Reaction #356933

Reaction equation

water

nitric acid

sulfuric acid

4-bromobutanol

→

4-bromobutyl nitrate

Yield 96.0%

Solvents

dichloromethane

Conditions

Workup

1. 1
   Otherthe temperature between −5° C. and 3° C
2. 2
   ExtractionAfter decantation, the upper aqueous phase was extracted with dichloromethane
3. 3
   Washthe combined organic phases were washed with water
4. 4
   workup.ADDITIONadjusted to pH=6-7 by addition of 27.65% sodium hydroxide
5. 5
   Washwashed with brine
6. 6
   Dryingdried over magnesium sulfate
7. 7
   workup.DISTILLATIONDichloromethane was distilled off under vacuum and crude 4-bromobutyl nitrate (12.7 g-64.1 mmol)
8. 8
   Otherwas recovered in a yield of about 96%

Procedure

In reactor cooled to −5 to 5° C., nitric acid fuming (8.5 g-135 mmol) was slowly added to a solution of 98% sulfuric acid (13.0 g-130 mmol) in dichloromethane (18.0 g-212 mmol). 4-bromobutanol (10.2 g-66.6 mmol) was then added to this mixture and the reaction medium was stirred at −5 to 5° C. over a period of 2-5 hours. The mixture was poured into cold water (110 g) keeping the temperature between −5° C. and 3° C. After decantation, the upper aqueous phase was extracted with dichloromethane and the combined organic phases were washed with water, adjusted to pH=6-7 by addition of 27.65% sodium hydroxide, washed with brine and dried over magnesium sulfate. Dichloromethane was distilled off under vacuum and crude 4-bromobutyl nitrate (12.7 g-64.1 mmol) was recovered in a yield of about 96%.

Source