Methyl chloroformate → HCID 57890181, compound

HRID 1819929Notes

Reaction equation

HRID 1819929 reaction equation
[CH2:1]([C:3]([C:12]1[CH:25]=[CH:24][C:15]([O:16][CH2:17][C:18]([OH:23])([CH2:21][CH3:22])[CH2:19][CH3:20])=[C:14]([CH3:26])[CH:13]=1)([C:6]1[S:7][CH:8]=[C:9]([CH3:11])[CH:10]=1)[CH2:4][CH3:5])[CH3:2].[Li]CCCC.Cl[C:33]([O:35][CH3:36])=[O:34]>C1COCC1>[CH3:36][O:35][C:33]([C:8]1[S:7][C:6]([C:3]([CH2:4][CH3:5])([C:12]2[CH:25]=[CH:24][C:15]([O:16][CH2:17][C:18]([CH2:21][CH3:22])([OH:23])[CH2:19][CH3:20])=[C:14]([CH3:26])[CH:13]=2)[CH2:1][CH3:2])=[CH:10][C:9]=1[CH3:11])=[O:34]

Participants

5

Reactant 3

HCID 6586Methyl chloroformateHCID 57890205HCID 57890205, compoundHCID 178418339Butyllithium

Product 1

HCID 57890181HCID 57890181, compoundYield 41%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

3-{4-[1-Ethyl-1-(4-methyl-thiophen-2-yl)-propyl]-2-methyl-phenoxymethyl}-pentan-3-ol, Example 51B (0.50 g, 1.34 mmol) is dissolved in THF (10 mL). The solution is cooled to 0° C., treated with nBuLi (1.6 M, 1.8 mL, 2.95 mmol). It is stirred at 0° C. for 20 min, and methyl chloroformate (113 μL, 1.47 mmol) is added. The reaction is stirred at 0° C. for 10 min and RT for 20 m before it is quenched with satd NH4Cl (5 mL). It is diluted with H2O (10 mL), treated with 0.1 M HCl (10 ml) and extracted with EtOAc (3×15 mL), dried and concentrated. The crude product is purified by chromatography to give the titled compound (0.24 g, 0.56 mmol, 41%). 1H NMR (CD3C3), δ 0.71 (t, J=7.1 Hz, 6H), 0.95 (t, J=7.9 Hz, 6H), 1.64-1.72 (m, 4H), 2.11 (q, J=7.1 Hz, 4H), 2.21 (s, 3H), 2.49 (s, 3H), 3.81 (s, 3H), 6.61 (s, 1H), 6.72 (d, J=8.4 Hz, 1H), 6.85-7.01 (m, 2H). LC/MS (m/z): calcd for C25H40NO4S (M+NH4)+: 450.3; found: 450.3.

Workup

  1. stirringThe reaction is stirred at 0° C. for 10 min and RT for 20 m before it
  2. customis quenched with satd NH4Cl (5 mL)
  3. additionIt is diluted with H2O (10 mL)
  4. additiontreated with 0.1 M HCl (10 ml)
  5. extractionextracted with EtOAc (3×15 mL)
  6. customdried
  7. concentrationconcentrated
  8. customThe crude product is purified by chromatography

Sources & evidence

ORD record
ord-3d2c6b445f494e0c88cccb80bb25200f
Source dataset
uspto-grants-2009_10
Patent number
US07601850B2

Reaction notes

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