Water → N-(1-{6-[2-(Anilinomethyl)-1-naphthyl]pyridin-2-yl}-1-methylethyl)-2,6-diisopropylaniline

HRID 634055Notes

Reaction equation

HRID 634055 reaction equation
CC1(C)C(C)(C)OB([C:9]2[C:18]3[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=3)[CH:12]=[CH:11][C:10]=2CNC2C=CC=CC=2)O1.Br[C:29]1[N:34]=[C:33]([C:35]([NH:38][C:39]2[C:44]([CH:45]([CH3:47])[CH3:46])=[CH:43][CH:42]=[CH:41][C:40]=2[CH:48]([CH3:50])[CH3:49])([CH3:37])[CH3:36])[CH:32]=[CH:31][CH:30]=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>[NH:38]([CH2:35][C:10]1[CH:11]=[CH:12][C:17]2[C:18](=[CH:13][CH:14]=[CH:15][CH:16]=2)[C:9]=1[C:29]1[N:34]=[C:33]([C:35]([NH:38][C:39]2[C:44]([CH:45]([CH3:47])[CH3:46])=[CH:43][CH:42]=[CH:41][C:40]=2[CH:48]([CH3:50])[CH3:49])([CH3:37])[CH3:36])[CH:32]=[CH:31][CH:30]=1)[C:39]1[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=1

Participants

8

Reactant 4

HCID 962WaterHCID 10340Sodium CarbonateHCID 117652744N-[1-(6-Bromopyridin-2-yl)-1-methylethyl]-2,6-diisopropylanilineHCID 131735478N-{[1-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-2-naphthyl]methyl}-aniline

Product 1

HCID 117653089N-(1-{6-[2-(Anilinomethyl)-1-naphthyl]pyridin-2-yl}-1-methylethyl)-2,6-diisopropylaniline

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 887MethanolSolventHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 2.02 g (5.64 mmol) of N-{[1-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-2-naphthyl]methyl}-aniline, 2.11 g (5.64 mmol) of N-[1-(6-bromopyridin-2-yl)-1-methylethyl]-2,6-diisopropylaniline, 4.03 g (14.10 mmol) of Na2CO3×10H2O, 63 ml of water, 18 ml of methanol, and 76 ml of toluene was purged with argon for 30 min. To the obtained solution 0.32 g (0.28 mmol) of Pd(PPh3)4 was added. In argon atmosphere, this mixture was stirred for 12 h at 80° C. Then, it was 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 1.56 g (52%) of yellow oil. Anal. calc. for C37H41N3: C, 84.21; H, 7.83; N, 7.96. Found: C, 84.37; H, 7.95; N, 7.84. 1H NMR (CDCl3): δ 7.89 (d, J=8.4 Hz, 1H, 4-H in naphtalene), 7.88 (m, 1H, 8-H in naphthalene), 7.82 (t, J=7.8 Hz, 1H, 4-H in pyridine), 7.67 (d, J=8.4 Hz, 1H, 3-H in naphtalene), 7.63 (dd, J=7.8 Hz, J=0.8 Hz, 1H, 5-H in pyridine), 7.44-7.49 (m, 2H, 5, 7-H in naphtalene), 7.37-7.41 (m, 1H, 6-H in naphtalene), 7.31 (dd, J=7.8 Hz, J=0.8 Hz, 1H, 3-H in pyridine), 7.11 (m, 2H, 3, 5-H in Ph), 7.02-7.06 (m, 3H, 3, 4, 5-H in 2, 6-iPr2C6H3), 6.65 (m, 1H, 4-H in Ph), 6.60 (m, 2H, 2.6-H in Ph), 4.17-4.27 (m, 4H, CH2NH and NHCMe2), 3.20 (sep, J=6.8 Hz, 2H, CHMe2), 1.54 (s, 3H, CMeMe′), 1.40 (s, 3H, CMeMe′), 1.02 (t, J=6.8 Hz, 12H, CHMe2).

Workup

  1. customwas purged with argon for 30 min
  2. temperatureThen, it was cooled 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-e4c3a1e9c9c246c298576016a91daaca
Source dataset
uspto-grants-2016_04
Patent number
US09321858B2

Reaction notes

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