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2,6-Lutidine → (3S, 4R)-3-[(R)-1-t-Butyldimethylsilyloxyethyl]-4-[(R)-1-methyl-2-(p-nitrobenzyloxycarbonylamino)ethylthio(thiocarbonyl)]thio-1-[1-(p-nitrobenzyloxycarbonyl)triphenylphosphoranylidenemethyl]azetidin-2-one

HRID 1075223
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HRID 1075223 반응식
[Si:1]([O:8][C@@H:9]([C@@H:11]1[C@@H:14]([S:15][C:16]([S:18][C@H:19]([CH3:35])[CH2:20][NH:21][C:22]([O:24][CH2:25][C:26]2[CH:31]=[CH:30][C:29]([N+:32]([O-:34])=[O:33])=[CH:28][CH:27]=2)=[O:23])=[S:17])[N:13]([CH:36](O)[C:37]([O:39][CH2:40][C:41]2[CH:46]=[CH:45][C:44]([N+:47]([O-:49])=[O:48])=[CH:43][CH:42]=2)=[O:38])[C:12]1=[O:51])[CH3:10])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].N1C(C)=CC=CC=1C.S(Cl)(Cl)=O.[C:64]1([P:70]([C:77]2[CH:82]=[CH:81][CH:80]=[CH:79][CH:78]=2)[C:71]2[CH:76]=[CH:75][CH:74]=[CH:73][CH:72]=2)[CH:69]=[CH:68][CH:67]=[CH:66][CH:65]=1>O1CCCC1.C(OCC)(=O)C>[Si:1]([O:8][C@@H:9]([C@@H:11]1[C@@H:14]([S:15][C:16]([S:18][C@H:19]([CH3:35])[CH2:20][NH:21][C:22]([O:24][CH2:25][C:26]2[CH:31]=[CH:30][C:29]([N+:32]([O-:34])=[O:33])=[CH:28][CH:27]=2)=[O:23])=[S:17])[N:13]([C:36](=[P:70]([C:71]2[CH:72]=[CH:73][CH:74]=[CH:75][CH:76]=2)([C:77]2[CH:82]=[CH:81][CH:80]=[CH:79][CH:78]=2)[C:64]2[CH:65]=[CH:66][CH:67]=[CH:68][CH:69]=2)[C:37]([O:39][CH2:40][C:41]2[CH:42]=[CH:43][C:44]([N+:47]([O-:49])=[O:48])=[CH:45][CH:46]=2)=[O:38])[C:12]1=[O:51])[CH3:10])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:2])[CH3:3]
참가 물질실험 절차후처리출처 및 근거반응 노트

참가 물질

7

반응물 4

HCID 79372,6-Lutidine2회HCID 11776TriphenylphosphineHCID 24386Thionyl ChlorideHCID 131713038HCID 131713038, 화합물

생성물 1

HCID 57179080(3S, 4R)-3-[(R)-1-t-Butyldimethylsilyloxyethyl]-4-[(R)-1-methyl-2-(p-nitrobenzyloxycarbonylamino)ethylthio(thiocarbonyl)]thio-1-[1-(p-nitrobenzyloxycarbonyl)triphenylphosphoranylidenemethyl]azetidin-2-one
수율 66%

시약·촉매·용매 2

HCID 8028Tetrahydrofuran용매HCID 8857Ethyl Acetate용매

실험 절차

To a solution of (3S, 4R)-3-[(R)-1-t-butyldimethylsilyloxyethyl]-1-[1-hydroxy-1-(p-nitrobenzyloxycarbonyl)methyl]-4-[(R)-1-methyl-2-(p-nitrobenzyloxycarbonylamino)ethylthio(thiocarbonyl)]thioazetidin-2-one (12.6 g, 16.1 mmole) in tetrahydrofuran (150 ml) were added at -15° C., in turn, 2,6-lutidine (2.00 g, 18.7 mmole) and thionyl chloride (2.11 g, 17.7 mmole), and the mixture was stirred at the same temperature for 15 minutes. 2,6-Lutidine (3.45 g, 32.2 mmole) and triphenylphosphine (12.6 g, 48.1 mmole) were then added and the mixture was stirred at 65° C. under a nitrogen stream for a further 35 hours. After completion of the reaction, the reaction mixture was diluted with ethyl acetate; washed with water and dried. The solvent was distilled off under reduced pressure and the residue was purified by column chromatography (250 g of silica gel); eluted with a 15-20% v/v solution of ethyl acetate in benzene; giving the desired compound (10.9 g; 66%) in the form of a yellow oil.

후처리

  1. stirringthe mixture was stirred at 65° C. under a nitrogen stream for a further 35 hours
  2. customAfter completion of the reaction
  3. washwashed with water
  4. customdried
  5. distillationThe solvent was distilled off under reduced pressure
  6. customthe residue was purified by column chromatography (250 g of silica gel)
  7. washeluted with a 15-20% v/v solution of ethyl acetate in benzene

출처 및 근거

ORD 기록
ord-b5d52899338f4075a7f7efd864802605
출처 데이터셋
uspto-grants-1983_07
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US04395418

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