Water → Octahydro-2H-azonin-2-one

HRID 2301900Notes

Reaction equation

HRID 2301900 reaction equation
NOS(O)(=O)=O.[C:7]1(=[O:15])[CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8]1.[Cl-].[NH4+:17].O>C(O)=O>[C:7]1(=[O:15])[CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][NH:17]1

Participants

6

Reactant 4

HCID 962WaterHCID 10403CyclooctanoneHCID 25517Ammonium ChlorideHCID 76284hydroxylamine-O-sulfonic acid

Product 1

HCID 13632Octahydro-2H-azonin-2-oneYield 65%

Reagents, catalysts & solvents 1

HCID 284Formic AcidSolvent2×

Conditions

Temperature
105 °C

Procedure

A 5 L three-neck round bottom flask was fitted with a heating mantle, an overhead mechanical stirrer, an addition funnel, and a thermometer. The reaction was performed under an argon atmosphere. Hydroxylamine-O-sulfonic acid (196.7 g, 1.74 moles, 1.10 equiv.) and formic acid (1 L) were charged into the round bottom flask and stirred to form a white slurry. A solution of cyclooctanone (200.0 g 1.58 moles, 1.0 equiv.) in formic acid (600 mL) was added dropwise to the white slurry via the addition funnel. After the addition, the addition funnel was replaced by a reflux condenser, and the reaction was heated to reflux (internal temperature about 105° C.) for 1 hour to give a brown solution. After the solution was cooled to room temperature, it was poured into a mixture of saturated aqueous ammonium chloride (1.5 L) and water (1.5 L). The aqueous mixture was extracted with chloroform (3×1200 mL). The combined chloroform layers were transferred into a breaker, and saturated sodium bicarbonate (2 L) was added slowly. The chloroform layer was then separated, dried over anhydrous sodium sulfate, and evaporated under reduced pressure to afford a. brown oil. The oil Was placed in a 5.00 mL round bottom flask with a magnetic stirrer. The round bottom flask was placed in a silicon oil bath and was fitted with a short path vacuum distillation head equipped with a thermometer. A Cow-type receiver was connected to three 250 mL flasks. 2-Azacyclononanone (145 g, 65%, mp 64-69° C.) was obtained by vacuum distillation (fraction with head temperature range from 80 to 120° C. at pressures between 3.0 and 3.4 mmHg).

Workup

  1. customA 5 L three-neck round bottom flask was fitted with a heating mantle, an overhead mechanical stirrer, an addition funnel
  2. customto form a white slurry
  3. additionAfter the addition
  4. customthe addition funnel was replaced by a reflux condenser
  5. temperaturethe reaction was heated
  6. customto give a brown solution
  7. temperatureAfter the solution was cooled to room temperature
  8. extractionThe aqueous mixture was extracted with chloroform (3×1200 mL)
  9. additionwas added slowly
  10. customThe chloroform layer was then separated
  11. dry with materialdried over anhydrous sodium sulfate
  12. customevaporated under reduced pressure
  13. customto afford a
  14. customThe oil Was placed in a 5.00 mL round bottom flask with a magnetic stirrer
  15. customThe round bottom flask was placed in a silicon oil bath
  16. customwas fitted with a short path vacuum distillation head
  17. customequipped with a thermometer

Sources & evidence

ORD record
ord-8c7997cfe08c469597b092b445b37548
Source dataset
uspto-grants-2002_08
Patent number
US06428780B2

Reaction notes

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