2,6-Lutidine → p-Nitrobenzyl 2-(4-Acetylthio-2-oxo-1-azetidinyl)-2-triphenylphosphoranylideneacetate

HRID 1680322Notes

Reaction equation

HRID 1680322 reaction equation
[C:1]([S:4][CH:5]1[N:8]([CH:9](Cl)[C:10]([O:12][CH2:13][C:14]2[CH:19]=[CH:18][C:17]([N+:20]([O-:22])=[O:21])=[CH:16][CH:15]=2)=[O:11])[C:7](=[O:24])[CH2:6]1)(=[O:3])[CH3:2].N1C(C)=CC=CC=1C.[C:33]1([P:39]([C:46]2[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=2)[C:40]2[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=2)[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1>O1CCOCC1>[C:1]([S:4][CH:5]1[N:8]([C:9](=[P:39]([C:40]2[CH:41]=[CH:42][CH:43]=[CH:44][CH:45]=2)([C:46]2[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=2)[C:33]2[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=2)[C:10]([O:12][CH2:13][C:14]2[CH:19]=[CH:18][C:17]([N+:20]([O-:22])=[O:21])=[CH:16][CH:15]=2)=[O:11])[C:7](=[O:24])[CH2:6]1)(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 79372,6-LutidineHCID 11776TriphenylphosphineHCID 13132062p-Nitrobenzyl 2-(4-Acetylthio-2-oxo-1-azetidinyl)-2-chloroacetate

Product 1

HCID 13132063p-Nitrobenzyl 2-(4-Acetylthio-2-oxo-1-azetidinyl)-2-triphenylphosphoranylideneacetateYield 50%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

To a solution of crude p-nitrobenzyl 2-(4-acetylthio-2-oxo-1-azetidinyl)-2-chloroacetate (92.9 g., 0.249 mole) in dioxane (1200 ml.) were added in succession 2,6-lutidine (31 ml., 0.274 mole) and triphenylphosphine (71.7 g., 0.274 mole). The resulting mixture was stirred at 45°-47° for 18 hours, cooled to 23° and filtered. The filtrate was concentrated on a rotary evaporator to leave a yellow oil which was purified as follows: absorption on a column of silica gel1 and elution with petroleum ether (4000 ml.), methylene chloride (4000 ml.) and ethyl acetate (4000 ml.). The petroleum-ether fraction was discarded since it contained only impurities. The ethyl acetate fraction was concentrated on a rotary evaporator and the oily residue was triturated with diethyl ether to give the title product as a white solid (74.5 g.), m.p. 162°-165°. The methylene chloride eluate was concentrated to dryness and the oily residue again purified by chromatography as above to give 15.0 g. of title product. The combined solids were dissolved in methylene chloride, treated with activated charcoal, concentrated and recrystallized in diethyl ether to give a total of 87 g. (58%) of title product.

Workup

  1. temperaturecooled to 23°
  2. filtrationfiltered
  3. concentrationThe filtrate was concentrated on a rotary evaporator
  4. customto leave a yellow oil which
  5. customwas purified
  6. customabsorption
  7. washon a column of silica gel1 and elution with petroleum ether (4000 ml.), methylene chloride (4000 ml.) and ethyl acetate (4000 ml.)
  8. concentrationThe ethyl acetate fraction was concentrated on a rotary evaporator
  9. customthe oily residue was triturated with diethyl ether

Sources & evidence

ORD record
ord-35e02ec41fef4646b619a8d896982a1a
Source dataset
uspto-grants-1981_06
Patent number
US04272437

Reaction notes

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