Ethanol → 6-Cyano-3,3a,7,7a-tetrahydro-1H-4-thia-2-aza-cyclopenta[alpha]pentalene-2-carboxylic acid ethyl ester

HRID 30240노트

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HRID 30240 반응식
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]

참가 물질

5

반응물 3

HCID 702EthanolHCID 10906Tert-Butyl nitriteHCID 116082745-Chloro-1,2,3,3a,7,7a-hexahydro-4-thia-2-aza-cyclopenta[alpha]pentalene-6-carbonitrile

생성물 1

HCID 1317270236-Cyano-3,3a,7,7a-tetrahydro-1H-4-thia-2-aza-cyclopenta[alpha]pentalene-2-carboxylic acid ethyl ester수율 27%

시약·촉매·용매 1

HCID 8895Cupric acetate촉매

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온도
60 °C

실험 절차

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.

후처리

  1. temperaturethe reaction mixture was cooled
  2. concentrationthe EtOH was concentrated
  3. customThe residue was partitioned between brine (5 ml) and EtOAc (10 ml)
  4. washThe brine layer was washed with EtOAc (4×10 ml)
  5. dry with materialthe combined organic layers were dried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated

출처 및 근거

ORD 기록
ord-e778a3ebb3e64323942fae4f1b14a61e
출처 데이터셋
uspto-grants-2008_09
특허 번호
US07423056B2

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