ZHURNAL
`VSESOYUZNOGO
`KHIMICHESKOGO
`OBSHCHESTVA
`Im. D. I. MENDELEEVA
`
`
`
`VOLUME
`XXII
`
`
`
`ISSUE DEVOTED
`TO HEAVY ORGANIC SYNTHESIS
`
`
`
`
`
`
`
`Petitioners' Exhibit 1014, Page 1 of 8
`
`

`
`Scientific papers of members of the D.I. Mendeleev All-Union Chemical
`Society
`
`2
`
`
`
`BRIEF REPORTS
`
`UDC542.971.2:547.722.2
`
`Liquid-Phase Catalytic Oxidation of 5-Methylfurfural
`D. R. KREILE, D. SILE, L. YA, KRUMINYA, A. M. STRAUTINYA, V. A. SLAVINSKAYA
`(Institute of Organic Synthesis of the Academy of Sciences of the Latvian SSR)
`
`
`
`Liquid-phase catalytic oxidation of 5-methylfurfural has been poorly investigated.
`Liquid-phase oxidation of 5-methylfurfural with hydrogen peroxide was previously studied
`[1-3]. The reaction products are β-acetylacrylic acid, levulinic acid and other compounds.
`
`In order to develop a catalytic method for synthesis of 2,5-furandicarboxylic acid, we
`investigated oxidation of 5-methylfurfural with atmospheric oxygen under pressure in the
`presence of a cobalt-manganese catalyst and bromine-containing compounds as initiators in
`acetic acid solution. 2,5-Furandicarboxylic acid, 2,5-furandialdehyde, 5-formyl-2-
`furancarboxylic acid and also products of destruction of the 5-methylfurfural molecule (oxalic
`acid and other compounds) were detected in the products of oxidation of 5-methylfurfural.
`
`Under optimal conditions of liquid-phase oxidation of 5-methylfurfural to
`2,5-furandicarboxylic acid, the yield of the latter is 36 mol%.
`
`Formation of 2,5-furandialdehyde as intermediate suggests that (together with oxidation
`of the aldehyde group) the first stage of the reaction is oxidation of the methyl group of
`5-methylfurfural. Similar to formation of 2-furanylmethyl radical (Ia), having resonance hybrids
`(Ib) and (Ic) [4],
`
`
`
`
`Ia
`
`Ib
`
`Ic
`
`
`
`349-33985_Kreile_OxidationOf5MFF_1977_RU into EN
`
`Petitioners' Exhibit 1014, Page 2 of 8
`
`

`
`we can assume that the 5-formyl-2-furanylmethyl radical is one of the leading radicals of
`oxidation during liquid phase oxidation of 5-methylfurfural
`
`
`Apparently liquid-phase oxidation of 5-methylfurfural to 2,5-furandicarboxylic acid
`
`occurs according to a parallel-consecutive scheme through formation of 5-methyl-2-
`furancarboxylic acid and 2,5-furandialdehyde:
`
`3
`
`
`
`The mentioned reactions are accompanied by oxidative cleavage of the furan ring, which
`
`is responsible for the comparatively low selectivity of oxidation of 5-methylfurfural to oxygen-
`containing derivatives of the furan series in comparison with the selectivity of oxidation of
`alkylbenzenes to corresponding aromatic carboxylic acids. Thus, during liquid-phase oxidation
`of pseudocumene at 130-150°C, at concentrations of pseudocumene of 0.2-0.3 mol/L, Co2+
`acetate 0.75·10-2 mol/L, Mn2+ acetate 0.89·10-3 mol/L, ammonium bromide 0.85·10-2 mol/L, air
`pressure 10-15 kg/cm2, the yield of trimellitic acid is 83 mol%.
`
`Thus, liquid phase oxidation of 5-methylfurfural with atmospheric oxygen in the presence
`of a cobalt-manganese catalyst is a one-stage method for synthesis of 2,5-furandicarboxylic acid.
`Only multistage methods are known for preparation of the latter [5-9].
`
`If during liquid-phase oxidation of 5-methylfurfural with hydrogen peroxide products of
`oxidative hydrolysis and lactones are obtained, then during catalytic oxidation of 5-methyl-
`furfural with atmospheric oxygen, 2,5-furandicarboxylic acid and other oxygen-containing
`compounds of the furan series are obtained.
`Experimental Part
`The studies were conducted at 100 to 135°C, initial concentration of 5-methylfurfural of
`
`0.5-0.9 mol/L, cobalt acetate 0.06-0.09 mol/L, manganese acetate (0.8-1.5)·10-3 mol/L and
`ammonium bromide (3.5-5.0)·10-3 mol/L, air consumption 1.5 L/min per 1 L of reaction mixture,
`air pressure 10-30 kg/cm2. Liquid-phase oxidation of 5-methylfurfural was investigated using an
`
`349-33985_Kreile_OxidationOf5MFF_1977_RU into EN
`
`Petitioners' Exhibit 1014, Page 3 of 8
`
`

`
`4
`
`apparatus for oxidation of liquefied hydrocarbon gases UOSUG-12M with a teflon coating on
`the inside surface of the reactor.
`
`The content of unreacted 5-methylfurfural, 2,5-furandialdehyde and
`5-formyl-2-furancarboxylic acid was determined by polarographic methods on an electronic
`self-regulating polarograph PE-312 (characteristics of the capillary 2.47 mg/s, t = 1.90 s).
`0.1N HCl was used as inert electrolyte. To plot the calibration curves in determining
`2,5-furandialdehyde, 5-formyl-2-furancarboxylic acid and 5-methylfurfural we used
`polarographic waves with E½ -0.36; -0.71; -0.93 V respectively.
`
`The amount of 2,5-furandicarboxylic acid in the form of dimethyl ester was determined
`by gas-liquid chromatography, using a mixture of 3% polyethylene glycol adipate and 1% H3PO4
`applied to chromosorb W as stationary phase. Flame ionization detector. Column temperature
`170°C. Diethyl phthalate was used as internal standard.
`
`Catalytic synthesis of 2,5-furandicarboxylic acid was accomplished as follows. 6.6 g
`(0.06 mol) 5-methylfurfural, 1.868 g (0.75·10-2 mol) cobalt acetate, 0.024 g (0.1·10-3 mol)
`manganese acetate and 0.041 g (0.4·10-3 mol) ammonium bromide are charged to the reactor,
`100 mL acetic acid is added and the reaction run for 4.5 hours at a temperature of 118°C and a
`pressure of 20 atm, air consumption 2 L/min per 1 L of reaction mixture. The temperature is then
`raised to 130°C, the pressure to 30 atm, the air consumption to 5 L/min. The process is run to
`complete termination of oxygen absorption (1.5 h). The product of oxidation is cooled, the
`precipitate filtered off and dried at 100°C. The amount of unreacted 5-methylfurfural is 0.58 g
`(8.8%). The obtained 2,5-furandicarboxylic acid is purified by recrystallization from water.
`Yield of 2,5-furandicarboxylic acid 3.26 g (36 mol%), mp > 320°C. Found, %: C 46.07, 45.79; H
`2.56, 2.56. C6H4O5. Calculated, %: C 46.16; H 2.58.
`
`
`References
`1. L. A. Badovskaya, V. G. Kul'nevich. USSR Certificate of Authorship No. 220257, 1970; , Bulletin of
`Inventions No. 47, 205 (1970).
`2. L. A. Badovskaya, V. G. Kul'nevich. Khimiya geterotsikl. soed., 1969, 198.
`3. L. A. Badovskaya et al. Tr. Krasnodarsk. politekhn. in-ta, No. 29, 107 (1970).
`4. L. D. Kispert, R. C. Quijano, C. U. Pittman. J. Org. Chem. 36, 3837 (1970).
`5. A. A. Ponomarev. In the book: Syntheses and reactions of furan compounds. Saratov, State University
`Publishers, 1960, p. 158.
`6. Czechoslovak Patent No. 94213, 1960; C. A., 55, 4531 (1961).
`7. S. P. Korshunov, A. S. Kornilov. USSR Certificate of Authorship No. 287963, 1970; Bulletin of Inventions,
`No. 36, 34 (1970).
`
`349-33985_Kreile_OxidationOf5MFF_1977_RU into EN
`
`Petitioners' Exhibit 1014, Page 4 of 8
`
`

`
`5
`
`Received May 23, 1975
`
`8. US Patent No. 3326944, 1967; C. A., 68, 49434 (1968).
`9. Belgian Patent No. 614724, 1962; C. A., 58, 10172 (1963).
`
`
`
`Translated by:
`
`April 24, 2015
`
`
`
`
`
`349-33985_Kreile_OxidationOf5MFF_1977_RU into EN
`
`Petitioners' Exhibit 1014, Page 5 of 8
`
`

`
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`Petitioners‘ Exhibi_t 1_p_1A,_Page 6 of 8
`\
`
`Petitioners' Exhibit 1014, Page 6 of 8
`
`

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`
`Petitioners‘ Exhibit 1014, Page 7 of 8
`
`Petitioners' Exhibit 1014, Page 7 of 8
`
`

`
`
`
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`L. D. Klspert. R.
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`J. Org. Chem, 36. 3837 (1970).
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`A. C. Knpniuloa.
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`7963, 1970; BIOJIJI. n3o6pe1'., N9 36, 34 (1970).
`8. H81‘. CIIIA N9 3326944. 1967; C. A..
`68. 49434 (1968).
`9. 56.1131‘. na-r., Ne 614724, 1962; C. 11.. 58. 10172 (1963). '
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`
`Petitioners‘ Exhibit 1014, Page 8 of 8
`
`99
`
`Petitioners' Exhibit 1014, Page 8 of 8