Cesium carbonate → (2-Phenyl-[1,2,4]triazolo[1,5-a]pyridin-7-yl)-carbamic acid tert-butyl ester

HRID 1802138노트

반응식

HRID 1802138 반응식
Br[C:2]1[CH:7]=[CH:6][N:5]2[N:8]=[C:9]([C:11]3[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=3)[N:10]=[C:4]2[CH:3]=1.[C:17](=[O:24])([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])[NH2:18].C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1>[C:20]([O:19][C:17](=[O:24])[NH:18][C:2]1[CH:7]=[CH:6][N:5]2[N:8]=[C:9]([C:11]3[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=3)[N:10]=[C:4]2[CH:3]=1)([CH3:23])([CH3:22])[CH3:21]

참가 물질

7

반응물 3

HCID 10796Cesium carbonateHCID 77922tert-Butyl carbamateHCID 677755007-Bromo-2-phenyl-[1,2,4]triazolo[1,5-A]pyridine

생성물 1

HCID 67773976(2-Phenyl-[1,2,4]triazolo[1,5-a]pyridin-7-yl)-carbamic acid tert-butyl ester수율 69.6%

시약·촉매·용매 3

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)촉매HCID 9811564Bis(dibenzylideneacetone)palladium촉매HCID 312751,4-Dioxane용매

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온도
100 °C

실험 절차

To an nitrogen purged suspension of 7-bromo-2-phenyl-[1,2,4]triazolo[1,5-a]pyridine (9 g, 32.8 mmol) in dioxane (180 ml) is added successively tert-butyl carbamate (4.71 g, 39.4 mmol), tris(dibenzylidene-acetone)dipalladium(0) (601 mg, 657 umol), 4,5-bis(diphenylphos-phino)-9,9-dimethylxanthene (760 mg, 1.31 mmol) and cesium carbonate (15 g, 46 mmol). The brown mixture is then stirred for 22 hours at 100° C. under nitrogen atmosphere. The solvent is removed in vacuo and the brown residue partitioned between ethyl acetate and water. The aqueous layer is extracted twice with ethyl acetate and the combined organic layers are washed with water (3×120 ml) and with brine and dried with magnesium sulfate. The solution is concentrated in vacuo to ca 80 ml: crystallization. The suspension is stirred for 10 min in an ice bath and the solid is collected by filtration, washed with little cold ethyl acetate and dried affording (2-phenyl-[1,2,4]triazolo[1,5-a]pyridin-7-yl)-carbamic acid tert-butyl ester (7.09 g) as an off-white solid. The mother liquor is evaporated and the residue (4.79 g) is loaded on silica (16 g). The product is isolated by chromatography on a 120 g silica cartridge (eluent heptane/ethyl acetate 10-50%, 45 min) yielding a second crop of 1.748 g of a white solid. mp.: 200-201° C. dec. MS: m/z=311.3 (M+H+).

후처리

  1. customTo an nitrogen purged
  2. customThe solvent is removed in vacuo
  3. customthe brown residue partitioned between ethyl acetate and water
  4. extractionThe aqueous layer is extracted twice with ethyl acetate
  5. washthe combined organic layers are washed with water (3×120 ml) and with brine
  6. dry with materialdried with magnesium sulfate
  7. concentrationThe solution is concentrated in vacuo to ca 80 ml
  8. customcrystallization
  9. stirringThe suspension is stirred for 10 min in an ice bath
  10. filtrationthe solid is collected by filtration
  11. washwashed with little cold ethyl acetate
  12. customdried

출처 및 근거

ORD 기록
ord-c29f72b38ce84edab5e7eb9a44da6fb9
출처 데이터셋
uspto-grants-2013_01
특허 번호
US08349824B2

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