Water → 4-tert-Butylbenzaldehyde

HRID 1722086Notes

Reaction equation

HRID 1722086 reaction equation
C1N2CN3CN(C2)CN1C3.[OH2:11].[C:12]([C:16]1[CH:23]=[CH:22][C:19]([CH2:20]Cl)=[CH:18][CH:17]=1)([CH3:15])([CH3:14])[CH3:13]>C(O)C>[C:12]([C:16]1[CH:23]=[CH:22][C:19]([CH:20]=[O:11])=[CH:18][CH:17]=1)([CH3:15])([CH3:14])[CH3:13]

Participants

5

Reactant 3

HCID 962WaterHCID 4101HexamethylenetetramineHCID 88198Benzene, 1-(chloromethyl)-4-(1,1-dimethylethyl)-

Product 1

HCID 703244-tert-ButylbenzaldehydeYield 60%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Conditions

Temperature
45 °C

Procedure

17 g of hexamethylenetetramine, 9 ml of water, 6 ml of ethanol and 21.5 g of 95% p-tert-butylbenzyl chloride are added to a three-necked flask provided with a thermometer, magnetic stirrer and reflux condenser. The mixture is now warmed slowly to 45° C. while stirring. At this temperature the mixture is initially slurry-like and thereafter thinly liquid. An exothermic reaction occurs. The temperature is held at 45° C. with the aid of an ice-bath until the reaction fades away. Thereupon the mixture is stirred with renewed warming at 45° C. for 30 minutes. The reflux condenser is now replaced by a distillation bridge and 5 ml of ethanol are distilled off from the mixture under a slight vacuum (70 Torr). Thereupon, the distillation bridge is removed and a water separator is attached, thus enabling the separated water to flow back into the reaction vessel. The water separator is filled with about 60 ml of water and 10 ml of toluene and the mixture is treated with 60 ml of water. The mixture is heated to 140° C. At the beginning of the steam distillation the pH-value is adjusted to 4.5-5 by means of 60% sulphuric acid. The liquid in the water separator is renewed several times. The organic phases are separated from the distillates and the aqueous fractions are extracted with ether. The ether extracts and organic phases are in each case combined and washed with, in each case, about 20 ml of 15% sulphuric acid, water, 10% sodium carbonate solution and finally again with water and then concentrated. There are thus obtained a total of 14.7 g of crude product which are fractionated at 17 Torr over a 5 cm Widmer column and give 11.8 g (60%) of p-tert-butylbenzaldehyde with a purity of 92% (NMR/GC).

Workup

  1. customprovided with a thermometer, magnetic stirrer
  2. temperaturereflux condenser
  3. customAn exothermic reaction
  4. customThe temperature is held at 45° C. with the aid of an ice-bath until the reaction fades away
  5. stirringThereupon the mixture is stirred
  6. temperaturewith renewed warming at 45° C. for 30 minutes
  7. distillationare distilled off from the mixture under a slight vacuum (70 Torr)
  8. customThereupon, the distillation bridge is removed
  9. additionThe water separator is filled with about 60 ml of water and 10 ml of toluene
  10. additionthe mixture is treated with 60 ml of water
  11. temperatureThe mixture is heated to 140° C
  12. distillationAt the beginning of the steam distillation the pH-value
  13. customThe organic phases are separated from the distillates
  14. extractionthe aqueous fractions are extracted with ether
  15. washwashed with, in each case, about 20 ml of 15% sulphuric acid, water, 10% sodium carbonate solution
  16. concentrationfinally again with water and then concentrated
  17. customThere are thus obtained a total of 14.7 g of crude product which

Sources & evidence

ORD record
ord-3c359bb64ecc41ef82ad9b750492d957
Source dataset
uspto-grants-1989_08
Patent number
US04853489

Reaction notes

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