Hydrochloric Acid → HCID 178450616, compound

HRID 840868Notes

Reaction equation

HRID 840868 reaction equation
[OH:1][CH2:2][C:3]([CH3:20])([CH3:19])[CH2:4][NH:5][S:6]([CH2:9][C:10]1[CH:15]=[CH:14][C:13]([N+:16]([O-])=O)=[CH:12][CH:11]=1)(=[O:8])=[O:7].Cl.CN([CH:25]=[C:26]1[C:37]2[C:29](=[CH:30][CH:31]=[C:32]3[C:36]=2[S:35][CH:34]=[N:33]3)[NH:28][C:27]1=[O:38])C>CO.[Pd]>[OH:1][CH2:2][C:3]([CH3:20])([CH3:19])[CH2:4][NH:5][S:6]([CH2:9][C:10]1[CH:15]=[CH:14][C:13]([NH:16][CH:25]=[C:26]2[C:37]3[C:29](=[CH:30][CH:31]=[C:32]4[C:36]=3[S:35][CH:34]=[N:33]4)[NH:28][C:27]2=[O:38])=[CH:12][CH:11]=1)(=[O:8])=[O:7]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 21956251N-(3-hydroxy-2,2-dimethyl-propyl)(4-nitro-phenyl)-methanesulfonamideHCID 537785418-Dimethylaminomethylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one

Product 1

HCID 178450616HCID 178450616, compoundYield 70.5%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

A solution of 3.16 g (30.6 mmol) of 3-amino-2,2-dimethylpropanol in 10 mL of CH2Cl2 was added at once to a solution of 2.40 g (10.2 mmol) of 4-nitrophenylmethanesulphonyl chloride (Lee, et al., Journal of the American Chemical Society 1987, 109, 7472-7; Macor, et al., Tetrahedron Letters 1992, 33, 8011-4) in 40 mL of CH2Cl2. The mixture was stirred at rt for 15 min, the solvent was removed in vacuo and the residue was redissolved in 50 mL of EtOAc. The solution was washed with three 50-mL portions of 1.0 N HCl and concentrated in vacuo. Purification of the residue by flash chromatography on silica gel (hexane/EtOAc 1:1) afforded N-(3-hydroxy-2,2-dimethyl-propyl)-(4-nitrophenyl)-methanesulfonamide as a white solid (0.84 g, 27%): 1H NMR (DMSO-d6): δ0.74 (s, 6H), 2.78 (d, J=6.4 Hz, 2H), 3.11 (d, J=5.3 Hz, 2H), 4.47 (t, J=5.3 Hz, 1H), 4.52 (s, 2H), 7.02 (t, J=6.4 Hz, 1H), 7.65 (d, J=8.8 Hz, 2H), 8.25 (d, J=8.8 Hz, 2H); APCI−MS: m/z 301 (M−H)−. A mixture of 0.66 g (2.2 mmol) of N-(3-hydroxy-2,2-dimethyl-propyl)-(4-nitro-phenyl)-methanesulfonamide and ˜0.06 g Pd/C 10% in 50 mL of MeOH was shaken on a Parr hydrogenator for 3.5 h. The catalyst was removed via filtration, and 0.273 mL (3.28 mmol) of conc. HCl was added. The solvent was removed in vacuo, and the solid residue was redissolved in 20 mL of EtOH and added to 0.486 g (1.98 mmol) of 8-dimethylaminomethylene-6,8-dihydro-1-thia-3,6-diaza-as-indacen-7-one. The mixture was heated to reflux for 4.5 h and cooled to ambient tempurature. The solid was collected by vacuum filtration, washed with water, and dried in a vacuum oven at 70° C. to afford the title compound as a yellow solid (0.66 g, 70%): mp 229-230° C. (dec); 1H NMR (DMSO-d6): δ0.74 (s, 6H), 2.73 (d, J=6.4 Hz, 2H), 3.08 (d, J=5.3 Hz, 2H), 4.27 (s, 2H), 4.43 (t, J=5.3 Hz, 1H), 6.84 (t, J=6.4 Hz, 1H), 7.09 (d, J=8.3 Hz, 1H), 7.37 (d, J=8.5 Hz, 2H), 7.42 (d, J=8.5 Hz, 2H), 7.77 (d, J=8.3 Hz, 1H), 8.03 (d, J=12.3 Hz, 1H), 9.24 (s, 1H), 10.84 (s, 1H), 11.04 (d, J=12.3 Hz, 1H); ESI−MS: m/z 471 (M−H)−. Anal. Calcd for C22H24N4O4S2.0.5H2O: C, 54.87; H, 5.23; N, 11.63; S, 13.32. Found: C, 54.90; H, 5.26; N, 11.68; S, 13.25.

Workup

  1. additionwas added
  2. customThe solvent was removed in vacuo
  3. dissolutionthe solid residue was redissolved in 20 mL of EtOH
  4. temperatureThe mixture was heated
  5. temperatureto reflux for 4.5 h
  6. temperaturecooled to ambient tempurature
  7. filtrationThe solid was collected by vacuum filtration
  8. washwashed with water
  9. customdried in a vacuum oven at 70° C.

Sources & evidence

ORD record
ord-ceb106779e474719bc39830e9e18b5a3
Source dataset
uspto-grants-2002_04
Patent number
US06369086B1

Reaction notes

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