Inventor’s Certificate
` SPECIFICATION
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` (11) 448177
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` Union of Soviet
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`Socialist Republics
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` (61) Supplemental to the Inv. Cert. –
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` (22) Filing date: 30-Oct-72 (21) 1842435/23-4 (51) Int. Cl.3:
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` C 07d 5/26
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` National Committee on with accession of Application No. ____
`Inventions and Discoveries
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` of the USSR
` (23) Priority –
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` Council of Ministers
` Publication date: 30-Oct-74. Bulletin No. 40 (53) UDK
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` 547.725 (088.8)
` Specification publishing date: 29-May-75
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`(72) Inventors:
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`(71) Applicant:
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` V.A. Slavinskaya, D.R. Kreyle, S.A. Giller, L.Ya. Kruminya,
` D.Ya. Eglite and A.K. Strautinya
` Order of Red Banner of Labor
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` Institute of Organic Synthesis, Academy of Sciences of Latvia
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`(54) A METHOD FOR PRODUCING 2,5-FURANDICARBOXYLIC
`ACID
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`VPTB
`EXPERT FUND
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`1
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`The invention relates to the method for
`producing 2,5-Furandicarboxylic acid, which is
`widely used as a monomer in the process of
`synthesis of high-molecular weight compounds, as
`well as a half-product of
`the synthesis of
`physiologically active compounds.
`The prior art discloses a method for producing
`2,5-Furandicarboxylic acid by way of liquid-phase
`air oxidation of 5-Hydroxymethylfurfural or 5-
`Hydroxymethyl-2-furancarboxylic acid
`in
`the
`presence of homogeneous or heterogeneous
`catalyst (Pt, Ag2O – CuO or Pd) under conditions
`of heating and pressure.
`The disadvantages of the disclosed method are
`low availability of the initial compounds and high
`cost of the catalyst.
`The objective of the invention is to simplify
`the process technology.
`This objective is achieved by subjecting 5-
`methylfurfural
`to
`liquid-phase air oxidation,
`typically conducted under 115-140oC and air
`pressure of 10-15 atm, and using as a catalyst
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`mixed valance metal salts, such as a mixture of
`cobalt acetate and manganese acetate, as well as
`bromine-containing
`compounds,
`such
`as
`ammonium bromide, in the aliphatic carboxylic
`acid solution.
`The oxidation is conducted using a UOSUG-
`12M unit with Teflon reactor.
`The amount of cobalt acetate
`Co(O2CCH3)2 · 4H2O
`constitutes 0.1-0.2 mol, manganese acetate
`Mn(O2CCH3)2 · 4H2O – 0.001-0.002 mol, and
`ammonium bromide (NH4Br) – 0.005-0.01 mol
`per 1 mol of oxidized substance (or per 1.67 l of
`acetic acid solution).
`The proposed method has a number of
`advantages compared to prior art: it utilizes readily
`available and inexpensive reagents as the initial
`compound and catalysts; the method is a one-step
`process.
`The overall conversion of 5-methylfurfural is
`91-99%, and the yield of 2,5-Furandicarboxylic
`acid is 23-36%.
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`Petitioners' Exhibit 1007, Page 1 of 5
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`448177
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`3
`Example 1. A reactor is loaded with 6.60 g
`(0.06 mol) of 5-methylfurfural, 1.868 g (0.0075
`mol) of cobalt acetate, 0.024 g (0.001 mol) of
`manganese acetate and 0.041 g (0.0004 mol) of
`ammonium bromide. After adding 100 ml of
`glacial acetic acid, the reaction is conducted for
`4.5 h at 118oC and 20 atm of pressure. The flow
`rate of air is 2 l/min per 1 l of reaction mixture.
`Once the reaction time has been reached, the
`temperature is increased to 130oC, pressure – to 30
`atm and air flow rate – to 5 l/min.
`The process
`is conducted until oxygen
`consumption is completely stopped. The oxidate is
`cooled down, and the residue is filtered and dried
`at 100oC. The
`amount of unreacted 5-
`methylfurfural is 0.58 g.
`The yield of 2,5-Furandicarboxylic acid is
`3.26 g (36%), (m.p. > 320oC).
`Example 2. Reactor is loaded with 3.31 g
`(0.03 mol) of 5-methylfurfural, 0.967 g (0.004
`mol) of cobalt acetate, 0.012 g (0.0005 mol) of
`manganese acetate and 0.023 g (0.002 mol) of
`ammonium bromide. After adding 50 ml of glacial
`acetic acid, the reaction is conducted for 4 h at
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`4
`116oC and 10 atm of pressure. The flow rate of air
`is 4 l/min per 1 l of reaction mixture. The oxidate
`is cooled down, and the residue is isolated and
`dried at 100oC.
`The yield of 2,5-Furandicarboxylic acid is
`1.32 g (29%).
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`Subject of the invention
`1. A method
`2,5-
`producing
`for
`Furandicarboxylic acid using the air oxidation
`reaction under condition of heating and pressure in
`the presence of a catalyst in the liquid phase,
`wherein,
`in order
`to simplify
`the process
`technology, 5-methylfurfural
`is
`subject
`to
`oxidation and mixed valance metal salts, such as a
`mixture of cobalt acetate and manganese acetate,
`as well as bromine-containing compounds, such as
`ammonium bromide, in the aliphatic carboxylic
`acid solution are used as a catalyst.
`2. The method according
`to Claim 1,
`wherein said oxidation
`is conducted at
`the
`temperature of 115-140oC and air pressure of 10-
`50 atm.
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`Compiler: R. Karakhanov
` Corrector: V. Petrova
` Technical editor: N. Kuklina
`Editor: N. Spiridonova
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` By subscription
`Order 944/19
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`Edition No. 1166
`Circulation: 506
`Research and Development Institute of the State Committee on Inventions and Discoveries,
`USSR State Committee On Science And Technology
`113035, Moscow, Zh-35, 4/5 Raushskaya nab.
`Publishing Center: 2, Sapunova pr.
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`Petitioners' Exhibit 1007, Page 2 of 5
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`TRANSLATION CERTIFICATION
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`County of New York
`State of New York
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`Date: August 27, 2015
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`To whom it may concern:
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`This is to certify that the attached translation from Russian into English is an accurate
`representation of the documents received by this office.
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`The documents are designated as:
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`
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`Inventor’s Certificate 448177 - A METHOD FOR PRODUCING 2,5-FURANDICARBOXYLIC
`ACID
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`Mohammed H. Masab, Project Manager in this company, attests to the following:
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`“To the best of my knowledge, the aforementioned documents are a true, full and accurate
`translation of the specified documents.”
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`Signature of Mohammed H. Masab
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`WI-44, 6/25/2015, Rev 0
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`Petitioners' Exhibit 1007, Page 3 of 5
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`Petitioners' Exhibit 1007, Page 4 of 5
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`Petitioners' Exhibit 1007, Page 5 of 5