Methyl isothiocyanate → (+/-)-N-methyl-2-oxo-1-(3-quinolinyl)cyclohexanecarbothioamide

HRID 1886375

反応式

HRID 1886375 の反応式
[N:1]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[C:3]([CH:11]2[CH2:16][CH2:15][CH2:14][CH2:13][C:12]2=[O:17])[CH:2]=1.[K].[O-]CCCC.[CH3:24][N:25]=[C:26]=[S:27]>O1CCCC1>[CH3:24][NH:25][C:26]([C:11]1([C:3]2[CH:2]=[N:1][C:10]3[C:5]([CH:4]=2)=[CH:6][CH:7]=[CH:8][CH:9]=3)[CH2:16][CH2:15][CH2:14][CH2:13][C:12]1=[O:17])=[S:27]

参加物

6

反応物 4

HCID 11167Methyl isothiocyanateHCID 5462222PotassiumHCID 12476378Butan-1-olateHCID 19794569(+/-)-2-(3-Quinolinyl)cyclohexanone

生成物 1

HCID 19794596(+/-)-N-methyl-2-oxo-1-(3-quinolinyl)cyclohexanecarbothioamide収率 9.4%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

A solution of (±)-2-(3-quinolinyl)cyclohexanone (0.78 g, 3.5 mmol) in tetrahydrofuran (10 ml) at -5° C. was treated with potassium t.-butoxide (0.43 g, 3.9 mmol) in one portion. After 25 minutes at -5° C. the deep red mixture was treated dropwise during 1 minute with a solution of methyl isothiocyanate (0.28 g, 3.9 mmol) in tetrahydrofuran (2 ml). After 4 hours at 0° C. the reaction mixture was partitioned between saturated aqueous ammonium chloride solution (50 ml) and chloroform (50 ml). The aqueous layer was extracted again with chloroform (50 ml). The combined organic extracts were then dried over sodium sulphate and concentrated in vacuo (20° C.; 14 mmHg) to give a crude oil which was purified by flash chromatography over silica gel eluting with ethyl acetate to give (±)-N -methyl-2-oxo-1-(3-quinolinyl)cyclohexanecarbothioamide (0.1 g, 0.33 mmol), m.p. 235°-236° C. N.M.R. (CDCl3) 1.7-2.18 (c, 4H), 2.46-2.64 (m, 2H) 2.72-2.90 (m, 1H), 2.96-3.16 (m, 1H), 3.16-3.22 (d, 3H), 7.50-7.62 (ddd, 1H), 7.66-7.76 (ddd, 1H), 7.76-8.02 (dd, 1M), 8.0 (d, 1M), 8.04-8.12 (dd, 1H), 8.78-8.80 (d, 1H), 8.92-9.18 (broad singlet, 1H). Calculated for C17H18N2OS: C,68.4; H, 6.08; N, 9.4; S, 10.7%: Found C, 68.0; H, 5.8; N, 9.0; S, 10.4%.

後処理

  1. customAfter 4 hours at 0° C. the reaction mixture was partitioned between saturated aqueous ammonium chloride solution (50 ml) and chloroform (50 ml)
  2. extractionThe aqueous layer was extracted again with chloroform (50 ml)
  3. dry with materialThe combined organic extracts were then dried over sodium sulphate
  4. concentrationconcentrated in vacuo (20° C.; 14 mmHg)
  5. customto give a crude oil which
  6. customwas purified by flash chromatography over silica gel eluting with ethyl acetate

出典と根拠

ORDレコード
ord-0b35d71a5a0b4df58277a087b158be78
出典データセット
uspto-grants-1992_09
特許番号
US05151436

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