Benzoic Acid → 1-(Benzoyloxy)-1H-1,2,3-benzotriazole

HRID 1091244Notes

Reaction equation

HRID 1091244 reaction equation
O[C:2]1[C:10]2[N:9]=[N:8][NH:7][C:6]=2[CH:5]=[CH:4][CH:3]=1.[C:11]([OH:19])(=[O:18])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.CC(C)N=C=NC(C)C>CN(C1C=CN=CC=1)C.CN(C=O)C.C(Cl)Cl>[N:9]1([O:19][C:11](=[O:18])[C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[C:10]2[CH:2]=[CH:3][CH:4]=[CH:5][C:6]=2[N:7]=[N:8]1

Participants

6

Reactant 3

HCID 243Benzoic AcidHCID 12734DiisopropylcarbodiimideHCID 178418300HCID 178418300, compound

Product 1

HCID 5552441-(Benzoyloxy)-1H-1,2,3-benzotriazole

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 22350042dichloromethane N,N-dimethylformamideSolvent

Procedure

Hydroxybenzotriazole resin (0.107 g, 0.196 mmol) was treated with benzoic acid (0.12 g, 0.982 mmol, 5 eq), DIC (0.152 mL, 0.982 mmol, 5 eq) and DMAP (0.024 g, 0.196 mmol, 1 eq) in DMF-CH2Cl2 (1:1) and shaken for 5 h. The mixture was filtered and the resin was washed with DMF (10×5 mL) and CH2Cl2 (10×5 mL) to give resin-supported benzoic acid benzotriazol-1-yl ester. To a suspension of the resin-ester (0.196 mmol, 1.5 eq) in CH2Cl2 (2 mL) were added i-Pr2NEt (0.033 mL, 0.196 mmol, 1.5 eq) and 2-amino-2-methyl-pentan-3-one (0.03 g, 0.131 mmol, 1 eq). The mixture was agitated for 16 h and filtered. The filtrate was shaken with a weakly basic ion exchange resin Amberlite IRA-95 (1 g, 4.7 mmol g−1, 25 eq) for 16 h to remove benzoic acid present in the solution and filtered. The filtrate was eluted through a short column of silica gel (hexane/ethyl acetate 50:50) to remove the unreacted amine. The organic solvent was evaporated to leave N-(1,1-dimethyl-2-oxo-butyl)-benzamide (0.03 g, 87%) as a white solid. 1H NMR (200 MHz, CDCl3) δ (ppm): 1.14 (t, J=7.2 Hz, 3H), 1.57 (s, 6H), 2.63 (q, J=7 Hz, 2H), 7.21 (bs, 1H), 7.38-7.56 (aromatic H's, 3H), 7.79 (dd, J=8, 1.8 Hz, 2H). MS (ESI, positive ion): m/z 220.2 (M+1)+.

Workup

  1. filtrationThe mixture was filtered
  2. washthe resin was washed with DMF (10×5 mL) and CH2Cl2 (10×5 mL)

Sources & evidence

ORD record
ord-b1a421fb6b72444189eccac4c652fe0d
Source dataset
uspto-grants-2012_03
Patent number
US08129355B2

Reaction notes

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