SYNTHESIS AND STRUCTURE OF 4-(9-HYDROXY-1,4,7-TRIOXYNONYL)PHTHALONITRILE

Abstract

4-(9-Hydroxy-1,4,7-trioxynonyl)phthalonitrile was prepared by reaction of 4-nitrophthalonitrile with triethylene glycol in dry DMSO in the presence of fresh-calcined fine milled K2CO3 at 60 °C for 12 hours. The reaction mixture was poured into cold distilled water and extracted by CH2Cl2. Then the crude product obtained after solvent evaporation was purified by column chromatography on silica gel using elution mixture of ethyl acetate : hexane (1:3) and after that end product was dried at reduced pressure at 80 oC for 4 h. The product was characterized by IR and 1Н NMR spectroscopies, mass-spectrometry, elemental analysis and X-ray diffraction data. In MALDI-TOF spectrum, two signals located at 299 [M+Na]+ and 315 [M+К]+ Da were detected. Conformity between the calculated isotopic distributions and those derived from experimental data proves these assignments. A colorless monocrystal suitable for X-Ray measurements was grown up by low temperature solvent evaporation from a solution of 4-(9-hydroxy-1,4,7-trioxynonyl)phthalonitrile in ethyl acetate. X-ray studying showed that this compound is a monohydrate of 4-(9-hydroxy-1,4,7-trioxynonil)phthalonitrile with a water molecule located in lateral chain. Four molecules of 4-(9-hydroxy-1,4,7-trioxynonil)phthalonitrile and four water molecules were founded to be located in one unit cell with formatting eight intermolecular hydrogen bonds. Hence triethylene glycol fragment forms a chelate-like cavity which is able to hold a water molecule or a cation of alkali metal. It was found that its structure is very similar to that optimized at DFT/B3LYP/6-31G(d,p) level. The some bond lengths of theoretical calculations are found to be greater than experiment data because of close intermolecular interactions in solid state.Forcitation:Kuznetsova A.S., Dmitriev M.V., Zav’yalov A.V., Koifman O.I., Islyaikin M.K. Synthesis and structure of 4-(9-hydroxy-1,4,7-trioxynonyl)phthalonitrile. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2017. V. 60. N 3. P. 15-21.