3,3-Bis4-(4'-fluorobenzoyl)phenylphthalide as a new monomer for the synthesis of cardo polyarylene-ether ketones

摘要

Mendeleev Communications Electronic Version, Issue 5, 1997 (pp. 169ndash;212) 3,3-Bis4-(4'-fluorobenzoyl)phenylphthalide as a new monomer for the synthesis of cardo polyarylene-ether ketones Sergei N. Salazkin,* Vera V. Shaposhnikova, Kirill I. Donetskii and Pavel V. Petrovskii A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 117813 Moscow, Russian Federation. Fax: +7 095 135 5085; e-mail: donetski@ineos.ac.ru 3,3-Bis4-(4'-fluorobenzoyl)phenylphthalide has been synthesised for the first time; this compound can be used for the preparation of polyarylene-ether ketones by nucleophilic substitution.Cardo aromatic polyketones occupy a prominent place among aromatic polyketones owing to their high glass transition temperature.1ndash;3 In the synthesis of cardo polyarylene-ether ketones by nucleophilic substitution, only one method for introducing cardo groups into a polymeric chain is known.This method is based on polycondensation involving bisphenols containing cardo groups (phthalide, fluorene, anthrone etc.), Scheme 1. Up to now, dihalo-derivatives incorporating cardo groups have not been employed in this polycondensation. This has limited the possibilities of synthesising cardo polyarylene-ether ketones possessing new valuable properties.We were the first to synthesise 3,3-bis4-(4'-fluorobenzoyl)phenylphthalide 3, which can be used in the synthesis of cardo polyarylene-ether ketones by nucleophilic substitution.dagger; In this case, a cardo group can be introduced for the first time into a macromolecule from an activated dihalo(difluoro)derivative containing a cardo (namely, phthalide) group.This monomer was synthesised according to Scheme 2.Dagger; dagger; Polyarylene-ether ketones were synthesised according to the procedure reported previously.4 Dagger; The dichloride of 4,4'-diphenylphthalidedicarboxylic acid (7.5 g, 0.018 mol), fluorobenzene (25 ml, 0.27 mol) and finely divided AlCl3 (9.5 g, 0.071 mol) were placed in a three-necked flask equipped with a stirrer and reflux condenser. The mixture was heated at reflux for 16 h, poured into icendash;water, filtered and washed with water up to a neutral pH.The remaining fluorobenzene was then removed by steam distillation. Yield 9.6 g (99). Extraction of impurities with boiling EtOH followed by crystallization from a mixture of EtOH and toluene (1:1 v/v) gave a white crystalline product with mp 184.5ndash;185.5 deg;C.Found (): C 77.29; H 3.66; F 7.28. Calc. for C34H20F2O4 (): C 76.98; H 3.77; F 7.17. The structure of 3 was confirmed by 13C, 19F and 1H NMR spectral data.sect; The IR spectrum of the compound 3 shows absorption bands at 1670 and 1780 cmndash;1 corresponding to a carbonyl group between aromatic rings and the carbonyl group of the phthalide ring, respectively.para; The use of this monomer provides new opportunities for the synthesis of cardo polyarylene-ether ketones.This monomer is highly reactive under polycondensation conditions and ensures the preparation of polyarylene-ether ketones with high molecular weights. The procedure was used to synthesise the first amorphous cardo homopolyarylene-ether ketone based on bisphenol A with hred = 0.97 cm3 gndash;1 in chloroform (Scheme 3).The resulting polymer is characterised by a glass transition temparature of 215 deg;C; it is readily soluble in many organic solvents, for example, in chloroform, N,N-dimethylacetamide, N,N-dimethylformamide, tetrahydrofuran, 1,4-dioxane, m-cresol, cyclohexanone. Strong transparent films can be prepared by casting solutions of the polymer into the above solvents.sect; The 13C and 1H NMR spectra were recorded on a lsquo;Bruker AMX-400rsquo; spectrometer (100.61 and 400.13 MHz respectively) in CDCl3, using TMS as internal standard. The 19F NMR spectrum was measured on a lsquo;Bruker WP-2000-SYrsquo; spectrometer (168.31 MHz) in CDCl3, using CF3CO2H as internal standard. Spectral data for 3. 1H NMR d: 7.983 (d, 1H, H7, 3JH6ndash;H7 7.5 Hz), 7.766 (t, 1H, H5, 3JH4ndash;H5 7.5 Hz, 3JH5ndash;H6 7.5 Hz), 7.654 (d, 1H, H4, 3JH4ndash;H5 7.5 Hz), 7.621 (t, 1H, H6, 3JH5ndash;H6 7.5 Hz, 3JH6ndash;H7 7.5 Hz); 7.804 (dd, 4H, H17 and H21, 3JH17ndash;H18 8.6 Hz, 4JFndash;H17 5.4 Hz), 7.122 (t, 4H, H18 and H20, 3JH17ndash;H18 8.6 Hz, 3JFndash;H18 8.6 Hz); 7.740 (d, 4H, H11 and H13, 3JH10ndash;H11 8.2 Hz), 7.492 (d, 4H, H10 and H14, 3JH10ndash;H11 8.2 Hz). 13C NMR d: 168.86 (s, C-1), 90.37 (s, C-2), 150.43 (s, C-3), 123.98, 126.34, 129.90, 134.48 (s, C-4, C-5, C-6, C-7), 125.22 (s, C-8), 144.27 (s, C-9), 126.88 (s, C-10), 129.96 (s, C-11), 137.71 (s, C-12), 129.96 (s, C-13), 126.88 (s, C-14), 194.16 (s, C-15), 133.09 (d, C-16, 4JCndash;F 3.0 Hz), 132.53 (d, C-17, 3JCndash;F 9.1 Hz), 115.44 (d, C-18, 2JCndash;F 22.1 Hz), 165.38 (d, C-19, 1JCndash;F 254.5 Hz), 115.44 (d, C-20, 2JCndash;F 22.1 Hz), 132.53 (d, C-21, 3JCndash;F 9.1 Hz). 19F NMR d: ndash;27.373 (s). para; The IR absorption spectrum was recorded using a lsquo;Perkin-Elmer-457rsquo; spectrophotometer. C O O C C C O , , R OM nMO CO nX X + + O R O CO n 1 2 X = F, Cl M = Na, K R = Scheme 1 C O O O C Cl Cl O C C O O O C O C F F 3 PhF AlCl3 Scheme 2 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21Mendeleev Communications Electronic Version, Issue 5, 1997 (pp. 169ndash;212) References 1 S. V. Vinogradova, V. V. Korshak, S. N. Salazkin and A. A. Kulrsquo;kov, Vysokomol. Soedin., Ser. A, 1972, 14, 2545 Polym. Sci. USSR (Engl. Transl.), 1972, A14, 2962. 2 V. V. Korshak, S. V. Vinogradova, S. N. Salazkin and A. A. Kulrsquo;kov, Dokl. Akad. Nauk SSSR, 1973, 208, 360 Dokl. Chem. (Engl. Transl.), 1973, 208, 29. 3 R. Singh and A. S. Hay, Macromolecules, 1992, 25, 1017. 4 V. V. Shaposhnikova, S. N. Salazkin, V. A. Sergeev, I. V. Blagodatskikh, L. V. Dubrovina, A. A. Sakunts and S.-S. A. Pavlova, Izv. Akad. Nauk, Ser. Khim., 1996, 2526 (Russ. Chem. Bull., 1996, 45, 2397). C n HO Me Me OH C O O O C O C nF F + C O Me Me O C O C O O O C n K2 CO3 Scheme 3 Received: Moscow, 1st August 1997 Cambridge, 11th September 1997; Com. 7/05903E