Water → 3-(Ethoxycarbonyl)-5-(hydroxymethyl)benzoic acid

HRID 348815Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 348815
[OH:1][CH2:2][C:3]1[CH:4]=[C:5]([C:14]([O:16]CC)=[O:15])[CH:6]=[C:7]([CH:13]=1)[C:8]([O:10][CH2:11][CH3:12])=[O:9].O.O.[OH-].[Li+]>C(O)C>[CH2:11]([O:10][C:8]([C:7]1[CH:6]=[C:5]([CH:4]=[C:3]([CH2:2][OH:1])[CH:13]=1)[C:14]([OH:16])=[O:15])=[O:9])[CH3:12]

Komponenten

5

Edukt 3

HCID 962WaterHCID 168937Lithium hydroxide, monohydrateHCID 610139Diethyl 5-(hydroxymethyl)isophthalate

Produkt 1

HCID 210858293-(Ethoxycarbonyl)-5-(hydroxymethyl)benzoic acid

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 702EthanolLösungsmittel

Versuchsvorschrift

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.

Aufarbeitung

  1. customat 20–25 degrees C
  2. customfor 3.5 hours at which time the solvents are removed under reduced pressure
  3. additionWater (100 mL) is added
  4. extractionThe mixture is extracted with ethyl acetate
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-9fcd7e587de14d1db89178ee8d6a642d
Quelldatensatz
uspto-grants-2007_02
Patentnummer
US07176242B2

Notizen zur Reaktion

Wird geladen…