Sodium Chloride → tert-butyl 3-(4-methoxybenzoylamino)-5-(1-methyl-1-phenylethylcarbamoyl)-1H-pyrazolo[4,3-d]thiazole-1-carboxylate

HRID 501230ノート

反応式

HRID 501230 の反応式
[NH2:1][C:2]1[C:6]2[N:7]=[C:8]([C:10](=[O:21])[NH:11][C:12]([CH3:20])([C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=3)[CH3:13])[S:9][C:5]=2[N:4]([C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[N:3]=1.[CH3:29][O:30][C:31]1[CH:39]=[CH:38][C:34]([C:35](Cl)=[O:36])=[CH:33][CH:32]=1.[Cl-].[Na+]>N1C=CC=CC=1.O1CCCC1>[CH3:29][O:30][C:31]1[CH:39]=[CH:38][C:34]([C:35]([NH:1][C:2]2[C:6]3[N:7]=[C:8]([C:10](=[O:21])[NH:11][C:12]([CH3:20])([C:14]4[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=4)[CH3:13])[S:9][C:5]=3[N:4]([C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[N:3]=2)=[O:36])=[CH:33][CH:32]=1

参加物

6

反応物 3

HCID 5234Sodium ChlorideHCID 7477p-Anisoyl chlorideHCID 68464944tert-butyl 3-amino-5-(1-methyl-1-phenylethylcarbamoyl)-1H-pyrazolo[4,3-d]thiazole-1-carboxylate

生成物 1

HCID 68460727tert-butyl 3-(4-methoxybenzoylamino)-5-(1-methyl-1-phenylethylcarbamoyl)-1H-pyrazolo[4,3-d]thiazole-1-carboxylate収率 18.7%

試薬・触媒・溶媒 2

HCID 1049Pyridine溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
25 °C

実験手順

0.20 g (0.50 mmol) of tert-butyl 3-amino-5-(1-methyl-1-phenylethylcarbamoyl)-1H-pyrazolo[4,3-d]thiazole-1-carboxylate dissolved in 5 ml of pyridine is placed in a 50 ml round-bottomed flask under argon. A solution of 0.09 g (0.53 mmol) of 4-methoxybenzoyl chloride (prepared according to J. Org. Chem. 1976, 41, 2566) in 2.0 ml of tetrahydrofuran is then added dropwise and the mixture is stirred for 15 hours at 25° C. The reaction medium is then concentrated to dryness under reduced pressure (40° C.) and the residue is taken up in 30 ml of dichloromethane and 30 ml of water, and basified with 0.1N sodium hydroxide solution. The emulsion obtained is resorbed by saturation with sodium chloride. After separation of the phases by settling, the organic phase is dried over magnesium sulfate and concentrated to dryness under reduced pressure. The residue is purified by flash chromatography (msilica=30 g; eluent: 95/5 dichloromethane/methanol). 0.05 g of tert-butyl 3-(4-methoxy-benzoylamino)-5-(1-methyl-1-phenylethylcarbamoyl)-1H-pyrazolo[4,3-d]thiazole-1-carboxylate is thus obtained in the form of a cream-coloured foam. 0.16 g of an impure batch is also obtained, and is repurified by flash chromatography (msilica=30 g; eluent: 95/5 dichloromethane/methanol). 0.04 g of tert-butyl 3-(4-methoxybenzoylamino)-5-(1-methyl-1-phenylethylcarbamoyl)-1H-pyrazolo[4,3-d]thiazole-1-carboxylate is thus obtained in the form of a cream-coloured foam. 1H NMR (400 MHz, DMSO-d6): δ ppm 1.61 (s, 9H); 1.71 (s, 6H); 3.86 (s, 3H); 7.10 (d, J=8.5 Hz, 2H); 7.20 (t, J=7.5 Hz, 1H); 7.30 (t, J=7.5 Hz, 2H); 7.40 (d, J=7.5 Hz, 2H); 8.07 (d, J=8.5 Hz, 2H); 8.71 (s, 1H); 11.25 (broad s, 1H). LC-MS-DAD-ELSD: 534(−)=(M−H)(−); 536(+)=(M+H)(+).

後処理

  1. customis placed in a 50 ml round-bottomed flask under argon
  2. concentrationThe reaction medium is then concentrated to dryness under reduced pressure (40° C.)
  3. customThe emulsion obtained
  4. customAfter separation of the phases
  5. dry with materialthe organic phase is dried over magnesium sulfate
  6. concentrationconcentrated to dryness under reduced pressure
  7. customThe residue is purified by flash chromatography (msilica=30 g; eluent: 95/5 dichloromethane/methanol)

出典と根拠

ORDレコード
ord-d847095aacd84c31acff1446b5268979
出典データセット
uspto-grants-2010_08
特許番号
US07772261B2

反応ノート

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