Aniline → HCID 51358155, compound

HRID 1785933Notes

Reaction equation

HRID 1785933 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:8]1(=[O:13])[O:12][C@H:10]([CH3:11])[CH2:9]1.C([O-])([O-])=O.[K+].[K+]>>[C:2]1([NH:1][C@@H:10]([CH3:11])[CH2:9][C:8]([OH:13])=[O:12])[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 3

HCID 6115AnilineHCID 11430Potassium CarbonateHCID 642786r-butyrolactone

Product 1

HCID 51358155HCID 51358155, compound

Conditions

Temperature
80.8499984741211 °C

Procedure

A jacketed 30-L 3-neck bottom-valve cylindrical reactor equipped with overhead stirrer, reflux condenser, addition funnel, and N2 inlet was flushed with N2. Water (8.7 L) was charged followed by aniline (423 L, 4.9 mol). Stirring was initiated and the internal temperature set for 80° C. After the internal temperature reached 77° C., (R)-β-butyrolactone was charged over 1.5 h via addition funnel. The internal temperature was maintained between 80-81.7° C. during the course of addition. Once addition was completed, reaction was cooled to 20° C. over 1 h. K2CO3 (250 g, 1.8 mol, 0.75 equiv) was charged as a solid, and the aqueous pH was determined to be 10. The aqueous phase was extracted with MTBE (3×2 L), and the extracts were discarded. After adjusting the pH of the aqueous phase to 5 with 6 N HCl (225 mL), it was extracted with EtOAc (3×2 L). After each extraction, the pH was checked and was readjusted to 5 with 6 N HCl as necessary. The combined EtOAc extracts were washed with saturated brine (2 L), dried with MgSO4, and concentrated via rotary evaporation to produce a pink oil. Recovery: 300 g (72%). Enantiomeric excess was determined by chiral HPLC to be 94%.

Workup

  1. customA jacketed 30-L 3-neck bottom-valve cylindrical reactor equipped with overhead stirrer
  2. temperaturereflux
  3. additioncondenser, addition funnel, and N2 inlet
  4. customwas flushed with N2
  5. additionWater (8.7 L) was charged
  6. customset for 80° C
  7. customreached 77° C.
  8. additionOnce addition
  9. customreaction
  10. temperaturewas cooled to 20° C. over 1 h
  11. extractionThe aqueous phase was extracted with MTBE (3×2 L)
  12. extractionwas extracted with EtOAc (3×2 L)
  13. extractionAfter each extraction
  14. washThe combined EtOAc extracts were washed with saturated brine (2 L)
  15. dry with materialdried with MgSO4
  16. concentrationconcentrated via rotary evaporation
  17. customto produce a pink oil

Sources & evidence

ORD record
ord-f649d38764ca405192464d9bfecda86b
Source dataset
uspto-grants-2009_03
Patent number
US07504508B2

Reaction notes

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