Hexane → HCID 69922444, 화합물

HRID 351834노트

반응식

HRID 351834 반응식
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]

참가 물질

9

반응물 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, 화합물

생성물 1

HCID 69922444HCID 69922444, 화합물

시약·촉매·용매 3

HCID 176Acetic Acid용매HCID 962Water용매HCID 8028Tetrahydrofuran용매2회

반응 조건

온도
-70 °C

실험 절차

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+).

후처리

  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

출처 및 근거

ORD 기록
ord-c468a6e2d1b44720b80458f643c101bf
출처 데이터셋
uspto-grants-2004_06
특허 번호
US06743789B2

반응 노트

불러오는 중…