Diethyl Ether → Di-tert-butyl (2-formyl-1,4-phenylene)dicarbamate

HRID 47874Notes

Reaction equation

HRID 47874 reaction equation
Br[C:2]1[CH:7]=[C:6]([NH:8][C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH:5]=[CH:4][C:3]=1[NH:16][C:17](=[O:23])[O:18][C:19]([CH3:22])([CH3:21])[CH3:20].C[CH2:25][O:26]CC.C([Li])(C)(C)C.CN(C)C=O>O1CCCC1.O>[C:12]([O:11][C:9]([NH:8][C:6]1[CH:5]=[CH:4][C:3]([NH:16][C:17](=[O:23])[O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[C:2]([CH:25]=[O:26])[CH:7]=1)=[O:10])([CH3:15])([CH3:14])[CH3:13]

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 6228DimethylformamideHCID 154289672,5-Bis-tert.-butyloxycarbonylaminobromobenzeneHCID 178418306HCID 178418306, compound

Product 1

HCID 15539052Di-tert-butyl (2-formyl-1,4-phenylene)dicarbamate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-20 °C

Procedure

3.3 g (0.01 mole) of tert.butyl (2-bromo-4-tert.butoxycarbonylaminophenyl)carbamate from step A was dissolved in 100 mL of anhydrous tetrahydrofuran under argon. Then, 17 mL (0.03 mole) of a 1.6-molar ether solution of methyllitrium was added stepwise. The reaction mixture was cooled to −20° C. and to it was added stepwise 7 mL (0.01 mole) of a 1.5-molar tert.butyllithium solution. At the end of the addition, the solution was allowed to agitate for an additional 30 min at −20° C. Then, 1.2 g (0.02 mole) of dimethylformamide was added, and the reaction mixture was allowed to agitate for one hour at −20° C. The reaction mixture was then slowly warmed up to room temperature, hydrolyzed with water and poured onto diethyl ether. The aqueous phase was then extracted with diethyl ether, and the organic phase was dried with magnesium sulfate. The solvent was distilled off in a rotary evaporator, and the residue was purified on silica gel with petroleum ether/ethyl acetate (9:1).

Workup

  1. additionAt the end of the addition
  2. stirringto agitate for one hour at −20° C
  3. additionpoured onto diethyl ether
  4. extractionThe aqueous phase was then extracted with diethyl ether
  5. dry with materialthe organic phase was dried with magnesium sulfate
  6. distillationThe solvent was distilled off in a rotary evaporator
  7. customthe residue was purified on silica gel with petroleum ether/ethyl acetate (9:1)

Sources & evidence

ORD record
ord-69be5b81955e41d0ac67506c1e3ed907
Source dataset
uspto-grants-2004_03
Patent number
US06699990B2

Reaction notes

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