Propargyl bromide → 1,2,4-Trichlorophenyl-3-(2-propynyloxy) benzene

HRID 1858120

反応式

HRID 1858120 の反応式
C1C2C(COC([C:18]3[C:31](OC)=[CH:30][C:21]([O:22][CH2:23][CH2:24][CH2:25]CC(O)=O)=[C:20](CN)[C:19]=3OC)=O)C3C(=CC=CC=3)C=2C=CC=1.[Cl:38][C:39]1[C:44]([Cl:45])=[CH:43][CH:42]=[C:41]([Cl:46])[C:40]=1O.C1OC2C(=C(O)C=CC=2)O1.CC(C)([O-])C.[K+].C(Br)C#C>CN(C=O)C>[Cl:45][C:44]1([C:19]2[CH:18]=[CH:31][CH:30]=[C:21]([O:22][CH2:23][C:24]#[CH:25])[CH:20]=2)[CH:43]=[CH:42][C:41]([Cl:46])=[CH:40][CH:39]1[Cl:38]

参加物

7

反応物 5

HCID 7842Propargyl bromideHCID 136182,3,6-TrichlorophenolHCID 5867271,3-Benzodioxol-4-olHCID 23665647Potassium tert-butoxideHCID 867560505-(4-Fmoc-aminomethyl-3,5-dimethoxyphenoxy)valeric acid

生成物 1

HCID 867560491,2,4-Trichlorophenyl-3-(2-propynyloxy) benzene

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

反応条件

温度
110 °C

実験手順

1,2,4-trichlorophenyl-3-(2-propynyloxy) benzene (TCPB) and 1-(2-propynyloxy)methylenedioxyphenyl ether (MDPPE) were synthesized by the method of F. Albericio et al., "Preparation and Application of the 5-(4-(9-Fluorenylmethyloxy carbonyl)-Aminomethyl-3,5-Dimethoxyphenoxy)-Valeric Acid Handle for the Solid Phase Synthesis of C-Terminal Peptide Amides under Mild Conditions," J. Org. Chem. vol. 55, pp. 3730-3743 (1990) (FIG. 2). A mixture of 2,3,6-trichlorophenol or methylenedioxyphenol (0.05 mole), potassium tert-butoxide (6.16 g, 0.055 mole), propargyl bromide (6.6 g, 0.055 mole) in dry DMF (60 mL) was heated and stirred at 110° C. for 5 h, after which the solvent was removed under high vacuum. Ethyl acetate was added, the inorganic salts were removed by filtration, and the organic extract was washed sequentially with water, 2 M NaOH, and saturated aqueous NaCl. The organic phase was dried overnight (Na2SO4) to give a crude product. MDPPE, a liquid product, was purified by silica gel chromatography using hexane-ethyl acetate (7:3) as the eluting solvent. Yield: 6.5 g (74%). 1H NMR (CDCl3): d 2.54 (t, 1H, CH), 4.61 (d, 2H, --OCH2 --), 5.92 (s, 2H, --OCH2O--), 6.38-6.73 (m, 3H, aromatics). GC-MS (m/z): M+· =176.

後処理

  1. temperaturewas heated
  2. customafter which the solvent was removed under high vacuum
  3. additionEthyl acetate was added
  4. customthe inorganic salts were removed by filtration
  5. extractionthe organic extract
  6. washwas washed sequentially with water, 2 M NaOH, and saturated aqueous NaCl
  7. dry with materialThe organic phase was dried overnight (Na2SO4)

出典と根拠

ORDレコード
ord-0cd46401290842c781b8e09766f3081f
出典データセット
uspto-grants-2000_11
特許番号
US06150404

関連ノート

読み込み中…