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

HRID 634055
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 634055
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
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Komponenten

8

Edukt 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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 178418397HCID 178418397, VerbindungKatalysatorHCID 887MethanolLösungsmittelHCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

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).

Aufarbeitung

  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.)

Quellen und Nachweise

ORD-Eintrag
ord-e4c3a1e9c9c246c298576016a91daaca
Quelldatensatz
uspto-grants-2016_04
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US09321858B2

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