N,N-dimethyl-p-phenylenediamine → N-(4-Chloro-5-trifluoromethyl-pyrimidin-2-yl)-N',N'-dimethyl-benzene-1,4-diamine

HRID 1244767

Reaktionsgleichung

Reaktionsgleichung von HRID 1244767
[F:1][C:2]([F:12])([F:11])[C:3]1[C:4]([Cl:10])=[N:5][C:6](Cl)=[N:7][CH:8]=1.[CH3:13][N:14]([CH3:22])[C:15]1[CH:20]=[CH:19][C:18]([NH2:21])=[CH:17][CH:16]=1.C(N(CC)CC)C>CCOCC.ClCCCl.CC(O)(C)C.[Cl-].[Zn+2].[Cl-]>[Cl:10][C:4]1[C:3]([C:2]([F:12])([F:11])[F:1])=[CH:8][N:7]=[C:6]([NH:21][C:18]2[CH:19]=[CH:20][C:15]([N:14]([CH3:22])[CH3:13])=[CH:16][CH:17]=2)[N:5]=1

Komponenten

7

Edukt 3

HCID 7472N,N-dimethyl-p-phenylenediamineHCID 8471TriethylamineHCID 27827742,4-Dichloro-5-(trifluoromethyl)pyrimidine

Produkt 1

HCID 21923099N-(4-Chloro-5-trifluoromethyl-pyrimidin-2-yl)-N',N'-dimethyl-benzene-1,4-diamine

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 3007855ZincchlorideKatalysatorHCID 3283Diethyl EtherLösungsmittelHCID 21868497Tert-butyl alcohol 1,2-dichloroethaneLösungsmittel2×

Versuchsvorschrift

To a solution of 5-trifluoromethyl-2,4-dichloropyrimidine (500 mg; 2.3 mmol) in 1:1 DCE/t-BuOH (20 mL) was added Zinc chloride (5.1 mL of a 1 M solution in ether; 2.2 eq) at 0° C. After 1 hour, N,N-dimethyl-1,4-phenylenediamine (313 mg; 1 eq) was added followed by dropwise addition of a solution of triethylamine (279 mg; 1.1 eq) in 5 mL of DCE/t-BuOH. After stirring for 24 hours the reaction was concentrated. The product was obtained as a pale green solid (531 mg; 73%) following crystallization from 25% H2O/methanol. 1H NMR (DMSO-d6, 400 MHz) δ 2.83 (s, 6H), 6.69 (m, 2H), 7.39 (m, 2H), 8.65 (s, 1H), 10.32 (s, 1H); 13C NMR (CDCl3, 100 MHz) δ 161.3, 158.8 (br), 158.5 (br), 148.3, 128.2, 123.8 (q, J=268 Hz), 123.0, 113.1, 110.8 (br), 41.0; HPLC ret. time: 7.901 min. LRMS (M+) 317.3, 319.3.

Aufarbeitung

  1. customat 0° C
  2. concentrationwas concentrated
  3. customThe product was obtained as a pale green solid (531 mg; 73%)
  4. customcrystallization from 25% H2O/methanol

Quellen und Nachweise

ORD-Eintrag
ord-bbbb13c2de724149bdc1e76078b2103c
Quelldatensatz
uspto-grants-2006_10
Patentnummer
US07122670B2

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