N,N-Diethyl-p-phenylenediamine → N'-(2,3-dihydro-1-benzofuran-5-yl)-N,N-diethylbenzene-1,4-diamine

HRID 1783290Notes

Reaction equation

HRID 1783290 reaction equation
[CH2:1]([N:3]([CH2:11][CH3:12])[C:4]1[CH:9]=[CH:8][C:7]([NH2:10])=[CH:6][CH:5]=1)[CH3:2].Br[C:14]1[CH:15]=[CH:16][C:17]2[O:21][CH2:20][CH2:19][C:18]=2[CH:22]=1.C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=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(C)C=CC=CC=1>[O:21]1[C:17]2[CH:16]=[CH:15][C:14]([NH:10][C:7]3[CH:8]=[CH:9][C:4]([N:3]([CH2:1][CH3:2])[CH2:11][CH3:12])=[CH:5][CH:6]=3)=[CH:22][C:18]=2[CH2:19][CH2:20]1

Participants

7

Reactant 4

HCID 7120N,N-Diethyl-p-phenylenediamineHCID 634876Binap, (A+-)-HCID 27761595-Bromo-2,3-dihydro-1-benzofuranHCID 23676156Sodium t-butoxide

Product 1

HCID 57589725N'-(2,3-dihydro-1-benzofuran-5-yl)-N,N-diethylbenzene-1,4-diamineYield 87%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

To a flask equipped with a magnetic stirrer, reflux condensor, and nitrogen inlet was added N,N-diethyl-1,4-phenylenediamine (3.35 grams, 20.4 mmoles), 5-bromo-2,3-dihydrobenzofuran (3.4 grams, 17.1 mmoles), tris(dibenzylideneacetone)dipalladium (0) (0.39 grams, 0.43 mmoles), rac-2,2′-bis(diphenylphosphino)-1,1′-binapthyl (2.1 grams, 3.4 mmoles), sodium tert-butoxide (0.71 grams, 1.28 mmoles) and anhydrous toluene (90 mL). The contents of the flask were heated to 80° C. for two days; cooled to room temperature; and filtered through a pad of silica gel. The silica gel pad was then eluted with dichloromethane (200 mL). The combined organic layers were concentrated in vacuo to yield a dark blue oil. The oil was chromatographed on silica gel, eluting with a hexane/ethyl acetate gradient to afford 4.2 grams of the desired product as a brown oil. 1H NMR (CDCl3) δ 6.6-7.0 (m, 7H), 5.15 (bs, 1H), 4.5 (t, 2H), 3.05-3.2 (m, 6H), 1.1 (t, 6H).

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 (200 mL)
  6. concentrationThe combined organic layers were concentrated in vacuo
  7. customto yield a dark blue oil
  8. customThe oil was chromatographed on silica gel
  9. washeluting with a hexane/ethyl acetate gradient

Sources & evidence

ORD record
ord-a3da1bc801bf499aa4187a62983239bd
Source dataset
uspto-grants-2009_03
Patent number
US07501386B2

Reaction notes

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