Epichlorohydrin → HCID 54757206, compound

HRID 632520Notes

Reaction equation

HRID 632520 reaction equation
[C:1]([O:5][C:6](=[O:31])[NH:7][C:8]1[CH:13]=[CH:12][C:11]([O:14][C:15]2[CH:20]=[CH:19][C:18]([S:21][C:22](=O)N(C)C)=[CH:17][CH:16]=2)=[CH:10][C:9]=1[O:27][CH2:28][O:29][CH3:30])([CH3:4])([CH3:3])[CH3:2].[OH-].[K+].C([CH:36]1[O:38][CH2:37]1)Cl>CO>[C:1]([O:5][C:6](=[O:31])[NH:7][C:8]1[CH:13]=[CH:12][C:11]([O:14][C:15]2[CH:20]=[CH:19][C:18]([S:21][CH2:22][CH:37]3[CH2:36][O:38]3)=[CH:17][CH:16]=2)=[CH:10][C:9]=1[O:27][CH2:28][O:29][CH3:30])([CH3:2])([CH3:4])[CH3:3]

Participants

5

Reactant 3

HCID 7835EpichlorohydrinHCID 14797Potassium HydroxideHCID 54757205HCID 54757205, compound

Product 1

HCID 54757206HCID 54757206, compoundYield 68%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a solution of compound 18 (0.65 g, 1.5 mmol) in anhydrous MeOH (10 mL) was added potassium hydroxide (0.42 g, 7.5 mmol). The mixture was refluxed for 4 h and then cooled to room temperature. Epichlorohydrin (0.21 g, 2.3 mmol) was added dropwise and the mixture was stirred at room temperature for 15 min, after which the solvent was removed under reduced pressure. The concentrate was diluted with water and extracted with EtOAc. The combined organic extracts were dried over anhydrous Na2SO4, the suspension was filtered, followed by concentration of the filtrate in vacuo. Purification by silica gel chromatography (hexanes/EtOAc=4/1) gave 19 in 68% yield (0.43 g) 1H NMR (500 MHz, CDCl3) δ 1.53 (s, 9H), 8.03 (br. s., 1H), 2.47 (dd, J=2.6, 5.0 Hz, 1H), 2.77 (t, J=4.4 Hz, 1H), 2.85 (dd, J=6.1, 13.9 Hz, 1H), 3.12-3.05 (m, 1H), 3.18-3.12 (m, 1H), 5.18 (s, 2H), 3.48 (s, 3H), 6.66 (dd, J=2.6, 8.8 Hz, 1H), 6.92-6.85 (m, 3H), 6.98 (br. s., 1H), 7.44-7.37 (m, 2H). 13C NMR (126 MHz, CDCl3) δ 28.5, 38.2, 47.6, 51.3, 56.5, 80.6, 95.4, 106.8, 113.1, 118.4, 119.4, 125.1, 128.0, 131.8, 133.8, 146.6, 151.2, 152.9, 157.9. HRMS (FAB) calcd for C22H28NO4S (M+H+) 434.1632. found 434.1637.

Workup

  1. temperatureThe mixture was refluxed for 4 h
  2. customafter which the solvent was removed under reduced pressure
  3. additionThe concentrate was diluted with water
  4. extractionextracted with EtOAc
  5. dry with materialThe combined organic extracts were dried over anhydrous Na2SO4
  6. filtrationthe suspension was filtered
  7. customPurification by silica gel chromatography (hexanes/EtOAc=4/1)

Sources & evidence

ORD record
ord-5566e5043fe04a84a0c0abf1c920a4a7
Source dataset
uspto-grants-2016_04
Patent number
US09321754B2

Reaction notes

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