Tributylstannane → 4-Benzyl-6,6-dimethyl-morpholine-3-carboxylic acid benzyl ester

HRID 12190

반응식

HRID 12190 반응식
[CH2:1]([O:8][C:9]([CH:11]1[CH2:16][O:15][C:14]([CH2:18]I)([CH3:17])[CH2:13][N:12]1[CH2:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([SnH](CCCC)CCCC)CCC.CC(N=NC(C#N)(C)C)(C#N)C>C1(C)C=CC=CC=1>[CH2:1]([O:8][C:9]([CH:11]1[CH2:16][O:15][C:14]([CH3:18])([CH3:17])[CH2:13][N:12]1[CH2:20][C:21]1[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=1)=[O:10])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

참가 물질

5

반응물 3

HCID 5948TributylstannaneHCID 6547AzobisisobutyronitrileHCID 671665234-Benzyl-6-iodomethyl-6-methyl-morpholine-3-carboxylic acid benzyl ester2회

생성물 1

HCID 671657664-Benzyl-6,6-dimethyl-morpholine-3-carboxylic acid benzyl ester수율 85%

시약·촉매·용매 1

HCID 1140Toluene용매2회

실험 절차

To a solution of 4-benzyl-6-iodomethyl-6-methyl-morpholine-3-carboxylic acid benzyl ester (Intermediate 17, 1.23 g) and tributyltin hydride (1.8 ml, 2.5 eq.) in 11 ml of toluene under gentle reflux was added over 1.5 hr a solution of AIBN in toluene (25 mg/1 ml). The mixture was allowed to cool down and was concentrated to dryness. The residue was partitioned into 15% 1M HCl in acetonitrile and hexane. The separated hexane phase was extracted two times with the acetonitrile solution. The combined acetonitrile solutions were washed with hexane two times and concentrated. The residue was partitioned into ether and 1M K2CO3. The separated ether phase was washed successively with 0.4M Na2S2O3 and brine, dried over MgSO4 and concentrated. The residue was purified on silica (7.5% EtOAc/hexane) to give 760 mg (oil, 85% yield) of compound 4-benzyl-6,6-dimethyl-morpholine-3-carboxylic acid benzyl ester.

후처리

  1. temperatureto cool down
  2. concentrationwas concentrated to dryness
  3. customThe residue was partitioned into 15% 1M HCl in acetonitrile and hexane
  4. extractionThe separated hexane phase was extracted two times with the acetonitrile solution
  5. washThe combined acetonitrile solutions were washed with hexane two times
  6. concentrationconcentrated
  7. customThe residue was partitioned into ether and 1M K2CO3
  8. washThe separated ether phase was washed successively with 0.4M Na2S2O3 and brine
  9. dry with materialdried over MgSO4
  10. concentrationconcentrated
  11. customThe residue was purified on silica (7.5% EtOAc/hexane)

출처 및 근거

ORD 기록
ord-de82173cc7804e4cae31af4e4fc9d489
출처 데이터셋
uspto-grants-2010_06
특허 번호
US07727985B2

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