Hydrochloric Acid → HCID 86736266, compound

HRID 2163823Notes

Reaction equation

HRID 2163823 reaction equation
[S:1]1[C:5]2([CH2:10][CH2:9][O:8][CH2:7][CH2:6]2)[CH:4]([C:11]([O:13]CC)=[O:12])[N:3]=C1.C(OCC)C.[ClH:21]>>[ClH:21].[NH2:3][CH:4]([C:5]1([SH:1])[CH2:6][CH2:7][O:8][CH2:9][CH2:10]1)[C:11]([OH:13])=[O:12]

Participants

4

Reactant 3

HCID 313Hydrochloric AcidHCID 3283Diethyl EtherHCID 22749576HCID 22749576, compound

Product 1

HCID 86736266HCID 86736266, compoundYield 80.5%

Procedure

53 g (0.25 mole) of ethyl alpha-formamido-2,3,5,6-tetrahydro-4H-pyran-Δ4,α -acetate and 14.5 g of phosphorous pentasulfide (P4S10) are suspended in 300 ml of anhydrous benzene. After boiling under reflux for 4 hours with stirring, the benzene solution is decanted off from insoluble material, treated with active carbon and filtered over "Hyflo-cel". After evaporating off the solvent, a brownish oil remains behind which distils at 130-135° C/0.5 mm Hg. In this way, there are obtained 30 g (yield 52% of theory) of ethyl 8-oxa-1-thia-3-azaspiro[4,5]-dec-2-ene-4carboxylate which is used without further purification for the continuation of the synthesis. I.1.c. alpha-Amino-4-mercapto-2,3,5,6-tetrahydro-4H-pyran-4acetic acid (formula III: n=m=2, X=0) 2 g (0.0087 mole) of ethyl 8-oxa-1-thia-3-azaspiro[4.5]-dec-2-ene-4-carboxylate are dissolved in 100 ml of 6 N hydrochloric acid. The reaction mixture is refluxed for 3 hours and is then concentrated in vacuo in a rotary evaporator. The gummy residue obtained is triturated 3 times with 50 ml of benzene, which are evaporated off under reduced pressure in order to eliminate remaining traces of water and hydrochloric acid. The residue is taken up in 100 ml of water and the solution is treated with "Norite" and then lyophilized. Trituration of the lyophilisate with dry diethyl ether gives 1.6 g of alpha-amino-4-mercapto-2,3,5,6-tetrahydro-4 H-pyran-4-acetic acid hydrochloride (yield: 80.5% of theory). The product gives a single spot in thin layer chromatography on silica (eluent: butanol, acetic acid, water: 4:1:1, Rf:0.35); M.P. 196-197° C (decomposition).

Workup

  1. customis used without further purification for the continuation of the synthesis
  2. temperatureThe reaction mixture is refluxed for 3 hours
  3. concentrationis then concentrated in vacuo in a rotary evaporator
  4. customThe gummy residue obtained
  5. customis triturated 3 times with 50 ml of benzene, which
  6. customare evaporated off under reduced pressure in order
  7. additionthe solution is treated with "Norite"

Sources & evidence

ORD record
ord-dca5babdea3a43c4a8cfcdf93c8639b8
Source dataset
uspto-grants-1979_01
Patent number
US04137236

Reaction notes

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