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

HRID 570211

反応式

HRID 570211 の反応式
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]

参加物

7

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 2

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

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-96b67c2677584114a4a89d2732ae1bde
出典データセット
uspto-grants-2015_05
特許番号
US09023846B2

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