4-Toluenesulfonyl chloride → 1,3-Di-tert-butyl 2-diazopropanedioate

HRID 1292332Notes

Reaction equation

HRID 1292332 reaction equation
[N-]=[N+:2]=[N-:3].[Na+].C1(C)C=CC(S(Cl)(=O)=O)=CC=1.[C:16]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])(=[O:25])[CH2:17][C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19].C(N(CC)CC)C>O.C(O)C>[C:21]([O:20][C:18](=[O:19])[C:17](=[N+:2]=[N-:3])[C:16]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])([CH3:23])([CH3:24])[CH3:22]

Participants

7

Reactant 4

HCID 73974-Toluenesulfonyl chlorideHCID 8471TriethylamineHCID 33557Sodium AzideHCID 68324Di-tert-butyl malonate

Product 1

HCID 50146001,3-Di-tert-butyl 2-diazopropanedioateYield 125.9%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent

Procedure

A mixture of sodium azide (1.37 grams, 21.0 mmol), p-toluenesulfonyl chloride (4.0 grams, 21.0 mmol), and 70% aqueous ethanol (60 mL) was stirred at room temperature for 1 hour. Di-t-butyl malonate (4.48 mL, 20.0 mmol) and triethylamine (2.92 grams, 21.0 mmol) were added. The reaction mixture was stirred at room temperature for 4 hours and then poured into deionized water (200 mL). The mixture was extracted with petroleum ether (2×200 mL). The extracts were combined and then washed with a saturated aqueous sodium chloride solution. The organic solution was dried using anhydrous magnesium sulfate, filtered, and concentrated to give 6.10 grams of di-t-butyl-2-diazomalonate as a yellow oil. IR(film): 2110 cm-1. Decomposition temperature: 178° C. (by DSC).

Workup

  1. stirringThe reaction mixture was stirred at room temperature for 4 hours
  2. extractionThe mixture was extracted with petroleum ether (2×200 mL)
  3. washwashed with a saturated aqueous sodium chloride solution
  4. customThe organic solution was dried
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-22f09d8ab7294db2a4b4ed393167528d
Source dataset
uspto-grants-1998_05
Patent number
US05756689

Reaction notes

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