Sodium Hydroxide → 4-Azido-4,4-Dinitro-1-Butyl Acetate

HRID 1199509Notes

Reaction equation

HRID 1199509 reaction equation
[C:1]([O:4][CH2:5][CH2:6][CH2:7][CH:8]([N+:12]([O-:14])=[O:13])[N+:9]([O-:11])=[O:10])(=[O:3])[CH3:2].[N-:15]=[N+:16]=[N-:17].[Na+].[OH-].[Na+]>>[C:1]([O:4][CH2:5][CH2:6][CH2:7][C:8]([N:15]=[N+:16]=[N-:17])([N+:12]([O-:14])=[O:13])[N+:9]([O-:11])=[O:10])(=[O:3])[CH3:2]

Participants

4

Reactant 3

HCID 14798Sodium HydroxideHCID 33557Sodium Azide2×HCID 144017674,4-Dinitrobutyl acetate

Product 1

HCID 144017684-Azido-4,4-Dinitro-1-Butyl Acetate

Procedure

A divided electrochemical H-cell was charged with 4,4-dinitro-1-butyl acetate (10.2 g), 30% aqueous NaN3 (25 ml) and 12N NaOH (4 ml) in the anode compartment and 30% NaN3 (35 ml) in the cathode compartment. This solution was electrolyzed at 650 mA using a platimum foil anode (6.5 cm2) and a stainless steel cathode. After 5.25 h the reaction was stopped, and the anolyte was extracted with CH2Cl2 (3×25 ml). Brine-washing, drying, and concentrating the extracts yielded a product which displayed a weak hydroxyl absorption in the infrared spectrum. The product was reacetylated by stirring with acetyl chloride (1 ml) in CH2Cl2 (30 ml) for 2 h. This reaction was quenched in ice water, dried, and concentrated. The crude yellow oil was purified by column chromatography on silica gel eluting with 10% ethyl acetate in hexanes. The purified product was a clear light yellow oil which was greater than 95 % pure by HPLC: nD =1.4649 (25C); IR: 2165, 1735, and 1590 cm-1 ; NMR (CDCl3): 4.07 (q, 2H), 2.58 (m, 2H), 2.07 (s, 3H), 1.73 (m, 2H). Elemental analyses calcluated for C6H9N5O6 : C, 29.15; H, 3.64; N, 28.34. Found: C, 29.59; H, 3.90; N, 27.89.

Workup

  1. extractionthe anolyte was extracted with CH2Cl2 (3×25 ml)
  2. washBrine-washing
  3. customdrying
  4. concentrationconcentrating the extracts
  5. customyielded a product which
  6. customa weak hydroxyl absorption in the infrared spectrum
  7. customThis reaction was quenched in ice water
  8. customdried
  9. concentrationconcentrated
  10. customThe crude yellow oil was purified by column chromatography on silica gel eluting with 10% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-401d09ed00a648e7aa61cb887f7cfd63
Source dataset
uspto-grants-1990_02
Patent number
US04900851

Reaction notes

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