Hydrochloric Acid → Dicyclohexylamine

HRID 1447444Notes

Reaction equation

HRID 1447444 reaction equation
CO[C@H:3]1[CH2:7][NH:6][C@H:5]([C:8](O)=O)[CH2:4]1.C(=O)([O-])[O-].[Na+].[Na+].[C:17]([CH2:20][CH2:21][C:22](Cl)=S)(=O)C.Cl.[Cl-].[Na+].C(S[CH2:32][CH2:33][C:34](N1C[C@H](OC)C[C@H]1C(O)=O)=O)(=O)C>C(OCC)(=O)C.O.CCOCC>[CH:7]1([NH:6][CH:5]2[CH2:4][CH2:34][CH2:33][CH2:32][CH2:8]2)[CH2:3][CH2:17][CH2:20][CH2:21][CH2:22]1

Participants

10

Reactant 6

HCID 313Hydrochloric AcidHCID 5234Sodium ChlorideHCID 10340Sodium Carbonate2×HCID 12849451(2S,4R)-4-MethoxyprolineHCID 12849455HCID 12849455, compoundHCID 200413153-Acetylthiopropionyl chloride

Product 1

HCID 7582Dicyclohexylamine

Reagents, catalysts & solvents 3

HCID 962WaterSolvent3×HCID 3283Diethyl EtherSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 3.5 g. (0.024 mole) of trans-4-methoxy-L-proline in 50 ml. of water is stirred, cooled to 5° and 3 g. of sodium carbonate are added. This mixture is treated with a solution of 4.0 g. (0.024 mole) of 3-acetylthiopropionyl chloride in 5 ml. of ether during the course of 10 minutes with the intermittent addition of 3 g. of sodium carbonate to maintain the pH at about 8.0. The mixture is stirred in the ice-bath for an additional hour, 25 ml. of water are added and then a solution of 5 ml. of concentrated hydrochloric acid in 25 ml. of water (CO2 evolution). The strongly acid solution is saturated with sodium chloride and extracted with 50 ml. of ethyl acetate (four times). The organic phases are combined, dried (MgSO4), filtered and the solvent evaporated to give 6.0 g. (90%) of colorless syrupy 1-(3-acetylthio-1-oxopropyl)-trans-4-methoxy-L-proline. This acid is dissolved in 25 ml. of ethyl acetate and treated with 4.7 g. of dicyclohexylamine to give a solution which rapidly becomes a solid mass. An additional 15 ml. of ethyl acetate are added and the mixture is digested on a steam bath, cooled and filtered to give 8.7 g. of the dicyclohexylamine salt, m.p. 170°-172°. After crystallization from 60 ml. of acetonitrile the colorless solid weighs 8.3 g. (75%) m.p. 171°-173°; [α]D25 -35° (c, 1% in EtOH).

Workup

  1. temperaturecooled to 5°
  2. additionThis mixture is treated with a solution of 4.0 g
  3. extractionextracted with 50 ml
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. customthe solvent evaporated
  7. customto give 6.0 g
  8. dissolutionThis acid is dissolved in 25 ml

Sources & evidence

ORD record
ord-cf34c3598aba4afd8f5188ea754f406d
Source dataset
uspto-grants-1982_02
Patent number
US04316906

Reaction notes

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