Acetic Acid → HCID 15052432, compound

HRID 1031596Notes

Reaction equation

HRID 1031596 reaction equation
C(O)(=O)C.C(O)CCC.[C:10]([C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1[CH2:19][C:20]([O:22][CH2:23][CH2:24][CH2:25][NH2:26])=[O:21])(O)=[O:11].P(Cl)(Cl)(Cl)(Cl)Cl>CO.[Pd].C1COCC1.O.N1C=CC=CC=1>[NH2:26][CH2:25][CH2:24][CH2:23][O:22][C:20]1[O:21][C:10]([C:13]2[C:14]([CH:19]=1)=[CH:15][CH:16]=[CH:17][CH:18]=2)=[O:11]

Participants

10

Reactant 4

HCID 176Acetic Acid2×HCID 2631-ButanolHCID 24819Phosphorus pentachlorideHCID 15052431HCID 15052431, compound

Product 1

HCID 15052432HCID 15052432, compoundYield 21.6%

Reagents, catalysts & solvents 5

HCID 23938PalladiumCatalystHCID 887MethanolSolventHCID 962WaterSolventHCID 1049PyridineSolventHCID 8028TetrahydrofuranSolvent

Procedure

Homophthalic acid (18 g, 0.1 mole) and 3-(benzyloxycarbonylamino)-1-propanol (41 g, 0.2 mole) were heated in 150 ml of benzene at 120°-130° C. for 2 hrs in the presence of a few drops of conc. H2SO4. Benzene was evaporated, and 200 ml of ethylacetate was added. The organic solution was washed with 4% NaHCO3 twice (150 ml×2). The aqueous layer which contained the monoester salt was acidified with 5N HCl and extracted with ethylacetate. 33 g of 3-(benzyloxycarbonylamino)propyl 2-carboxyphenylacetate (yield, 89%) was obtained after the solvent was evaporated. Hydrogenation of this monoester (1.86 g, 5 mmole) was performed in methanol containing 0.3 ml of acetic acid and 10% palladium on carbon to give 1 g of 3-aminopropyl 2-carboxphenylacetate.HAc (yield, 67%). This compound was identified by its NMR spectrum and TLC (Butanol:acetic acid:pyridine:water=4:1:1:2). 1 g of 3-aminopropyl 2-carboxyphenylacetate.HAc (3 mmole) was heated with 1.6 g of PCl5 (7.5 mmole) in 50 ml of anhydrous THF at 70°-80° C. for 2 hrs, a white precipitate formed. This white solid was purified by column chromatography (methylene chloride:methanol=5:1) and crystallized from MeOH-ether to give 0.2 g of 3-(3-aminopropoxy)isocoumarin.HCl (yield, 26%), m.p. 173°-174° C.; mass spectrum, m/e=220 (M+ -Cl). Anal. Calc. for C12H14N1O3Cl1 : C, 56.37; H, 5.52; N, 5.48; Cl, 13.87. Found: C, 56.15; H, 5.49; N, 5.44; Cl 13.95.

Workup

  1. customwas evaporated
  2. customto give 1 g of 3-aminopropyl 2-carboxphenylacetate.HAc (yield, 67%)
  3. customa white precipitate formed
  4. customThis white solid was purified by column chromatography (methylene chloride:methanol=5:1)
  5. customcrystallized from MeOH-ether

Sources & evidence

ORD record
ord-bf09bb3fa7764b77a0c41127f3bdc652
Source dataset
uspto-grants-1990_09
Patent number
US04954519

Reaction notes

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