Methanol → HCID 11379713, compound

HRID 1531594Notes

Reaction equation

HRID 1531594 reaction equation
[Na].[C:2]([O:23]CC)(=O)[CH2:3][CH2:4]/[CH:5]=[CH:6]/[CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12]/[CH:13]=[CH:14]/[CH2:15][CH2:16][C:17]([O:19]CC)=O.Cl[Si](C)(C)C.CO>C1(C)C=CC=CC=1>[OH:19][CH:17]1[C:2](=[O:23])[CH2:3][CH2:4][CH:5]=[CH:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH:13]=[CH:14][CH2:15][CH2:16]1

Participants

6

Reactant 4

HCID 887MethanolHCID 6397ChlorotrimethylsilaneHCID 5360545SodiumHCID 131722422HCID 131722422, compound

Product 1

HCID 11379713HCID 11379713, compoundYield 109.4%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

In a 2 L Morton flask a mixture of sodium (7.48 g, 0.34 mole) in toluene (600 ml) was heated to reflux and stirred vigorously for 1 hour. To this solution was added dropwise (very slowly) a mixture of diethyl hexadeca-4E,12E-diene-1,16-dioate (24.86 g, 0.073 mole) and chlorotrimethylsilane (41.7 ml, 0.33 mole) in toluene (100 ml) over 2 hours. The reaction was heated to reflux for an additional 4 hours, then cooled to room temperature and stirred for an additional 16 hours. To the reaction mixture was added methanol (˜100 ml), the mixture is stirred 1 hour, and then left to stand for 1 hour. The resulting bi-phasic mixture was separated and the top layer is washed with 10% aqueous hydrochloric acid. The aqueous wash was re-extracted with ether and the organic layers are combined. The bottom layer from the bi-phasic mixture described above was combined with the aqueous wash and extracted again with diethyl ether. All organic layers were combined, dried with magnesium sulfate, filtered and evaporated to give the 16-hydroxycyclohexadeca-4E,12E-dien-1-one (20.0 g, 93% yield) as a brown oil which can be used directly in the next step. If desired, the material can be purified via reduced pressure distillation (210-220° C./0.3 mm Hg). C16H26O2 (250.38 g/mole). bp. 210-220° C./0.3 mm Hg. HNMR (500 MHz, CDCl3): 1.20-1.80 (m, 10H), 1.90-2.09 (m, 4H), 2.10-2.30 (m, 4H) 2.35 (m, 2H), 2.50 (m, 2H), 4.10 (m, 1H), 5.40 (m, 4H) ppm. 13CNMR (125 MHz, CDCl3): 27.8, 27.9*, 28.1, 28.5*, 31.4, 31.5, 32.8, 37.9, 76.2, 127.6, 128.8, 132.6, 133.1, 214 ppm. IR (νmax(cm−1)): 3450(b), 2940(s), 2910(s), 2850(s), 1720(s), 1440(m), 970(s). MS(m/z): 250(M+), 232, 221, 203, 189, 176, 161, 149, 135, 121, 109, 95, 81, 67, 55, 41.

Workup

  1. temperaturewas heated
  2. temperatureto reflux
  3. additionTo this solution was added dropwise (very slowly)
  4. temperatureThe reaction was heated
  5. temperatureto reflux for an additional 4 hours
  6. stirringstirred for an additional 16 hours
  7. stirringthe mixture is stirred 1 hour
  8. waitleft
  9. waitto stand for 1 hour
  10. customThe resulting bi-phasic mixture was separated
  11. washthe top layer is washed with 10% aqueous hydrochloric acid
  12. washThe aqueous wash
  13. extractionwas re-extracted with ether
  14. washaqueous wash
  15. extractionextracted again with diethyl ether
  16. dry with materialdried with magnesium sulfate
  17. filtrationfiltered
  18. customevaporated

Sources & evidence

ORD record
ord-d706d1e8fa5845948266586ab6dd31cf
Source dataset
uspto-grants-2001_03
Patent number
US06200254B1

Reaction notes

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