Iodine → HCID 178443479, compound

HRID 1440515Notes

Reaction equation

HRID 1440515 reaction equation
C[O:2][C:3](=[S:19])[C@@H:4]([CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18])[CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12].[I-].[Na+].II.Cl[Si](C)(C)C>CCCCCC.C(#N)C>[CH2:13]([C@@H:4]([CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12])[C:3]([OH:2])=[S:19])[CH2:14][CH2:15][CH2:16][CH2:17][CH3:18]

Participants

7

Reactant 4

HCID 807IodineHCID 5238Sodium IodideHCID 6397Chlorotrimethylsilane2×HCID 18656172(S)-methyl-2-hexylthiodecanoate

Product 1

HCID 178443479HCID 178443479, compoundYield 90%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 8058HexaneSolvent

Conditions

Temperature
55 °C

Procedure

To a 12 L flask equipped with a condenser and overhead stirrer was added (S)-methyl-2-hexylthiodecanoate (302.5 g, 1.00 mol), and 3 L of dry acetonitrile. To this solution was added sodium iodide (600 g, 4.00 mol) and iodine (25.4 g, 0.10 mol) followed by chlorotrimethylsilane (543 g, 635 ml, 5.00 mol). The reaction was heated to an internal temperature of 55° C. After 12 hours, an additional portion of chlorotrimethylsilane (130 g, 152 mL, 1.20 mol) was added and heating continued for 8 hours. The reaction was cooled to 0° C., 6 L of hexane was added followed by 1 L of ice water, and the layers were allowed to separate. The top hexane layer was separated and set aside. The combined CH3CN/water layers were extracted with hexane (2×6 L). The combined hexane layers were washed with 1 L of water, 0.1M Na2S2O3 (2×3 L) and once with 3 L of 1:1 brine/water. The combined hexane extracts were dried with MgSO4, filtered and concentrated to give (S)-2-hexylthiodecanoic acid (260 g, 0.90 mol, 90%) a colorless oil: [α]D =-59.40° (C=1, MeOH); 1H NMR δ3.19 (m, 1H), 2.63 (m, 2H), 1.95-1.18 (m, 22H), 0.95 (m, 6H).

Workup

  1. customTo a 12 L flask equipped with a condenser and overhead stirrer
  2. temperatureheating
  3. waitcontinued for 8 hours
  4. temperatureThe reaction was cooled to 0° C.
  5. customto separate
  6. customThe top hexane layer was separated
  7. extractionThe combined CH3CN/water layers were extracted with hexane (2×6 L)
  8. washThe combined hexane layers were washed with 1 L of water, 0.1M Na2S2O3 (2×3 L) and once with 3 L of 1:1 brine/water
  9. dry with materialThe combined hexane extracts were dried with MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-c7f31bf238fc45f2bc3ac24235d93d10
Source dataset
uspto-grants-1996_03
Patent number
US05498786

Reaction notes

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