Hydroquinone → HCID 13219905, compound

HRID 342288Notes

Reaction equation

HRID 342288 reaction equation
[Si](O[C@@H]([C@@H]1[C@@H](CC(S[C@H]2CCN(C(OCC3C=CC([N+]([O-])=O)=CC=3)=O)C2)=O)N(CCOCC2C=CC([N+]([O-])=O)=CC=2)C1=O)C)(C(C)(C)C)(C)C.P(OCC)(OCC)OCC.C1(C=CC(O)=CC=1)O.[Si:69]([O:76][C@@H:77]([C@@H:79]1[C@@H:82]([CH2:83][C:84]([S:86][C@H:87]2[CH2:91][CH2:90][N:89]([C:92]([O:94][CH2:95][C:96]3[CH:101]=[CH:100][C:99]([N+:102]([O-:104])=[O:103])=[CH:98][CH:97]=3)=[O:93])[CH2:88]2)=O)[N:81]([C:105]([C:116]([O:118][CH2:119][C:120]2[CH:125]=[CH:124][C:123]([N+:126]([O-:128])=[O:127])=[CH:122][CH:121]=2)=[O:117])=P(OCC)(OCC)OCC)[C:80]1=[O:129])[CH3:78])([C:72]([CH3:75])([CH3:74])[CH3:73])([CH3:71])[CH3:70]>C1(C)C=CC=CC=1>[Si:69]([O:76][C@@H:77]([C@H:79]1[C:80](=[O:129])[N:81]2[C:105]([C:116]([O:118][CH2:119][C:120]3[CH:121]=[CH:122][C:123]([N+:126]([O-:128])=[O:127])=[CH:124][CH:125]=3)=[O:117])=[C:84]([S:86][C@H:87]3[CH2:91][CH2:90][N:89]([C:92]([O:94][CH2:95][C:96]4[CH:101]=[CH:100][C:99]([N+:102]([O-:104])=[O:103])=[CH:98][CH:97]=4)=[O:93])[CH2:88]3)[CH2:83][C@H:82]12)[CH3:78])([C:72]([CH3:74])([CH3:75])[CH3:73])([CH3:71])[CH3:70]

Participants

6

Reactant 4

HCID 785HydroquinoneHCID 31215Triethyl phosphiteHCID 13219885HCID 13219885, compoundHCID 131721068HCID 131721068, compound

Product 1

HCID 13219905HCID 13219905, compoundYield 83%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
95 °C

Procedure

A solution of 190 mg (0.25 mmole) of (3S, 4R)-3-[(R)-1-t-butyldimethylsilyloxyethyl]-1-(p-nitrobenzyloxyethyl)-4-([(S)-1-(p-nitrobenzyloxycarbonyl)pyrrolidin-3-ylthio]carbonylmethyl)-2-azetidinone, 250 mg (1.5 mmole) of triethyl phosphite and 10 mg (0.90 mmole) of hydroquinone in 20 ml of toluene was heated at 95° C. for 15 hours. On thin layer chromatography, disappearance of the starting materials and appearance of 1-(N-methylformimidoyl)pyrrolidin-3-yl, (3S,4R)-3-[(R)-1-t-butyldimethylsilyloxyethyl]-1-[1-(p-nitrobenzyloxycarbonyl)-1-triethoxyphosphoranylidenemethyl]-4-([(S)-1-(p-nitrobenzyloxy-carbonyl)pyrrolidin-3-ylthio]carbonylmethyl)-2-azetidinone and the desired carbapenem compound were observed. The solvent and excess triethyl phosphite were evaporated off under reduced pressure. To the oily residue were added 20 ml of toluene and the mixture was heated at 95° C. For 57 hours to complete the cyclization reaction of the phosphoranylidene compound. After evaporation of the solvent, the residue was purified with a Lobar column. The fraction eluted with a 2:1 by volume mixture of benzene and ethyl acetate was collected and 151.5 mg (yield 83%) of the title compound was obtained as an oil.

Workup

  1. customThe solvent and excess triethyl phosphite were evaporated off under reduced pressure
  2. additionTo the oily residue were added 20 ml of toluene
  3. customthe cyclization reaction of the phosphoranylidene compound
  4. customAfter evaporation of the solvent
  5. customthe residue was purified with a Lobar column
  6. washThe fraction eluted with a 2:1 by volume mixture of benzene and ethyl acetate
  7. customwas collected

Sources & evidence

ORD record
ord-a4adbea44b084b5289547430e069af54
Source dataset
uspto-grants-1999_01
Patent number
US05856556

Reaction notes

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