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

HRID 30240ノート

反応式

HRID 30240 の反応式
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]

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 8895Cupric acetate触媒

反応条件

温度
60 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-e778a3ebb3e64323942fae4f1b14a61e
出典データセット
uspto-grants-2008_09
特許番号
US07423056B2

反応ノート

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