Hydrochloric Acid → Phthalonitrile

Temperature

140 °C

To a 2000 mL, three-necked flask fitted with a thermometer, a Dean-Stark trap with condenser, and a nitrogen inlet were added resorcinol (26.0 g, 0.236 mol), 4,4′-dichlorobenzophenone (22.8 g, 0.0907 mol), sodium hydroxide (20.8 g, 0.520 mol), toluene (25 mL), and dimethylsulfoxide (DMSO) (500 mL). Toluene was used to control the refluxing azeotropic removal of water and to control the temperature of the reaction content. The resulting mixture was degassed with nitrogen at ambient temperature and the Dean-Stark trap was filled with toluene. The mixture was refluxed at 135-145° C. under a nitrogen atmosphere for 6 h or until no more water was observed being collected in the Dean-Stark trap. The toluene was then slowly distilled off causing the temperature to rise in the reaction vessel to enhance the yield of the intermediate hydroxyl salt and high conversion to this intermediate. The mixture was cooled to 50° C. At this time, 4-nitrophthalonitrile (52.7 g, 0.304 mol) was added in one portion and the reaction mixture was heated at 80° C. for 6-8 h. The mixture was allowed to cool to ambient temperature and poured into a 5% aqueous HCl solution resulting in the formation of a solid. The material was broken up and collected using a Büchner funnel. The white solid was washed with 200 mL of a 5% aqueous KOH solution, with 200 mL portions of distilled water until neutral, with 200 mL of a 5% aqueous HCl solution, and finally with 200 mL portions of water until neutral. The isolated solid was vacuum dried to yield the 2:1 oligomeric phthalonitrile and the resorcinol phthalonitrile composition (70.6 g, 90% yield). IR [cm−1]: ν 3072 (C═CH), 2234 (CN), 1586 (C═C), 1478 (aromatic), 1307 (aromatic), 1308 (C—O), 1245 (CH3), 1162 (C—O), 930 (C—O), 847 (aromatic).

1. customTo a 2000 mL, three-necked flask fitted with a thermometer
2. customthe refluxing azeotropic removal of water
3. customThe resulting mixture was degassed with nitrogen at ambient temperature
4. additionthe Dean-Stark trap was filled with toluene
5. customwas observed being collected in the Dean-Stark trap
6. distillationThe toluene was then slowly distilled off
7. temperatureThe mixture was cooled to 50° C
8. temperaturethe reaction mixture was heated at 80° C. for 6-8 h
9. temperatureto cool to ambient temperature
10. customresulting in the formation of a solid
11. customcollected
12. washThe white solid was washed with 200 mL of a 5% aqueous KOH solution, with 200 mL portions of distilled water until neutral, with 200 mL of a 5% aqueous HCl solution
13. customdried

ORD record

ord-9b9c4dfeebc84aa88b1b8d7fc611006b

Source dataset

uspto-grants-2015_03

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08981036B2