Sodium hydride → 4-[(3-(tetrahydropyran-2-yloxy)-4-bromobenzyl)(4-cyanophenyl)amino]-4H-[1,2,4]triazole

HRID 1685660

Reaktionsgleichung

Reaktionsgleichung von HRID 1685660
C(OC1C=C(C=CC=1)CN(C1C=CC(C#N)=CC=1)N1C=NN=C1)C1C=CC=CC=1.[H-].[Na+].[C:32]([C:34]1[CH:39]=[CH:38][C:37]([NH:40][N:41]2[CH:45]=[N:44][N:43]=[CH:42]2)=[CH:36][CH:35]=1)#[N:33].[Br:46][C:47]1[CH:54]=[CH:53][C:50]([CH2:51]Br)=[CH:49][C:48]=1[O:55][CH:56]1[CH2:61][CH2:60][CH2:59][CH2:58][O:57]1>CN(C=O)C.CCOC(C)=O>[O:57]1[CH2:58][CH2:59][CH2:60][CH2:61][CH:56]1[O:55][C:48]1[CH:49]=[C:50]([CH:53]=[CH:54][C:47]=1[Br:46])[CH2:51][N:40]([C:37]1[CH:36]=[CH:35][C:34]([C:32]#[N:33])=[CH:39][CH:38]=1)[N:41]1[CH:42]=[N:43][N:44]=[CH:45]1

Komponenten

7

Edukt 4

HCID 24758Sodium hydrideHCID 10307909Benzonitrile, 4-(4H-1,2,4-triazol-4-ylamino)-HCID 167478424-Bromo-3-(tetrahydropyran-2-yloxy)benzyl bromideHCID 219768914-[(3-benzyloxybenzyl)(4-cyanophenyl)amino]-4H-[1,2,4]triazole

Produkt 1

HCID 167493314-[(3-(tetrahydropyran-2-yloxy)-4-bromobenzyl)(4-cyanophenyl)amino]-4H-[1,2,4]triazoleAusbeute 99 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6228DimethylformamideLösungsmittel3×HCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

The title compound was prepared by adapting the method for 4-[(3-benzyloxybenzyl)(4-cyanophenyl)amino]-4H-[1,2,4]triazole using the following modifications. To a stirred suspension of NaH (60% dispersion in oil, 0.27 g, 6.78 mmol) in anhydrous DMF (10 mL) was added a solution of 4-[(4-cyanophenyl)amino]-4H-[1,2,4]triazole (1.26 g, 6.78 mmol) in anhydrous DMF (5 mL) and the mixture stirred at r.t. for 0.5 h. A solution of 4-bromo-3-(tetrahydropyran-2-yloxy)benzyl bromide (2.61 g, 7.46 mmol) in anhydrous DMF (5 mL) was then added and the mixture heated at 80-90° C. for 3 h. The mixture was cooled, diluted with EtOAc (50 mL), washed with water (4×100 mL), brine (100 mL) and dried (Na2SO4). Concentration in vacuo and subsequent purification by flash column chromatography [SiO2, EtOAc (100%)] gave 4-[(3-(tetrahydropyran-2-yloxy)-4-bromobenzyl)(4-cyanophenyl)amino]-4H-[1,2,4]triazole as a yellow oil (3.05 g, 99%); δH (270 MHz, CDCl3) 1.61-1.99 (m, 6H), 3.55-3.59 (m, 1H), 3.73 (m, 1H), 4.75 (d, J=14.6, 1H), 4.90 (d, J=14.6, 1H), 5.41 (m, 1H), 6.64 (AA′BB′, 2H), 6.69 (dd, J=8.2, 2.2, 1H), 7.00 (d, J=2.2, 1H), 7.49 (d, J=7.9, 1H), 7.57 (AA′BB′, 2H), 8.15 (s, 2H); LRMS (FAB+) m/z (rel. intensity) 456.1 (54, [C21H20N5O281Br+H]), 454.1 (54, [C21H20N5O279Br+H]); LC-MS (APCI+): tR=2.0 min, m/z 456.1 (94, [C21H20N5O281Br+H]), 454.1 (100, [C21H20N5O279Br+H]); HPLC: tR=2.21 min (94%); HRMS (FAB+): Found 454.08627 C21H21N5O279Br requires 454.08786.

Aufarbeitung

  1. customThe title compound was prepared
  2. temperaturethe mixture heated at 80-90° C. for 3 h
  3. temperatureThe mixture was cooled
  4. washwashed with water (4×100 mL), brine (100 mL)
  5. dry with materialdried (Na2SO4)
  6. concentrationConcentration
  7. customin vacuo and subsequent purification by flash column chromatography [SiO2, EtOAc (100%)]

Quellen und Nachweise

ORD-Eintrag
ord-d1292452a6204aac98c556d40430f9f6
Quelldatensatz
uspto-grants-2012_04
Patentnummer
US08148415B2

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