Pyridine → HCID 131726782, compound

HRID 1466716Notes

Reaction equation

HRID 1466716 reaction equation
[N:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Cl.[C:8](Cl)(=[O:15])[C:9]1[CH:14]=[CH:13][CH:12]=[N:11][CH:10]=1.[CH3:17][C:18]([CH3:44])([CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH:26]([O:37][CH:38]1[CH2:43][CH2:42][CH2:41][CH2:40][O:39]1)[CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][C:32]([CH3:36])([CH3:35])[CH2:33][OH:34])[CH2:19]O.C[C:46]([O:49]C)(C)C>>[O:39]1[CH2:40][CH2:41][CH2:42][CH2:43][CH:38]1[O:37][CH:26]([CH2:25][CH2:24][CH2:23][CH2:22][CH2:21][C:18]([CH3:44])([CH3:19])[CH2:17][C:8](=[O:15])[C:9]1[CH:14]=[CH:13][CH:12]=[N:11][CH:10]=1)[CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][C:32]([CH3:36])([CH3:35])[CH2:33][O:34][C:46](=[O:49])[C:3]1[CH:4]=[CH:5][CH:6]=[N:1][CH:2]=1

Participants

5

Reactant 4

HCID 1049PyridineHCID 15413tert-Butyl methyl ether2×HCID 884383-Pyridinecarbonyl chloride, hydrochloride (1:1)HCID 66617066HCID 66617066, compound

Product 1

HCID 131726782HCID 131726782, compoundYield 69%

Procedure

Anhydrous tert-butyl methyl ether (MTBE, 200 mL) and anhydrous pyridine (30 mL) were added to nicotinoyl chloride hydrochloride (12.3 g, 69 mmol). The mixture was stirred at room temperature under nitrogen atmosphere for 1 h, then cooled to 0° C. A solution of 2,2,14,14-tetramethyl-8-(tetrahydropyran-2-yloxy)-pentadecane-1,15-diol (8.8 g, 21.9 mmol) in anhydrous MTBE (50 mL) was added and the mixture was stirred overnight at room temperature. The mixture was washed with deionized water (3×50 mL), saturated NaHCO3 solution (2×50 mL) and brine (50 mL), and dried over magnesium sulfate. The solvent was removed under reduced pressure to give the crude product as a light yellow oil (11.1 g), which was purified by chromatography (silica gel, 75 g, heptanes:ethyl acetate=10:1, 7:1, 5:1) to give nicotinic acid 8-(tetrahydropyran-2-yloxy)-2,2,14,14-tetramethyl-15-nicotinoylpentadecyl ester (9.2 g, 69%) as a viscous, yellow oil. 1H NMR (300 MHz, CDCl3/TMS): δ (ppm): 9.37-9.15 (m, 2H), 8.79 (dd, J=4.8, 1.7 Hz, 2H), 8.30 (dt, J=7.9, 1.9 Hz, 2H), 7.41 (dd, J=4.8, 7.9 Hz, 2H), 4.71-4.55 (m, 1H), 4.07 (s, 4H), 3.99-3.80 (m, 1H), 3.69-3.52 (m, 1H), 3.52-3.35 (m, 1H), 1.92-1.08 (m, 26H), 1.00 (s, 12H). 13C NMR (75 MHz, CDCl3/TMS): δ (ppm): 165.23, 153.34, 150.85, 136.99, 126.40, 123.36, 97.69, 76.77, 73.45, 62.91, 39.54, 39.49, 35.19, 34.23, 33.70, 31.42, 30.97, 30.88, 25.84, 25.74, 25.26, 24.61, 24.07, 20.25. HRMS (EI, POS): Calcd for C36H54H2O6 (M+): 610.3982. found: 610.3977. Elemental analysis (C36H54N2O6): Calcd for C, 70.79; H, 8.91; N, 4.59. Found: C, 70.71; H, 9.06; N, 4.48.

Workup

  1. temperaturecooled to 0° C
  2. stirringthe mixture was stirred overnight at room temperature
  3. washThe mixture was washed with deionized water (3×50 mL), saturated NaHCO3 solution (2×50 mL) and brine (50 mL)
  4. dry with materialdried over magnesium sulfate
  5. customThe solvent was removed under reduced pressure
  6. customto give the crude product as a light yellow oil (11.1 g), which
  7. customwas purified by chromatography (silica gel, 75 g, heptanes:ethyl acetate=10:1, 7:1, 5:1)

Sources & evidence

ORD record
ord-27b7440389c34a7e9f3ecbe385d78fdd
Source dataset
uspto-grants-2015_04
Patent number
US09000041B2

Reaction notes

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