Ethanol → tert-Butyl 2-nitro-4-(thiophen-2-yl)phenylcarbamate

HRID 2093046Notes

Reaction equation

HRID 2093046 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[C:4]([N+:16]([O-:18])=[O:17])[CH:3]=1.C([O-])([O-])=O.[K+].[K+].C(O)C.[S:28]1[CH:32]=[CH:31][CH:30]=[C:29]1B(O)O>C1(C)C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Pd].O>[N+:16]([C:4]1[CH:3]=[C:2]([C:29]2[S:28][CH:32]=[CH:31][CH:30]=2)[CH:7]=[CH:6][C:5]=1[NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])([O-:18])=[O:17]

Participants

8

Reactant 4

HCID 702EthanolHCID 11430Potassium CarbonateHCID 27339602-Thiopheneboronic acidHCID 52904808tert-Butyl (4-bromo-2-nitrophenyl)carbamate

Product 1

HCID 59736984tert-Butyl 2-nitro-4-(thiophen-2-yl)phenylcarbamateYield 88%

Reagents, catalysts & solvents 3

HCID 178527696HCID 178527696, compoundCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
90 °C

Procedure

To a solution of tert-butyl 4-bromo-2-nitrophenylcarbamate obtained in step IV above (1.0 eq) in toluene, was added 10 mol % of tetrakis Pd, heated to 90° C. for 30 min, then aq K2CO3 and ethanol were added, followed by addition of 2-thienyl boronic acid portionwise and then reaction was refluxed overnight. Water was added to the reaction mixture and the organic layer was separated, dried over anhydrous Na2SO4 and concentrated under reduced pressure to afford crude product, which, on purification by column chromatography afforded the desired tert-butyl 2-nitro-4-thien-2-ylphenylcarbamate. (Yield=88%)

Workup

  1. customreaction
  2. temperaturewas refluxed overnight
  3. customthe organic layer was separated
  4. dry with materialdried over anhydrous Na2SO4
  5. concentrationconcentrated under reduced pressure
  6. customto afford crude product, which
  7. customon purification by column chromatography

Sources & evidence

ORD record
ord-92e15174868443a6a1f902272c0159c3
Source dataset
uspto-grants-2013_05
Patent number
US08440830B2

Reaction notes

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