Hydrochloric Acid → HCID 178450616、化合物

HRID 1935535ノート

反応式

HRID 1935535 の反応式
[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]

参加物

6

反応物 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

生成物 1

HCID 178450616HCID 178450616、化合物収率 70.5%

試薬・触媒・溶媒 2

HCID 23938Palladium触媒HCID 887Methanol溶媒

実験手順

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): δ 0.74 (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 temperature. 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): δ 0.74 (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,1 H), 10.84 (s, 1H), 11.04 (d, J=12.3 Hz, 1H); ESI−MS: m/z 471 (M−H)−. Anal. Calcd for C22H24N4O4S2.0.5 H2O: 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.

後処理

  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. filtrationThe solid was collected by vacuum filtration
  7. washwashed with water
  8. customdried in a vacuum oven at 70° C.

出典と根拠

ORDレコード
ord-d3e426bce106497c8422c65545e0ea3c
出典データセット
uspto-grants-2002_05
特許番号
US06387919B1

反応ノート

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