Propanoic acid, 2-bromo-2-methyl-, ethyl ester → HCID 59268005, compound

HRID 1809401Notes

Reaction equation

HRID 1809401 reaction equation
[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][C@H:2]1[CH2:7][S:8]C(=O)C.[OH-].[K+].Br[C:15]([CH3:22])([CH3:21])[C:16]([O:18][CH2:19][CH3:20])=[O:17]>C(O)C>[CH3:21][C:15]([S:8][CH2:7][C@@H:2]1[CH2:3][CH2:4][CH2:5][CH2:6][O:1]1)([CH3:22])[C:16]([O:18][CH2:19][CH3:20])=[O:17]

Participants

5

Reactant 3

HCID 11745Propanoic acid, 2-bromo-2-methyl-, ethyl esterHCID 14797Potassium HydroxideHCID 59268001HCID 59268001, compound

Product 1

HCID 59268005HCID 59268005, compoundYield 80.9%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A solution of 2.79 g (13.45 mmol) of 1-{[(2S)-oxan-2-ylmethyl]sulfanyl}ethan-1-one in ethanol (60 mL) is degassed with nitrogen over 0.5 h and 1.51 g (26.91 mmol) of KOH are added. Then 3.99 mL (26.91 mmol) of ethyl α-bromoisobutyrate are added slowly. The reaction is stirred for 18 h at room temperature under a nitrogen atmosphere. The reaction mixture is filtered, the solid is rinsed with ethanol and the filtrate is concentrated under reduced pressure. The crude material is purified by column chromatography (silica, eluent: n-heptanes, 0-20% ethyl acetate) to afford 2.68 g of ethyl 2-methyl-2-{[(2S)-oxan-2-ylmethyl]sulfanyl}propanoate (purity 90%). Yield: 72%; ES-MS: m/z 247 [M+H]; 1H NMR (500 MHz, CHLOROFORM-d) δ ppm 1.23-1.36 (5H, m), 1.45-1.59 (8H, m), 1.68 (1H, d, J=13.12 Hz), 1.83 (1H, d, J=10.99 Hz), 2.62-2.71 (1H, m), 2.72-2.80 (1H, m), 3.25-3.47 (2H, m), 3.95-4.03 (1H, m), 4.17 (2H, q, J=7.12 Hz).

Workup

  1. filtrationThe reaction mixture is filtered
  2. washthe solid is rinsed with ethanol
  3. concentrationthe filtrate is concentrated under reduced pressure
  4. customThe crude material is purified by column chromatography (silica, eluent: n-heptanes, 0-20% ethyl acetate)

Sources & evidence

ORD record
ord-58c1e0c62672464784d28d2d4c4f0135
Source dataset
uspto-grants-2013_01
Patent number
US08362039B2

Reaction notes

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