Hydrochloric Acid → HCID 59660189, compound

HRID 1466708Notes

Reaction equation

HRID 1466708 reaction equation
[BH4-].[Li+].CO.[H][H].C([O:9][C:10](=O)[C:11]([CH3:30])([CH3:29])[CH2:12][CH2:13][CH2:14][CH2:15][C:16](=[O:28])[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][C:22]([CH3:27])([CH3:26])[C:23](O)=[O:24])C.Cl.[Cl-].[NH4+]>ClCCl>[CH3:29][C:11]([CH3:30])([CH2:12][CH2:13][CH2:14][CH2:15][CH:16]([OH:28])[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][C:22]([CH3:27])([CH3:26])[CH2:23][OH:24])[CH2:10][OH:9]

Participants

8

Reactant 6

HCID 313Hydrochloric AcidHCID 887MethanolHCID 25517Ammonium ChlorideHCID 4148881Lithium borohydrideHCID 11416993HCID 11416993, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 59660189HCID 59660189, compoundYield 65%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
45 °C

Procedure

Under Ar atmosphere, to a stirred suspension of lithium borohydride (0.30 g, 95%, 13 mmol) in dichloromethane (80 mL) was added dropwise methanol (0.42 g, 13 mmol), keeping a gentle reflux while hydrogen gas was formed. The mixture was stirred for 10 min at 45° C. and a solution of 2,2,13,13-tetramethyl-7-oxo-tetradecanedioic acid 1-ethyl ester (1.57 g, 4.36 mol) in dichloromethane (10 mL) was added dropwise at such a rate as to maintain a gentle reflux. The reaction mixture was heated at reflux for 24 h, then cooled to room temperature and carefully hydrolyzed with 2 N hydrochloric acid (50 mL) and saturated ammonium chloride solution (120 mL). The aqueous layer was extracted with dichloromethane (4×50 mL). The combined organic layers were washed with water (100 mL) and dried over anhydrous magnesium sulfate. The reaction mixture was concentrated to yield the crude product as a yellow oil (1.28 g). Purification by column chromatography on silica gel eluting with hexanes/ethyl acetate (4:1, then 3:1) followed by recrystallization from dichloromethane gave pure 2,2,13,13-tetramethyltetradecane-1,7,14-triol (0.86 g, 65%) as white needles. M.p.: 79 80° C. 1H NMR (300 MHz, CDCl3/TMS): δ (ppm): 3.57 (br. s, 1H), 3.29 (s, 4H), 2.17 (br. s, 3H), 1.46-1.40 (m, 4H), 1.33-1.24 (m, 12H), 0.85 (s, 12H). 13C NMR (75 MHz, CDCl3/TMS): δ (ppm): 71.8, 71.7, 71.5, 38.7, 37.5, 37.3, 35.1, 30.7, 26.6, 25.7, 24.2, 24.0, 23.9, 23.8. HRMS (LSIMS, gly): Calcd. for C18H39O3 (MH+): 303.2899. found: 303.2897. HPLC: 97% purity.

Workup

  1. customwas formed
  2. temperatureto maintain a gentle reflux
  3. temperatureThe reaction mixture was heated
  4. temperatureat reflux for 24 h
  5. temperaturecooled to room temperature
  6. extractionThe aqueous layer was extracted with dichloromethane (4×50 mL)
  7. washThe combined organic layers were washed with water (100 mL)
  8. dry with materialdried over anhydrous magnesium sulfate
  9. concentrationThe reaction mixture was concentrated
  10. customto yield the crude product as a yellow oil (1.28 g)
  11. customPurification by column chromatography on silica gel eluting with hexanes/ethyl acetate (4:1
  12. custom3:1) followed by recrystallization from dichloromethane

Sources & evidence

ORD record
ord-78013bc61b23437e8cb7a51aae1ca995
Source dataset
uspto-grants-2015_04
Patent number
US09000041B2

Reaction notes

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