1-Bromo-3,4-(methylenedioxy)benzene → HCID 58980587, compound

HRID 1181184Notes

Reaction equation

HRID 1181184 reaction equation
[CH2:1]1[O:10][C:9]2[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][C:3]=2[O:2]1.Br[C:12]1[CH:17]=[CH:16][C:15]2[O:18][CH2:19][O:20][C:14]=2[CH:13]=1.CC(C)([O-])C.[Na+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].C1(C)C=CC=CC=1>[O:10]1[C:9]2[CH:8]=[CH:7][C:5]([NH:6][C:12]3[CH:17]=[CH:16][C:15]4[O:18][CH2:19][O:20][C:14]=4[CH:13]=3)=[CH:4][C:3]=2[O:2][CH2:1]1

Participants

7

Reactant 3

HCID 758311-Bromo-3,4-(methylenedioxy)benzeneHCID 843101,3-Benzodioxol-5-amineHCID 23676156Sodium t-butoxide

Product 1

HCID 58980587HCID 58980587, compoundYield 73.1%

Reagents, catalysts & solvents 3

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

To a flask equipped with a magnetic stirrer, reflux condensor, and nitrogen inlet was added 3,4-(methylenedioxy) aniline (5.34 grams, 38.9 mmoles), 4-bromo-1,2-(methylenedioxy) benzene (6.41 grams, 31.9 mmoles), tris(dibenzylideneacetone)dipalladium (0) (0.71 grams, 0.8 mmoles), 1,1′-bis(diphenylphosphino)-ferrocene (1.29 grams, 2.3 mmoles), sodium tert-butoxide (4.20 grams, 43.7 mmoles) and anhydrous toluene (40 mL). The contents of the flask were heated to 80° C. for three days; cooled to room temperature; and filtered through a pad of silica gel. The silica gel pad was then eluted with dichloromethane (240 mL). The combined organic layers were concentrated in vacuo to yield a dark yellow oil. The oil was chromatographed on silica gel, eluting with a hexane/ethyl acetate gradient to afford 6 grams of yellow solid. The solid was triturated with hexane and filtered to afford 3.9 grams of the desired product as a white solid. 1H NMR (CDCl3) δ 6.7 (d, 2H), 6.55 (s, 2H), 6.35 (d, 2H), 5.85 (s, 4H), 5.35 (bs, 1H).

Workup

  1. customTo a flask equipped with a magnetic stirrer
  2. temperaturereflux condensor, and nitrogen inlet
  3. temperaturecooled to room temperature
  4. filtrationand filtered through a pad of silica gel
  5. washThe silica gel pad was then eluted with dichloromethane (240 mL)
  6. concentrationThe combined organic layers were concentrated in vacuo
  7. customto yield a dark yellow oil
  8. customThe oil was chromatographed on silica gel
  9. washeluting with a hexane/ethyl acetate gradient

Sources & evidence

ORD record
ord-de09eedddedd4b6a975bcfaf26671440
Source dataset
uspto-grants-2007_10
Patent number
US07285518B2

Reaction notes

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