Pyridine → HCID 59996114, compound

HRID 1733345Notes

Reaction equation

HRID 1733345 reaction equation
[C:1]([N:11]1[CH2:19][CH:18]([OH:20])[CH2:17][C@H:12]1[C:13]([O:15][CH3:16])=[O:14])([O:3][CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)=[O:2].N1C=CC=CC=1.[S:27](Cl)([C:30]1[CH:36]=[CH:35][C:33]([CH3:34])=[CH:32][CH:31]=1)(=[O:29])=[O:28]>CO>[C:1]([N:11]1[CH2:19][CH:18]([O:20][S:27]([C:30]2[CH:36]=[CH:35][C:33]([CH3:34])=[CH:32][CH:31]=2)(=[O:29])=[O:28])[CH2:17][C@H:12]1[C:13]([O:15][CH3:16])=[O:14])([O:3][CH2:4][C:5]1[CH:6]=[CH:7][CH:8]=[CH:9][CH:10]=1)=[O:2]

Participants

5

Reactant 3

HCID 1049Pyridine2×HCID 73974-Toluenesulfonyl chlorideHCID 13942746HCID 13942746, compound

Product 1

HCID 59996114HCID 59996114, compound

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A stirred solution of 14.5 g. (0.052 mole) of N-carbobenzyloxy-4-hydroxy-L-proline, methyl ester in 30 ml. of pyridine is treated dropwise at -5° to -8° with a solution of 11 g. (0.058 mole) of tosyl chloride in 15 ml. of pyridine. The pale yellow solution is stored in the cold for 3 days, then added with stirring to 300 ml. of ice-cold 2 N hydrochloric acid. The precipitated gum is extracted with 200 ml. of chloroform. The aqueous phase is extracted with additional chloroform (3×100 ml.). The organic layers are combined, dried (MgSO4), and the solvent evaporated to give a pale yellow viscous oil. The oil is dissolved in 100 ml. of methanol and diluted to 400 ml. with water to precipitate the product as an oil which gradually crystallizes on seeding, rubbing, and cooling: yield 17.4 g. (77%); m.p. 62°-65°. Following crystallization from 85 ml. of isopropanol, the colorless solid N-carbobenzyloxy-4-tosyloxy-L-proline, methyl ester weighs 15.9 g. (70%); m.p. 67°-69°; [α]D26 -30° (c=1; methanol).

Workup

  1. customcold for 3 days
  2. additionadded
  3. extractionThe precipitated gum is extracted with 200 ml
  4. extractionThe aqueous phase is extracted with additional chloroform (3×100 ml.)
  5. dry with materialdried (MgSO4)
  6. customthe solvent evaporated
  7. customto give a pale yellow viscous oil
  8. dissolutionThe oil is dissolved in 100 ml
  9. customwith water to precipitate the product as an oil which
  10. customgradually crystallizes on seeding
  11. temperaturecooling
  12. customcrystallization from 85 ml

Sources & evidence

ORD record
ord-58a3e699da004feaa5ee99d9eccc0a81
Source dataset
uspto-grants-1980_12
Patent number
US04241076

Reaction notes

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