1,2-Dibromoethane → HCID 90423580, compound

HRID 2272451Notes

Reaction equation

HRID 2272451 reaction equation
BrCCBr.[Mg].Br[CH:7]1[CH2:10][CH2:9][CH2:8]1.[CH2:11]([O:18][C:19]1[CH:28]=[C:27](I)[CH:26]=[CH:25][C:20]=1[C:21]([O:23][CH3:24])=[O:22])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1>[Cl-].[Zn+2].[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].[Zn].II.C1COCC1.C(OCC)C>[CH2:11]([O:18][C:19]1[CH:28]=[C:27]([CH:7]2[CH2:10][CH2:9][CH2:8]2)[CH:26]=[CH:25][C:20]=1[C:21]([O:23][CH3:24])=[O:22])[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

Participants

12

Reactant 5

HCID 78391,2-DibromoethaneHCID 78110BromocyclobutaneHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 5462224MagnesiumHCID 66990993Methyl 2-(benzyloxy)-4-iodobenzoate

Product 1

HCID 90423580HCID 90423580, compoundYield 59%

Reagents, catalysts & solvents 6

HCID 807IodineCatalystHCID 23994ZincCatalystHCID 3007855ZincchlorideCatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

Iodine (40 mg) and 1,2-dibromoethane (0.5 mL) were added to a mixture of magnesium (11.8 g) and anhydrous diethyl ether (250 mL), then bromocyclobutane (44.0 g) was slowly added thereto, and the mixture was stirred at 40C for 2 hours. A THF (450 mL) solution of zinc chloride (54 g) prepared at 160 C under high vacuum was added to the reaction mixture at 0 C, and the mixture was stirred at the same temperature as above for 1 hour. A mixture of methyl 2-(benzyloxy)-4-iodobenzoate (20 g), tris(dibenzylideneacetone)dipalladium(0) (4.97 g), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (3.14 g), and THF (500 mL) was deaerated in an argon stream. The zinc reagent (350 mL) prepared above was added thereto, and the mixture was stirred overnight at 60 C. The reaction mixture was filtered through celite. The solvent was concentrated under reduced pressure. Water was added to the obtained residue, followed by extraction with ethyl acetate three times. Combined organic layers were washed with water and dried over anhydrous sodium sulfate, and then, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain the title compound (9.5 g).

Workup

  1. additionwas added to the reaction mixture at 0 C
  2. additionabove was added
  3. stirringthe mixture was stirred overnight at 60 C
  4. filtrationThe reaction mixture was filtered through celite
  5. concentrationThe solvent was concentrated under reduced pressure
  6. additionWater was added to the obtained residue
  7. extractionfollowed by extraction with ethyl acetate three times
  8. washCombined organic layers were washed with water
  9. dry with materialdried over anhydrous sodium sulfate
  10. distillationthe solvent was distilled off under reduced pressure
  11. customThe obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate)

Sources & evidence

ORD record
ord-3e5b10b4fe214f34bb0a01ac09bef9c5
Source dataset
uspto-grants-2015_09
Patent number
US09120777B2

Reaction notes

Loading…