Water → N-[(1-{6-[1-(Mesitylamino)-1-methylethyl]pyridin-2-yl}-2-naphthyl)methyl]-2,4,6-trimethylaniline

HRID 634058Notes

Reaction equation

HRID 634058 reaction equation
[CH3:1][C:2]1[CH:28]=[C:27]([CH3:29])[CH:26]=[C:25]([CH3:30])[C:3]=1[NH:4][CH2:5][C:6]1[CH:15]=[CH:14][C:13]2[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=2)[C:7]=1B1OC(C)(C)C(C)(C)O1.Br[C:32]1[N:37]=[C:36]([C:38]([NH:41][C:42]2[C:47]([CH3:48])=[CH:46][C:45]([CH3:49])=[CH:44][C:43]=2[CH3:50])([CH3:40])[CH3:39])[CH:35]=[CH:34][CH:33]=1.C([O-])([O-])=O.[Na+].[Na+].O>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.C1(C)C=CC=CC=1.CO>[C:43]1([CH3:50])[CH:44]=[C:45]([CH3:49])[CH:46]=[C:47]([CH3:48])[C:42]=1[NH:41][C:38]([C:36]1[N:37]=[C:32]([C:7]2[C:8]3[C:13](=[CH:12][CH:11]=[CH:10][CH:9]=3)[CH:14]=[CH:15][C:6]=2[CH2:5][NH:4][C:3]2[C:2]([CH3:1])=[CH:28][C:27]([CH3:29])=[CH:26][C:25]=2[CH3:30])[CH:33]=[CH:34][CH:35]=1)([CH3:40])[CH3:39]

Participants

8

Reactant 4

HCID 962WaterHCID 10340Sodium CarbonateHCID 667957632,4,6-Trimethyl-N-{[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-naphthyl]methyl}anilineHCID 117652629N-[1-(6-Bromopyridin-2-yl)-1-methylethyl]-2,4,6-trimethylaniline

Product 1

HCID 117652952N-[(1-{6-[1-(Mesitylamino)-1-methylethyl]pyridin-2-yl}-2-naphthyl)methyl]-2,4,6-trimethylaniline

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 887MethanolSolventHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 1.70 g (4.20 mmol) of 2,4,6-trimethyl-N-{[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-naphthyl]methyl}aniline, 1.40 g (4.20 mmol) of N-[1-(6-bromopyridin-2-yl)-1-methylethyl]-2,4,6-trimethylaniline, 3.00 g (10.50 mmol) of Na2CO3×10H2O, 48 ml of water, 13 ml of methanol, and 56 ml of toluene was purged with argon for 30 min. To this solution 0.24 g (0.21 mmol) of Pd(PPh3)4 was added. The resulting mixture was stirred for 12 h at 80° C. and then cooled to room temperature. The organic layer was separated, the aqueous layer was extracted with 3×200 ml of ethyl acetate. The combined organic extract was washed with brine, dried over Na2SO4 and evaporated to dryness. The crude product was purified by flash chromatography on silica gel 60 (40-63 um, eluent: dichloromethane-ethyl acetate=20:1, vol.). Yield 1.25 g (56%) of yellow oil. Anal. calc. for C37H41N3: C, 84.21; H, 7.83; N, 7.96. Found: C, 84.38; H, 7.69; N, 8.02. 1H NMR (CDCl3): δ 7.90 (m, 1H, 8-H in naphthalene), 7.86 (d, J=8.4 Hz, 1H, 4-H in naphthalene), 7.77-7.82 (m, 2H, 4, 5-H in pyridine), 7.37-7.50 (m, 4H, 3, 5, 6, 7-H in naphthalene), 7.23 (dd, J=6.1 Hz, J=2.3 Hz, 1H, 3-H in pyridine), 6.79 (s, 2H, 3, 5-H in mesityl), 6.78 (s, 2H, 3, 5-H in mesityl), 3.99 (m, 2H, CH2N), 3.66 (br.s, 2H, NH), 2.24 (s, 3H, 4-Me in mesityl), 2.23 (s, 3H, 4-Me in mesityl), 2.06 (s, 6H, 2, 6-Me in mesityl), 2.05 (s, 6H, 2, 6-Me in mesityl), 1.57 (s, 3H, CMeMe′), 1.54 (s, 3H, CMeMe′).

Workup

  1. customwas purged with argon for 30 min
  2. temperaturecooled to room temperature
  3. customThe organic layer was separated
  4. extractionthe aqueous layer was extracted with 3×200 ml of ethyl acetate
  5. extractionThe combined organic extract
  6. washwas washed with brine
  7. dry with materialdried over Na2SO4
  8. customevaporated to dryness
  9. customThe crude product was purified by flash chromatography on silica gel 60 (40-63 um, eluent: dichloromethane-ethyl acetate=20:1, vol.)

Sources & evidence

ORD record
ord-c4dc456df3b047459051874490cca1c8
Source dataset
uspto-grants-2016_04
Patent number
US09321858B2

Reaction notes

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