Russian Journal of Applied Chemistry, Vol. 76, No. 2, 2003, pp. 330!331.

Translated from Zhurnal Prikladnoi Khimii, Vol. 76, No. 2, 2003, pp. 340!341. Original Russian Text Copyright + 2003 by Aslanov.

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Synthesis of Bis(Amido Sulfimides) from 2-Sulfoterephthalic Acid Imide Chloride

T. A. Aslanov
Institute of Polymeric Materials, National Academy of Sciences of Azerbaijan, Sumgait, Azerbaijan
Received May 13, 2002

Abstract A series of bis(amido sulfimides) were prepared by condensation of 2-sulfoterephthalic acid imide chloride with aliphatic and aromatic diamines.

Trimellitic acid and its derivatives are widely used as monomers in production of polyimide polymers [1, 2]. Synthesis of less studied 2-sulfoterephthalic acid imide, 4-sulfoisophthalic acid imide, and their esters was reported in [3]. This paper describes previously unknown 2-sulfoterephthalic acid imide chloride I [4] and its amide derivatives II3VII containing amide and imide groups, which show promise as monomers for preparing poly(amido imides).

Chloride I was prepared by heating 2-sulfoterephthalic acid imide with PCl5 in the presence of a small amount of POCl3 [4]. The IR spectrum of I contains characteristic absorption bands of the imide ring at 1380, 1720, 1780, 1210 31136, and 3220 cm!1. Bis(amido sulfimides) II3VII were prepared by reactions of chloride I with aliphatic and aromatic diamines:

OC 2H N

Sdd Qj 5
O2 S COCl I

H2N!X!NH2, (C2H5)3N, pyridine 2HCl

77777777776 !

R = (CH2)2 (II), (CH2)4 (III), (CH2)6 (IV),

j Sddcc d Qj g cg S jQ 5c 5 djcc ccc 5 4 44

OC CO HN NH O2 S C NH X NH C O O II VII SO2

(V),

(VI), and

(VII).

Condensations of I with diamines were performed at 40 3 45oC; a solution of acid chloride was gradually added with stirring to a solution of an appropriate diamine in dimethylacetamide, and an equimolar amount of triethylamine was added to bind the HCl released. The reactions give bis(amido sulfimides) II3VII in high yields. The compositions and structures of II3VII were confirmed by elemental analysis (see table) and IR spectroscopy. The IR spectra of II3VII contain C3N absorption bands at 1660 31600 cm!1, bands at 1380 31300 and 1200 31130 cm!1 belonging to asymmetric stretching vibrations of the SO2

group in the saccharin ring, and N3H bands at 3350 3 3310 cm!1 [4, 5]. EXPERIMENTAL Dimethylacetamide, triethylamine, and pyridine were purified as described in [6, 7]; diamines, by recrystallization and vacuum distillation; and hexamethylenediamine, by distillation in an argon flow at 1983199oC (mp 40oC). 2-Sulfoterephthalic acid imide chloride I. A 250-ml round-bottomed flask with a reflux con-

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SYNTHESIS OF BIS(AMIDO SULFIMIDES) FROM 2-SULFOTEREPHTHALIC ACID IMIDE CHLORIDE Bis(amido sulfimides) II VII

331

Com- Found, % Calculated, % M Yield, pound Formula % no. C H N S C H N S found calculated I 85 40.3 1.60 5.66 12.9 C8H4NO4SCl 39.10 1.63 5.70 13.08 244 245.5 II 94 46.0 2.88 11.3 13.3 C18H14N4O8S2 45.18 2.92 11.71 13.38 473 478 III 91 47.0 3.45 10.85 12.5 C20H18N4O8S2 47.43 3.55 11.06 12.64 502 506 IV 90 50.1 4.15 10.3 12.0 C22H22N4O8S2 49.44 4.12 10.48 11.98 531 534 V 84 51.1 2.58 10.44 12.22 C22H14N4O8S2 50.19 2.66 10.64 12.16 520 526 VI 83 49.9 2.54 10.37 12.40 C22H14N4O8S2 50.19 2.66 10.64 12.16 521 526 602 VII 78 54.5 2.86 8.87 10.31 C28H12N4O8S2 49.83 2.99 9.30 10.63 595
denser and a calcium chloride tube was charged with 2.1 g (0.01 mol) of PCl5 and 2.27 g (0.01 mol) of sulfoterephthalic acid imide. The mixture was stirred. In the process, the mixture spontaneously warmed up to 40 3 45oC. After completion of the exothermic reaction, the temperature was raised to 953100oC, and the heating was continued for an additional 2 h. After reaction completion, POCl3 was distilled off in a water-jet-pump vacuum. Then 50 ml of benzene was added, and the mixture was stirred for 10 315 min. The solvent and POCl3 were distilled off from the filtrate. The remaining oily product was successively washed on a glass frit with dry carbon tetrachloride, chloroform, and benzene, after which it was recrystallized successively from dry toluene and acetone. The resulting light brown product was dried in a desiccator to constant weight. Bis(amido sulfimide) VII derived from 2-sulfoterephthalic acid imide chloride and p, p -diaminobiphenyl. A three-necked round-bottomed flask with a power-driven stirrer and a tube for nitrogen outlet was charged with 30 ml of dimethylacetamide and 1.85 g (0.01 mol) of p, p`-diaminobiphenyl. Then 5 g (0.02 mol) of chloride I was added in an inert atmosphere. Triethylamine or pyridine was added to neutralize the HCl released. The reaction temperature was maintained at 40 3 45oC. After adding the whole amount of I, the mixture was stirred for an additional 30 min. In the course of the reaction, a dark product formed. After reaction completion, 150 ml of distilled water was added, and the mixture was filtered through a glass frit. The product was dried at room temperature and then brought to constant weight in a vacuum oven.
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Bis(amido sulfimides) derived from m- and p-phenylene-, ethylene-, tetramethylene-, and hexamethylenediamines were prepared similarly. CONCLUSION Previously unknown 2-sulfoterephthalic acid imide chloride was prepared, and bis(amido sulfimides) showing promise as monomers were prepared by its reactions with diamines. REFERENCES
1. Suvorov, B.V., Zhubanov, B.A., and Mashkevich, S.A., Trimellitovaya kislota i polimery na ee osnove (Trimellitic Acid and Polymers Derived from It), AlmaAta: Nauka, 1975. 2. Arkhipova, I.A., Zhubanov, B.A., Kim, L.V., and Ivashchenko, N., Zh. Prikl. Khim., 1976, vol. 49, no. 6, pp. 1399 1402. 3. Tagiev, B.A. and Aslanov, T.A., Azerb. Khim. Zh., 1997, nos. 1 4, pp. 62 66. 4. Smiles, S. and Harrison, D.C., J. Chem. Soc., 1922, vol. 121, p. 2022. 5. Kazitsyna, L.A. and Kupletskaya, N.B., Primenenie UF, IK, YaMR i mass-spektroskopii v organicheskoi khimii (Applications of UV, IR, NMR, and Mass Spectroscopy in Organic Chemistry), Moscow: Mosk. Gos. Univ., 1979. 6. Gordon, A.J. and Ford, R.A., The Chemists Companion. A Handbook of Practical Data, Techniques, and References, New York: Wiley, 1972. 7. Becker, H., Berger, W., Domschke, G., et al., Organikum. Organisch-chemisches Grundpraktikum, Berlin: Wissenschaften, 1976.

RUSSIAN JOURNAL OF APPLIED CHEMISTRY

Vol. 76

No. 2

2003