Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1) → HCID 57814831, compound

HRID 1254177Notes

Reaction equation

HRID 1254177 reaction equation
[Cl:1][C@H:2]1[C@H:6]([CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][C:13]([O:15][CH2:16][CH2:17][CH3:18])=[O:14])[C@@H:5](/[CH:19]=[CH:20]/[C@@H:21]([OH:28])[CH2:22][CH2:23][CH2:24][C@H:25]([OH:27])[CH3:26])[C@H:4]([O:29]C2CCCCO2)[CH2:3]1.C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1>CO.CCOC(C)=O>[Cl:1][C@H:2]1[C@H:6]([CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][C:13]([O:15][CH2:16][CH2:17][CH3:18])=[O:14])[C@@H:5](/[CH:19]=[CH:20]/[C@@H:21]([OH:28])[CH2:22][CH2:23][CH2:24][C@H:25]([OH:27])[CH3:26])[C@H:4]([OH:29])[CH2:3]1

Participants

5

Reactant 2

HCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 57814824HCID 57814824, compound

Product 1

HCID 57814831HCID 57814831, compoundYield 85.8%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
25 °C

Procedure

A 20 mL vial equipped with a magnetic stirbar was charged with 218 mg (0.42 mmol) of THP-ether 15 dissolved in 5 mL of methanol. To this was then added 350 mg (1.39 mmol) of pyridinium p-toluenesulfonate and the mixture was stirred at 25° C. over 8 h. The reaction was sampled by TLC (Rf of product was 0.5 in EtOAc) and worked up by concentration in vacuo to remove methanol. The residual products were taken up in ethyl acetate and filtered through 20 g of silica gel eluting with 300 mL of EtOAc. The filtrate was concentrated to yield 156 mg of products which were further purified by FCC through 25 g of silica gel, eluting with 1:1 EA-hexanes then 100% EA to yield 140 mg of product triol 16 as an oil; 1H NMR (CDCl3): 0.94 (t, J=7.2 Hz, 3H), 1.17 (d, J=6 Hz, 3H), 1.22-1.72 (m, 18H), 1.91 (m, 2H), 2.05-2.36 (m, 4H), 3.30 (br s, 1H), 3.78 (m, 1H), 4.02 (m, 5H), 4.5 (m, 2H), 5.50 (m, 2H). 13C NMR: 10.53, 21.52, 22.09, 23.74, 25.03, 26.83, 29.08, 29.49, 32.90, 34.42, 36.75, 38.52, 43.59, 53.53, 57.75, 60.98, 66.06, 67.50, 72.56, 74.98, 133.27, 135.79, 174.24.

Workup

  1. customA 20 mL vial equipped with a magnetic stirbar
  2. concentrationworked up by concentration in vacuo
  3. customto remove methanol
  4. filtrationfiltered through 20 g of silica gel eluting with 300 mL of EtOAc
  5. concentrationThe filtrate was concentrated

Sources & evidence

ORD record
ord-70c1a43952ac4369bcc85f6f5e6b6449
Source dataset
uspto-grants-2013_06
Patent number
US08455547B2

Reaction notes

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