4-Methyloxybenzyl chloride → HCID 86708464, compound

HRID 921617Notes

Reaction equation

HRID 921617 reaction equation
[Br:1][C:2]1[C:3]([Cl:21])=[C:4]([NH:16][C:17](=[O:20])[O:18][CH3:19])[CH:5]=[C:6]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])[CH:7]=1.C[Si]([N-][Si](C)(C)C)(C)C.[Na+].Cl[CH2:33][C:34]1[CH:39]=[CH:38][C:37]([O:40][CH3:41])=[CH:36][CH:35]=1>CN(C=O)C>[Br:1][C:2]1[C:3]([Cl:21])=[C:4]([N:16]([CH2:33][C:34]2[CH:39]=[CH:38][C:37]([O:40][CH3:41])=[CH:36][CH:35]=2)[C:17](=[O:20])[O:18][CH3:19])[CH:5]=[C:6]([N:8]([CH2:33][C:34]2[CH:39]=[CH:38][C:37]([O:40][CH3:41])=[CH:36][CH:35]=2)[C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:12])[CH3:13])[CH:7]=1

Participants

5

Reactant 3

HCID 699934-Methyloxybenzyl chlorideHCID 2724254Sodium bis(trimethylsilyl)amideHCID 86708465HCID 86708465, compound

Product 1

HCID 86708464HCID 86708464, compoundYield 82.2%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
75 °C

Procedure

A stirred solution of tert-butyl methyl (5-bromo-4-chloro-1,3-phenylene)dicarbamate (710 mg, 1.870 mmol) in DMF (10 mL) was treated with NaHMDS (3.93 mL, 3.93 mmol) at 0° C. dropwise. The reaction mixture was stirred for 15 min, and 1-(chloromethyl)-4-methoxybenzene (0.533 mL, 3.93 mmol) was added. The reaction was stirred for 45 min, then heated at 75° C. for 1.5 h. The reaction was quenched with half saturated NH4Cl solution and extracted with EtOAc 3×. The organic layers were combined, dried over Mg2SO4, filtered and concentrated. The crude material was purified by flash column chromatography, eluting with 0%-40% EtOAc/Hex. The desired fractions were concentrated to yield tert-butyl methyl (5-bromo-4-chloro-1,3-phenylene)bis(4-methoxybenzylcarbamate) (953.4 mg).

Workup

  1. stirringThe reaction was stirred for 45 min
  2. customThe reaction was quenched with half saturated NH4Cl solution
  3. extractionextracted with EtOAc 3×
  4. dry with materialdried over Mg2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude material was purified by flash column chromatography
  8. washeluting with 0%-40% EtOAc/Hex
  9. concentrationThe desired fractions were concentrated

Sources & evidence

ORD record
ord-7dc297b0eace4785acdfdd59718e4520
Source dataset
uspto-grants-2016_03
Patent number
US09273057B2

Reaction notes

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