Dichloromethane → 6-Methyl-5-nitro-2-(2-trifluoromethyl-phenyl)-pyrimidin-4-ylamine

HRID 1481531Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1481531
Cl[C:2]1[N:7]=[C:6]([NH2:8])[C:5]([N+:9]([O-:11])=[O:10])=[C:4]([CH3:12])[N:3]=1.[F:13][C:14]([F:25])([F:24])[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=1B(O)O.[O-]P([O-])([O-])=O.[K+].[K+].[K+].C(Cl)Cl>O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:12][C:4]1[N:3]=[C:2]([C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=2[C:14]([F:25])([F:24])[F:13])[N:7]=[C:6]([NH2:8])[C:5]=1[N+:9]([O-:11])=[O:10]

Komponenten

7

Edukt 4

HCID 6344DichloromethaneHCID 62657Potassium Phosphate, TribasicHCID 2274594-Amino-2-chloro-6-methyl-5-nitropyrimidineHCID 27343872-(Trifluoromethyl)benzeneboronic acid

Produkt 1

HCID 674097756-Methyl-5-nitro-2-(2-trifluoromethyl-phenyl)-pyrimidin-4-ylamine

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)KatalysatorHCID 312751,4-DioxaneLösungsmittel

Versuchsvorschrift

To a solution of 2-chloro-6-methyl-5-nitro-pyrimidin-4-ylamine (920 mg, 4.89 mmol) in 1,4-dioxane (50 mL) was treated with (2-trifluoromethylphenyl)boronic acid (1.3 g, 6.8 mmol), K3PO4 (2.07 g, 9.78 mmol), and (dppf)PdCl2.DCM (318 mg, 0.487 mmol) was heated to 100° C. for 4 h under Ar. The cooled mixture was filtered through a pad of diatomaceous earth, diluted with water, and extracted thrice with EtOAc. The combined organic layers were dried over MgSO4 and concentrated in vacuo. The residue was purified on silica (0:100 v/v to 100:0 v/v EtOAc-hexanes over 20 min) to yield 6-methyl-5-nitro-2-(2-trifluoromethyl-phenyl)-pyrimidin-4-ylamine. 1H-NMR (400 MHz, CDCl3) δ: 7.80 (d, J=7.6 Hz, 1H), 7.71-7.75 (m, 1H), 7.65 (t, J=6.9 Hz, 1H), 7.57-7.62 (m, 1H), 2.84 (s, 3H).

Aufarbeitung

  1. filtrationThe cooled mixture was filtered through a pad of diatomaceous earth
  2. additiondiluted with water
  3. extractionextracted thrice with EtOAc
  4. dry with materialThe combined organic layers were dried over MgSO4
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified on silica (0:100 v/v to 100:0 v/v EtOAc-hexanes over 20 min)

Quellen und Nachweise

ORD-Eintrag
ord-7f3f94c3028e406ba8af16b056bae6e7
Quelldatensatz
uspto-grants-2016_08
Patentnummer
US09409915B2

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