Triphenylphosphine → Tert-butyl 2-(aminomethyl)-4-chlorobenzylcarbamate

HRID 1859402Notes

Reaction equation

HRID 1859402 reaction equation
[N:1]([CH2:4][C:5]1[CH:10]=[C:9]([Cl:11])[CH:8]=[CH:7][C:6]=1[CH2:12][NH:13][C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])=[N+]=[N-].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1COCC1.O>[C:17]([O:16][C:14]([NH:13][CH2:12][C:6]1[CH:7]=[CH:8][C:9]([Cl:11])=[CH:10][C:5]=1[CH2:4][NH2:1])=[O:15])([CH3:20])([CH3:18])[CH3:19]

Participants

5

Reactant 2

HCID 11776TriphenylphosphineHCID 12052445Tert-butyl 2-(azidomethyl)-4-chlorobenzylcarbamate

Product 1

HCID 11149921Tert-butyl 2-(aminomethyl)-4-chlorobenzylcarbamateYield 88.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

To a stirred solution of 1-azidomethyl-2-(tert-butyloxycarbonylaminomethyl)-5-chlorobenzene (10.9 g, 36.73 mmol) in THF (60 mL) and water (6 mL) was added triphenylphospine (10.59 g, 40.40 mmol). The reaction was heated to 50° C. and stirred for 18 h. The reaction was concentrated in vacuo and the residue was purified by flash chromatography using a gradient elution of 2%, 3%, 4%, 5% A in dichloromethane (A=95:5 MeOH:NH4OH). Concentration of product-containing fractions in vacuo gave 2-(tert-butyloxycarbonylaminomethyl)-5-chlorobenzylamine as a solid (8.8 g, 88% yield). TLC Rf=0.3 (95:5:0.25 CH2Cl2:MeOH:NH4OH); HPLC RT=2.64 min (Method A); LC-MS m/z=271; 1H NMR (CDCl3, 400 MHz) 7.21-7.52 ppm (m, 3H); 4.32 ppm (b d, 2H); 3.90 ppm (s, 2H); 1.44 ppm (s, 9H).

Workup

  1. concentrationThe reaction was concentrated in vacuo
  2. customthe residue was purified by flash chromatography
  3. washa gradient elution of 2%, 3%, 4%, 5% A in dichloromethane (A=95:5 MeOH

Sources & evidence

ORD record
ord-b3512bd97e6f43a5bc5801c50a306c45
Source dataset
uspto-grants-2003_03
Patent number
US06528503B2

Reaction notes

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