Triethylamine → t-Butyloxycarbonyl-3-aminomethylbenzoic acid

HRID 1682508Notes

Reaction equation

HRID 1682508 reaction equation
[NH2:1][CH2:2][C:3]1[CH:4]=[C:5]([CH:9]=[CH:10][CH:11]=1)[C:6]([OH:8])=[O:7].[CH3:12][C:13]([O:16][C:17](ON=C(C1C=CC=CC=1)C#N)=[O:18])([CH3:15])[CH3:14].C(N(CC)CC)C>O.CC(C)=O>[C:13]([O:16][C:17]([C:4]1[C:3]([CH2:2][NH2:1])=[CH:11][CH:10]=[CH:9][C:5]=1[C:6]([OH:8])=[O:7])=[O:18])([CH3:15])([CH3:14])[CH3:12]

Participants

6

Reactant 3

HCID 8471Triethylamine2×HCID 938652-(tert-Butoxycarbonyloxyimino)-2-phenylacetonitrileHCID 5060733-(aminomethyl)benzoic acid

Product 1

HCID 22497759t-Butyloxycarbonyl-3-aminomethylbenzoic acidYield 64.2%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolvent2×HCID 962WaterSolvent

Procedure

The title compound was prepared according to a modification of standard procedures previously reported in the literature (Itoh, Hagiwara, and Kamiya (1975) Tett. Lett., 4393). 3-Aminomethylbenzoic acid (hydrochloride salt) (3.0 g, 16.0 mmol) was dissolved in 60 ml H2O. To this was added a solution of Boc-ON (4.33 g, 17.6 mmol) in 60 ml acetone followed by triethylamine (5.56 ml, 39.9 mmol). The solution turned yellow and the pH was adjusted to 9 (wet pH paper) by adding an additional 1.0 ml (7.2 mmol) triethylamine. The solution was stirred overnight at room temperature at which time the acetone was removed under reduced pressure and the remaining aqueous layer was washed three times with ether. The aqueous layer was then acidified to pH 2 with 2N HCl and then extracted three times with ethyl acetate. The combined organic layers were washed three times with H2O, dried over anhydrous magnesium sulfate, and evaporated to dryness under reduced pressure. The material was recrystallized from ethyl acetate/hexane to give two crops of the title compound (2.58 g, 64%) as an off-white solid. mp 123°-125° C.; 1H NMR (CDCl3) 1.47 (s, 9H), 4.38 (br s, 2H), 4.95 (br s, 1H), 7.45 (t, 1H), 7.55 (d, 1H), 8.02 (d, 2H).

Workup

  1. customThe title compound was prepared
  2. customwas removed under reduced pressure
  3. washthe remaining aqueous layer was washed three times with ether
  4. extractionextracted three times with ethyl acetate
  5. washThe combined organic layers were washed three times with H2O
  6. dry with materialdried over anhydrous magnesium sulfate
  7. customevaporated to dryness under reduced pressure
  8. customThe material was recrystallized from ethyl acetate/hexane

Sources & evidence

ORD record
ord-53a5d7cc982b4ccc98ed19a16d09862f
Source dataset
uspto-grants-1997_06
Patent number
US05635477

Reaction notes

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