1,2-Dichloroethane → Ethyl 3-[(dipropylamino)carbonyl]-5-(hydroxymethyl)benzoate

HRID 1783233

反応式

HRID 1783233 の反応式
[CH2:1]([O:3][C:4]([C:6]1[CH:7]=[C:8]([CH:12]=[C:13]([CH2:15][OH:16])[CH:14]=1)[C:9]([OH:11])=O)=[O:5])[CH3:2].C(Cl)CCl.C(N(C(C)C)CC)(C)C.[CH2:30]([NH:33][CH2:34][CH2:35][CH3:36])[CH2:31][CH3:32]>CN(C=O)C>[CH2:30]([N:33]([CH2:34][CH2:35][CH3:36])[C:9]([C:8]1[CH:7]=[C:6]([CH:14]=[C:13]([CH2:15][OH:16])[CH:12]=1)[C:4]([O:3][CH2:1][CH3:2])=[O:5])=[O:11])[CH2:31][CH3:32]

参加物

6

反応物 4

HCID 111,2-DichloroethaneHCID 8902DipropylamineHCID 81531DiisopropylethylamineHCID 210858293-(Ethoxycarbonyl)-5-(hydroxymethyl)benzoic acid

生成物 1

HCID 21086103Ethyl 3-[(dipropylamino)carbonyl]-5-(hydroxymethyl)benzoate

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

A mixture of diethyl 1,3,5-benzenetricarboxylate (5.2 g) and borane methylsulfide complex (6.1 g) is stirred in THF (150 mL) at 20-25 degrees C. overnight. The mixture is then treated with methanol, concentrated to dryness, and chouromatographed (silica gel) to give diethyl 5-(hydroxymethyl)isophthalate. Diethyl 5-(hydroxymethyl)isophthalate (3.4 g) is hydroyzed in ethanol and water with lithium hydroxide monohydrate (0.57 g) at 20-25 degrees C. for 3.5 hours at which time the solvents are removed under reduced pressure. Water (100 mL) is added and the mixture is acidified to pH=4 with concentrated hydrochloric acid. The mixture is extracted with ethyl acetate and dried over magnesium sulfate, filtered, and concentrated to give 3-(ethoxycarbonyl)-5-(hydroxymethyl)benzoic acid, high resolution MS MH+=225.0769. 3-(Ethoxycarbonyl)-5-(hydroxymethyl)benzoic acid (2.3 g), EDC (3.0 g), 1-HOBT (2.1 g), diisopropylethylamine (2.7 mL), dipropyl amine (2.8 mL), and DMF (50 mL) are stirred at 20-25 degrees C. overnight. The mixture is then partitioned between ethyl acetate, water, and saline. The organic phase is separated and dried over magnesium sulfate, filtered, and concentrated. Chromatography (silica gel) gives ethyl 3-[(dipropylamino)carbonyl]-5-(hydroxymethyl)benzoate, NMR (CDCl3) δ 0.77, 1.0, 1.4, 1.6, 1.7, 3.2, 3.5, 4.4, 4.8, 7.6, 8.0 and 8.1.

後処理

  1. customovernight
  2. customThe mixture is then partitioned between ethyl acetate, water, and saline
  3. customThe organic phase is separated
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated

出典と根拠

ORDレコード
ord-2a178ecf83f346c0b9b4d34eb4fb567d
出典データセット
uspto-grants-2009_03
特許番号
US07498436B2

関連ノート

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