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Diethyl chlorophosphate → 8-Bromo-4-methyl-6-phenyl-4H-2,5,10b-triaza-benzo [e]azulene-3-carboxylic acid ethyl ester

HRID 75254
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HRID 75254 반응식
[Br:1][C:2]1[CH:20]=[CH:19][C:5]2[NH:6][C:7](=O)[CH:8]([CH3:17])[N:9]=[C:10]([C:11]3[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=3)[C:4]=2[CH:3]=1.[H-].[Na+].P(Cl)(OCC)(OCC)=O.[N+:32]([CH2:34][C:35]([O:37][CH2:38][CH3:39])=[O:36])#[C-:33].[H-].[Na+].C1COCC1>C1COCC1>[CH2:38]([O:37][C:35]([C:34]1[N:32]=[CH:33][N:6]2[C:7]=1[CH:8]([CH3:17])[N:9]=[C:10]([C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)[C:4]1[CH:3]=[C:2]([Br:1])[CH:20]=[CH:19][C:5]2=1)=[O:36])[CH3:39]
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참가 물질

7

반응물 5

HCID 13139Diethyl chlorophosphateHCID 24758Sodium hydride2회HCID 533707Ethyl isocyanoacetateHCID 6255777-Bromo-3-methyl-5-phenyl-1,3-dihydro-benzo[e][1,4]diazepin-2-oneHCID 23694757NaH THF

생성물 1

HCID 685284058-Bromo-4-methyl-6-phenyl-4H-2,5,10b-triaza-benzo [e]azulene-3-carboxylic acid ethyl ester

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

반응 조건

온도
-10 °C

실험 절차

7-Bromo-3-methyl-5-phenyl-1,3-dihydrobenzo[e][1,4]diazepin-2-one 111 (16.6 g, 0.052 mol) was suspended in dry THF (250 mL) and cooled to −10° C. Sodium hydride (60% dispersion in mineral oil, 4.36 g, 0.109 mol) was added into the suspension in one portion. The reaction mixture was allowed to stir and warm to rt over a 3 h period. The reaction mixture was again cooled to −10° C. and diethyl chlorophosphate (12.7 ml, 0.09 mol) was added. The cooling bath was then removed and stirring continued for 3 h. At this time, sodium hydride (60% dispersion in mineral oil, 4.2 g, 0.1 mol) was suspended in dry THF (250 mL) at −10° C. in another flask. Ethyl isocyanoacetate (6.78 mL, 0.06 mol) was added to the NaH/THF suspension, the solution which resulted was allowed to stir for 3 h. After 3 h the first flask was cooled to −30° C. and the solution in the 2nd reaction flask was added to the first flask via a cannula. The reaction mixture was allowed to stir for 24 h, and then cooled with an ice-water bath and slowly quenched with acetic acid (10 mL). Water was added to the reaction mixture after which it was extracted with EtOAc. The EtOAc layers were combined, washed with aq NaHCO3, brine and dried (Na2SO4). After removal of the solvent under reduced pressure, the solid was purified by flash chromatography (silica gel, EtOAc:hexane, gradient elution 1:2, 1:1, 2:1). The ester 112 was a white solid (8.76 g, 40%). mp 164-165° C.; IR (KBr, cm−1) 2925, 1706, 1622, 1557, 1495, 1266, 1185; 1H NMR (CDCl3) δ 7.89 (s, 1 H), 7.73 (dd, J=1.73 Hz, 1 H), 7.51-7.36 (m, 7 H), 6.66 (q, J=7.30, 1 H), 4.45-4.30 (m, 2 H), 1.40 (t, J=7.11, 3 H), 1.25 (d, J=7.38 Hz, 3H). MS (EI) m/e (relative intensity) 426 (M++2, 15), 425 (M++1, 58), 424 (M+, 15), 423 (58), 380 (24), 379 (71), 378 (35), 377 (69), 352 (50), 351(100), 350 (67), 349 (92), 270 (38), 229 (16); [α]26D=−38.0 (c 0.45, EtOAc).

후처리

  1. temperaturewarm to rt over a 3 h period
  2. temperatureThe reaction mixture was again cooled to −10° C.
  3. customThe cooling bath was then removed
  4. stirringstirring
  5. customthe solution which resulted
  6. stirringto stir for 3 h
  7. temperatureAfter 3 h the first flask was cooled to −30° C.
  8. customthe solution in the 2nd reaction flask
  9. additionwas added to the first flask via a cannula
  10. stirringto stir for 24 h
  11. temperaturecooled with an ice-water bath
  12. customslowly quenched with acetic acid (10 mL)
  13. additionWater was added to the reaction mixture after which it
  14. extractionwas extracted with EtOAc
  15. washwashed with aq NaHCO3, brine
  16. dry with materialdried (Na2SO4)
  17. customAfter removal of the solvent under reduced pressure
  18. customthe solid was purified by flash chromatography (silica gel, EtOAc:hexane, gradient elution 1:2, 1:1, 2:1)

출처 및 근거

ORD 기록
ord-52b6c5319432402f97568dcf3a3ad329
출처 데이터셋
uspto-grants-2014_09
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US08835424B2

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