Ammonia → Cyclododecanone, oxime

HRID 1854778Notes

Reaction equation

HRID 1854778 reaction equation
[NH3:1].S(O)(O)(=O)=O.N[OH:8].S(=O)(=O)(O)O.S([O-])([O-])(=O)=O.[NH4+].[NH4+].[C:21]1(=O)[CH2:32][CH2:31][CH2:30][CH2:29][CH2:28][CH2:27][CH2:26][CH2:25][CH2:24][CH2:23][CH2:22]1>C1(C)C=CC=CC=1>[C:21]1(=[N:1][OH:8])[CH2:32][CH2:31][CH2:30][CH2:29][CH2:28][CH2:27][CH2:26][CH2:25][CH2:24][CH2:23][CH2:22]1

Participants

7

Reactant 5

HCID 222Ammonia2×HCID 1118Sulfuric AcidHCID 13246CyclododecanoneHCID 159255Hydroxylamine, sulfate (1:1)3×HCID 6097028Ammonium Sulfate2×

Product 1

HCID 136762Cyclododecanone, oxime

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
85 °C

Procedure

A 25% by weight aqueous ammonia (Wako Pure Chemical Industries, Ltd.) was added to an aqueous solution having a composition of 14.8% by weight of hydroxylamine sulfate, 9.5% by weight of sulfuric acid and 27.1% by weight of ammonium sulfate to adjust pH to 4 (neutralized amine). To the aqueous neutralized amine solution was added a 42.4% by weight aqueous solution of ammonium sulfate such that a concentration of hydroxylamine sulfate was 7.69% by weight. Then, 25383.3 g of the hydroxylamine sulfate solution thus prepared was added to a pillow type oxime reactor having a liquid-phase volume 40 L equipped with a mixing blade, and the mixture was heated to 85° C. and then 7241 g of cyclododecanone and 3113.7 g of toluene were added. A 25% by weight aqueous ammonia was continuously added such that pH became 5.8 at a temperature of 85° C. to promote the reaction. Once a hydroxylamine concentration in the aqueous layer became 1000 ppm or less, stirring and feeding of the aqueous ammonia were stopped and the mixture was allowed to stand, and the aqueous layer was drained. To the remaining oil layer were added 4127.3 g of toluene and 25022.6 g of neutralized amine and feeding of a 25% by weight aqueous ammonia was initiated to adjust pH to 5.8 at a temperature of 85° C. Once a cyclododecanone concentration became 1000 ppm or less, stirring was stopped and after standing, an aqueous layer was drained and the reaction was quenched. The obtained oil layer (cyclododecanone oxime-toluene solution) was analyzed by a Karl Fischer type moisture tester (Hiranuma Sangyo Co., Ltd., type AQ-2100 micro moisture tester) and a water content was 2000 ppm.

Workup

  1. additionwas added to a pillow type oxime reactor
  2. customequipped with a mixing blade
  3. customat a temperature of 85° C.
  4. customthe reaction
  5. concentrationOnce a hydroxylamine concentration in the aqueous layer
  6. additionTo the remaining oil layer were added 4127.3 g of toluene and 25022.6 g of neutralized amine and feeding of a 25% by weight aqueous ammonia
  7. customto adjust pH to 5.8 at a temperature of 85° C
  8. concentrationOnce a cyclododecanone concentration
  9. stirringstirring
  10. customthe reaction was quenched

Sources & evidence

ORD record
ord-723ce9a53ffe4debb742742baf142481
Source dataset
uspto-grants-2015_02
Patent number
US08962826B2

Reaction notes

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