ethyl N-ethoxycarbonyliminocarbamate → HCID 21058145, 화합물

HRID 2218191노트

반응식

HRID 2218191 반응식
[C:1]([N:4]1[C@@H:8]([C:9]([OH:11])=[O:10])[C:7]([CH3:13])([CH3:12])[S:6][C@H:5]1[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)(=[O:3])[CH3:2].[C:20]([N:23]1[C:27]2[CH:28]=[CH:29][C:30]([Cl:32])=[CH:31][C:26]=2[S:25][CH:24]1[C:33]1[CH:38]=[C:37]([O:39][CH3:40])[CH:36]=[CH:35][C:34]=1O)(=[O:22])[CH3:21].N(C(OCC)=O)=NC(OCC)=O>CN(C=O)C>[C:20]([N:23]1[C:27]2[CH:28]=[CH:29][C:30]([Cl:32])=[CH:31][C:26]=2[S:25][CH:24]1[C:33]1[CH:38]=[C:37]([O:39][CH3:40])[CH:36]=[CH:35][C:34]=1[O:10][C:9]([C@H:8]1[C:7]([CH3:13])([CH3:12])[S:6][C@@H:5]([C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=2)[N:4]1[C:1](=[O:3])[CH3:2])=[O:11])(=[O:22])[CH3:21]

참가 물질

5

반응물 3

HCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 2825757HCID 2825757, 화합물HCID 14053536HCID 14053536, 화합물

생성물 1

HCID 21058145HCID 21058145, 화합물수율 15.3%

시약·촉매·용매 1

HCID 6228Dimethylformamide용매2회

실험 절차

A solution of (2S,4S)-3-acetyl-5,5-dimethyl-2-phenyl-4-thiazolidinecarboxylic acid [compound described in Reference Example 4 (b)] (102 g, 0.38 mol) in anhydrous DMF (500 ml) was added to a solution of 3-acetyl-6-chloro-2-(2-hydroxy-5-methoxyphenyl)-benzothiazoline (127 g, 0.38 mol) in anhydrous DMF (500 ml) at room temperature. N,N-Dimethylaminopyridine (5.58 g, 45.7 mmol) was added thereto under a nitrogen-atmosphere at room temperature with stirring. After ice-cooling, diethyl azodicarboxylate (87 g, 0.50 mol) was added thereto. The mixture was stirred under ice-cooling for 15 minutes, at room temperature for one hour and further at an internal temperature of about 40° C. for three days. The reaction mixture was concentrated under reduced pressure, a 10% aqueous citric acid solution (1,000 ml) was added to the residue, and the whole was extracted with ethyl acetate (1,000 ml). The organic layer was washed with water (1,000 ml) and saturated brine (1,000 ml) successively and dehydrated with magnesium sulfate, and ethyl acetate was evaporated under reduced pressure. A mixed solvent (ethanol/diisopropyl ether=200 ml/1000 ml) was added to the residue, the residue was dissolved by heating, and then the solution was allowed to stand at room temperature overnight. The precipitated crystals were filtered off and dried to give 34.7 g of the target compound. The mother liquor was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (mobile phase:hexane/ethyl acetate=1/1) to give further 43.8 g of the target compound (total 43%).

후처리

  1. temperatureAfter ice-cooling
  2. stirringThe mixture was stirred under ice-
  3. temperaturecooling for 15 minutes, at room temperature for one hour and further at an internal temperature of about 40° C. for three days
  4. concentrationThe reaction mixture was concentrated under reduced pressure
  5. additiona 10% aqueous citric acid solution (1,000 ml) was added to the residue
  6. extractionthe whole was extracted with ethyl acetate (1,000 ml)
  7. washThe organic layer was washed with water (1,000 ml) and saturated brine (1,000 ml) successively
  8. customwas evaporated under reduced pressure
  9. additionA mixed solvent (ethanol/diisopropyl ether=200 ml/1000 ml) was added to the residue
  10. dissolutionthe residue was dissolved
  11. temperatureby heating
  12. filtrationThe precipitated crystals were filtered off
  13. customdried

출처 및 근거

ORD 기록
ord-03d4a091d2714eab94f05f979371c1fd
출처 데이터셋
uspto-grants-2008_08
특허 번호
US07410987B2

반응 노트

불러오는 중…