Hydrochloric Acid → 2-(3-Formyl-benzyl)-1,1-dioxo-1lambda6 isothiazolidine-3-carboxylic acid methyl ester

HRID 1879463ノート

反応式

HRID 1879463 の反応式
Br[CH2:2][C:3]1[CH:4]=[C:5]([CH:8]=[CH:9][CH:10]=1)[CH:6]=[O:7].C(=O)([O-])[O-].[Cs+].[Cs+].[CH3:17][O:18][C:19]([CH:21]1[CH2:25][CH2:24][S:23](=[O:27])(=[O:26])[NH:22]1)=[O:20].[CH2:28]([O:30][C:31]([CH:33]1[CH2:37][CH2:36][S:35](=[O:39])(=[O:38])[NH:34]1)=[O:32])[CH3:29].[Cl-].[NH4+].Cl>CN(C)C=O.ClCCl>[CH2:28]([O:30][C:31]([CH:33]1[CH2:37][CH2:36][S:35](=[O:38])(=[O:39])[N:34]1[CH2:2][C:3]1[CH:10]=[CH:9][CH:8]=[C:5]([CH:6]=[O:7])[CH:4]=1)=[O:32])[CH3:29].[CH3:17][O:18][C:19]([CH:21]1[CH2:25][CH2:24][S:23](=[O:27])(=[O:26])[N:22]1[CH2:2][C:3]1[CH:10]=[CH:9][CH:8]=[C:5]([CH:6]=[O:7])[CH:4]=1)=[O:20]

参加物

10

反応物 6

HCID 313Hydrochloric AcidHCID 10796Cesium carbonateHCID 25517Ammonium ChlorideHCID 71278253-(Bromomethyl)benzaldehydeHCID 11240805Methyl 1,1-dioxo-1lambda6,2-thiazolidine-3-carboxylateHCID 53487526Ethyl 1,1-dioxo-isothiazolidine-3-carboxylate2 回

生成物 2

HCID 582804492-(3-Formyl-benzyl)-1,1-dioxo-1lambda6 isothiazolidine-3-carboxylic acid ethyl ester収率 37%HCID 866538012-(3-Formyl-benzyl)-1,1-dioxo-1lambda6 isothiazolidine-3-carboxylic acid methyl ester収率 53%

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide溶媒HCID 6344Dichloromethane溶媒

実験手順

3-Bromomethyl-benzaldehyde (2.44 g, 12.3 mmol) and cesium carbonate (9.08 g, 27.9 mmol) were added to a solution of a 4:3 mixture of 1,1-dioxo-isothiazolidine-3-carboxylic acid methyl ester and 1,1-dioxo-isothiazolidine-3-carboxylic acid ethyl ester (Intermediate 7 Step 2; 2.01 g, 10.8 mmol) in N,N-dimethylformamide (60 mL). The mixture was stirred at room temperature for 20 h and then dichloromethane (100 mL) was added. Saturated aqueous ammonium chloride solution (25 mL) was added followed by 1 M hydrochloric acid to bring the pH to 2-3. The two layers were separated and the organic layer was washed twice with brine. The solution was dried over sodium sulfate, and filtered. Celite was added and the solvents were evaporated under reduced pressure. The residue (containing the mixture of crude products coated onto Celite) was purified using flash chromatography (Analogix SF40-240 g Si), eluting with 30-70% ethyl acetate/hexanes to give 2-(3-formyl-benzyl)-1,1-dioxo-1λ6 isothiazolidine-3-carboxylic acid ethyl ester (first eluting peak; 1.26 g, 37%) and 2-(3-formyl-benzyl)-1,1-dioxo-1λ6 isothiazolidine-3-carboxylic acid methyl ester (second eluting peak; 1.69 g, 53%).

後処理

  1. customThe two layers were separated
  2. washthe organic layer was washed twice with brine
  3. dry with materialThe solution was dried over sodium sulfate
  4. filtrationfiltered
  5. additionCelite was added
  6. customthe solvents were evaporated under reduced pressure
  7. additionThe residue (containing
  8. additionthe mixture of crude products coated onto Celite)
  9. customwas purified
  10. washeluting with 30-70% ethyl acetate/hexanes

出典と根拠

ORDレコード
ord-1f0561d9bc064e5e8cdbcc9b86bca687
出典データセット
uspto-grants-2012_11
特許番号
US08314250B2

反応ノート

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