Potassium Hydroxide → 2,3,4,5-Tetrahydro-7-nitro-1,5-benzoxazepine

HRID 1041666ノート

反応式

HRID 1041666 の反応式
[OH-].[K+].C(OC([N:8]1[C:14]2[CH:15]=[C:16]([N+:19]([O-:21])=[O:20])[CH:17]=[CH:18][C:13]=2[O:12][CH2:11][CH2:10][CH2:9]1)=O)C>O.COCCO>[N+:19]([C:16]1[CH:17]=[CH:18][C:13]2[O:12][CH2:11][CH2:10][CH2:9][NH:8][C:14]=2[CH:15]=1)([O-:21])=[O:20]

参加物

5

反応物 2

HCID 14797Potassium HydroxideHCID 672634892-Nitro-7,8-dihydro-6H-5-oxa-9-aza-benzocycloheptene-9-carboxylic acid ethyl ester

生成物 1

HCID 109871302,3,4,5-Tetrahydro-7-nitro-1,5-benzoxazepine収率 79%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 80192-Methoxyethanol溶媒

反応条件

温度
110 °C

実験手順

1.00 M of Potassium hydroxide in Water (25 mL) was added to 2-Nitro-7,8-dihydro-6H-5-oxa-9-aza-benzocycloheptene-9-carboxylic acid ethyl ester (2.84 g, 10.7 mmol) in 2-Methoxyethanol (50 mL) and the reaction was heated at 110° C. After overnight heating, the mixture was cooled, extracted with DCM (2×50 mL); the combined organics were washed with water (50 mL) and brine (50 mL), dried and conc. in vacuo. The residue was chromatographed (120 g SiO2, ISCO, 0-20% EtOAc:Hex) to afford 2-Nitro-6,7,8,9-tetrahydro-5-oxa-9-aza-benzocycloheptene as an orange solid (1.64 g, 79%). 1697d) 2-Nitro-6,7,8,9-tetrahydro-5-oxa-9-aza-benzocycloheptene (278 mg, 1.43 mmol) was dissolved in Acetonitrile (15 mL) and Acetaldehyde (0.80 mL, 14 mmol) was added. Acetic acid (0.15 mL, 2.6 mmol) was added, followed by Sodium triacetoxyborohydride (0.85 g, 4.0 mmol), and the mixture was stirred under an atmosphere of Nitrogen at room temperature for 1 h. The solution was diluted with ethyl acetate (50 mL) and satd. sodium bicarbonate (50 mL). The layers were separated, the organic washed with brine (50 mL) and dried over sodium sulfate. Conc. in vacuo followed by chromatography (ISCO, g SiO2, 0-50% EtOAc:Hex) afforded 9-Ethyl-2-nitro-6,7,8,9-tetrahydro-5-oxa-9-aza-benzocycloheptene as an orange oil (272 mg, 85%). 1H-NMR (CDCl3) 7.58 (m, 2H), 6.87 (d, 1H, J=8.1 Hz), 4.31 (t, 2H, J=5.2 Hz), 3.40 (t, 2H, J=5.2 Hz), 3.33 (q, 2H, J=6.8 Hz), 2.05 (tt, 2H, J=5.2, 5.2 Hz), 1.24 (t, 3H, J=6.8 Hz).

後処理

  1. temperatureAfter overnight heating
  2. temperaturethe mixture was cooled
  3. extractionextracted with DCM (2×50 mL)
  4. washthe combined organics were washed with water (50 mL) and brine (50 mL)
  5. customdried and conc. in vacuo
  6. customThe residue was chromatographed (120 g SiO2, ISCO, 0-20% EtOAc:Hex)

出典と根拠

ORDレコード
ord-b27372d9ed9e476ab94f945b01976a0a
出典データセット
uspto-grants-2013_10
特許番号
US08552186B2

反応ノート

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