Triphenylphosphine → 2-(5-Chloropyridin-2-yl)-2,2-difluoroethan-1-amine

HRID 1987071노트

반응식

HRID 1987071 반응식
[N:1]([CH2:4][C:5]([C:8]1[CH:13]=[CH:12][C:11]([Cl:14])=[CH:10][N:9]=1)([F:7])[F:6])=[N+]=[N-].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[OH-].[NH4+].[OH-].[Na+]>C1COCC1>[F:7][C:5]([F:6])([C:8]1[CH:13]=[CH:12][C:11]([Cl:14])=[CH:10][N:9]=1)[CH2:4][NH2:1]

참가 물질

6

반응물 4

HCID 11776TriphenylphosphineHCID 14798Sodium HydroxideHCID 14923Ammonium HydroxideHCID 86006460HCID 86006460, 화합물

생성물 1

HCID 534408412-(5-Chloropyridin-2-yl)-2,2-difluoroethan-1-amine수율 93.7%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

To a solution of 2-(2-Azido-1,1-difluoro-ethyl)-5-chloro-pyridine (1.94 g, 8.87 mmol) (prepared essentially as described for Example 14b) in THF (30 mL) cooled in an ice bath were added triphenylphosphine pellets (2.6 g, 9.76 mmol). The mixture was stirred at room temperature for 16 h. Ammonium hydroxide solution (10 mL) was added to the mixture followed by additional stirring for 4 h. NaOH solution (3 N, 40 mL) was then added and the mixture was heated at 40° C. for 1 h. The organic layer was separated and washed with HCl solution (2 N, 60 mL). The aqueous layer was then basified with 4 N NaOH solution and extracted with EtOAc twice. The solvent was evaporated to leave a pale yellow oil (1.6 g, 93% yield). 1H NMR (300 Hz, CDCl3) δ 8.59 (d, 1H), 7.78 (dd, 1H), 7.62 (d, 1H), 3.40 (t, 2H); LC/MS (m/z) [M+1]+ 193.0 (calculated for C7H7ClF2N2, 192.0).

후처리

  1. temperaturecooled in an ice bath
  2. stirringby additional stirring for 4 h
  3. temperaturethe mixture was heated at 40° C. for 1 h
  4. customThe organic layer was separated
  5. washwashed with HCl solution (2 N, 60 mL)
  6. extractionextracted with EtOAc twice
  7. customThe solvent was evaporated

출처 및 근거

ORD 기록
ord-62fcd205c3684cdfb7ff75622e628822
출처 데이터셋
uspto-grants-2009_06
특허 번호
US07550474B2

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