Ammonia → HCID 86751655, compound

HRID 2294723Notes

Reaction equation

HRID 2294723 reaction equation
[N-:1]=[N+:2]=[N-:3].[Na+].S(=O)(=O)(O)O.N.[CH:11]1([CH2:17][C@H:18]2[C@H:22]([C@@H:23]([CH:25]3[CH2:27][CH2:26]3)O)[O:21][C:20]([CH3:29])([CH3:28])[N:19]2[C:30]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:31])[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>C1C=CC=CC=1.O>[CH:11]1([CH2:17][C@H:18]2[C@H:22]([C@H:23]([CH:25]3[CH2:26][CH2:27]3)[N:1]=[N+:2]=[N-:3])[O:21][C:20]([CH3:29])([CH3:28])[N:19]2[C:30]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:31])[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12]1

Participants

9

Reactant 6

HCID 222AmmoniaHCID 1118Sulfuric AcidHCID 11776TriphenylphosphineHCID 33557Sodium AzideHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 86751656HCID 86751656, compound

Product 1

HCID 86751655HCID 86751655, compoundYield 53.5%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolvent2×HCID 962WaterSolvent

Procedure

A mixture of 1.63 g (25 mmol) of sodium azide, 1.5 ml of water and 10 ml of benzene is treated dropwise with 0.67 ml (12.5 mmol) of concentrated sulphuric acid while cooling with ice (<10°) and stirring. Thereafter, the mixture is cooled to 0°, the benzene phase is decanted off and dried over magnesium sulphate. The thus-obtained nitrogen hydride solution is added to a mixture of 368 mg (1 mmol) of tert-butyl (4S,5R)-4-(cyclohexylmethyl)-5-[(R)-cyclopropylhydroxymethyl]-2,2-dimethyl-3-oxazolidinecarboxylate and 289 mg (1.1 mmol) of triphenylphosphine in 5 ml of benzene. Subsequently, 0.15 ml (1.1 mmol) of diethyl azodicarboxylate is added and the reaction mixture is stirred at room temperature overnight under argon. Thereafter, the reaction mixture is evaporated and, for purification, the residue is chromatographed on 50 g of silica gel using a 3:1 mixture of toluene and ethyl acetate as the eluent. There are obtained 210 mg of tert-butyl (4S,5R)-4-(cyclohexylmethyl)-5-[(S)-cyclopropylazidomethyl]-2,2-dimethyl-3-oxazolidinecarboxylate, MS: 393 (M+H)+, as an oil which gradually crystallizes as well as 130 mg of educt.

Workup

  1. temperaturewhile cooling with ice (<10°)
  2. temperatureThereafter, the mixture is cooled to 0°
  3. customthe benzene phase is decanted off
  4. dry with materialdried over magnesium sulphate
  5. stirringthe reaction mixture is stirred at room temperature overnight under argon
  6. customThereafter, the reaction mixture is evaporated and, for purification
  7. customthe residue is chromatographed on 50 g of silica gel using
  8. additiona 3:1 mixture of toluene and ethyl acetate as the eluent

Sources & evidence

ORD record
ord-e4181202eff44f90b7f495b814655d6d
Source dataset
uspto-grants-1997_11
Patent number
US05688946

Reaction notes

Loading…