Oxalic Acid → (E)-3-{2-(4-fluoro-3-methylphenyl)-4-(pyrrolidin-1-yl)-6,6-dimethylcyclohex-1-en-1-yl}propenal

HRID 359566ノート

反応式

HRID 359566 の反応式
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH2:13][CH:12]([N:14]3[CH2:18][CH2:17][CH2:16][CH2:15]3)[CH2:11][C:10]([CH3:20])([CH3:19])[C:9]=2[CH:21]=O)=[CH:4][C:3]=1[CH3:23].[Li+].CC([N-]C(C)C)C.C(=NC1CCCCC1)C.[C:41]([OH:46])(=O)[C:42](O)=O>CCOCC.O.C([O-])(O)=O.[Na+]>[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH2:13][CH:12]([N:14]3[CH2:15][CH2:16][CH2:17][CH2:18]3)[CH2:11][C:10]([CH3:19])([CH3:20])[C:9]=2/[CH:21]=[CH:42]/[CH:41]=[O:46])=[CH:4][C:3]=1[CH3:23]

参加物

8

反応物 4

HCID 971Oxalic AcidHCID 2724682Lithium diisopropylamideHCID 10964544N-cyclohexylethanimineHCID 150569662-(4-Fluoro-3-methylphenyl)-4-(pyrrolidin-1-yl)-6, 6-dimethylcyclohex-1-en-1-carboxaldehyde

生成物 1

HCID 15056967(E)-3-{2-(4-fluoro-3-methylphenyl)-4-(pyrrolidin-1-yl)-6,6-dimethylcyclohex-1-en-1-yl}propenal収率 54.9%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 3283Diethyl Ether溶媒2 回HCID 516892Sodium Bicarbonate溶媒

実験手順

In a manner similar to Scheme I, 32 (3.80 g, 12.1 mmol) was treated with the LDA-derived anion of ethylidenecyclohexylamine (2.90 g, 23.2 mmol) in anhydrous ether. Workup and purification of the residue by HPLC. using 1% Et3N in 10:l hexanes:EtOAc as eluent provided the dieneimine (2.4 g). The imine and oxalic acid (10 g) in 40 mL H2O was heated at 100° C. for 2 h, cooled, diluted with saturated NaHCO3 and ether. The organic layer was washed with H2O and brine and dried (MgSO4). Removal of volatiles in vacuo provided 2.27 g of gum which was taken forward without further purification.

後処理

  1. customWorkup and purification of the residue by HPLC
  2. customl hexanes:EtOAc as eluent provided the dieneimine (2.4 g)
  3. temperaturecooled
  4. washThe organic layer was washed with H2O and brine
  5. dry with materialdried (MgSO4)
  6. customRemoval of volatiles in vacuo

出典と根拠

ORDレコード
ord-7d12770473ea4395909f18527ad57bb1
出典データセット
uspto-grants-1991_03
特許番号
US05001144

反応ノート

読み込み中…