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

HRID 252836Notes

Reaction equation

HRID 252836 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.[S:19]1[CH:23]=[CH:22][CH:21]=[C:20]1B(O)O.C(=O)([O-])[O-].[Na+].[Na+]>COCCOC.O.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>[N+:16]([C:4]1[CH:3]=[C:2]([C:20]2[S:19][CH:23]=[CH:22][CH:21]=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

7

Reactant 3

HCID 10340Sodium CarbonateHCID 27339602-Thiopheneboronic acidHCID 52904808tert-Butyl (4-bromo-2-nitrophenyl)carbamate

Product 1

HCID 59736984tert-Butyl 2-nitro-4-(thiophen-2-yl)phenylcarbamateYield 53.4%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

A solution of tert-butyl 4-bromo-2-nitrophenylcarbamate 175 (3.97 g, 12.5 mmol), 2-thiophene boronic acid 176 (1.68 g, 13.4 mmol), sodium carbonate (3.98 g, 37.56 mmol) and Pd(PPh3)4 (0.94 g, 0.814 mmol) were stirred at 110° C. in a mixture of DME and water (2:1, 70 mL overnight. The solution was evaporated to dryness, diluted with water and extracted with ethyl acetate. The organic phase was washed with brine, dried over sodium sulfate, filtered and evaporated to provide the crude product which was purified by flash chromatography (10% ethyl acetate in hexane) to provide the title compound 177 (2.14 g, 53% yield). 1H NMR: (DMSO) δ (ppm): 400 MHz, (DMSO) d (ppm): 9.63 (s, 1H), 8.12 (d, J=2.3 Hz, 1H), 7.92 (dd, J=8.4, 2.2 Hz, 1H), 7.66 (d, J=8.4 Hz, 1H), 7.61 (q, J=2.2 Hz, 2H), 7.15 (dd, J=5.1, 3.7 Hz, 1H), 1.46 (s, 9H). MS: (calc.) 320.08; (obt.) 343.1 (M+Na).

Workup

  1. customThe solution was evaporated to dryness
  2. additiondiluted with water
  3. extractionextracted with ethyl acetate
  4. washThe organic phase was washed with brine
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. customevaporated
  8. customto provide the crude product which
  9. customwas purified by flash chromatography (10% ethyl acetate in hexane)

Sources & evidence

ORD record
ord-f0c2d42f17774d1497806084efa9c12f
Source dataset
uspto-grants-2011_01
Patent number
US07868205B2

Reaction notes

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