Diisopropylamine → HCID 86739932, compound

HRID 615658Notes

Reaction equation

HRID 615658 reaction equation
C(N[CH:5]([CH3:7])[CH3:6])(C)C.C([Li])CCC.C([N-]C(C)C)(C)C.[Li+].[C:21]([NH:29][C@@H:30]([CH2:36][C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1)[CH2:31][C:32]([O:34][CH3:35])=[O:33])(=[O:28])[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1.COC1C=C[C:48]([S:51]SC)=CC=1.[O:54]1[CH2:58][CH2:57][CH2:56][CH2:55]1>C(OCC)(=O)C.C1C=CC=CC=1.CCCCCC>[C:21]([NH:29][CH:30]([CH2:36][C:37]1[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=1)[C@H:31]([S:51][CH2:48][C:6]1[CH:5]=[CH:7][C:55]([O:54][CH3:58])=[CH:56][CH:57]=1)[C:32]([O:34][CH3:35])=[O:33])(=[O:28])[C:22]1[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=1

Participants

10

Reactant 6

HCID 7912DiisopropylamineHCID 8028Tetrahydrofuran3×HCID 2724682Lithium diisopropylamideHCID 11171426HCID 11171426, compoundHCID 13501894HCID 13501894, compoundHCID 178418339Butyllithium

Product 1

HCID 86739932HCID 86739932, compound

Reagents, catalysts & solvents 3

HCID 241BenzeneSolventHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of freshly distilled diisopropylamine (2.07 ml., 14.8 mmole) in dry tetrahydrofuran (20 ml.) at 0° under argon is added a hexane solution of n-butyl lithium (6.02 ml. of a 2.4 M solution, 14.5 mmole). After stirring at 0° for 30 minutes, the resulting solution of lithium diisopropylamide is cooled to -78° and a solution of (S)-β-(benzoylamino)-benzenebutanoic acid, methyl ester (2.0 g., 6.72 mmole) in tetrahydrofuran (20 ml.) is added dropwise over a period of 5 minutes. After stirring at -78° for 15 minutes, a solution of (4-methoxyphenyl)methyl disulfide (2.5 g., 8.07 mmole) in tetrahydrofuran (9 ml.) is added. After 5 minutes at -78°, the mixture is warmed to 0° and stirring continued for 45 minutes. The reaction is quenched with 1N hydrochloric acid and diluted with ethyl acetate. The resulting solution is washed with water, 1N hydrochloric acid, 1N sodium bicarbonate, and brine. After drying over anhydrous MgSO4, the solvent is removed at reduced pressure and the residue is flash chromatographed (silica gel LPS-1; benzene:ethyl acetate, 93:7) to give 1.85 g. of pale yellow solid (S)-β-(benzoylamino)-ε-[[(4-methoxyphenyl)methyl]thio]-benzenebutanoic acid, methyl ester as a mixture of diastereomers. TLC (silica gel; benzene:ethyl acetate, 9:1) Rf =0.29 and 0.26.

Workup

  1. stirringAfter stirring at -78° for 15 minutes
  2. waitAfter 5 minutes at -78°
  3. temperaturethe mixture is warmed to 0°
  4. stirringstirring
  5. waitcontinued for 45 minutes
  6. customThe reaction is quenched with 1N hydrochloric acid
  7. additiondiluted with ethyl acetate
  8. washThe resulting solution is washed with water, 1N hydrochloric acid, 1N sodium bicarbonate, and brine
  9. dry with materialAfter drying over anhydrous MgSO4
  10. customthe solvent is removed at reduced pressure
  11. customchromatographed (silica gel LPS-1; benzene:ethyl acetate, 93:7)
  12. customto give 1.85 g

Sources & evidence

ORD record
ord-20cd5caeb4d34779b79db4992cecaa1e
Source dataset
uspto-grants-1985_02
Patent number
US04500518

Reaction notes

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