Methylenecyclohexane → HCID 67515548、化合物

HRID 1754336ノート

反応式

HRID 1754336 の反応式
[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

参加物

7

反応物 4

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

生成物 1

HCID 67515548HCID 67515548、化合物収率 23.9%

試薬・触媒・溶媒 2

HCID 6547Azobisisobutyronitrile触媒HCID 6212Chloroform溶媒2 回

実験手順

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].

後処理

  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)

出典と根拠

ORDレコード
ord-3e8ddc976ece4129adfe4225724b923a
出典データセット
uspto-grants-2015_10
特許番号
US09169242B2

反応ノート

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