Oxygen → HCID 54140861, compound

HRID 361956Notes

Reaction equation

HRID 361956 reaction equation
[C:1](Cl)(=[O:5])[C:2](Cl)=[O:3].[C:7]([O:11][O:12][C:13]([CH3:19])([CH3:18])[CH2:14][CH:15]([CH3:17])[OH:16])([CH3:10])([CH3:9])[CH3:8].N1C=CC=CC=1.[C:26]([O:34][O:35][C:36]([CH3:42])([CH3:41])[CH2:37][CH:38]([OH:40])[CH3:39])(=[O:33])[CH2:27][CH2:28][C:29]([CH3:32])([CH3:31])[CH3:30].O=O>CC(OC)(C)C>[C:1]([O:16][CH:15]([CH3:17])[CH2:14][C:13]([O:12][O:11][C:7]([CH3:10])([CH3:9])[CH3:8])([CH3:18])[CH3:19])(=[O:5])[C:2]([O:40][CH:38]([CH3:39])[CH2:37][C:36]([O:35][O:34][C:26](=[O:33])[CH2:27][CH2:28][C:29]([CH3:32])([CH3:31])[CH3:30])([CH3:42])[CH3:41])=[O:3]

Participants

7

Reactant 5

HCID 977OxygenHCID 1049PyridineHCID 65578Oxalyl chlorideHCID 220654633-t-Butylperoxy-1,3-dimethylbutanolHCID 86161360HCID 86161360, compound

Product 1

HCID 54140861HCID 54140861, compoundYield 100%

Reagents, catalysts & solvents 1

HCID 15413tert-Butyl methyl etherSolvent2×

Procedure

A 250 mL 3-necked flask equipped with a magnetic stirring bar, a nitrogen inlet line, a thermometer and an addition funnel was charged with 75 mL ofMTBE and 2.5 g (19.3 mmoles) of oxalyl chloride and the flask contents werecooled to 0° C. Then a solution of 3.9 g (19 mmoles) of 92.6% 3-t-butylperoxy-1,3-dimethylbutanol and 1.5 g (19.0 mmoles)of pyridine in 10 mL of MTBE was added dropwise over 30 minutes while the temperature wasmaintained at 0°-5° C. After the addition was completed the reaction mass was stirred for 60 minutes at 0°-5° C. To the stirred reaction mass was added a solution of 5.0 g (19.2 mmoles) of 94.4%3-hydroxy- 1,1-dimethylbutyl peroxyneoheptanoate and 1.5 g (19.0 mmoles) ofpyridine in 10 mL of MTBE over a period of 15 minutes. The reaction mixturewas then stirred for an additional 45 minutes at 20°-25° C. after which it was quenched with water. After separating and discarding the aqueous phase the organic was washed once with cold aqueous 10% HCl solution, three times with water and once with dilute aqueous NaHCO3 solution. The product solution was dried over 5% by weight of anhydrous MgSO4, and, after separation of the spent desiccant by filtration, the solvent was removed in vacuo leaving 9.3 g (100% of theory, uncorrected) of a hazy colorless oil. The product contained 6.78% active oxygen (theory, 6.52%), therefore, I-5 was obtained with an assay of 100% and in a corrected yield of 100%. A Differential Scanning Calorimeter (DSC) scan showed two peroxide decomposition temperatures, one at 71° C. for the 3-neoheptanoylperoxy-1,3-dimethylbutyl moiety and one at 169° C. for the 3-t-butylperoxy-1,3-dimethylbutyl moiety.

Workup

  1. customA 250 mL 3-necked flask equipped with a magnetic stirring bar, a nitrogen inlet line
  2. customwerecooled to 0° C
  3. customwasmaintained at 0°-5° C
  4. additionAfter the addition
  5. customTo the stirred reaction mass
  6. stirringThe reaction mixturewas then stirred for an additional 45 minutes at 20°-25° C. after which it
  7. customwas quenched with water
  8. customAfter separating
  9. washorganic was washed once with cold aqueous 10% HCl solution, three times with water and once with dilute aqueous NaHCO3 solution
  10. dry with materialThe product solution was dried over 5% by weight of anhydrous MgSO4
  11. customafter separation of the spent desiccant
  12. filtrationby filtration
  13. customthe solvent was removed in vacuo
  14. customleaving 9.3 g (100% of theory, uncorrected) of a hazy colorless oil
  15. customwas obtained with an assay of 100% and in a corrected yield of 100%
  16. customat 71° C.
  17. customat 169° C.

Sources & evidence

ORD record
ord-44b09a40a8894c5c9f2aecc3289a754e
Source dataset
uspto-grants-1999_02
Patent number
US05866712

Reaction notes

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