Methylenecyclohexane → HCID 67515548, 화합물

HRID 1754336노트

반응식

HRID 1754336 반응식
[Br:1][C:2]1[CH:3]=[C:4]([C:9]2[CH2:13][C:12]3([CH2:18][CH2:17][CH2:16][CH2:15][CH2:14]3)[O:11][N:10]=2)[CH:5]=[CH:6][C:7]=1[CH3:8].CC1C=C(C=CC=1C)C=NO.C=C1CCCCC1.C1C(=O)N([Br:44])C(=O)C1>C(Cl)(Cl)Cl.CC(N=NC(C#N)(C)C)(C#N)C>[Br:44][CH:13]1[C:12]2([CH2:14][CH2:15][CH2:16][CH2:17][CH2:18]2)[O:11][N:10]=[C:9]1[C:4]1[CH:5]=[CH:6][C:7]([CH3:8])=[C:2]([Br:1])[CH:3]=1

참가 물질

7

반응물 4

HCID 14502MethylenecyclohexaneHCID 67184N-bromobutanimideHCID 53395410N-[(3,4-Dimethylphenyl)methylidene]hydroxylamineHCID 67515835HCID 67515835, 화합물

생성물 1

HCID 67515548HCID 67515548, 화합물수율 23.9%

시약·촉매·용매 2

HCID 6547Azobisisobutyronitrile촉매HCID 6212Chloroform용매2회

실험 절차

To a solution of 3-(3-bromo-4-methylphenyl)-1-oxa-2-azaspiro[4.5]dec-2-ene (2.0 g, 6.49 mmol, 1.0 eq) (prepared by following the procedure described for step-2 of the intermediate 27 by the reaction of 3-methyl-4-methylbenzaldehyde oxime with methylenecyclohexane) in chloroform (20 mL) was added NBS (1.15 g, 6.49 mmol, 1.0 eq) followed by catalytic amount of AIBN (21 mg, 0.13 mmol, 0.02 eq). The resulting mixture was stirred at room temperature overnight. The reaction was diluted with chloroform (50 mL) and washed with water (50 mL) and brine (50 mL). The organic layer was dried (Na2SO4) and filtered. The filtrate was concentrated under vacuum. The crude product was purified by flash column chromatography (silica gel, ethyl acetate and hexane) to afford 600 mg of the title product as a white solid. 1HNMR (400 MHz, CDCl3) δ 7.97 (d, J=2.0 Hz, 1H), 7.65 (dd, J=8.0, 2.0 Hz, 1H), 7.29 (d, J=8.0 Hz, 1H), 5.14 (s, 1H), 2.43 (s, 3H), 2.13-2.10 (m, 1H), 2.01-1.99 (m, 1H), 1.82-1.76 (m, 4H), 1.65-1.62 (m, 1H), 1.52-1.45 (m, 3H); ESI-MS (m/z) 386, 388, 390 [(MH)+ Br79,81].

후처리

  1. washwashed with water (50 mL) and brine (50 mL)
  2. dry with materialThe organic layer was dried (Na2SO4)
  3. filtrationfiltered
  4. concentrationThe filtrate was concentrated under vacuum
  5. customThe crude product was purified by flash column chromatography (silica gel, ethyl acetate and hexane)

출처 및 근거

ORD 기록
ord-3e8ddc976ece4129adfe4225724b923a
출처 데이터셋
uspto-grants-2015_10
특허 번호
US09169242B2

반응 노트

불러오는 중…