Ethanol → 6-Cyano-3,3a,7,7a-tetrahydro-1H-4-thia-2-aza-cyclopenta[alpha]pentalene-2-carboxylic acid ethyl ester
Reaction equation
Cl[C:2]1[S:12][C:5]2[CH:6]3[CH:10]([CH2:11][C:4]=2[C:3]=1[C:13]#[N:14])[CH2:9][NH:8][CH2:7]3.N([O:17][C:18]([CH3:21])(C)C)=O.C[CH2:23][OH:24]>CC([O-])=O.CC([O-])=O.[Cu+2]>[CH2:18]([O:17][C:23]([N:8]1[CH2:7][CH:6]2[CH:10]([CH2:11][C:4]3[C:3]([C:13]#[N:14])=[CH:2][S:12][C:5]=32)[CH2:9]1)=[O:24])[CH3:21]Participants
5
Reactant 3
Product 1
Reagents, catalysts & solvents 1
Conditions
- Temperature
- 60 °C
Procedure
The product from Example 12, step a) (105 mg, 0.38 mmol) was dissolved in EtOH (1.9 ml) and treated with t-butyl nitrite (59 mg, 0.57 mmol) followed by Cu(OAc)2 (103 mg, 0.57 mmol). The contents were heated to 60° C. for 1 hour and then the reaction mixture was cooled and the EtOH was concentrated. The residue was partitioned between brine (5 ml) and EtOAc (10 ml). The brine layer was washed with EtOAc (4×10 ml) and the combined organic layers were dried (MgSO4), filtered and concentrated. The crude residue was passed through a plug of silica gel (7:3) hexanes:EtOAc (150 ml) providing the subtitled product as an orange oil (26.7 mg, 27%). MS calculated for C13H14N2O2S+H 263, observed 263.
Workup
- temperaturethe reaction mixture was cooled
- concentrationthe EtOH was concentrated
- customThe residue was partitioned between brine (5 ml) and EtOAc (10 ml)
- washThe brine layer was washed with EtOAc (4×10 ml)
- dry with materialthe combined organic layers were dried (MgSO4)
- filtrationfiltered
- concentrationconcentrated
Sources & evidence
- ORD record
- ord-e778a3ebb3e64323942fae4f1b14a61e
- Source dataset
- uspto-grants-2008_09
- Patent number
- US07423056B2
Reaction notes
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