Benzylamine → Benzyl-(3-bromo-5-ethoxymethyl-2-methyl-phenyl)-amine

HRID 1667510Notes

Reaction equation

Br[C:2]1[CH:7]=[C:6]([CH2:8][O:9][CH2:10][CH3:11])[CH:5]=[C:4]([Br:12])[C:3]=1[CH3:13].[CH2:14]([NH2:21])[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.CC([O-])(C)C.[Na+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(C)C=CC=CC=1>[CH2:14]([NH:21][C:2]1[CH:7]=[C:6]([CH2:8][O:9][CH2:10][CH3:11])[CH:5]=[C:4]([Br:12])[C:3]=1[CH3:13])[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1

Participants

Conditions

Temperature: 80 °C

Procedure

A mixture of 1,3-dibromo-5-ethoxymethyl-2-methyl-benzene (1.322 g, 4.29 mmol), benzylamine (0.49 mL, 4.507 mmol), Pd2(dba)3 (409 mg, 0.447 mmol), rac-BINAP (811 mg, 1.302 mmol), NaOtBu (618 mg, 6.435 mmol) and toluene (30 mL) was heated at 80° C. for 1 h 45 minutes. The reaction was cooled, poured onto water and extracted with EtOAc (×3). The organics were washed with water, brine and dried (Na2SO4). Chromatography (Hexanes/EtOAc) afforded benzyl-(3-bromo-5-ethoxymethyl-2-methyl-phenyl)-amine (1.268 g) as a yellow liquid. 1H NMR (400 MHz, d6-DMSO) δ: 1.24 (t, 3H), 2.32 (s, 3H), 3.50 (q, 2H), 4.04 (bs, 1H), 4.41 (s, 4H), 6.61 (s, 1H), 7.00 (s, 1H), 7.35 (m, 5H) ppm.

Workup

temperatureThe reaction was cooled
additionpoured onto water
extractionextracted with EtOAc (×3)
washThe organics were washed with water, brine
dry with materialdried (Na2SO4)

Sources & evidence

ORD record: ord-f6cd386beec34debb7d378e324bba82a
Source dataset: uspto-grants-2011_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08044041B2

Reaction notes

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