4-Hydroxybenzaldehyde → HCID 178436341, compound

HRID 483191Notes

Reaction equation

HRID 483191 reaction equation
C[C:2]1[CH:7]=[C:6](C)[CH:5]=[C:4]([CH3:9])[N:3]=1.[OH:10][C:11]1[CH:18]=[CH:17][C:14]([CH:15]=O)=[CH:13][CH:12]=1.N#CBr.C(N(CC)CC)C>CC(C)=O>[O-:10][C:4]#[N:3].[CH:9]([C:4]1[CH:5]=[CH:6][CH:7]=[CH:2][N:3]=1)=[CH:15][C:14]1[CH:17]=[CH:18][CH:11]=[CH:12][CH:13]=1

Participants

6

Reactant 4

HCID 1264-HydroxybenzaldehydeHCID 79532,4,6-TrimethylpyridineHCID 8471TriethylamineHCID 10476Cyanogen Bromide

Product 1

HCID 178436341HCID 178436341, compound

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

A portion of the reaction product of a 1 to 1.5 to 1 mole ratio of 2,4,6-trimethyl pyridine to p-hydroxy benzaldehyde to 2,6-dimethylpyridine (100.0 grams, 0.473 mole of hydroxyl groups) from 3-A above and acetone (750 milliliters) were added to a 2-liter glass resin kettle and maintained under a nitrogen atmosphere. Stirring was started and allowed to progress for 40 minutes (2400 s) then cooling of the reactor commenced. When the reaction temperature reached -5° C., cyanogen bromide (105.67 grams, 0.9975 mole) was added. After five minutes (300 s), triethylamine (96.64 grams, 0.955 mole) was added dropwise over a 20 minute (1200 s) period and so as to maintain the reaction temperature between -5° and 0° C. The reaction was allowed to progress for an additional 45 minutes (2700 s) between reaction temperatures of -5° to 5° C. After this time, the reaction slurry was filtered. The recovered filtrate was added to 1 gallon (3.79 l) of deionized water producing an amber oil precipitate. The oil product was recovered by extraction with three 500 milliliter portions of methylene chloride. The combined methylene chloride extract was washed with 1500 milliliters of deionized water, dried over anhydrous sodium sulfate and then filtered. The dry methylene chloride solution was rotary evaporated under vacuum to a constant weight of 118.6 grams. Infrared spectrophotometric analysis of a film sample of the amber colored, viscous oil product confirmed the product structure for the styryl pyridine cyanate (presence of cyanate group absorbance accompanied by total absence of hydroxyl group absorbance, retention of trans-unsaturation absorbance and aromatic carbon-oxygen absorbance).

Workup

  1. temperaturemaintained under a nitrogen atmosphere
  2. temperature(2400 s) then cooling of the reactor
  3. customreached -5° C.
  4. temperatureso as to maintain the reaction temperature between -5° and 0° C
  5. waitto progress for an additional 45 minutes
  6. custom(2700 s) between reaction temperatures of -5° to 5° C
  7. filtrationAfter this time, the reaction slurry was filtered
  8. additionThe recovered filtrate was added to 1 gallon (3.79 l) of deionized water producing an amber oil precipitate
  9. customThe oil product was recovered by extraction with three 500 milliliter portions of methylene chloride
  10. extractionThe combined methylene chloride extract
  11. washwas washed with 1500 milliliters of deionized water
  12. dry with materialdried over anhydrous sodium sulfate
  13. filtrationfiltered
  14. customThe dry methylene chloride solution was rotary evaporated under vacuum to a constant weight of 118.6 grams

Sources & evidence

ORD record
ord-998c28ebdc4f49fc802e32bae96ad6de
Source dataset
uspto-grants-1986_03
Patent number
US04578439

Reaction notes

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