p-Toluenesulfonic acid → HCID 86674681, compound

HRID 1523010Notes

Reaction equation

HRID 1523010 reaction equation
O1CCCCC1[O:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][C:16](=[C:22]([CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][O:36]C1CCCCO1)[CH2:23][C:24]([O:26][CH3:27])=[O:25])[CH2:17][C:18]([O:20][CH3:21])=[O:19].CC1C=CC(S(O)(=O)=O)=CC=1>CO>[OH:36][CH2:35][CH2:34][CH2:33][CH2:32][CH2:31][CH2:30][CH2:29][CH2:28][C:22](=[C:16]([CH2:15][CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][OH:7])[CH2:17][C:18]([O:20][CH3:21])=[O:19])[CH2:23][C:24]([O:26][CH3:27])=[O:25]

Participants

4

Reactant 2

HCID 6101p-Toluenesulfonic acidHCID 86674680HCID 86674680, compound

Product 1

HCID 86674681HCID 86674681, compoundYield 88%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A flamed-dried 20 mL vial fitted with screw-cap septa was charged with Dimethyl 3,4-bis(8-((tetrahydro-2H-pyran-2-yl)oxy)octyl)hex-3-enedioate (1 equiv, 0.855 mmol, 510 mg), MeOH (10 mL) and PTSA (0.1 equiv, 0.086 mmol, 16.4 mg). The reaction was stirred at rt for 14 h, quenched with sat. aq. NaHCO3, and diluted with CH2Cl2 (20 mL) and H2O (10 mL). The layers were separated and the aqueous layer was extracted with CH2Cl2 (2×20 mL). The combined organic layers were washed with H2O (20 mL), dried with Na2SO4, concentrated in vacuo, and purified by flash chromatography (65% EtOAc/Hex) to afford Dimethyl 3,4-bis(8-hydroxyoctyl)hex-3-enedioate (321 mg, 0.75 mmol, 88%) as an inseparable 2:1 mixture of isomers. TLC Rf=0.19 (50% EtOAc/Hex); 1HNMR (500 MHz): δ 3.61-3.70 (t plus two ovlp. s, 10H, J=6.7 Hz), 3.13 (s, 2.7H), 3.11 (s, 1.3H), 2.07-2.18 (4H), 1.57 (quint., 4H, J=7.8 Hz), 1.49 (bs, 2H), 1.26-1.40 (20H); 13CNMR (125 MHz): δ 174.4, 174.3, 130.7, 130.6, 62.99, 51.8, 37.6, 37.2, 33.2, 32.82, 32.75, 29.6, 29.5, 29.44, 29.35, 29.32, 28.3, 28.0, 25.71, 25.68; FTIR: 3375, 2926, 2854, 1736, 1434, 1332, 1242, 1192, 1155, 1048 cm−1; HRMS-ESI: calc. for C24H44NaO6 (M+Na)+: 451.3036. found: 451.3022.

Workup

  1. customA flamed-dried 20 mL vial fitted
  2. customwith screw-cap septa
  3. customquenched with sat. aq. NaHCO3
  4. additiondiluted with CH2Cl2 (20 mL) and H2O (10 mL)
  5. customThe layers were separated
  6. extractionthe aqueous layer was extracted with CH2Cl2 (2×20 mL)
  7. washThe combined organic layers were washed with H2O (20 mL)
  8. dry with materialdried with Na2SO4
  9. concentrationconcentrated in vacuo
  10. custompurified by flash chromatography (65% EtOAc/Hex)

Sources & evidence

ORD record
ord-d36c281c4010452aa21f7a2c2256782a
Source dataset
uspto-grants-2015_07
Patent number
US09079835B2

Reaction notes

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