(Triphenylphosphoranylidene)acetonitrile → methylene-(2S,5R)-6-[(Z)-cyanomethylene]-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate pivalate

HRID 1981203Notes

Reaction equation

HRID 1981203 reaction equation
[C:1]([OH:7])(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3].[CH2:8]=[S:9]1[CH:15]2[N:12]([C:13](=[O:17])[C:14]2=O)[CH:11]([C:18]([OH:20])=[O:19])[C:10]1([CH3:22])[CH3:21].[C:23]([CH:25]=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)#[N:24]>C1C=CC=CC=1>[C:1]([OH:7])(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3].[CH2:8]=[S:9]1[C@H:15]2[N:12]([C:13](=[O:17])/[C:14]/2=[CH:25]/[C:23]#[N:24])[C@@H:11]([C:18]([OH:20])=[O:19])[C:10]1([CH3:22])[CH3:21].[C:1]([OH:7])(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3].[CH2:8]=[S:9]1[C@H:15]2[N:12]([C:13](=[O:17])/[C:14]/2=[CH:25]\[C:23]#[N:24])[C@@H:11]([C:18]([OH:20])=[O:19])[C:10]1([CH3:22])[CH3:21]

Participants

5

Reactant 2

HCID 85524(Triphenylphosphoranylidene)acetonitrileHCID 86740043Methylene-6,7-dioxo-3,3-dimethyl-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate pivalate

Product 2

HCID 86740045methylene-(2S,5R)-6-[(Z)-cyanomethylene]-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate pivalateHCID 86740047methylene-(2S,5R)-6-[(E)-cyanomethylene]-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate pivalate

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A solution of 3.2 g of methylene-6,7-dioxo-3,3-dimethyl-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate pivalate in 150 ml of benzene is treated at room temperature with 5 g of cyanomethylenetriphenylphosphorane. After 10 minutes, the reaction mixture is evaporated. The residue is chromatographed on silica gel with cyclohexane/ethyl acetate (7:3). There are obtained methylene-(2S,5R)-6-[(Z)-cyanomethylene]-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate pivalate as a reddish oil [Rf: 0.38; cyclohexane/ethyl acetate (6:4); NMR (CDCl3) δ (ppm): 1.24 (9H); 1.53 (3H); 1.59 (3H); 4.59 (1H); 5.84 (2H); 5.89 (1H); 5.97 (1H)] and methylene-(2S,5R)-6-[(E)-cyanomethylene]-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylate pivalate as a reddish oil [Rf: 0.33; cyclohexane/ethyl acetate (6:4); NMR (CDCl3), δ (ppm): 1.24 (9H); 1.51 (3H); 1.6 (3H); 4.64 (1H); 5.59 (1H); 5.84 (3H)].

Workup

  1. customthe reaction mixture is evaporated
  2. customThe residue is chromatographed on silica gel with cyclohexane/ethyl acetate (7:3)

Sources & evidence

ORD record
ord-2c5e73e3ea40438f8323deb0dadb65be
Source dataset
uspto-grants-1985_04
Patent number
US04512999

Reaction notes

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