Ethyl Acetate → 4-(5-Chloro-2-methylbenzoxazol-6-yl)phenylamine

HRID 530783

反応式

HRID 530783 の反応式
Br[C:2]1[C:11]([Cl:12])=[CH:10][C:5]2[N:6]=[C:7]([CH3:9])[O:8][C:4]=2[CH:3]=1.Cl.[NH2:14][C:15]1[CH:20]=[C:19](B(O)O)[CH:18]=[CH:17][CH:16]=1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].CC(=O)OCC>C(#N)C.O1CCOCC1.O.CCCCCC.CC(P(C(C)(C)C)C1C=CC(N(C)C)=CC=1)(C)C.CC(P(C(C)(C)C)C1C=CC(N(C)C)=CC=1)(C)C.Cl[Pd]Cl>[Cl:12][C:11]1[C:2]([C:18]2[CH:19]=[CH:20][C:15]([NH2:14])=[CH:16][CH:17]=2)=[CH:3][C:4]2[O:8][C:7]([CH3:9])=[N:6][C:5]=2[CH:10]=1

参加物

10

反応物 4

HCID 8857Ethyl AcetateHCID 62657Potassium Phosphate, TribasicHCID 27632413-Aminophenylboronic acid hydrochlorideHCID 584874386-Bromo-5-chloro-2-methylbenzoxazole

生成物 1

HCID 674672954-(5-Chloro-2-methylbenzoxazol-6-yl)phenylamine収率 42%

試薬・触媒・溶媒 5

HCID 11714597Bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II)触媒HCID 962Water溶媒HCID 6342Acetonitrile溶媒HCID 8058Hexane溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
85 °C

実験手順

A mixture of 6-bromo-5-chloro-2-methylbenzoxazole (54) (160 mg, 0.65 mmol), anilin-5-boronic acid hydrochloride salt (55) (135 mg, 1.2 eq), Bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium (II) (A-Phos) (46 mg, 0.1 mmol) and K3PO4 (165 mg) in 2 ml ACN, 2 ml dioxane and 0.5 ml H2O was bubbled with argon before heated at 85° C. for 2 h. After cooling down to r.t., the reaction mixture was taken up in EA, washed with aq. NaHCO3 and brine, dried over Na2SO4, concentrated to dryness. The resulting red solid was dissolved in DCM and subjected to silica gel column purification using 0-60% B (A: hexane; B: 50% EA in hexane) to furnish 70.6 mg 56 as yellow solid (yield: 42%)

後処理

  1. customwas bubbled with argon
  2. temperatureAfter cooling down to r.t.
  3. washwashed with aq. NaHCO3 and brine
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated to dryness
  6. dissolutionThe resulting red solid was dissolved in DCM
  7. customsubjected to silica gel column purification

出典と根拠

ORDレコード
ord-a225d33d61544ebfb79172505de33767
出典データセット
uspto-grants-2016_05
特許番号
US09353099B2

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