1,3-Dibromobenzene → 4-(3-bromophenyl)-N,N-dimethylmorpholine-2-carboxamide

HRID 1852935Notes

Reaction equation

Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([Br:8])[CH:3]=1.[CH3:9][N:10]([CH3:19])[C:11]([CH:13]1[O:18][CH2:17][CH2:16][NH:15][CH2:14]1)=[O:12].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+]>C1(C)C=CC=CC=1.C(Cl)Cl.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]>[Br:8][C:4]1[CH:3]=[C:2]([N:15]2[CH2:16][CH2:17][O:18][CH:13]([C:11]([N:10]([CH3:19])[CH3:9])=[O:12])[CH2:14]2)[CH:7]=[CH:6][CH:5]=1

Participants

Conditions

Temperature: 80 °C

Procedure

A mixture of 1,3-dibromobenzene (387 μL, 3.20 mmol), N,N-dimethylmorpholine-2-carboxamide (506 mg, 3.20 mmol), Pd2(dba)3 (73.3 mg, 0.0800 mmol), rac-BINAP (154 mg, 0.240 mmol) and NaOtBu (369 mg, 3.84 mmol) in toluene (8 mL) was heated at 80° C. for 5 hours under nitrogen. After cooling to room temperature, the mixture was diluted with DCM and filtered through a Celite pad. The combined filtrate and washings were concentrated. The residue was purified by silica gel column chromatography (EtOAc/hexane=95:5→90:10→80:20→67:33→50:50) to afford desired product (424 mg, 42.3%) as orange oil.

Workup

temperatureAfter cooling to room temperature
filtrationfiltered through a Celite pad
concentrationThe combined filtrate and washings were concentrated
customThe residue was purified by silica gel column chromatography (EtOAc/hexane=95:5→90:10→80:20→67:33→50:50)

Sources & evidence

ORD record: ord-1f9d617b52674e358a1d6762263a57cf
Source dataset: uspto-grants-2015_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08962619B2

Reaction notes

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