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Cesium hydroxide → (Z)-7-Chloro-5-(4-(4-methoxybenzyloxy)phenyl)-1-methyl-1H-benzo[e][1,4]diazepin-2(3H)-one

HRID 2263701
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인쇄 미리보기

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HRID 2263701 반응식
Cl[C:2]1[C:3]2[CH:14]=[C:13]([Cl:15])[CH:12]=[CH:11][C:4]=2[N:5]([CH3:10])[C:6](=[O:9])[CH2:7][N:8]=1.[OH-].[Cs+].[CH3:18][O:19][C:20]1[CH:42]=[CH:41][C:23]([CH2:24][O:25][C:26]2[CH:31]=[CH:30][C:29](B3OC(C)(C)C(C)(C)O3)=[CH:28][CH:27]=2)=[CH:22][CH:21]=1>O1CCOCC1.O.C(OCC)(=O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:15][C:13]1[CH:12]=[CH:11][C:4]2[N:5]([CH3:10])[C:6](=[O:9])[CH2:7][N:8]=[C:2]([C:29]3[CH:28]=[CH:27][C:26]([O:25][CH2:24][C:23]4[CH:22]=[CH:21][C:20]([O:19][CH3:18])=[CH:42][CH:41]=4)=[CH:31][CH:30]=3)[C:3]=2[CH:14]=1
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참가 물질

7

반응물 3

HCID 62750Cesium hydroxideHCID 123385855,7-Dichloro-1-methyl-1,3-dihydro-2H-1,4-benzodiazepin-2-oneHCID 595943752-{4-[(4-Methoxyphenyl)methoxy]phenyl}-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

생성물 1

HCID 59594389(Z)-7-Chloro-5-(4-(4-methoxybenzyloxy)phenyl)-1-methyl-1H-benzo[e][1,4]diazepin-2(3H)-one

시약·촉매·용매 3

HCID 178418397
HCID 178418397, 화합물
촉매
HCID 8857Ethyl Acetate용매
HCID 218864351,4-Dioxane--water (1/1)용매

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온도
90 °C

실험 절차

(E)-5,7-Dichloro-1-methyl-1H-benzo[e][1,4]diazepin-2(3H)-one (5.00 g, 20.57 mmol), cesium hydroxide (6.91 g, 41.1 mmol), and 2-(4-(4-methoxybenzyloxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (9.10 g, 26.7 mmol) were dissolved in dioxane/water (100 mL/30 mL), and the mixture was subjected to vacuum followed by nitrogen gas. The de-gassing was repeated twice, and then tetrakis(triphenylphosphine)palladium (0) (475 mg, 0.41 mmol) was added. The reaction was then heated to 90° C. for 18 hours, and then cooled to room temperature. The crude mixture was diluted with ethyl acetate, and the organic solution was washed with water, then brine, and then dried over sodium sulfate, and concentrated. The crude product was vacuum pulled through a silica plug eluting with 6:4 ethyl acetate:hexanes. The filtrate was concentrated and then washed with methyl-tert-butyl ether. The product was collected as a light yellow solid by filtration (5.13 g, 59%). 1HNMR (300 MHz, CDCl3) δ 3.36 (s, 3H), 3.73 (d, 1H), 3.81 (s, 3H), 4.77 (d, 1H), 5.03 (s, 2H), 6.91 (d, 2H), 6.98 (d, 2H), 7.27 (d, 1H), 7.32 (d, 1H), 7.36 (d, 2H), 7.49 (dd, 1H), 7.55 (d, 2H).

후처리

  1. temperaturecooled to room temperature
  2. washthe organic solution was washed with water
  3. dry with materialbrine, and then dried over sodium sulfate
  4. concentrationconcentrated
  5. washeluting with 6:4 ethyl acetate
  6. concentrationThe filtrate was concentrated
  7. washwashed with methyl-tert-butyl ether
  8. filtrationThe product was collected as a light yellow solid by filtration (5.13 g, 59%)

출처 및 근거

ORD 기록
ord-af6c9973cd97404ba2c83b1ee58de9c4
출처 데이터셋
uspto-grants-2010_12
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US07851465B2

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