Water → HCID 23534609, compound

HRID 874708Notes

Reaction equation

HRID 874708 reaction equation
Br[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH3:15].[CH3:16][C:17]1[CH:22]=[CH:21][C:20]([CH3:23])=[CH:19][C:18]=1[OH:24].C([O-])([O-])=O.[K+].[K+].O>C(#N)C>[CH2:2]([O:24][C:18]1[CH:19]=[C:20]([CH3:23])[CH:21]=[CH:22][C:17]=1[CH3:16])[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH3:15]

Participants

6

Reactant 4

HCID 962WaterHCID 72672,5-DimethylphenolHCID 8208Myristyl bromideHCID 11430Potassium Carbonate

Product 1

HCID 23534609HCID 23534609, compoundYield 86.4%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

1-bromotetradecane (44.4 mL, 0.149 mol), 2,5-dimethylphenol (20.0 g, 0.164 mol) and K2CO3 (82.4 g, 0.596 mol) were combined in a round bottom flask in acetonitrile (200 mL). The flask was equipped with a stir-bar, and a water-cooled condenser and protected under a nitrogen atmosphere. The mixture was heated at reflux for overnight. Synthetic progress was monitored by the disappearance of the signal (triplet) from the C1 hydrogens on the alkyl bromide (˜3.5 ppm) in 1H NMR. Upon completion, the reaction was removed from heat and excess K2CO3 was removed by gravity filtration (rinsed with CH2Cl2). The crude product was concentrated in vacuo and the resulting material was dissolved in CH2Cl2, washed with 1 M NaOH (2×, to remove unreacted 2,5-dimethylphenol or p-cresol), dH2O (2×) and brine (1×), dried over Na2SO4, gravity filtered, and concentrated in vacuo to remove the solvent. The material was of sufficient purity (by 1H and 13C NMR) to be used in the subsequent reactions. Yielded 41.0 g (86%) of an off-white solid, mp=36.9-37.9° C. 1H NMR (CDCl3, 400 MHz) δ: 7.01 (d, 3J=7.4 Hz, 1H, Ar—H); 6.66 (d, 3J=7.6 Hz, 1H, Ar—H); 6.65 (s, 1H, Ar—H); 3.95 (t, 3J=6.5 Hz, 2H, OCH2); 2.33 (s, 3H); 2.20 (s, 3H); 1.80 (m, 2H, OCH2CH2); 1.49 (m, 2H, OCH2CH2CH2); 1.42-1.26 (m, 20H); 0.90 (t, 3J=6.8 Hz, 3H, CH2CH3). 13C NMR (CDCl3, 100 MHz) δ: 157.15, 136.40, 130.25, 123.65, 120.53, 112.01, 67.88, 31.93, 29.70, 29.68, 29,66, 29.62, 29.42, 29.40, 29.37, 26.16, 22.70, 21.40, 15.78, 14.11. HRMS (DART): [M+H]+=319.29460 (calcd for C22H39O 319.29954).

Workup

  1. customThe flask was equipped with a stir-bar
  2. temperatureThe mixture was heated
  3. temperatureat reflux for overnight
  4. customUpon completion, the reaction was removed
  5. temperaturefrom heat
  6. customexcess K2CO3 was removed by gravity filtration (rinsed with CH2Cl2)
  7. concentrationThe crude product was concentrated in vacuo
  8. dissolutionthe resulting material was dissolved in CH2Cl2
  9. washwashed with 1 M NaOH (2×, to remove unreacted 2,5-dimethylphenol or p-cresol), dH2O (2×) and brine (1×)
  10. dry with materialdried over Na2SO4, gravity
  11. filtrationfiltered
  12. concentrationconcentrated in vacuo
  13. customto remove the solvent

Sources & evidence

ORD record
ord-e0ec3fe1a3374ffa8e5f3566c68059ff
Source dataset
uspto-grants-2015_03
Patent number
US08980925B2

Reaction notes

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