4-Fluorobenzylamine → Bis(4-fluorobenzyl)aMine, 97%

HRID 392827Notes

Reaction equation

HRID 392827 reaction equation
[F:1][C:2]1[CH:9]=[CH:8][C:5]([CH2:6][NH2:7])=[CH:4][CH:3]=1.[F:10][C:11]1[CH:18]=[CH:17][C:14]([CH2:15]Br)=[CH:13][CH:12]=1>C1COCC1>[F:1][C:2]1[CH:9]=[CH:8][C:5]([CH2:6][NH:7][CH2:15][C:14]2[CH:17]=[CH:18][C:11]([F:10])=[CH:12][CH:13]=2)=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 673264-FluorobenzylamineHCID 680214-Fluorobenzyl bromide

Product 1

HCID 834401Bis(4-fluorobenzyl)aMine, 97%Yield 98.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To 4-flourobenzylamine (1.17 g, 9.4 mmol) dissolved in 5 mL of THF was added 4-fluorobenzyl-bromide (0.88 g, 4.7 mmol) dropwise. The reaction was stirred overnight resulting in the formation of a white solid. After filtering off the solid solvent was removed to yield 1.08 g crude di-(4-fluorobenzyl) amine. To this was added 19 mL of CH2Cl2 and 19 mL of saturated (aq.) NaHCO3. Acetyl chloride (0.67 mL, 9.4 mmol) was added to the rapidly stirring mixture and the reaction allowed to proceed overnight. The mixture was diluted with CH2Cl2, transferred to a separatory funnel. The organic layer was separated, washed with satd (aq.) NaCl, dried over Na2SO4 and the solvent removed to yield 1.01 g oil. The product was purified by column chromatography (4×7 cm SiO2, 20-40% EtOAc/Hexanes) to yield 603 mg (55% yield) oil. LC/MS (M+H) calcd for C14H14NF2: 276.12, found: 276.13. HRMS (M+H) calcd for C14H14NF2: 276.1200, found: 276.1192. Anal calcd for C16H15F2NO: C, 69.80; H, 5.49; N, 5.08; found: C, 59.53; H, 5.41; N, 5.06. 1H NMR (500 MHz, DMSO) δ: 2.10 (s, 3), 4.45 (s, 2), 4.49 (s, 2), 7.18-7.27 (m, 8). 13C NMR (125 MHz, DMSO) δ; 21.34, 47.04, 50.04, 114.90, 115.07, 115.27, 115.45, 128.51, 128.58, 129.57, 129.64, 133.32, 133.34, 133.86, 133.89, 160.25, 160.33, 162.17, 162.27, 170.22.

Workup

  1. customresulting in the formation of a white solid
  2. filtrationAfter filtering off the solid solvent
  3. customwas removed

Sources & evidence

ORD record
ord-2850a09dc08c451689523c9af810fdff
Source dataset
uspto-grants-2004_10
Patent number
US06803378B2

Reaction notes

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