Triphenylphosphine → HCID 86671497、化合物

HRID 536618ノート

反応式

HRID 536618 の反応式
Br[C:2]1[C:3]([C:7]2[CH:14]=[CH:13][C:10]([C:11]#[N:12])=[CH:9][C:8]=2[CH3:15])=[CH:4][S:5][CH:6]=1.C(P(=[CH:37][C:38]([O:40][CH2:41][CH3:42])=[O:39])=O)(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[CH:43]1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>CN(C=O)C.CCOC(C)=O.CC([O-])=O.CC([O-])=O.[Pd+2]>[C:11]([C:10]1[CH:13]=[CH:14][C:7]([C:3]2[C:2](/[CH:43]=[CH:37]/[C:38]([O:40][CH2:41][CH3:42])=[O:39])=[CH:6][S:5][CH:4]=2)=[C:8]([CH3:15])[CH:9]=1)#[N:12]

参加物

7

反応物 3

HCID 11776TriphenylphosphineHCID 67254694HCID 67254694、化合物HCID 86671498HCID 86671498、化合物

生成物 1

HCID 86671497HCID 86671497、化合物収率 386.5%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 6228Dimethylformamide溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
150 °C

実験手順

To a solution of 4-(4-bromothiophen-3-yl)-3-methylbenzonitrile (2.4 g, 8.7 mmol) and ethyl 2-(tritylphosphinylidene)acetate (2.6 g, 26 mmol) in DMF (10 mL) was added Pd(OAc)2 (194 mg, 0.87 mmol) and PPh3 (228 mg, 0.87 mmol), and the mixture was stirred at 150° C. under nitrogen overnight. The mixture was diluted with EtOAc. The organic layer was washed with water and brine, dried over Na2SO4, concentrated in vacuo, and purified on silica gel column (PE: EtOAc=20:1) to give (E)-ethyl 3-(4-(4-cyano-2-methylphenyl)thiophen-3-yl)acrylate (Scheme III, 14, X1=4-cyano-2-methylphenyl) (1 g, yield 39%) as yellow oil. 1H NMR (CD3OD 400 MHz): δ 8.03 (d, J=2.8 Hz, 1H), 7.71 (s, 1H), 7.64 (d, J=7.6 Hz, 1H), 7.39-7.34 (m, 2H), 7.28 (d, J=16 Hz, 1H), 6.06 (d, J=16.4 Hz, 1H), 4.15 (q, J=7.2 Hz, 2H), 2.15 (s, 3H), 1.24 (t, J=7.2 Hz, 3H).

後処理

  1. washThe organic layer was washed with water and brine
  2. dry with materialdried over Na2SO4
  3. concentrationconcentrated in vacuo
  4. custompurified on silica gel column (PE: EtOAc=20:1)

出典と根拠

ORDレコード
ord-606158940f5140e9bc79109abfa30b5f
出典データセット
uspto-grants-2014_10
特許番号
US08859611B2

反応ノート

読み込み中…