Water → 2,6-Diisopropyl-N-{[6-(2-{[(2-methylphenyl)amino]methyl}phenyl)pyridin-2-yl]methyl}aniline

HRID 634069Notes

Reaction equation

HRID 634069 reaction equation
C([O-])([O-])=O.[Na+].[Na+].O.[CH3:8][C:9]1[CH:31]=[CH:30][CH:29]=[CH:28][C:10]=1[NH:11][CH2:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1B1OC(C)(C)C(C)(C)O1.Br[C:33]1[N:38]=[C:37]([CH2:39][NH:40][C:41]2[C:46]([CH:47]([CH3:49])[CH3:48])=[CH:45][CH:44]=[CH:43][C:42]=2[CH:50]([CH3:52])[CH3:51])[CH:36]=[CH:35][CH:34]=1>C1(C)C=CC=CC=1.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.CO>[CH:50]([C:42]1[CH:43]=[CH:44][CH:45]=[C:46]([CH:47]([CH3:49])[CH3:48])[C:41]=1[NH:40][CH2:39][C:37]1[CH:36]=[CH:35][CH:34]=[C:33]([C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][C:13]=2[CH2:12][NH:11][C:10]2[CH:28]=[CH:29][CH:30]=[CH:31][C:9]=2[CH3:8])[N:38]=1)([CH3:52])[CH3:51]

Participants

8

Reactant 4

HCID 962WaterHCID 10340Sodium CarbonateHCID 90311811N-[(6-Bromopyridin-2-yl)methyl]-2,6-diisopropylanilineHCID 1317354792-Methyl-N-[2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzyl]aniline

Product 1

HCID 1176528882,6-Diisopropyl-N-{[6-(2-{[(2-methylphenyl)amino]methyl}phenyl)pyridin-2-yl]methyl}aniline

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 887MethanolSolventHCID 1140TolueneSolvent

Conditions

Temperature
70 °C

Procedure

A mixture of 4.00 g (14 mmol) of Na2CO3×10H2O, 60 ml of water and 20 ml of methanol was purged with argon for 30 min. The obtained solution was added to a mixture of 1.82 g (5.6 mmol) of 2-methyl-N-[2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzyl]aniline, 1.95 g (6.7 mmol) of N-[(6-Bromopyridin-2-yl)methyl]-2,6-diisopropylaniline, and 0.32 g (0.28 mmol) of Pd(PPh3)4 in 75 ml of toluene. This mixture was stirred for 12 h at 70° C., then cooled to room temperature. The organic layer was separated, the aqueous layer was extracted with 3×50 ml of ethyl acetate. The combined organic extract was washed with brine, dried over Na2SO4, and evaporated to dryness. The residue was re-crystallized from 15 ml of diethyl ether. Yield 1.79 g (69%) of white crystalline powder. Anal. calc. for C32H37N3: C, 82.89; H, 8.04; N, 9.04. Found: C, 82.68; H, 7.98; N, 8.80. 1H NMR (CDCl3): δ 7.70 (m, 1H), 7.49-7.55 (m, 2H), 7.41 (d, J=8.4 Hz, 1H), 7.37-7.40 (m, 2H), 7.28 (m, 1H), 6.99-7.11 (m, 5H), 6.60 (m, 1H), 6.55 (m, 1H), 4.48 (d, J=4.6 Hz, 2H), 4.21 (s, 2H), 4.07 (br.s, 1H), 3.98 (br.s, 1H), 3.33 (sept, J=6.8 Hz, 2H), 2.04 (s, 3H), 1.19 (d, J=6.8 Hz, 12H).

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 3×50 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 residue was re-crystallized from 15 ml of diethyl ether

Sources & evidence

ORD record
ord-4dbf850135704789aaf367a409add4da
Source dataset
uspto-grants-2016_04
Patent number
US09321858B2

Reaction notes

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