Hydrochloric Acid → 3-(ethoxycarbonyl)-8-methyl-2-(trifluoromethyl)-2H-chromene-6-carboxylic acid

HRID 855110ノート

反応式

HRID 855110 の反応式
[CH:1]([C:3]1[CH:4]=[C:5]([CH:9]=[C:10]([CH3:13])[C:11]=1[OH:12])[C:6]([OH:8])=[O:7])=O.C([O-])([O-])=O.[K+].[K+].C(N(CC)CC)C.[F:27][C:28]([F:37])([F:36])/[CH:29]=[CH:30]/[C:31]([O:33][CH2:34][CH3:35])=[O:32].Cl>CS(C)=O.CC(C)=O>[CH2:34]([O:33][C:31]([C:30]1[CH:29]([C:28]([F:27])([F:36])[F:37])[O:12][C:11]2[C:3]([CH:1]=1)=[CH:4][C:5]([C:6]([OH:8])=[O:7])=[CH:9][C:10]=2[CH3:13])=[O:32])[CH3:35]

参加物

8

反応物 5

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 11430Potassium CarbonateHCID 5371261Ethyl (2E)-4,4,4-trifluoro-2-butenoateHCID 865994903-Formyl-4-hydroxy-5-methylbenzoic acid

生成物 1

HCID 695174193-(ethoxycarbonyl)-8-methyl-2-(trifluoromethyl)-2H-chromene-6-carboxylic acid

試薬・触媒・溶媒 2

HCID 180Acetone溶媒HCID 679Dimethyl Sulfoxide溶媒

反応条件

温度
90 °C

実験手順

A mixture of 3-formyl-4-hydroxy-5-methylbenzoic acid (8.8 g, 48.89 mmole), K2CO3 (13.49 g, 97.78 mmole), triethylamine (19.79 g, 195.56 mmole), and ethyl 4,4,4-trifluorocrotonate (32.85 g, 195.56 mmole) in anhydrous DMSO (20.0 mL) was heated to 90° C. under a dry N2 atmosphere for 18 hrs. The mixture was then cooled, poured into 2.0 N HCl (100 ml), and extracted with EtOAc (2×100 mL). The combined extracts were washed with brine (100 mL), dried over MgSO4, filtered, and concentrated in vacuo to give an oily solid. Redissolved in acetone to givea white precipitat, which was filtered and dried on high vacuum (7.2 g, 51%). GCMS m/z 330.0 (M+). 1H NMR (DMSO/400 MHz) 12.99 (s, 1H), 8.11 (s, 1H), 8.06 (s, 1H), 7.94 (s, 1H), 6.19 (q, 1H, J=7.0 Hz), 4.35 (m, 2H), 2.31 (s, 3H), 1.36 (m, 3H).

後処理

  1. temperatureThe mixture was then cooled
  2. extractionextracted with EtOAc (2×100 mL)
  3. washThe combined extracts were washed with brine (100 mL)
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customto give an oily solid
  8. filtrationwas filtered
  9. customdried on high vacuum (7.2 g, 51%)

出典と根拠

ORDレコード
ord-0ed30349f05e423aa02780fb30775c83
出典データセット
uspto-grants-2007_08
特許番号
US07259266B2

反応ノート

読み込み中…