Toluene → HCID 53859630, compound

HRID 617760Notes

Reaction equation

HRID 617760 reaction equation
[C:1]([N:11]([C@@H:13]([CH3:21])[C:14]1[CH:19]=[CH:18][C:17](N)=[CH:16][CH:15]=1)[CH3:12])([O:3][CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)=[O:2].N([O-])=[O:23].[Na+].C1(C)C=CC=CC=1>S(=O)(=O)(O)O.O>[C:1]([N:11]([C@@H:13]([CH3:21])[C:14]1[CH:19]=[CH:18][C:17]([OH:23])=[CH:16][CH:15]=1)[CH3:12])([O:3][CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)=[O:2]

Participants

6

Reactant 3

HCID 1140TolueneHCID 23668193Sodium NitriteHCID 53706962HCID 53706962, compound

Product 1

HCID 53859630HCID 53859630, compoundYield 58.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1118Sulfuric AcidSolvent

Conditions

Temperature
82.5 °C

Procedure

The above (S)-(-)-N-carbobenzyloxy-N-methyl-4-amino-α-methylbenzylamine (6.0 gm, assume 21 mmol) was dissolved in 2N sulfuric acid (63 mL) and cooled in an ice salt bath. A solution of sodium nitrite (1.6 gm, 23 mmol) in water (25 mL) was added over 15 min at 0-5° C. and the reaction stirred for another 0.5 hr. Toluene (100 mL) was then added and the reaction was rapidly heated to 80-85° C. on a steam bath. The reaction turned very dark and after 10 min was poured onto ice and extracted with 2 portions of ether. The ether layers were each washed with brine, combined, dried over sodium sulfate and evaporated. The residue was purified by flash chromatography using 20-30% ethyl acetate/hexanes to give 3.5 gm (58%) of the title compound.

Workup

  1. temperaturecooled in an ice salt bath
  2. waitThe reaction turned very dark and after 10 min
  3. additionwas poured onto ice
  4. extractionextracted with 2 portions of ether
  5. washeach washed with brine
  6. dry with materialdried over sodium sulfate
  7. customevaporated
  8. customThe residue was purified by flash chromatography

Sources & evidence

ORD record
ord-5cd691acf64e4df8910f8f29817be491
Source dataset
uspto-grants-1999_09
Patent number
US05952321

Reaction notes

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