Triethylamine → HCID 86674682, compound

HRID 1523011Notes

Reaction equation

HRID 1523011 reaction equation
[OH:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][C:10](=[C:16]([CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][OH:30])[CH2:17][C:18]([O:20][CH3:21])=[O:19])[CH2:11][C:12]([O:14][CH3:15])=[O:13].CCN(CC)CC.[CH3:38][S:39](Cl)(=[O:41])=[O:40]>CN(C1C=CN=CC=1)C.C(Cl)Cl>[CH3:38][S:39]([O:30][CH2:29][CH2:28][CH2:27][CH2:26][CH2:25][CH2:24][CH2:23][CH2:22][C:16](=[C:10]([CH2:9][CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][CH2:2][O:1][S:39]([CH3:38])(=[O:41])=[O:40])[CH2:11][C:12]([O:14][CH3:15])=[O:13])[CH2:17][C:18]([O:20][CH3:21])=[O:19])(=[O:41])=[O:40]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 86674681HCID 86674681, compound

Product 1

HCID 86674682HCID 86674682, compoundYield 82%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a flamed-dried 20 mL vial fitted with a screw-cap septa was added Dimethyl 3,4-bis(8-hydroxyoctyl)hex-3-enedioate (1 equiv, 0.642 mmol, 275 mg), CH2Cl2 (6 mL), and Et3N (4 equiv, 2.57 mmol, 0.36 mL). The mixture was cooled to 0° C. and DMAP (0.1 equiv, 0.064 mmol, ˜8 mg) was added followed by the dropwise addition of MsCl (3 equiv, 1.93 mmol, 0.15 mL). The reaction was allowed to come to ambient temperature over 14 h at which time the reaction was quenched with sat. aq. NaHCO3 (10 mL). The layers were separated and the aqueous layer was extracted with CH2Cl2 (3×15 mL). The combined organic layers were washed with H2O (20 mL), dried with Na2SO4, concentrated in vacuo, and purified by flash column chromatography (45% EtOAc/Hex) to afford Dimethyl 3,4-bis(8-((methylsulfonyl)oxy)octyl)hex-3-enedioate (309 mg, 0.526 mmol, 82%) as an inseparable 2:1 mixture of isomers. TLC Rf=0.24 (45% EtOAc/Hex); 1HNMR (500 MHz): δ 4.20-4.25 (ovlp. t's, 4H), 3.68 (s, 4H), 3.66 (s, 2H), 2.13 (s, 2.7H), 3.11 (s, 1.3H), 3.02 (s, 6H), 2.07-2.17 (4H), 1.71-1.79 (4H), 1.25-1.45 (20H); 13CNMR (125 MHz): δ 172.3, 172.2, 130.7, 130.6, 70.20, 70.18, 51.8, 37.6, 37.4, 37.2, 33.2, 32.8, 31.6, 29.58, 29.55, 29.33, 29.29, 29.1, 29.00, 28.97, 28.3, 28.0, 25.4; FTIR: 2929, 2855, 1732, 1435, 1350, 1170, 972, 935, 833, 721 cm−1; HRMS-ESI: calc. for C36H48NaO10S2 (M+Na)+: 607.2587. found: 607.2570.

Workup

  1. customTo a flamed-dried 20 mL vial fitted with a screw-cap septa
  2. customthe reaction was quenched with sat. aq. NaHCO3 (10 mL)
  3. customThe layers were separated
  4. extractionthe aqueous layer was extracted with CH2Cl2 (3×15 mL)
  5. washThe combined organic layers were washed with H2O (20 mL)
  6. dry with materialdried with Na2SO4
  7. concentrationconcentrated in vacuo
  8. custompurified by flash column chromatography (45% EtOAc/Hex)

Sources & evidence

ORD record
ord-73a13e71a442446b8af9216964a15411
Source dataset
uspto-grants-2015_07
Patent number
US09079835B2

Reaction notes

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