Ammonium Chloride → HCID 86751632, compound

HRID 2294684Notes

Reaction equation

HRID 2294684 reaction equation
[CH:1]1([CH2:7][C@H:8]2[C@H:12]([CH:13]=[O:14])[O:11][C:10]([CH3:16])([CH3:15])[N:9]2[C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.[CH:24]1(Br)[CH2:26][CH2:25]1.[Mg].[Cl-].[NH4+]>O1CCCC1.C(OCC)(=O)C.C1(C)C=CC=CC=1>[CH:1]1([CH2:7][C@H:8]2[C@H:12]([C@H:13]([CH:24]3[CH2:26][CH2:25]3)[OH:14])[O:11][C:10]([CH3:16])([CH3:15])[N:9]2[C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6]1

Participants

8

Reactant 4

HCID 25517Ammonium ChlorideHCID 78037BromocyclopropaneHCID 5462224MagnesiumHCID 14552357HCID 14552357, compound

Product 1

HCID 86751632HCID 86751632, compoundYield 52.8%

Reagents, catalysts & solvents 3

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

A solution of 3.21 g (9.8 mmol) of tert-butyl (4S,5R)-4-(cyclohexylmethyl)-5-formyl-2,2-dimethyl-3-oxazolidinecarboxylate (WO 87/05302) in 25 ml of tetrahydrofuran is added dropwise at about 15° to a solution of the Grignard compound prepared from 3.94 ml (49 mmol) of cyclopropyl bromide and 1.2 g (0.049 gram atom) of magnesium shavings in 22 ml of tetrahydrofuran and the reaction mixture is subsequently stirred at room temperature under argon for 16 hours. Thereafter, the reaction mixture is poured into 40 ml of an ice-cold, saturated ammonium chloride solution and extracted twice with 50 ml of ethyl acetate each time. The ethyl acetate extracts are washed with 40 ml of ice-cold, saturated ammonium chloride solution, combined, dried over sodium sulphate and evaporated. For purification, the residue (4.33 g) is chromatographed over a column of 110 g of silica gel, prepared with toluene and 1% triethylamine, using a 95:5 mixture of toluene and ethyl acetate as the eluent. There are obtained 1.9 g of tert-butyl (4S,5R)-4-(cyclohexylmethyl)-5-[(S)-cyclopropylhydroxymethyl]-2,2-dimethyl-3-oxazolidinecarboxylate, MS: 368 (M+H)+, and 0.5 g of tert-butyl (4S,5R)-4-(cyclohexylmethyl)-5-[(R)-cyclopropylhydroxymethyl]-2,2-dimethyl-3-oxazolidinecarboxylate, MS: 368 (M+H)+, both as a colourless oil.

Workup

  1. extractionextracted twice with 50 ml of ethyl acetate each time
  2. washThe ethyl acetate extracts are washed with 40 ml of ice-cold, saturated ammonium chloride solution
  3. dry with materialdried over sodium sulphate
  4. customevaporated
  5. customFor purification
  6. customthe residue (4.33 g) is chromatographed over a column of 110 g of silica gel
  7. customprepared with toluene and 1% triethylamine

Sources & evidence

ORD record
ord-fc3ab013208347aa9bc894ecaa7e1c0d
Source dataset
uspto-grants-1997_11
Patent number
US05688946

Reaction notes

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