1-Bromo-3-chloro-5-nitrobenzene → Tert-butyl 2-(3-chloro-5-nitrophenyl)acetate

HRID 1628297Notes

Reaction equation

HRID 1628297 reaction equation
Br[C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[C:4]([Cl:11])[CH:3]=1.[Cl-].[C:13]([O:17][C:18](=[O:21])[CH2:19][Zn+])([CH3:16])([CH3:15])[CH3:14]>C1COCC1.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].CC(P(C(C)(C)C)[C-]1C=CC=C1)(C)C.C1C=CC([C-]2C(C3C=CC=CC=3)=C(C3C=CC=CC=3)C(C3C=CC=CC=3)=C2C2C=CC=CC=2)=CC=1.[Fe+2]>[Cl:11][C:4]1[CH:3]=[C:2]([CH2:19][C:18]([O:17][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:21])[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=1

Participants

6

Reactant 2

HCID 178398381-Bromo-3-chloro-5-nitrobenzeneHCID 178451183HCID 178451183, compound

Product 1

HCID 69620897Tert-butyl 2-(3-chloro-5-nitrophenyl)acetateYield 82.2%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 129828017Ditert-butyl(cyclopenta-2,4-dien-1-yl)phosphane;iron(2+);(2,3,4,5-tetraphenylcyclopenta-1,4-dien-1-yl)benzeneCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 1-bromo-3-chloro-5-nitrobenzene 52.A (10.23 g, 43 mmol, available from Synchem Inc), Pd2(dba)3 (0.79 g, 0.87 mmol) and CTC-QPhos (1.20 g, 1.40 mmol) in THF (100 mL) was added 2-tert-Butoxy-2-oxoethylzinc chloride (95 mL, 0.5M solution in diethyl ether, 48 mmol, available from Rieke Metals). The mixture was stirred for 3 hours at room temperature. The reaction was then quenched by adding water (100 mL), washed with 1N HCl solution (2×100 mL), concentrated and purified by using flash chromatography on silica gel (0-10% AcOEt/Hexanes) to afford tert-butyl 2-(3-chloro-5-nitrophenyl)acetate 52.B (9.60 g, 82% yield) as a light pink oil.

Workup

  1. customThe reaction was then quenched
  2. additionby adding water (100 mL)
  3. washwashed with 1N HCl solution (2×100 mL)
  4. concentrationconcentrated
  5. custompurified

Sources & evidence

ORD record
ord-e8cedd90e2014d4188d5094501243149
Source dataset
uspto-grants-2014_07
Patent number
US08785468B2

Reaction notes

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