Hydrochloric Acid → 4-(2-(6-Chloropyridin-3-ylamino)pyridin-3-YL)-N,N-bis(4-methoxybenzyl)-6-methyl-1,3,5-triazin-2-amine

HRID 1811837

Reaktionsgleichung

Reaktionsgleichung von HRID 1811837
[Li+].C[Si]([N-][Si](C)(C)C)(C)C.[NH2:11][C:12]1[CH:13]=[CH:14][C:15]([Cl:18])=[N:16][CH:17]=1.F[C:20]1[C:25]([C:26]2[N:31]=[C:30]([CH3:32])[N:29]=[C:28]([N:33]([CH2:43][C:44]3[CH:49]=[CH:48][C:47]([O:50][CH3:51])=[CH:46][CH:45]=3)[CH2:34][C:35]3[CH:40]=[CH:39][C:38]([O:41][CH3:42])=[CH:37][CH:36]=3)[N:27]=2)=[CH:24][CH:23]=[CH:22][N:21]=1.Cl>C1COCC1.CCOC(C)=O.O>[Cl:18][C:15]1[N:16]=[CH:17][C:12]([NH:11][C:20]2[C:25]([C:26]3[N:31]=[C:30]([CH3:32])[N:29]=[C:28]([N:33]([CH2:34][C:35]4[CH:36]=[CH:37][C:38]([O:41][CH3:42])=[CH:39][CH:40]=4)[CH2:43][C:44]4[CH:45]=[CH:46][C:47]([O:50][CH3:51])=[CH:48][CH:49]=4)[N:27]=3)=[CH:24][CH:23]=[CH:22][N:21]=2)=[CH:13][CH:14]=1

Komponenten

8

Edukt 4

HCID 313Hydrochloric AcidHCID 793055-Amino-2-chloropyridine2×HCID 2733832Lithium Hexamethyldisilazide2×HCID 595482404-(2-fluoropyridin-3-yl)-N,N-bis(4-methoxybenzyl)-6-methyl-1,3,5-triazin-2-amine

Produkt 1

HCID 595482274-(2-(6-Chloropyridin-3-ylamino)pyridin-3-YL)-N,N-bis(4-methoxybenzyl)-6-methyl-1,3,5-triazin-2-amineAusbeute 70,2 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 962WaterLösungsmittelHCID 8028TetrahydrofuranLösungsmittel2×HCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
50 °C

Versuchsvorschrift

1.0 M LHMDS in THF (600 μL, 0.600 mmol) was added to a solution of 5-amino-2-chloropyridine (49 mg, 0.381 mmol) and 4-(2-fluoropyridin-3-yl)-N,N-bis(4-methoxybenzyl)-6-methyl-1,3,5-triazin-2-amine (80 mg, 0.180 mmol) in THF (4 mL) under nitrogen at rt. A dark orange mixture formed. After 1.5 h, the mixture was heated to about 50° C. After overnight, more 5-amino-2-chloropyridine (49 mg, 0.381 mmol) and LHMDS (600 μL, 0.600 mmol) were added. The reaction mixture was heated for another 2 h and cooled to rt. The mixture was neutralized with HCl (5 N, 0.3 mL) and diluted with EtOAc (10 mL) and water (10 mL). The aqueous layer was extracted with DCM twice and the combined organic was dried over Na2SO4 and concentrated. The residue was purified on silica (10-80% EtOAc in hexane) to give a yellow oil (70 mg). LCMS (ES, pos.): calcd for C30H28FN7O2: 553.2. found: 554.1 (M+H)+. 1H NMR (400 MHz, CDCl3) δ 12.19 (s, 1H); 8.84 (dd, J=7.83, 1.76 Hz, 1H); 8.47 (d, J=2.74 Hz, 1H); 8.33 (dd, J=4.70, 1.76 Hz, 1H); 8.26 (dd, J=8.71, 2.84 Hz, 1H); 7.16-7.24 (m, 5H); 6.80-6.91 (m, 5H); 4.84 (s, 4H); 3.80 (d, J=5.87 Hz, 6H); 2.59 (s, 3H).

Aufarbeitung

  1. customA dark orange mixture formed
  2. waitAfter overnight
  3. temperatureThe reaction mixture was heated for another 2 h
  4. temperaturecooled to rt
  5. extractionThe aqueous layer was extracted with DCM twice
  6. dry with materialthe combined organic was dried over Na2SO4
  7. concentrationconcentrated
  8. customThe residue was purified on silica (10-80% EtOAc in hexane)

Quellen und Nachweise

ORD-Eintrag
ord-e940dddd4a3a4c0198962b735c1ef1b2
Quelldatensatz
uspto-grants-2013_01
Patentnummer
US08362241B2

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