1-Naphthylamine → N-(3-(1,3-dioxolan-2-yl)phenyl)naphthalen-1-amine

HRID 42395

Reaction equation

HRID 42395 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:8]2[O:12][CH2:11][CH2:10][O:9]2)[CH:5]=[CH:6][CH:7]=1.[C:13]1([NH2:23])[C:22]2[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=2)[CH:16]=[CH:15][CH:14]=1.CC(C)([O-])C.[Na+].C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>C1(C)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[O:9]1[CH2:10][CH2:11][O:12][CH:8]1[C:4]1[CH:3]=[C:2]([NH:23][C:13]2[C:22]3[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=3)[CH:16]=[CH:15][CH:14]=2)[CH:7]=[CH:6][CH:5]=1

Participants

7

Reactant 4

HCID 86401-NaphthylamineHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 873062-(3-Bromophenyl)-1,3-dioxolaneHCID 23676156Sodium t-butoxide

Product 1

HCID 58028518N-(3-(1,3-dioxolan-2-yl)phenyl)naphthalen-1-amine

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

A clean and dry 500 ml round bottom flask equipped with a reflux condenser, magnetic stir bar, and thermometer with adapter was prepared and purged with nitrogen Anhydrous toluene (250.0 ml) was transferred to this flask by cannula. 2-(3-bromophenyl)-1,3-dioxolane (6.0 ml, 0.0397 mol) was added by syringe followed by the manual addition of 1-naphthylamine (5.08 g, 0.0355 mol). The reaction solution was purged with a strong nitrogen flow for 30 minutes. Sodium tert-butoxide (5.60 g, 0.0583 mol) and Pd2dba3 (0.65 g, 0.0007 mol) were then added manually, followed by the addition of tri-tert-butylphosphine (1.30 g, 0.0064 mol) in toluene (˜10 ml) via syringe. The vessel was heated to reflux for approximately 5 hours. The reaction was then cooled to room temperature and filtered through a Celite and silica gel pad washing thoroughly with acetone and chloroform. Solvent was removed by rotary evaporation. The crude material was purified by flash column chromatography using ethyl acetate/hexane as an eluent. This provided pure product confirmed by NMR spectroscopy.

Workup

  1. customA clean and dry 500 ml round bottom flask
  2. customequipped with a reflux condenser, magnetic stir bar
  3. customthermometer with adapter was prepared
  4. custompurged with nitrogen Anhydrous toluene (250.0 ml)
  5. customwas transferred to this flask by cannula
  6. customThe reaction solution was purged with a strong nitrogen flow for 30 minutes
  7. temperatureThe vessel was heated
  8. temperatureto reflux for approximately 5 hours
  9. filtrationfiltered through a Celite and silica gel pad
  10. washwashing thoroughly with acetone and chloroform
  11. customSolvent was removed by rotary evaporation
  12. customThe crude material was purified by flash column chromatography

Sources & evidence

ORD record
ord-e6054a3a14fb43a2bff01a7ca1b28c62
Source dataset
uspto-grants-2013_09
Patent number
US08535974B2

Linked notes

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