Citric Acid → 3-(aminomethyl)benzoic acid

HRID 1417887Notes

Reaction equation

HRID 1417887 reaction equation
Cl.CCN([CH:8]([CH3:10])[CH3:9])C(C)C.[NH:11](C(OC(C)(C)C)=O)[C@H](C(ON1C(=O)CCC1=O)=O)CC(=O)OCC1C=CC=CC=1.[C:41](O)(=O)[CH2:42][C:43]([CH2:48][C:49]([OH:51])=[O:50])(C(O)=O)O>CN(C=O)C.[Au]>[NH2:11][CH2:41][C:42]1[CH:43]=[C:48]([CH:10]=[CH:8][CH:9]=1)[C:49]([OH:51])=[O:50]

Participants

7

Reactant 4

HCID 311Citric AcidHCID 313Hydrochloric AcidHCID 81531DiisopropylethylamineHCID 135177984-Benzyl 1-(2,5-dioxopyrrolidin-1-yl) N-(tert-butoxycarbonyl)-L-aspartate

Product 1

HCID 5060733-(aminomethyl)benzoic acidYield 92%

Reagents, catalysts & solvents 2

HCID 23985GoldCatalystHCID 6228DimethylformamideSolvent2×

Conditions

Temperature
5 °C

Procedure

HCl (Mamb; 13.08 g, 70.0 mmol) was dissolved in 120 ml DMF and DIEA (24.32 ml, 140 mmol) was added, changing the pH from 4 to 7.5. The white suspension was stirred for 30 min at room temperature before a solution of Boc-Asp(OBzl)-OSu (29.40 g, 70.0 mmol) in DMF (50 ml) was added. The mixture was allowed to stir 24 hr, during which time it turned to a gold solution. The solution was added to 5% citric acid (2000 ml) and cooled to 5° C. for 3 hr. The solids were then collected by filtration, washed with ice cold water (200 ml) and ice cold ethyl ether (100 ml), and dried under reduced pressure to give the title compound as a colorless solid (29.62 g, 92%); MP=149°-151° C.; DCI-MS: [M+NH4 ]=474.

Workup

  1. additionwas added
  2. filtrationThe solids were then collected by filtration
  3. washwashed with ice cold water (200 ml) and ice cold ethyl ether (100 ml)
  4. customdried under reduced pressure

Sources & evidence

ORD record
ord-8a26820398594c0497459aa4666308a9
Source dataset
uspto-grants-1999_03
Patent number
US05879657

Reaction notes

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