Trichloroisocyanuric Acid → 4-(tert-Butoxycarbonyl)morpholine-3-carboxylic acid

HRID 1048845Notes

Reaction equation

HRID 1048845 reaction equation
C([O-])(O)=[O:2].[Na+].[OH:6][CH2:7][CH:8]1[CH2:13][O:12][CH2:11][CH2:10][N:9]1[C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15].[Na+].[Br-].ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O>CC(C)=O.CC1(C)N([O])C(C)(C)CCC1.CC(O)C>[C:17]([O:16][C:14]([N:9]1[CH2:10][CH2:11][O:12][CH2:13][CH:8]1[C:7]([OH:2])=[O:6])=[O:15])([CH3:20])([CH3:19])[CH3:18]

Participants

8

Reactant 4

HCID 6909Trichloroisocyanuric AcidHCID 253881Sodium BromideHCID 516892Sodium BicarbonateHCID 5058359Tert-butyl 3-(hydroxymethyl)morpholine-4-carboxylate

Product 1

HCID 27601334-(tert-Butoxycarbonyl)morpholine-3-carboxylic acid

Reagents, catalysts & solvents 3

HCID 2724126TempoCatalystHCID 180AcetoneSolventHCID 3776IsopropanolSolvent

Procedure

Saturated aqueous NaHCO3 (15 mL) was added to a stirred solution of tert-butyl 3-(hydroxymethyl)morpholine-4-carboxylate (1.09 g, 5.0 mmol) (Organic and Bio-Organic Chemistry (1972-1999); (1985); 2577-2580, WO 2006/114606 and US 2010/210640) in acetone (50 mL) at 0° C. Solid NaBr (0.1 g, 1 mmol) and TEMPO (0.015 g, 0.1 mmol) were added. Trichloroisocyanuric acid (2.32 g, 10.0 mmol) was then added for 20 min at 0° C. After addition, the reaction mixture was allowed to room temperature (RT) and further maintained overnight. 2-Propanol (3 mL) was added and the resulting solution was stirred at RT for 30 min, filtered through a pad of Celite, concentrated under vacuum, and treated with saturated aqueous Na2CO3 solution (15 mL) The aqueous solution was extracted with EtOAc (5 mL), acidified with 6N HCl and extracted with EtOAc (5×10 mL). The combined organic layers were dried over Na2SO4 and the solvent was concentrated to give title compound as a white solid (760 mg). (M−H)−229.9.

Workup

  1. additionAfter addition
  2. customwas allowed to room temperature
  3. custom(RT)
  4. temperaturefurther maintained overnight
  5. filtrationfiltered through a pad of Celite
  6. concentrationconcentrated under vacuum
  7. additiontreated with saturated aqueous Na2CO3 solution (15 mL) The aqueous solution
  8. extractionwas extracted with EtOAc (5 mL)
  9. extractionextracted with EtOAc (5×10 mL)
  10. dry with materialThe combined organic layers were dried over Na2SO4
  11. concentrationthe solvent was concentrated

Sources & evidence

ORD record
ord-31c48fb0a6984262ae21ab8a2d13d0dc
Source dataset
uspto-grants-2016_07
Patent number
US09382216B2

Reaction notes

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