Hexane → HCID 69922444、化合物

HRID 351834ノート

反応式

HRID 351834 の反応式
C[Si](C)(C)N[Si](C)(C)C.[Li]CCCC.CCCCCC.[CH2:21]([O:23][C:24](=[O:31])[CH2:25]/[N:26]=[CH:27]/[N:28]([CH3:30])[CH3:29])[CH3:22].ClC1[CH2:34][N:35]([CH2:46][C:47]2[CH:52]=[CH:51][C:50]([O:53][CH3:54])=[CH:49][C:48]=2[O:55][CH3:56])[C:36](=[O:45])[C:37]2[CH:43]=[C:42]([CH3:44])[CH:41]=[CH:40]C=2N=1>C1COCC1.O.C(O)(=O)C>[CH2:21]([O:23][C:24]([C:25]1[N:26]=[CH:27][N:28]2[C:30]=1[CH2:34][N:35]([CH2:46][C:47]1[CH:52]=[CH:51][C:50]([O:53][CH3:54])=[CH:49][C:48]=1[O:55][CH3:56])[C:36](=[O:45])[C:37]1[CH:43]=[C:42]([CH3:44])[CH:41]=[CH:40][C:29]2=1)=[O:31])[CH3:22]

参加物

9

反応物 5

HCID 8058HexaneHCID 13838HexamethyldisilazaneHCID 227134712-Chloro-4-(2,4-dimethoxy-benzyl)-7-methyl-3,4-dihydro-benzo[e][1,4]diazepin-5-oneHCID 178418339ButyllithiumHCID 178472743HCID 178472743、化合物

生成物 1

HCID 69922444HCID 69922444、化合物

試薬・触媒・溶媒 3

HCID 176Acetic Acid溶媒HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-70 °C

実験手順

Hexamethyldisilazane (68.7 mL, 330 mmol) was dissolved in THF (350 mL), cooled under Argon to −70° C., and treated slowly with a 1.6 M solution of n-BuLi in hexane (206 mL, 330 mmol). After stirring for 1 h at −70° C., a solution of (E)-(dimethylamino-methyleneamino)-acetic acid ethyl ester (31.6 g, 200 mmol) in THF (30 mL) was added, and stirring continued for 1 h at −70° C. Then a solution of 2-chloro-4-(2,4-dimethoxy-benzyl)-7-methyl-3,4-dihydro-benzo[e][1,4]diazepin-5-one (35.9 g, 100 mmol) (prepared as described above) was added at −70° C., and subsequently allowed to warm up to at 10° C. over 1 h, then cooled again to −30° C. After 30 min, acetic acid (57 mL) was added at −30° C. and the suspension was allowed to warm up to room temperature and water (57 mL) added and the resulting mixture heated under reflux for 14 h. After cooling, the mixture was evaporated and then dissolved in DCM (300 mL). This solution was then washed with HCl (1 M, 2×100 mL) and 10% sodium hydrogen carbonate (100 ml), dried (Na2SO4) and evaporated. Chromatography on silica gel eluting with EtOAc. Yield: 17.6 g (41%). m/z 436 (MH+).

後処理

  1. stirringstirring
  2. waitcontinued for 1 h at −70° C
  3. temperatureto warm up to at 10° C. over 1 h
  4. temperaturecooled again to −30° C
  5. waitAfter 30 min
  6. temperatureto warm up to room temperature
  7. temperaturethe resulting mixture heated
  8. temperatureunder reflux for 14 h
  9. temperatureAfter cooling
  10. customthe mixture was evaporated
  11. dissolutiondissolved in DCM (300 mL)
  12. washThis solution was then washed with HCl (1 M, 2×100 mL) and 10% sodium hydrogen carbonate (100 ml)
  13. dry with materialdried (Na2SO4)
  14. customevaporated

出典と根拠

ORDレコード
ord-c468a6e2d1b44720b80458f643c101bf
出典データセット
uspto-grants-2004_06
特許番号
US06743789B2

反応ノート

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