HCID 10489752, compound → HCID 10518900, compound

HRID 1824626Notes

Reaction equation

HRID 1824626 reaction equation
[CH2:1]([C:4]1[CH:9]=[CH:8][C:7]([CH:10]2[O:15][CH2:14][C:13]([CH3:17])([CH3:16])[CH2:12][O:11]2)=[CH:6][CH:5]=1)[CH:2]=[CH2:3].[C:18]([OH:21])(=[S:20])[CH3:19]>C1(C)C=CC=CC=1>[C:18]([S:20][CH2:3][CH2:2][CH2:1][C:4]1[CH:5]=[CH:6][C:7]([CH:10]2[O:11][CH2:12][C:13]([CH3:17])([CH3:16])[CH2:14][O:15]2)=[CH:8][CH:9]=1)(=[O:21])[CH3:19]

Participants

4

Reactant 2

HCID 10489752HCID 10489752, compoundHCID 178418634HCID 178418634, compound

Product 1

HCID 10518900HCID 10518900, compoundYield 63.8%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
90 °C

Procedure

Following a general procedure (Lub et al. (1997) Liebigs Ann. Recueil, 2281–2288), 13 (845 mg, 3.60 mmol) and thioacetic acid (910 μL, 12.7 mmol) were dissolved in toluene (20 mL) and the solution was purged with argon for 15 min. Then AIBN (200 mg) was added and the mixture was heated to 90° C. Over a period of 23 h more AIBN (1.10 g) was added in several portions. Then aq NaHCO3 (10%, 50 mL) was added and the phases were separated. The aqueous phase was washed with ether and the combined organic phases were dried (Na2SO4). Purification by column chromatography (silica, ether/hexanes, 1:4) gave an orange oil, which solidified upon standing at −20° C. and was recrystallized from pentane to give 708 mg (63%) of colorless needles. mp 44° C. IR (neat): {tilde over (v)} 2951, 2850, 1692, 1620, 1518; 1H NMR δ 0.79 (s, 3H), 1.29 (s, 3H), 1.78–1.94 (m, 2H), 2.33 (s, 3H), 2.68 (t, 3J=7.3 Hz, 2H), 2.86 (t, 3J=7.3 Hz, 2H), 3.64 (d, 2J=1.0 Hz, 2H), 3.76 (d, 2J=11.0 Hz, 2H), 5.37 (s, 1H), 7.18, 7.42 (AA′BB′, 2×2H); 13C NMR (APT) δ 21.6 (−), 22.8 (−), 28.1 (+), 29.9 (+), 30.4 (−), 30.8 (+), 34.3 (+), 77.3 (+), 101.4 (−), 126.0 (−), 128.1 (−), 136.1 (+), 141.5 (+), 195.3 (+); GC-MS (EI) obsd 308, 307, 265, 232, 221, 204, 199, 180, 146, 133, 115, 91, 69, 43; Anal. Calcd for C17H24O3S: C, 66.20; H, 7.84; S, 10.40; Found: C, 66.19; H, 7.89; S, 10.54.

Workup

  1. customthe solution was purged with argon for 15 min
  2. additionThen AIBN (200 mg) was added
  3. additionOver a period of 23 h more AIBN (1.10 g) was added in several portions
  4. additionThen aq NaHCO3 (10%, 50 mL) was added
  5. customthe phases were separated
  6. washThe aqueous phase was washed with ether
  7. dry with materialthe combined organic phases were dried (Na2SO4)
  8. customPurification by column chromatography (silica, ether/hexanes, 1:4)
  9. customgave an orange oil, which
  10. customupon standing at −20° C.
  11. customwas recrystallized from pentane

Sources & evidence

ORD record
ord-04fc831ccf7744c7adf30b99d2b44d9f
Source dataset
uspto-grants-2006_05
Patent number
US07042755B1

Reaction notes

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