O-Xylene → Phthalazine

HRID 991431ノート

反応式

HRID 991431 の反応式
O=[N:2][NH2:3].Cl.C(N(CC)CC)C.[C:12]1([CH3:19])[C:13]([CH3:18])=[CH:14][CH:15]=[CH:16][CH:17]=1>>[CH:18]1[C:13]2[C:12](=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH:19]=[N:3][N:2]=1

参加物

4

反応物 3

HCID 7237O-XyleneHCID 11130Triethylamine hydrochlorideHCID 37183Nitrosamine

生成物 1

HCID 9207Phthalazine収率 63%

実験手順

1,1′-Carbonyldiimidazole (2.0 g, 12.6 mmol) was added to a stirred solution of 5-methylisoxazole-3-carboxylic acid in DMF (50 ml). The solution was stirred for 0.5 h before adding the preceding hydrazine (2.63 g, 11.7 mmol). After 1 h at room temperature, the solution was poured into water and the resultant precipitate was filtered, washed with water (30 ml) and hexane (100 ml), and dried in vacuo to give the ketohydrazine (3.1 g, 79%); MS (ES+) m/e 334 [MH]+. A solution of the ketohydrazine (1.0 g, 3.0 mmol) and triethylamine hydrochloride (0.2 g, 1.45 mmol), in xylene (30 ml), was heated at reflux for 4 h. The solution was cooled to room temperature and the solvent removed in vacuo. The residue was chromatographed through silica gel, eluting with ethyl acetate, to give the title-phthalazine (0.60 g, 63%), mp 186-188° C.; 1H NMR (250 MHz, CDCl3) δ1.22-1.54 (4H, m, 2 of CH2), 1.94-2.06 (4H, m, 2 of CH2), 2.58 (3H, s, Me), 3.60 (1H, s, CH), 4.08 (1H, s, CH), 6.90 (1H, s, Ar—H); MS (ES+) m/e 316 [MH]+.

後処理

  1. temperatureat reflux for 4 h
  2. customthe solvent removed in vacuo
  3. customThe residue was chromatographed through silica gel
  4. washeluting with ethyl acetate

出典と根拠

ORDレコード
ord-9913f1aeaf764cccafb8ed6d9df03066
出典データセット
uspto-grants-2002_10
特許番号
US06465462B1

反応ノート

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