1,3-Dibromo-5-chlorobenzene → 1-Bromo-3-chloro-5-cyclopropylbenzene

HRID 19789Notes

Reaction equation

Br[C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[C:4]([Br:9])[CH:3]=1.[CH:10]1([Mg]Br)[CH2:12][CH2:11]1>C1COCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Br:9][C:4]1[CH:3]=[C:2]([CH:10]2[CH2:12][CH2:11]2)[CH:7]=[C:6]([Cl:8])[CH:5]=1

Participants

Conditions

Temperature: 70 °C

Procedure

To a solution of 1,3-dibromo-5-chlorobenzene (500 mg, 1.85 mmol) in THF (1 ml) was added cyclopropylmagnesium bromide (3698 μl, 0.5M solution in THF, 1.85 mmol) in a sealed tube and the reaction mixture was degassed with argon for 5 min before tetrakis(triphenylphosphine)palladium (0) (107 mg, 0.09 mmol) was added. The resulting solution was heated to 70° C. overnight, cooled to RT and then quenched with sat. NH4Cl solution and extracted with pentane. The organic phases were combined, washed with water and brine, dried over MgSO4 and filtered through a short pad of silica gel to give the desired product (272 mg, 64%) which did not require further purification. 1H NMR (CDCl3, 300 MHz): 7.28 (aptt, J=2.0 Hz, 1H), 7.08 (aptt, J=1.5 Hz, 1H), 6.97 (aptt, J=1.5 Hz, 1H), 1.83 (m, 1H), 1.04-0.97 (m, 2H), 0.72-0.67 (m, 2H).

Workup

additionwas added
temperaturecooled to RT
customquenched with sat. NH4Cl solution
extractionextracted with pentane
washwashed with water and brine
dry with materialdried over MgSO4
filtrationfiltered through a short pad of silica gel

Sources & evidence

ORD record: ord-2b7debaa34934d1abbc3bc7f4dd483ae
Source dataset: uspto-grants-2010_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07745477B2

Reaction notes

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