CHEMICAL SYNTHESES AND TECHNOLOGIES
FOR THE SUSTAINABLE DEVELOPMENT III.

Facile Synthesis of Butane-1,2,3,4-tetracarboxylic Acid¹

Pavel PAZDERA and Jan ŠIMBERA

Research Group for Chemical Syntheses and Technologies of the Sustainable Development, Department of Organic Chemistry, Masaryk University, CZ-611 37 Brno, Czech Republic; [email protected]

Abstract

Environmental friendly synthesis of butane-1,2,3,4-tetracarboxylic acid starting from succinic anhydride is described. Major synthetic step,
i. e. coupling between bromosuccinic anhydride and succinic anhydride was realized under ultrasonochemical solid – liquid phase transpher catalysis (US s-l PTC) conditions.

1. Introduction
2. Results and discussion
3. References

1. Introduction

     Butane-1,2,3,4-tetracarboxylic acid is produced as broad applicable product  in relative sizable volumes². It is a very good formaldehyde-free durable press finishing agent, which has high reaction activity and no irritant odor. In addition, this carboxylic acid can be used in manufacturing polyimide materials which have heat-proof, acid-proof and hydrocarbon-proof properties, used in production of functional polymer materials such as photosensitive materials, biomedical materials and functional polymeric membrane materials. Furthermore, the derivatives and polymers of butane-1,2,3,4-tetracarboxylic acid are excellent electricity insulator, and are widely used in the producing of electricity insulative rings, wire enamels and electricity insulator materials.

     Common processes of butane-1,2,3,4-tetracarboxylic acid fabrication³ copy the three steps synthetic scheme (Scheme 1).

Scheme 1.  Common synthetic way to butane-1,2,3,4-tetracarboxylic acid production

      3a,4,7,7a-Tetrahydro-2-benzofuran-1,3-dione is prepared by Diels-Alder reaction of butane-1,3-diene and maleic anhydride in the first step. Second synthetic step is its hydrolysis to cyclohex-4-ene-1,2-dicarboxylic acid and synthesis is finished by oxidative hydrolysis of this intermediate product. This last step is not environmental friendly because it makes using of strong oxidizing reagents (hydrogen peroxide, nitric acid, potassium permanganate, ozone) and heavy metal compounds (copper, vanadium, tungsten). Further problem is also contamination of final butane-1,2,3,4-tetracarboxylic acid by these heavy metal compounds and an occasion its refinement. On the other hand, the overall process
of butane-1,2,3,4-tetracarboxylic acid production is started from relatively moderate petrochemical products.

2. Results and discussion

     Now we yield new different way for the butane-1,2,3,4-tetracarboxylic acid synthesis according to the Chemical Syntheses and Technologies for the Sustainable Development.  

     The synthesis of butane-1,2,3,4-tetracarboxylic acid followed the next scheme, all process is started from succinic anhydride as a relatively moderate petrochemical product without the presence of heavy metals or further hazardous reagents:

Scheme 2.  Synthetic way to butane-1,2,3,4-tetracarboxylic acid according to the Sustainable Chemistry  

   The first step of the synthesis is brominating of succinic anhydride into acetic acid solution in the presence of sodium acetate as the base at room temperature. The bromine may be generated from bromide anion in situ by electrolysis. This spontaneous brominating reaction is known generally and gives bromosuccinic anhydride quantitatively. This product should not to be purified. After evaporation of liquid (acetic acid can be recycled) follow the next step realized in dioxane solution.

   The second step presents the sonochemical s-l PTC^4,5 coupling between bromosuccinic anhydride and the carbanion generated from succinic anhydride by an action of equimolar mixture of calcium carbonate – calcium oxide in the Cetrimide presence at temperature 30-40 °C.  This coupling gives tetrahydro-3,3'-bifuran-2,2',5,5'-tetrone (butane-1,2,3,4-tetracarboxylic acid bis-anhydride) in the course ca 60 min in very good yield. The bis-anhydride should not to be purified.  Silica is added ending of this reaction and a solid complex is filtered off (bromides may be regenerated to bromine by electrolysis).

   After dioxane evaporation (recycling of dioxane is necessary) is the solid pure product mixed with water and a hydrolysis proceeds
at 90-100°C. The final product is separated by suction after cooling. The last step is quantitative, purity and quality of the product after drying
is very good.

3. References:

1. Supported by the grant of Ministry of Education of the Czech Republic
   (Grant No. MSM 143100011).
2. Yang Y. Q., Li S. Q.: Text. Res. J. 73, 809 (2003); Vukusic S. B., Katovic D., Schramm C.: Text. Res. J. 73, 733 (2003); Zhou L.M., Yeung K. W., Yuen C. W. M.: AATCC REV 2, 29 (2002); Kim C., Lee S. C., Kwon I. C.: Macromolecules 35, 193 (2002); Bajaj P.: J. Appl. Polym. Sci. 83, 631 (2002); Schramm C., Rinderer B.: Cell. Chem. Technol. 35, 73 (2001);  Granit N. F., Korin E., Bettelheim A.: Chem. Eng. Technol. 26, 341 (2003); and more references presented herein.
3. Kohler J. F., Jansen R.: J. Amer. Chem. Soc. 60, 2142 (1938); Moldavskou B. L., Babel' V. G.: J. Appl. Chem. USSR (Engl. Transl.) 36, 1553 (1963); Zh. Prikl. Khim. (Leningrad) 36,  1614 (1963);  Kurosawa K., Obara H.: Bull. Chem. Soc. Jpn. 39, 525 (1966); Copolymer Rubber + Chemical Corp., US 3218353 (1962); Chem.  Abstr. 64; 3376g (1966); Odinokow Yu. P. et al.: Neftekhimiya 14; 441, 444 (1974); Chem. Abstr. 82; 30919 (1975); Andrist J., Kovelan F. J.: J. Chem. Soc., Perkin Trans. 1, 918,922 (1978); ; Cuppen D., Laarhoven E.: J.Amer. Chem. Soc. 94, 5914 (1972); Franz J. E.: J. Org. Chem. 30, 1488 (1965); Lynn J. W., Roberts R. L.: J. Org. Chem. 26, 4303 (1961); Franz J. E.: J. Org. Chem. 30,; 4328 (1965) and reference presented herein.
4. Dehmlow E.V., Dehmlow S.S., Phase Transfer Catalysis, Verlag Chemie GmbH, Weinheim 1983, Chapter 3.9 - C-Alkylation of Activated C-H Bonds, and references presented herein.
5. Pazdera P., Facile Direct a-Ethoxycarbonylation and a-Carbamoylation Reaction on Cyclic Ketones Promoted by s-l PTC and/or by Ultrasound, Synlett, submitted.