Acetic Acid → N-(2-cyanoethyl)-6-pentafluoroethyl-3,4-dihydro-3-hydroxy-2,2-dimethyl-2H-1-benzopyran-4-carbamide

HRID 264817노트

반응식

HRID 264817 반응식
C([BH3-])#N.[Na+].[C:5]([CH2:7][CH2:8][NH:9][C:10]([C:12]1[C:17]2[CH:18]=[C:19]([C:22]([F:28])([F:27])[C:23]([F:26])([F:25])[F:24])[CH:20]=[CH:21][C:16]=2[O:15][C:14]([CH3:30])([CH3:29])[C:13]=1[OH:31])=[O:11])#[N:6].C(O)(=O)C.O1CCCC1>C(OCC)(=O)C>[C:5]([CH2:7][CH2:8][NH:9][C:10]([CH:12]1[C:17]2[CH:18]=[C:19]([C:22]([F:27])([F:28])[C:23]([F:24])([F:26])[F:25])[CH:20]=[CH:21][C:16]=2[O:15][C:14]([CH3:29])([CH3:30])[CH:13]1[OH:31])=[O:11])#[N:6]

참가 물질

6

반응물 4

HCID 176Acetic AcidHCID 8028TetrahydrofuranHCID 5003444Sodium cyanoborohydrideHCID 86751045N-(2-cyanoethyl)-6-pentafluoroethyl-3-hydroxy-2,2-dimethyl-2H-1-benzopyran-4-carbamide

생성물 1

HCID 19037099N-(2-cyanoethyl)-6-pentafluoroethyl-3,4-dihydro-3-hydroxy-2,2-dimethyl-2H-1-benzopyran-4-carbamide수율 99.5%

시약·촉매·용매 1

HCID 8857Ethyl Acetate용매

실험 절차

1.1 g of tertiary-butoxy potassium and 2 ml of a dimethylformamide solution of 2 g of 2-cyanoethyl isothiocyanate were subsequently added to a mixture of 2.6 g of 6-pentafluoroethyl-3,4-dihydro-2,2-dimethyl-2H-1-benzopyran-3-one and 28 ml of dimethylformamide while stirring at -5° C., followed by stirring at 5° C. for 15 hours. Then, 2N hydrochloric acid was added thereto, and the mixture was extracted with ether. After washing the organic layer with water and drying, the residue obtained by distilling off the solvent was purified by silica gel column chromatography (a developing solution, hexane:methylene chloride=1:2) to obtain 2.6 g of N-(2-cyanoethyl)-6-pentafluoroethyl-3-hydroxy-2,2-dimethyl-2H-1-benzopyran-4-carbamide. 2.1 g of sodium cyanoborohydride was added to a mixture of 2.6 g of N-(2-cyanoethyl)-6-pentafluoroethyl-3-hydroxy-2,2-dimethyl-2H-1-benzopyran-4-carbamide obtained above, 15 ml of acetic acid and 45 ml of tetrahydrofuran while ice-cooling and stirring, and the resulting mixture was stirred at room temperature for 13 hours. The mixture was diluted with ethyl acetate, and, after washing the organic layer with a saturated aqueous solution of sodium bicarbonate and water and drying, the solvent was distilled off to obtain 2.6 g of N-(2-cyanoethyl)-6-pentafluoroethyl-3,4-dihydro-3-hydroxy-2,2-dimethyl-2H-1-benzopyran-4-carbamide. Then, the product was added to 90 ml of pyridine and 3.4 g of tosyl chloride, and the mixture was heated while refluxing for 1 hour. After concentration under reduced pressure, water and concentrated hydrochloric acid were added thereto, followed by extracting with methylene chloride. After washing the organic layer with water and drying, the residue obtained by distilling off the solvent was purified by silica gel column chromatography (a developing solution, hexane:ethyl acetate=1:1) to obtain 460 mg of N-(2-cyanoethyl)-6-pentafluoroethyl-2,2-dimethyl-2H-1-benzopyran-4-carbamide having a melting point of 163°-164° C.

후처리

  1. temperaturecooling
  2. stirringthe resulting mixture was stirred at room temperature for 13 hours
  3. washafter washing the organic layer with a saturated aqueous solution of sodium bicarbonate and water
  4. customdrying
  5. distillationthe solvent was distilled off

출처 및 근거

ORD 기록
ord-ca09122cf7974eefaba8c6aa2a03d3f0
출처 데이터셋
uspto-grants-1997_07
특허 번호
US05646310

반응 노트

불러오는 중…