N,N'-Diphenyl-P-Phenylenediamine → HCID 66643440, compound

HRID 1026366Notes

Reaction equation

HRID 1026366 reaction equation
C1(NC2C=CC(NC3C=CC=CC=3)=CC=2)C=CC=CC=1.[CH3:21][C:22]([S:27][C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)([CH3:26])[CH2:23][CH2:24][OH:25].[C:34](OCC)(=[O:37])[CH:35]=[CH2:36]>>[C:34]([O:25][CH2:24][CH2:23][C:22]([CH3:21])([S:27][C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)[CH3:26])(=[O:37])[CH:35]=[CH2:36]

Participants

4

Reactant 3

HCID 6319N,N'-Diphenyl-P-PhenylenediamineHCID 8821Ethyl AcrylateHCID 10888853HCID 10888853, compound

Product 1

HCID 66643440HCID 66643440, compound

Conditions

Temperature
112.5 °C

Procedure

Into a 3-neck round-bottomed flask was placed (in order): N,N′-diphenyl-1,4-phenylenediamine (0.53 g, 2.04×10−3 moles), 3-Methyl-3-(phenylthio)butan-1-ol (50.0 g, 0.255 moles) and ethyl acrylate (276 mL, 2.55 moles). The apparatus was then assembled for reactive distillation through a Claisen head and purge-filled with nitrogen gas. The reaction flask was heated to 110-115° C. and after ca. 5 mL of ethyl acrylate had distilled over, titanium(IV) isoproproxide (TPT, 2.26 mL, 7.65×10−3 moles) was added to the reaction mixture via syringe in one portion. The rate of distillation immediately increased significantly and the distillate vapour temperature decreased from 99° C. to 90° C. These distillation conditions were maintained for a period of 150 minutes before the apparatus was evacuated by means of a 10 mbar PTFE-diaphragm pump and the remaining ethyl acrylate was stripped from the reaction mixture. The apparatus was then pumped down using a two-stage oil pump and the crude product distilled over at a vapour temperature of 109.5-112° C. (0.18 Torr, appearance: golden liquid, yield: 50.8 g).

Workup

  1. customInto a 3-neck round-bottomed flask was placed
  2. distillationThe apparatus was then assembled for reactive distillation through a Claisen head
  3. additionpurge-filled with nitrogen gas
  4. distillationafter ca. 5 mL of ethyl acrylate had distilled over, titanium(IV) isoproproxide (TPT, 2.26 mL, 7.65×10−3 moles)
  5. additionwas added to the reaction mixture via syringe in one portion
  6. distillationThe rate of distillation
  7. temperatureimmediately increased significantly
  8. customdecreased from 99° C. to 90° C
  9. distillationThese distillation conditions
  10. temperaturewere maintained for a period of 150 minutes before the apparatus
  11. customwas evacuated by means of a 10 mbar PTFE-diaphragm pump
  12. distillationthe crude product distilled over at a vapour temperature of 109.5-112° C. (0.18 Torr, appearance: golden liquid, yield: 50.8 g)

Sources & evidence

ORD record
ord-37329e03f2674494a13a1925ff33211e
Source dataset
uspto-grants-2014_05
Patent number
US08729203B2

Reaction notes

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