Trimethyl borate → Ammonia

HRID 450946노트

반응식

HRID 450946 반응식
C([Li])CCC.Br[C:7]1[CH:8]=[C:9]([CH:38]=[CH:39][CH:40]=1)[CH2:10][O:11][CH:12]1[CH2:17][CH2:16][N:15]([C:18]([CH3:37])([CH3:36])[CH2:19][CH2:20][C:21]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C:22]#[N:23])[CH2:14][CH2:13]1.C[O:42]B(OC)OC.C[N+]1([O-])CCOCC1>O1CCCC1>[NH3:15].[OH:42][C:7]1[CH:8]=[C:9]([CH:38]=[CH:39][CH:40]=1)[CH2:10][O:11][CH:12]1[CH2:17][CH2:16][N:15]([C:18]([CH3:37])([CH3:36])[CH2:19][CH2:20][C:21]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C:22]#[N:23])[CH2:14][CH2:13]1

참가 물질

7

반응물 4

HCID 8470Trimethyl borateHCID 82029Methyl morpholine oxideHCID 59423969HCID 59423969, 화합물HCID 178418339Butyllithium

생성물 2

HCID 222AmmoniaHCID 59423983HCID 59423983, 화합물

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

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온도
-78 °C

실험 절차

n-Butyl lithium (2.5M in hexanes, 0.18 mL, 0.45 mmol) was added dropwise to a solution of the product of example 87 (200 mg, 0.38 mmol) in tetrahydrofuran (5 mL), cooled to −78° C., and the mixture was stirred for 15 minutes. Trimethylborate (0.13 mL, 1.13 mmol) was added and the mixture was stirred at −78° C. for 30 minutes and at room temperature for 2 hours. 4-methylmorpholine N-oxide (132 mg, 1.13 mmol) was added and the mixture was heated under reflux for 4 hours and stirred at room temperature for 18 hours. The reaction mixture was then partitioned between ethyl acetate (30 mL) and water (30 mL) and the organic layer was separated and washed with water (20 mL). The organic solution was dried over sodium sulfate, concentrated in vacuo and the residue was purified by column chromatography on silica gel, eluting with dichloromethane:methanol:0.88 ammonia, 100:0:0 to 90:10:1. The appropriate fractions were evaporated under reduced pressure and the residue was further purified by preparative tlc, eluting with dichloromethane:methanol:0.88 ammonia, 90:10:1, to afford the title compound as a gum in 3% yield, 5 mg.

후처리

  1. stirringthe mixture was stirred at −78° C. for 30 minutes and at room temperature for 2 hours
  2. temperaturethe mixture was heated
  3. temperatureunder reflux for 4 hours
  4. stirringstirred at room temperature for 18 hours
  5. customThe reaction mixture was then partitioned between ethyl acetate (30 mL) and water (30 mL)
  6. customthe organic layer was separated
  7. washwashed with water (20 mL)
  8. dry with materialThe organic solution was dried over sodium sulfate
  9. concentrationconcentrated in vacuo
  10. customthe residue was purified by column chromatography on silica gel
  11. washeluting with dichloromethane
  12. customThe appropriate fractions were evaporated under reduced pressure
  13. customthe residue was further purified by preparative tlc
  14. washeluting with dichloromethane

출처 및 근거

ORD 기록
ord-6896c725a1b041fb85d81ed913cc51cf
출처 데이터셋
uspto-grants-2013_07
특허 번호
US08486992B2

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