C., stirred solution of bis(tetra-N-butyl)ammonium salt of 5-amino-2-[(E)-2-(4-{[4-(2-methoxyethoxy)benzoyl]amino}-2-sulfophenyl)ethenyl]-benzenesulfonic acid (Example 39a, 0.50 g, 0.5 mmol) and triethylamine (0.14 g, 1.0 mmol) indichloromethane (25 mL). The resulting yellow mixture was allowed to warm to room temperature and was stirred for 20 hours. Water (15 mL) was added and the layers were separated. The organic phase was dried (MgSO4) and concentrated to provide a yellow powder that was chromatographed (gradient elution MeOH:CH2Cl2) to afford bis(tetra-N-butyl)ammonium salt of the title compound as a yellow foam (280 mg). A solution of this yellow foam in water:methanol/90:10 (300 mL) was passed through a sodium ion exchange resin (300 g, Toyopearl SP-650 resin). The fractions were combined and concentrated to about 20 mL. This concentrate was subjected to freeze drying which afforded the bis(sodium) salt of the title compound as a yellow powder (146 mg, 43% yield): 1HNMR (DMSO-d6) δ3.35 (s, 3H), 3.39 (s, 3H), 3.70 (t, J=5 Hz, 2H), 4.20 (t, J=5 Hz, 2H), 7.05 (d, J=14 Hz, 2H), 7.60 (t, 9 Hz, 2H), 7.88 (dt, J=17, 2 Hz, 2H), 7.98 (d, J=18 Hz, 2H), 8.04 (dd, J=1 Hz, 2H), 8.04 (d, J=11 Hz, 2H), 8.19 (dd, 10, 2 Hz, 2H), 8.21 (d, 15 Hz, 2H), 10.26 (s, 1H), 10.68 (s, 1H): MS (ESI) [M−H]− at m/z 729.

Workup

  1. concentrationConcentration in vacuum
  2. customafforded an off white powder
  3. customthe layers were separated
  4. dry with materialThe organic phase was dried (MgSO4)
  5. concentrationconcentrated
  6. customto provide a yellow powder that
  7. customwas chromatographed
  8. wash(gradient elution MeOH:CH2Cl2)

Sources & evidence

ORD record
ord-bcaae12b127b4323a4358118ad1e1d76
Source dataset
uspto-grants-2002_03
Patent number
US06355633B1

Reaction notes

Loading…