Triethylamine → Ethyl phenyl-{4-(isopropoxy)-3-vinylphenyl}phosphinate

HRID 1618073ノート

反応式

HRID 1618073 の反応式
[C:1]1([PH:7](=[O:11])[O:8][CH2:9][CH3:10])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Br[C:13]1[CH:18]=[CH:17][C:16]([O:19][CH:20]([CH3:22])[CH3:21])=[C:15]([CH:23]=[CH2:24])[CH:14]=1.C(N(CC)CC)C>C(#N)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[C:1]1([P:7]([C:13]2[CH:18]=[CH:17][C:16]([O:19][CH:20]([CH3:21])[CH3:22])=[C:15]([CH:23]=[CH2:24])[CH:14]=2)(=[O:11])[O:8][CH2:9][CH3:10])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

参加物

7

反応物 3

HCID 8471TriethylamineHCID 125424254-Bromo-1-isopropoxy-2-vinylbenzeneHCID 178476779HCID 178476779、化合物

生成物 1

HCID 66650560Ethyl phenyl-{4-(isopropoxy)-3-vinylphenyl}phosphinate収率 87%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)触媒HCID 6342Acetonitrile溶媒

反応条件

温度
68 °C

実験手順

To a degassed mixture of ethyl phenylphosphinate (1.87 g, 11.0 mmol) and 4-bromo-1-isopropoxy-2-vinylbenzene (2.43 g, 10.0 mmol), which was commercially available, in acetonitrile (66 mL) were added triethylamine (3.1 mL, 22.0 mmol), palladium acetate (112 mg, 0.5 mmol), and 1,1′-bis(diphenylphosphino)ferrocene (277 mg, 0.5 mmol). The mixture was further degassed and heated at 68° C. for 24 hrs. The volatiles were removed in vacuo, and the crude was purified by column chromatography using 50 to 80% ethyl acetate in petroleum ether to afford compound BA4 (3.74 g) in 87% yield. 1H NMR (CDCl3, 400 MHz): δ (ppm) 1.36 (d, J=5.7 Hz, 6H), 1.37 (t, J=6.9 Hz, 3H), 4.15-4.05 (m, 2H), 4.62 (sept., J=6.0 Hz, 1H), 5.28 (dd, J=11.2 and 1.4 Hz, 1H), 5.78 (dd, J=17.7 and 1.4 Hz, 1H), 6.91 (dd, J=8.45 and 3.0 Hz, 1H), 6.99 (dd, J=17.9 and 11.4 Hz, 1H), 7.41-7.47 (m, 2H), 7.47-7.55 (m, 1H), 7.63 (ddd, J=11.7, 8.5 and 2.0 Hz, 1H), 7.79 (dd, J=12.3 and 1.4 Hz, 1H), 7.81 (dt, J=12.3 and 1.4 Hz, 1H), 7.90 (dd, J=12.4 and 2.0 Hz, 1H); 31P NMR (CDCl3, 161.8 MHz): δ (ppm) 32.61.

後処理

  1. customThe mixture was further degassed
  2. customThe volatiles were removed in vacuo
  3. customthe crude was purified by column chromatography
  4. customto afford compound BA4 (3.74 g) in 87% yield

出典と根拠

ORDレコード
ord-18f6e7546c3543bcac2b597a9d97822d
出典データセット
uspto-grants-2014_07
特許番号
US08765966B2

反応ノート

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