Tetrahydrofuran → N1-(4-(3-bromopropoxy)phenyl)-N1,N4,N4-tris(4-methoxyphenyl)benzene-1,4-diamine

HRID 2041851Notes

Reaction equation

HRID 2041851 reaction equation
CS(O[CH2:6][CH2:7][CH2:8][O:9][C:10]1[CH:15]=[CH:14][C:13]([N:16]([C:25]2[CH:30]=[CH:29][C:28]([N:31]([C:40]3[CH:45]=[CH:44][C:43]([O:46][CH3:47])=[CH:42][CH:41]=3)[C:32]3[CH:37]=[CH:36][C:35]([O:38][CH3:39])=[CH:34][CH:33]=3)=[CH:27][CH:26]=2)[C:17]2[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[CH:19][CH:18]=2)=[CH:12][CH:11]=1)(=O)=O.[Br-:48].[Li+].O1CCCC1>O>[Br:48][CH2:6][CH2:7][CH2:8][O:9][C:10]1[CH:15]=[CH:14][C:13]([N:16]([C:17]2[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[CH:19][CH:18]=2)[C:25]2[CH:30]=[CH:29][C:28]([N:31]([C:40]3[CH:45]=[CH:44][C:43]([O:46][CH3:47])=[CH:42][CH:41]=3)[C:32]3[CH:37]=[CH:36][C:35]([O:38][CH3:39])=[CH:34][CH:33]=3)=[CH:27][CH:26]=2)=[CH:12][CH:11]=1

Participants

5

Reactant 3

HCID 8028TetrahydrofuranHCID 82050Lithium BromideHCID 86653413HCID 86653413, compound

Product 1

HCID 67159998N1-(4-(3-bromopropoxy)phenyl)-N1,N4,N4-tris(4-methoxyphenyl)benzene-1,4-diamine

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
60 °C

Procedure

To a dry schlenk flask was added 3-(4-((4-(bis(4-methoxyphenyl)amino)phenyl)(4-methoxyphenyl)amino)phenoxy)propyl methanesulfonate (4.06 g, 6.20 mmol). The flask was evacuated under vacuum and filled with nitrogen. Lithium bromide (5.39 g; 62.0 mmol) and tetrahydrofuran (6.2 mL) were added under nitrogen. The mixture was allowed to stir at 60° C. overnight. Upon disappearance of the starting material the reaction mixture was poured into a separatory funnel containing 100 mL of cold water. The product was extracted using 3×50 mL ether. The organic layers were combined and washed with 3×50 mL of water. The resulting ether layers were dried over Na2SO4. The drying agent was removed by filtration and the solvent was removed under reduced pressure. The residual solvent was removed in vacuo (3.12 g, 78.2%). 1H NMR (400 MHz, C3D6O) δ 6.97 (m, 8H), 6.86 (m, 8H), 6.80 (s, 4H), 4.09 (t, J=5.9 Hz, 2H), 3.75 (s, 9H), 3.66 (t, J=6.6 Hz, 2H), 2.28 (q, J=6.2 Hz, 2H). 13C{1H} NMR (400 MHz, C3D6O) δ 156.39, 155.34, 143.71, 143.51, 142.22, 127.05, 126.27, 126.03, 123.90, 123.70, 116.10, 115.40, 114.61, 66.34, 55.62, 33.25, 31.05. HRMS-EI (m/z): [M]+ calcd for C36H35BrN2O4, 640.18; found, 640.1). Anal. Calcd for C36H35BrN2O4: C, 67.60; H, 5.52; N, 4.38. Found: C, 67.43; H, 5.61; N, 4.24.

Workup

  1. customThe flask was evacuated under vacuum
  2. additionfilled with nitrogen
  3. additionUpon disappearance of the starting material the reaction mixture was poured into a separatory funnel
  4. extractionThe product was extracted
  5. washwashed with 3×50 mL of water
  6. dry with materialThe resulting ether layers were dried over Na2SO4
  7. customThe drying agent was removed by filtration
  8. customthe solvent was removed under reduced pressure
  9. customThe residual solvent was removed in vacuo (3.12 g, 78.2%)

Sources & evidence

ORD record
ord-f9c3a5459d7a4a359e61b14810262042
Source dataset
uspto-grants-2013_11
Patent number
US08586208B2

Reaction notes

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