Hydrochloric Acid → HCID 11638232, compound

HRID 969012Notes

Reaction equation

HRID 969012 reaction equation
OCC(C)(C)CCCCC(CCCCC(C)(C)CO)C(O)=O.C[Li].Cl.[OH:26][C:27]([CH:30]([CH2:40][CH2:41][CH2:42][CH2:43][C:44]([CH3:48])([CH3:47])[CH2:45][OH:46])[CH2:31][CH2:32][CH2:33][CH2:34][C:35]([CH3:39])([CH3:38])[CH2:36][OH:37])(C)[CH3:28]>C1COCC1.C(OCC)(=O)C>[OH:46][CH2:45][C:44]([CH3:48])([CH3:47])[CH2:43][CH2:42][CH2:41][CH2:40][CH:30]([CH2:31][CH2:32][CH2:33][CH2:34][C:35]([CH3:39])([CH3:38])[CH2:36][OH:37])[C:27](=[O:26])[CH3:28]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 115807627-(1-Hydroxy-1-methylethyl)-2,2,12,12-tetramethyltridecan-1,13-diolHCID 117024498-Hydroxy-2-(6-hydroxy-5,5-dimethylhexyl)-7,7-dimethyloctanoic acidHCID 178418348HCID 178418348, compound

Product 1

HCID 11638232HCID 11638232, compoundYield 41%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

8-Hydroxy-2-(6-hydroxy-5,5-dimethyl-hexyl)-7,7-dimethyl-octanoic acid (1.0 g, 3.16 mmol) was dissolved in THF (40 mL) and cooled in an ice-water bath. Methyl lithium (27 mL) was then added at once. The reaction was continued for 2 h at 0 C. The reaction mixture was poured into dilute hydrochloric acid (5 mL concentrated hydrochloric acid in 60 mL water). The organic layer was separated and the aqueous layer was extracted with diethyl ether (2×50 mL). The combined organic layers were dried over sodium sulfate and concentrated in vacuo to give the crude product (1.0 g). The crude product was purified by column chromatography (hexanes:ethyl acetate=4:1, then 1:1) to give 9-hydroxy-3-(6-hydroxy-5,5-dimethyl-hexyl)-8,8-dimethyl-nonan-2-one (0.41 g, yield 41%) and 7-(1-hydroxy-1-methylethyl)-2,2,12,12-tetramethyltridecan-1,13-diol (0.4 g, 38%, not shown) as a by-product. 1H NMR (300 MHz, CDCl3/TMS): (ppm) 3.46 (s, 4H), 2.65-2.50 (m, 1H), 2.28 (s, 3H), 2.60 (br., 2H), 1.82-1.50 (m, 4H), 1.50-1.25 (m, 12H), 1.02 (s, 12H). 13C NMR (75 MHz, CDCl3/TMS): (ppm) 213.4, 71.7, 53.2, 38.3, 34.9, 31.6, 28.7, 28.3, 23.8. HRMS (LSIMS, nba): Calcd. for C19H39O3 (MH+): 315.2899, found: 315.2866.

Workup

  1. temperaturecooled in an ice-water bath
  2. customThe organic layer was separated
  3. extractionthe aqueous layer was extracted with diethyl ether (2×50 mL)
  4. dry with materialThe combined organic layers were dried over sodium sulfate
  5. concentrationconcentrated in vacuo
  6. customto give the crude product (1.0 g)
  7. customThe crude product was purified by column chromatography (hexanes

Sources & evidence

ORD record
ord-dcb33ce353c344e5ae8c932583517990
Source dataset
uspto-grants-2007_12
Patent number
US07304093B2

Reaction notes

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