Methanol → 2-((5-Methyl-2-(1-methylethyl)cyclohexyl)oxy)acetic acid

HRID 1110143Notes

Reaction equation

HRID 1110143 reaction equation
CCCC=S.[CH3:6][CH:7]1[CH2:12][CH:11]([O:13][CH2:14][C:15](Cl)=[O:16])[CH:10]([CH:18]([CH3:20])[CH3:19])[CH2:9][CH2:8]1.C[OH:22]>N1C=CC=CC=1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[CH3:6][CH:7]1[CH2:12][CH:11]([O:13][CH2:14][C:15]([OH:22])=[O:16])[CH:10]([CH:18]([CH3:20])[CH3:19])[CH2:9][CH2:8]1

Participants

7

Reactant 3

HCID 887MethanolHCID 556978HCID 556978, compoundHCID 12463483Butanthial

Product 1

HCID 978142-((5-Methyl-2-(1-methylethyl)cyclohexyl)oxy)acetic acid

Reagents, catalysts & solvents 3

HCID 1049PyridineCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
100 °C

Procedure

1-L-methoxyacetyloxy-3-methylthiopropene is prepared from 3-methylthiopropionaldehyde, L-menthoxyacetyl chloride, and pyridine catalyst. A 70 mL stainless steel high pressure reactor fitted with a Pyrex glass liner and magnetic stir bar is charged with THF (5 mL), (PPh3)2PdCl2 (0.05 mmol), CH3OH (0.5 mmol), and 1-L-menthoxyacetyloxy-3-methylthiopropene (0.5 mmol). The reactor is sealed, pressurized to 1000 psig with CO, and stirred for 24 hours at 100° C. The product mixture, isolated after removal of gas from the reactor vessel, contains a diastereomeric mixture of methyl 2-L-menthoxyacetyl-4-methylthio-L-2-hydroxybutyrate and methyl 2-L-menthoxyacetyl-4-methylthio-D-2-hydroxybutyrate. The diastereomers are separated by preparative gas chromatography using an SE-30 liquid phase column. Each diastereomer is hydrolyzed separately by treatment with 2N HCI (aq) for 2 hours at 100° C. to give pure L- and D-4-methylthio-2-hydroxybutyric acid (methionine hydroxy analog), methanol, and L-menthoxyacetic acid.

Workup

  1. customA 70 mL stainless steel high pressure reactor fitted with a Pyrex glass liner and magnetic stir bar
  2. customThe reactor is sealed
  3. customThe product mixture, isolated
  4. customafter removal of gas from the reactor vessel
  5. additiona diastereomeric mixture of methyl 2-L-menthoxyacetyl-4-methylthio-L-2-hydroxybutyrate and methyl 2-L-menthoxyacetyl-4-methylthio-D-2-hydroxybutyrate
  6. customThe diastereomers are separated by preparative gas chromatography
  7. waitEach diastereomer is hydrolyzed separately by treatment with 2N HCI (aq) for 2 hours at 100° C.

Sources & evidence

ORD record
ord-ba31b59c2bb1432295cfd761030f06ec
Source dataset
uspto-grants-1994_06
Patent number
US05324856

Reaction notes

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