1-Bromo-4-nitrobenzene → 1-(3,4-Ethylenedioxythien-2-yl)-4-nitrobenzene

HRID 366862Notes

Reaction equation

HRID 366862 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=1.C([Sn](CCCC)(CCCC)[C:16]1[S:17][CH:18]=[C:19]2[O:24][CH2:23][CH2:22][O:21][C:20]=12)CCC>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>[CH2:22]1[CH2:23][O:24][C:19]2[C:20](=[C:16]([C:2]3[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=3)[S:17][CH:18]=2)[O:21]1

Participants

5

Reactant 2

HCID 114661-Bromo-4-nitrobenzeneHCID 15891053Tributyl(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)stannane

Product 1

HCID 154774201-(3,4-Ethylenedioxythien-2-yl)-4-nitrobenzeneYield 68%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Procedure

To a refluxing solution of 1-bromo-4-nitrobenzene (2.762 g, 13.67 mmol) in toluene (250 mL) was added tetrakis(triphenylphosphine)palladium(0) (75 mg). After 20 min, 2-(tributylstannyl) 3,4-(ethylenedioxy)thiophene (6.05 g, 14.03 mmol) was added via a syringe. After complete addition, the mixture was refluxed for a total of 20 h. After cooling, the mixture was filtered and the solvent was evaporated to afford a solid. Filtration using hot hexane gave 1-(3,4-ethylenedioxythien-2-yl)-4-nitrobenzene, 2.46 g, yield=68%, mp=184-186° C. IR (KBr; in cm-1) 3066, 2946, 1592, 1506, 1477, 1338, 1066 and 851. 1H NMR (CDCl3 ; δ in ppm): 4.285 (m, 2H), 4.376 (m, 2H), 6.468 (s, 1H), 7.852 (d, J=9.9 Hz, 2H) and 8.197 (d, J=9.9 Hz, 2H). 13C NMR (CDCl3 ; δ in ppm): 64.25, 64.94, 100.93, 115.10, 124.03, 125.61, 139.72, 140.53, 142.43 and 145.37. MS(EI) m/z (rel int): 263 [(M)+, 27%], 233 [(M+ --NO), 8%] and 166[(M+ --C5H5O2), 9%]. Anal. Calcd for C12H9NO4S: C, 54.75; H, 3.45;, N, 5.32; S, 12.18. Found: C, 55.04; H, 2.99; N, 4.05; S, 11.57.

Workup

  1. additionAfter complete addition
  2. temperaturethe mixture was refluxed for a total of 20 h
  3. temperatureAfter cooling
  4. filtrationthe mixture was filtered
  5. customthe solvent was evaporated
  6. customto afford a solid
  7. filtrationFiltration

Sources & evidence

ORD record
ord-b7f9009e6f0b4d0d873b84bad44901ee
Source dataset
uspto-grants-2000_10
Patent number
US06130339

Reaction notes

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