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

HRID 392006Notes

Reaction equation

HRID 392006 reaction equation
[C:1]([O:5][C:6]([NH:8][C:9]1[CH:14]=[CH:13][C:12]([NH:15][C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])=[CH:11][C:10]=1Br)=[O:7])([CH3:4])([CH3:3])[CH3:2].C[Li].C([Li])(C)(C)C.CN(C)[CH:33]=[O:34]>O.CCOCC>[C:1]([O:5][C:6](=[O:7])[NH:8][C:9]1[CH:14]=[CH:13][C:12]([NH:15][C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])=[CH:11][C:10]=1[CH:33]=[O:34])([CH3:4])([CH3:3])[CH3:2]

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 154289672,5-Bis-tert.-butyloxycarbonylaminobromobenzeneHCID 178418306HCID 178418306, compoundHCID 178418348HCID 178418348, compound

Product 1

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

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 3283Diethyl EtherSolvent

Conditions

Temperature
-20 °C

Procedure

3.3 g (0.01 mol) 2,5-bis-tert.-butyloxycarbonylaminobromobenzene from step A are dissolved in 100 ml of water-free tetrahydrofuran under argon. 17 ml of a 1.6 molar etheric methyl lithium solution (0.03 mol) are gradually added. The reaction mixture is cooled to −20° C., 7 ml of a 1.5 molar tert.-butyl lithium solution (0.01 mol) are gradually added. After the addition has ended the solution is stirred for 30 minutes at the given temperature. Subsequently 1.2 g of dimethyl formamide (0.02 mol) are added and the reaction mixture is stirred for one hour at −20° C. After slowly heating to room temperature the reaction mixture is hydrolyzed with water and then poured into ether, the aqueous phase is extracted with ether and then the organic phase is dried over magnesium sulfate. The solvent is distilled away in a rotary evaporator and the residue is purified on silica gel with a petroleum ether/ethyl acetate solvent (9/1).

Workup

  1. additionAfter the addition
  2. stirringthe reaction mixture is stirred for one hour at −20° C
  3. temperatureAfter slowly heating to room temperature the reaction mixture
  4. extractionthe aqueous phase is extracted with ether
  5. dry with materialthe organic phase is dried over magnesium sulfate
  6. distillationThe solvent is distilled away in a rotary evaporator
  7. customthe residue is purified on silica gel with a petroleum ether/ethyl acetate solvent (9/1)

Sources & evidence

ORD record
ord-06234f2939e34f27afc0a33a3ff0805f
Source dataset
uspto-grants-2004_10
Patent number
US06800097B2

Reaction notes

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