USRE48674E1 - Method for the synthesis of 5-amino-1-phenyl-3-cyano-4-trifluoromethyl sulfinyl - Google Patents

Method for the synthesis of 5-amino-1-phenyl-3-cyano-4-trifluoromethyl sulfinyl Download PDF

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USRE48674E1
USRE48674E1 US14/534,001 US201114534001A USRE48674E US RE48674 E1 USRE48674 E1 US RE48674E1 US 201114534001 A US201114534001 A US 201114534001A US RE48674 E USRE48674 E US RE48674E
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acid
oxidation
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Andrea Pastorio
Paolo Betti
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Finchimica SRL
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to a method for the synthesis of 5-amino-1-phenyl-3-cyano-4-trifluoromethyl sulfinyl pyrazole having the following general formula (I), particularly preferred for the synthesis of Fipronil.
  • patent EP 0295117 B1 shows a synthesis method using a 3-chlorobenzoic derivative.
  • TCPA is the effective oxidising species and is formed in situ by the reaction of an oxidising agent with trichloroacetic acid (TCA).
  • TCA should also conveniently act as a reaction solvent.
  • TCA is solid (melting point—54-58° C.) so that, for its use as a reaction solvent, a second solvent needs to be added to the TCA to lower its melting point to a temperature compatible with the reaction temperature.
  • the solvents suitable for this purpose are, among others, dichloroacetic (DCA) and monochloroacetic (MCA) acids.
  • reaction forming the by-product consumes useful product to the detriment of the yield.
  • a further disadvantageous aspect is that the oxidant species TCA can only be used at temperatures compatible with the oxidation reaction of the compound having the general formula (II) to the compound having the general formula (I) if the reaction is conducted in the presence of a species acting as a solvent both for the reagent having the general formula (II) and for the oxidant TCA itself, making both the recovery operation of the product having the general formula (I) and the recovery of the oxidant TCA more complicated.
  • the present invention therefore sets out to provide a new method for the preparation of the compound having the general formula (I) using an economically advantageous oxidation method convenient to implement in industrial applications.
  • the present invention relates to a method for the preparation of the 5-amino-1-phenyl-3-cyano-4-trifluoromethyl sulfinyl pyrazole having the described general formula (I), particularly preferred for the synthesis of Fipronil, through oxidation of a compound having the general formula (II) as follows:
  • R 1 and R 2 are independently hydrogen or halogen, and wherein the oxidising agent can be dichloroperacetic acid.
  • R 1 and R 2 are independently hydrogen or halogen; through oxidation of a compound having the general formula (II) in the presence of dichloroacetic acid and of an oxidising agent:
  • R 1 and R 2 are defined as above.
  • the chemical species causing oxidation of the compound having the general formula (II) to a compound having the general formula (I) is preferably dichloroperacetic acid, formed by oxidation of DCA acid through the oxidising agent.
  • dichloroperacetic acid as an oxidant has never been described in literature. Surprisingly it was found that DCA, in the presence of an oxidant species such as hydrogen peroxide, peroxide or similar, is also itself transformed at low temperatures into the corresponding dichloroperacetic acid and that this species is an excellent oxidant of the compound having the general formula (II).
  • the aforesaid oxidation is conducted in the absence of trichloroacetic and/or trichloroperacetic acid, so that the process of the present invention does not require prior solubilisation of the oxidant.
  • R 1 and R 2 are chlorine or bromine.
  • the compound having the general formula (I) is 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluorometansulfinyl-1H-pyrazole-3-carbonitril, commercially known by the name of Fipronil (CAS Registry No. 120068-37-3).
  • the production of the dichloroperacetic acid used in the oxidation of the compound having the general formula (II) is performed in situ, by means of the reaction with the oxidising agent.
  • the dichloroacetic acid performs, after its partial oxidation in dichloroperacetic acid, the dual function of transferring oxygen to the compound having the general formula (II), and acting as a reaction solvent inasmuch as already liquid at the reaction conditions.
  • the oxidation of the compound having the general formula (II) to a compound having the general formula (I) is a critical operation, in that the reagent used must be sufficiently energetic to quantitatively conduct such reaction, but without generating the (by-)product of subsequent oxidation having the general formula (III):
  • R 1 and R 2 are again defined as above.
  • Dichloroperacetic acid proves to be an excellent oxidant for conducting the reaction with good yields and selectivity towards the compound having the general formula (I), without however producing excessive quantities of the undesired product having the general formula (III).
  • the present invention therefore allows to operate in the absence of solvents at the same temperatures and to achieve excellent selectivity similar to the ones achieved with trifluoroperacetic acid but without having to use an extremely expensive solvent such as TFA and without having to add corrosion inhibitors which limit, without eliminating, the problem of corrosion of the enamels caused by the hydrogen fluoride generated by such solvent.
  • the oxidising agent used is selected from the group comprising benzoyl peroxides, sodium peroxides, t-butyl peroxides and/or hydrogen peroxides.
  • the one that is particularly preferred to oxidise dichloroacetic acid is hydrogen peroxide, in that it can be used in the form of a concentrated aqueous solution.
  • the concentration of the aqueous solution of hydrogen peroxide is 50%-70% depending on commercial availability, but different concentrations may be just as acceptable.
  • oxidising agent for each mole of compound having the general formula (I),1.0-5.0 moles of oxidising agent are used, preferably 1.1-2.0 equivalents of such agent, more appropriately 1.5 equivalents for each mole.
  • the temperature at which oxidation takes place is between 0° C. and 35° C.
  • oxidation takes place at a temperature below 20° C., advantageously at a temperature of 0° C.-15° C., more appropriately at about 5° C.
  • the present invention it is preferable, acting on the reaction time or on the quantity of oxidising agent, to conduct the oxidation reaction up to a conversion level of the compound having the general formula (II) of 80%-98%, preferably 90%-95%.
  • the method of the present invention further comprises a step of recovering the non-oxidised compound having the general formula (II).
  • the step of recovering comprises a step of dissolving and subsequently recrystallising the compound having the general formula (I) with one or more of the solvents selected from the group comprising toluene, xylenes, chlorobenzene, chlorinated aliphatic solvents and isopropanol.
  • the solvents selected from the group comprising toluene, xylenes, chlorobenzene, chlorinated aliphatic solvents and isopropanol.
  • the unconverted compound having the general formula (II), as a result of its greater solubility than the oxidised forms of formulas (I) and (III) in some organic solvents can be easily removed by means of a solvent and recovered for re-utilisation as a reagent. This way, during the oxidation process the product loss and the waste production is reduced to a minimum, becoming absolutely negligible.
  • the oxidation of the compound having the general formula (II) occurs in the presence of an acid catalyst, advantageously homogenous.
  • This embodiment has proven particularly advantageous, especially in virtue of the large volumes involved in the reaction, to achieve reasonable productivity of the plants.
  • the aforesaid oxidation reaction of the compound of general formula (II) is conducted for relatively long periods, with large quantities of solvent to avoid the precipitation of the compounds having the general formula (II) and/or general formula (I), and furthermore at relatively low temperatures, such as below 20° C.
  • the acid catalyst is a strong mineral acid, advantageously chosen from the group consisting in sulphuric acid, methansulphonic acid, hydrochloric acid, nitric acid and their mixtures.
  • the ratio in moles of the compound having the general formula (II) and the acid catalyst is between 0.3 and 1.5, appropriately between 0.5 and 0.9 and, advantageously, is substantially equal to 0.7.
  • reaction is monitored using HPLC analysis until it reaches a conversion level of more than 95% of the reagent sulphide, after which the reaction mixture is diluted with 4 liters of water until the product has precipitated entirely.
  • reaction is monitored using HPLC analysis until it reaches a conversion level of 92% of the reagent sulphide, so as to limit the formation of the by-product (III) difficult to remove by means of re-crystallisation.
  • the reaction mixture is diluted with 4 liters of water until the product has precipitated entirely.
  • the filtrate containing only sulphide and small quantities of Fipronil, is deprived of the solvent chlorobenzene and added as a reagent to a subsequent oxidation reaction.
  • the reaction is conducted at a temperature of 5 to 10° C. and monitored by means of HPLC analysis until it reaches a conversion level of over 95% of the reagent sulphide, after which the reaction mixture is diluted with 4 liters of water until the product has precipitated entirely.
  • the solid thus obtained is filtered, washed with water and dried to obtain 420 grams of a product with a titre of 93.5%.
  • the desired conversion level is reached in about 3 hours compared to the 20 hours of the previous example 1.
  • the method of the present invention is conducted in the presence of an oxidising agent and of dichloroacetic acid making a plurality of operations superfluous, for example dissolution, otherwise essential in the known methods.
  • the method of the present invention allows to achieve higher yields compared to the methods of the prior art, in that the reaction takes place with improved selectivity thereby preventing the consumption of useful product in parasite reactions.
  • the method of the present invention once the excess of unconverted reagent (II) has been easily recovered, makes subsequent purification of the compound having the general formula (I) superfluous, which as well as being burdensome in itself is economically disadvantageous.
  • the use of the oxidising agent of the present invention does not require the use of solvents for the reaction, making the entire process much simpler and economically advantageous in industrial applications.
  • the cost of such oxidant is lower than the cost of the oxidants traditionally used.
  • the function performed by the DCA in the method of the present invention enables economies in terms of costs of the reagents, and simplification of the plant for implementing the teaching.
  • the process of the present invention makes the use of corrosion inhibitors superfluous and allows to drastically increase the useful life of the equipment used.
  • the aforesaid advantage is twofold in that it derives both from the non-use of a corrosion inhibitor and from the increased useful life of the equipment.
  • an acid catalyst makes it possible to considerably reduce reaction times while maintaining a high degree of selectivity of oxidation of the compound having the general formula (II).
  • dichloroperacetic acid may be prepared separately from the place where oxidation of the compound having the general formula (II) takes place, for subsequent addition to the latter.
  • one embodiment envisages that the peroxides illustrated earlier may be replaced or used in conjunction with a peracid and/or a persulphate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Cosmetics (AREA)
  • Pyridine Compounds (AREA)
US14/534,001 2010-07-07 2011-05-26 Method for the synthesis of 5-amino-1-phenyl-3-cyano-4-trifluoromethyl sulfinyl Active USRE48674E1 (en)

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US14/534,001 USRE48674E1 (en) 2010-07-07 2011-05-26 Method for the synthesis of 5-amino-1-phenyl-3-cyano-4-trifluoromethyl sulfinyl

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ITBS2010A000118A IT1400666B1 (it) 2010-07-07 2010-07-07 Procedimento per la sintesi di 5-amino, 1-fenil, 3-ciano, 4-trifluorometil sulfinil pirazoli.
ITBS2010A0118 2010-07-07
US13/498,245 US8304559B2 (en) 2010-07-07 2011-05-26 Method for the synthesis of 5-amino-1-phenyl-3-cyano-4-trifluoromethyl sulfinyl
PCT/IB2011/052304 WO2012004692A1 (en) 2010-07-07 2011-05-26 Method for the synthesis of 5-amino, 1-phenyl, 3-cyano, 4-trifluoromethyl sulfinyl pyrazole
US14/534,001 USRE48674E1 (en) 2010-07-07 2011-05-26 Method for the synthesis of 5-amino-1-phenyl-3-cyano-4-trifluoromethyl sulfinyl

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EP (1) EP2477971B1 (it)
CN (1) CN102812009B (it)
BR (1) BR112012007362B1 (it)
CA (1) CA2815338C (it)
DK (1) DK2477971T3 (it)
IL (1) IL221005A (it)
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IT1400666B1 (it) 2010-07-07 2013-06-28 Finchimica Srl Procedimento per la sintesi di 5-amino, 1-fenil, 3-ciano, 4-trifluorometil sulfinil pirazoli.
EP2593436A1 (en) * 2010-07-12 2013-05-22 Irvita Plant Protection, A Branch of Celsius Property B.V. Fipronil production process
CN114213330A (zh) * 2021-12-29 2022-03-22 天和药业股份有限公司 一种氟虫腈精制母液的处理方法

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Curriculum Vitae of Dennis P. Curran, Ph.D., Patent Interference No. 105,995 (SGL), Sep. 3, 2015, 58 pages (Exhibit 2086).
Curriculum vitae of Gordon W. Gribble, Ph.D., filed Jul. 18, 2014 in Patent Interference No. 105,995.
Curriculum Vitae of Gordon W. Gribble, Ph.D., IPR2016-00577, Feb. 4, 2016, 82 pages (Exhibit 1011).
Curriculum vitae of Gordon W. Gribble, Ph.D., Patent Interference No. 105,995 (SGL), Jul. 18, 2014, 80 pages (Exhibit 1002).
Curriculum Vitae of Paolo Betti, Ph.D., Patent Interference No. 105,995 (SGL), Aug. 25, 2015, 3 pages (Exhibit 2065).
Curriculum Vitae of Roberto Pellegri, Patent Interference No. 105,995 (SGL), Aug. 25, 2015, 1 page (Exhibit 2064).
Daniel Swern, "Organic Peracids," Chem. Rev., 1949, 45 (1), pp. 1-68 (Exhibit 1015).
Dec. 22, 2009 experiment report PS/43/2009/PB; English translation; certification of translation, Patent Interference No. 105,995 (SGL), 5 pages (Exhibit 2037).
Dec. 22, 2009 experiment report PS/43/2009/PB; English translation; certification of translation; submitted as Exhibit 2037 in Interference No. 105,995, IPR2016-00577, 5 pages (Exhibit 1032).
Dec. 22, 2009 experiment report PS/43/2009/PB—Mettler Toledo Report, Patent Interference No. 105,995 (SGL), 6 pages (Exhibit 2038).
Dec. 22, 2009 experiment report PS/44/2009/PB; English translation; certification of translation, Patent Interference No. 105,995 (SGL), 5 pages (Exhibit 2039).
Dec. 22, 2009 experiment report PS/44/2009/PB; English translation; certification of translation; submitted as Exhibit 2039 in Interference No. 105,995, IPR2016-00577, 5 pages (Exhibit 1033).
Dec. 23, 2009 experiment report PS/45/2009/PB; English translation; certification of translation, Patent Interference No. 105,995 (SGL), 5 pages (Exhibit 2040).
Dec. 23, 2009 experiment report PS/45/2009/PB; English translation; certification of translation; submitted as Exhibit 2040 in Interference No. 105,995, IPR 2016-00577, 5 pages (Exhibit 1034).
Decision on Motions—Bd. R. 121(a), filed on Jun. 26, 2015, in Interference No. 105,995 (Paper 144), IPR2016-00577, 28 pages (Exhibit 2012).
Decision on Motions—Bd. R. 121(a)—Paper 144, Patent Interference No. 105,995 (SGL), 2015, 28 pages.
Decision on Priority and other Motions—Bd. R. 121(a), filed on Mar. 16, 2016, in Interference No. 105,995 (Paper 259), IPR2016-00577, 20 pages (Exhibit 2002).
Decision on Priority and Other Motions—Bd.R. 121(a)—Paper 259, Patent Interference No. 105,995 (SGL), 2016, 20 pages.
Decision on Request for Rehearing—Bd.R. 125(c) and 127(d)—Paper 271, Patent Interference No. 105,995 (SGL), 2016, 9 pages.
Decision—Institution of Inter Partes Review—37 C.F.R. § 42.108—Paper 7, IPR2016-00577, 2016, 18 pages.
Decision—Miscellaneous Motion—Bd.R. 121(a)(3)—Paper 258, Patent Interference No. 105,995 (SGL), 2016, 4 pages.
Decision—Miscellaneous Motion—Bd.R. 121(a)(3)—Paper 62, Patent Interference No. 105,995 (SGL), 2014, 5 pages.
Decision—Motion—Bd.R. 121(a)(3)—Paper 219, Patent Interference No. 105,995 (SGL), 2015, 7 pages.
Decision—Motion—Bd.R. 121(a)(3)—Paper 231, Patent Interference No. 105,995 (SGL), 2015, 6 pages.
Decision—Request for Rehearing—37 C.F.R. § 42.71(a)—Paper 11, IPR2016-00577, 2016, 6 pages.
Decision—Request for Rehearing—37 C.F.R. § 42.71(a)—Paper 17, IPR2016-00577, 2016, 5 pages.
Declaration of Anat Levin, Ph.D., Patent Interference No. 105,995 (SGL), Aug. 17, 2015, 4 pages (Exhibit 1045).
Declaration of Andrea Pastorio, Patent Interference No. 105,995 (SGL), Aug. 25, 2015, 13 pages (Exhibit 2074).
Declaration of Barry M. Trost, Ph.D., dated May 23, 2014, filed May 23, 2014 in Patent Interference No. 105,995.
Declaration of Barry M. Trost, Ph.D., Patent Interference No. 105,995 (SGL), May 23, 2014, 20 pages (Exhibit 2003).
Declaration of Claudia Mora, Patent Interference No. 105,995 (SGL), Aug. 25, 2015, 11 pages (Exhibit 2075).
Declaration of David P. Gitkos, Patent Interference No. 105,995 (SGL), Sep. 30, 2015, 77 pages (Exhibit 2080).
Declaration of Dennis Curran, Ph.D., IPR2016-00577, Aug. 31, 2016, 45 pages (Exhibit 2026).
Declaration of Dennis P. Curran, Ph.D., Patent Interference No. 105,995 (SGL), Oct. 6, 2015, 28 pages (Exhibit 2085).
Declaration of Giacomo Ravetta, Patent Interference No. 105,995 (SGL), Aug. 25, 2015, 3 pages (Exhibit 2072).
Declaration of Gordon W. Gribble, Ph.D., dated Jul. 18, 2014, filed Jul. 18, 2014 in Patent Interference No. 105,995.
Declaration of Gordon W. Gribble, Ph.D., IPR2016-00577, Feb. 4, 2016, 50 pages (Exhibit 1010).
Declaration of Gordon W. Gribble, Ph.D., Patent Interference No. 105,995 (SGL), Jul. 18, 2014, 11 pages (Exhibit 1001).
Declaration of Maria Grazia Renzi and Rodolfo Peveri, Patent Interference No. 105,995 (SGL), Aug. 25, 2015, 3 pages (Exhibit 2068).
Declaration of Michael Grabarnick, Ph.D., Patent Interference No. 105,995 (SGL), Aug. 16, 2015, 12 pages (Exhibit 1039).
Declaration of Michael Mogilnitsky, M.Sc., Patent Interference No. 105,995 (SGL), Aug. 16, 2015, 5 pages (Exhibit 1041).
Declaration of Paolo Betti, Ph.D., Patent Interference No. 105,995 (SGL), Aug. 25, 2015, 12 pages (Exhibit 2073).
Declaration of Roberto Pellegri, Patent Interference No. 105,995 (SGL), Aug. 25, 2015, 10 pages (Exhibit 2077).
Declaration—Bd.R. 203(b)—Paper 1, Patent Interference No. 105,995 (SGL), 2014, 7 pages.
Dennis P. Curran and Sung-Bo Ko. "Synthesis of Optically Active a-Hydroxy Lactones by Sharpless Asymmetric Dihydroxylations of Ketene Acetals, Enol Ethers, and Ene Lactones." The Journal of Organic Chemistry J. Org. Chem. 59.21 (1994): 6139-141 (Exhibit 1047).
Dennis P. Curran, Ulf Diederichsen, and Michael Palovich. "Radical Cyclizations of Acylgermanes. New Reagent Equivalents of the Carbonyl Radical Acceptor Synthon." J. Am. Chem. Soc. Journal of the American Chemical Society 119.21 (1997): 4797-804 (Exhibit 1048).
Deposition transcript of Barry M. Trost, Ph.D., dated Oct. 13, 2014, filed Oct. 31, 2014 in Patent Interference No. 105,995.
Deposition transcript of Barry M. Trost, Ph.D., Patent Interference No. 105,995 (SGL), Oct. 13, 2014, 98 pages (Exhibit 2016).
Deposition Transcript of Gordon Gribble, Ph.D., dated Aug. 3, 2016, IPR2016-00577, 98 pages (Exhibit 2021).
Deposition transcript of Gordon W. Gribble, Ph.D., Patent Interference No. 105,995 (SGL), Aug. 29, 2014, 103 pages (Exhibit 2015).
Deposition transcript of Gordon W. Gribble, Ph.D., Patent Interference No. 105,995 (SGL), Sep. 17, 2015, 102 pages (Exhibit 2083).
Email correspondence between Andrea Pastorio and Giacomo Ravetta on Feb. 15, 2010 (redacted) with attached document titled @I0139145.Finchimica—Testo BR IT—Fipronil revisione J . . . ; English translation of redacted email and attached document; certifications for translations, Patent Interference No. 105,995 (SGL), 38 pages (Exhibit 2043).
Email from Gary Gershik, counsel for Levin, to the Patent Trial and Appeal Board, dated Jul. 31, 2015, IPR2016-00577, 1 page (Exhibit 2005).
Email from Levin Counsel, Patent Interference No. 105,995 (SGL), Dec. 1, 2014, 1 page (Exhibit 2034).
Errata—Paper 147, Patent Interference No. 105,995 (SGL), 2015, 2 pages.
Errata—Paper 266, Patent Interference No. 105,995 (SGL), 2016, 2 pages.
Errata—Paper 39, Patent Interference No. 105,995 (SGL), 2014, 2 pages.
Ex parte Koninklijke Philips Electronics N.V., 2013 WL 2139858 (BPAI Apr. 24, 2013), 6 pages (Exhibit 2025).
Ex parte Stam, 2012 WL 1961900 (BPAI May 24, 2012), 7 pages (Exhibit 2024).
Ex parte Viola, 2008 U.S. Pat. App. Lexis 5135 (BPAI Mar. 12, 2008), 3 pages (Exhibit 2023).
Ex parte Woodruff, No. 2001-1055, 2003 WL 25277886 (B.P.A.I. Sep. 30, 2003), 3 pages (Exhibit 2088).
Ex parte Yu-Piao Wang, Appeal 2011-011246, 2013 Pat. App. Lexis 8918 (P.T.A.B. Dec. 2, 2013), 4 pages (Exhibit 2087).
Excerpts from laboratory notebook of Claudia Mora; English translation; certification of translation, Patent Interference No. 105,995 (SGL), Nov. 10, 2015, 46 pages (Exhibit 2062).
Excerpts from laboratory notebook of Roberto Pellegri; English translation; certification of translation, Patent Interference No. 105,995 (SGL), Aug. 15, 2015, 31 pages (Exhibit 2070).
Feb. 1, 2010 experiment report PS/10/2010/PB; English translation; certification of translation, Patent Interference No. 105,995 (SGL), 7 pages (Exhibit 2052).
Feb. 11, 2010 experiment report PS/02/2010/CM; English translation; certification of translation, Patent Interference No. 105,995 (SGL), 22 pages (Exhibit 2060).
Feb. 2, 2010 experiment report PS/04/2010/RP; English translation; certification of translation, Patent Interference No. 105,995 (SGL), 7 pages (Exhibit 2053).
Feb. 3-10, 2010 chromatograms for experiment report PS/05/2010/RP, Patent. Interference No. 105,995 (SGL), 14 pages (Exhibit 2056).
Feb. 4, 2010 experiment report PS/05/2010/RP; English translation; certification of translation, Patent Interference No. 105,995 (SGL), 9 pages (Exhibit 2054).
Feb. 5, 2010 chromatograms for experiment report PS/05/2010/RP, Patent Interference No. 105,995 (SGL), 6 pages (Exhibit 2055).
Feb. 5, 2010 experiment report PS/06/2010/RP; English translation; certification of translation, Patent Interference No. 105,995 (SGL), 5 pages (Exhibit 2057).
Feb. 8, 2010 experiment report PS/12/2010/PB; English translation; certification of translation, Patent Interference No. 105,995 (SGL), 5 pages (Exhibit 2058).
Federal Register vol. 69, No. 155, pp. 49960-50020 (Aug. 12, 2004), 62 pages (Exhibit 1025).
Fifth Declaration of Gordon W. Gribble, Ph.D., Patent Interference No. 105,995 (SGL), Aug. 17, 2015, 9 pages (Exhibit 1042).
Final Written Decision—35 U.S.C. § 318(a) and 37 C.F.R. § 42.73—Paper 30, IPR2016-00577, 2017, 22 pages.
First Preliminary Amendment filed in connection with U.S. Appl. No. 13/498,245, Patent Interference No. 105,995 (SGL), Mar. 26, 2012, 7 pages (Exhibit 1003).
Fourth Declaration of Gordon W. Gribble, Ph.D., dated Oct. 31, 2014, filed Oct. 31, 2014 in Patent Interference No. 105,995.
Fourth Declaration of Gordon W. Gribble, Ph.D., filed in Interference No. 105,995 (Levin Exhibit 1022), IPR2016-00577, Oct. 31, 2014, 19 pages (Exhibit 2019).
Fourth Declaration of Gordon W. Gribble, Ph.D., Patent Interference No. 105,995 (SGL), Oct. 31, 2014, 18 pages (Exhibit 1022).
Golchoubian et al., "Effective Oxidation of Sulfides to Sulfoxides with Hydrogen Peroxide under Transition-Metal Free Conditions," Molecules, 2007, 12, 304-311 (Exhibit 2019).
H. Harry Szmant, Chapter 16, "Chemistry of the Sulfoxide Group," Organic Sulfur Compounds (1961): 154-69 (Exhibit 1046).
H.C. Brown, D.H. McDaniel, and O.Haflinger, "Determination of Organic Structures by Physical Methods, vol. 1" E.A. Braude and F.C. Nachold, Eds., Academic Press, NY, 1955, p. 567 (Exhibit 1018).
Hawley's Condensed Chemical Dictionary, p. 1032 (Richard J. Lewis, Sr. ed., John Wiley & Sons, Inc., 14th ed., 2001), 3 pages (Exhibit 2023).
Information Disclosure Statement, filed on June 25, 2013, in U.S. Appl. No. 13/926,389, 7 pages (Exhibit 2090).
Information Disclosure Statement, filed on June 25, 2013, in U.S. Appl. No. 13/926,389, IPR2016-00577, 8 pages (Exhibit 2007).
International Preliminary Report on Patentability filed on Jan. 15, 2013, in International Application No. PCT/IL2011/000546, 8 pages. (Exhibit 2030).
International Search Report and Written Opinion for PCT/IB2011/052304, mailed Sep. 26, 2011; ISA/EP.
Inventor Declaration of Anat Levin in U.S. Appl. No. 13/926,389, Patent Interference No. 105,995 (SGL), Jul. 7, 2013, 3 pages (Exhibit 1051).
Jan. 12, 2010 experiment report PS/04/2010/PB; English translation; certification of translation, Patent Interference No. 105,995 (SGL), 5 pages (Exhibit 2044).
Jan. 21, 2010 document titled Relazione fipronil x pellegri.doc (redacted); English translation; certification of translation, Patent Interference No. 105,995 (SGL), 67 pages (Exhibit 2046).
Jan. 21, 2010 email; English translation; certification of translation, Patent Interference No. 105,995 (SGL), 5 pages (Exhibit 2045).
Jan. 26, 2010 experiment report PS/02/2010/RP; English translation; certification of translation, Patent Interference No. 105,995 (SGL), 7 pages (Exhibit 2048).
Jan. 26, 2010 experiment report PS/07/2010/PB; English translation; certification of translation, Patent Interference No. 105,995 (SGL), 5 pages (Exhibit 2047).
Jan. 28, 2010 experiment report PS/03/2010/RP; English translation; certification of translation, Patent Interference No. 105,995 (SGL), 5 pages (Exhibit 2051).
Jan. 28, 2010 experiment report PS/08/2010/PB; English translation; certification of translation, Patent Interference No. 105,995 (SGL), 5 pages (Exhibit 2050).
Jan. 4, 2010 experiment report PS/01/2010/PB; English translation; certification of Translation, Patent Interference No. 105,995 (SGL), 5 pages (Exhibit 2041).
Jan. 6, 2010 experiment report PS/02/2010/PB; English translation; certification of Translation, Patent Interference No. 105,995 (SGL), 5 pages (Exhibit 2071).
Jan. 7, 2010 experiment report PS/03/2010/PB; English translation; certification of Translation, Patent Interference No. 105,995 (SGL), 5 pages (Exhibit 2042).
Jerry March, Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (Fourth Ed. 1992) at pp. 1201-1203 (Exhibit 2013).
Jerry March, Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (Fourth Ed. 1992) at pp. 887-888, 1236 (Exhibit 2008).
Joint Appendix—Dkt. 36 & 37, Fed. Cir. Appeal No. 17-2195, 2018, 367 pages.
Judgment—Bd.R. 127(a)—Paper 260, Patent Interference No. 105,995 (SGL), 2016, 3 pages.
Judgment—Dkt. 48, Fed. Cir. Appeal No. 17-2195, 2018, 5 pages.
Jun. 13, 2010 email from Dr. Michael Grabarnick to Michal Telnoy with invention disclosure attached, Patent Interference No. 105,995 (SGL), 7 pages (Exhibit 1035).
Jun. 30, 2010 email from Benjamin Schneider to Bertha Fuxman with invention disclosure document attached, Patent Interference No. 105,995 (SGL), 7 pages (Exhibit 1036).
Kaczorowska et al.,"Oxidation of Sulfides to Sulfoxides. Part 2: Oxidation by Hydrgen Peroxide," Tetrahedron, 61: 8315-8327 (2005) (Exhibit 2005).
Kaneko v. Wengel, 2014 Pat. App. Lexis 3279, at *64 (PTAB May 29, 2014), 21 pages (Exhibit 2033).
Kenney et al., "An Acid-catalyzed Cleavage of Sulfoxides," J. Am. Chem. Soc., 83: 4019-4022 (1961) (Exhibit 2007).
Lakouraj et al., "Ion Exchange Resin Catalyzed Selective Oxidation of Sulfides to Sulfoxides Using Hydrogen Peroxide," Monatsheft fur Chemie, 2007, 138, 83-88 (Exhibit 2021).
Lee v. Dryja, Interference No. 105,182, 2005 Pat. App. Lexis 38 (B.P.A.I. Dec. 7, 2005), 24 pages (Exhibit 2015).
Letter from Micaela Nadia Modiano to the Examining Division of the EPO, dated Sep. 20, 2013, in European Patent Application No. 11752348.0-1462, 3 pages (Exhibit 2031).
Letter, dated Sep. 20, 2013, filed in European Patent Application No. 11752348.0-1462, Patent Interference No. 105,995 (SGL), 10 pages (Exhibit 2084).
Levin Amendment—Paper 71, Patent Interference No. 105,995 (SGL), 2014, 11 pages.
Levin List of Proposed Motions, filed on May 7, 2014, in Interference No. 105,995 (Paper 21), IPR2016-00577, 6 pages (Exhibit 2003).
Levin List of Proposed Motions—Paper 21, Patent Interference No. 105,995 (SGL), 2014, 6 pages.
Levin Miscellaneous Motion 3—Paper 130, Patent Interference No. 105,995 (SGL), 2014, 9 pages.
Levin Motion No. 3 (Judgment Based on Priority of Invention)—Paper 174, Patent Interference No. 105,995 (SGL), 2015, 29 pages.
Levin Motion No. 4 (Judgment Based on Invalidity [sic] of the Pastorio Claims over the Prior Art), filed on Aug. 17, 2015, in Interference No. 105,995 (Paper 175), IPR2016-00577, 38 pages (Exhibit 2008).
Levin Motion No. 4 (Judgment Based on Invalidity of the Pastorio Claims Over the Prior Art)—Paper 175, Patent Interference No. 105,995 (SGL), 2015, 38 pages.
Levin Objection to Second Declaration of Barry M. Trost, Ph.D. (Ex. 2018) Served by Pastorio on Oct. 31, 2014, Patent Interference No. 105,995 (SGL), 3 pages (Exhibit 1027).
Levin Opposition 1—Paper 96, Patent Interference No. 105,995 (SGL), 2014, 45 pages.
Levin Opposition 2—Paper 97, Patent Interference No. 105,995 (SGL), 2014, 13 pages.
Levin Opposition 3, filed Oct. 31, 2014 in Patent Interference No. 105,995.
Levin Opposition 3—Paper 98, Patent Interference No. 105,995 (SGL), 2014, 38 pages.
Levin Opposition 4—Paper 230, Patent Interference No. 105,995 (SGL), 2015, 30 pages.
Levin Reply 1, filed Dec. 19, 2014 in Patent Interference No. 105,995.
Levin Reply 1—Paper 121, Patent Interference No. 105,995 (SGL), 2014, 37 pages.
Levin Reply 2—Paper 122, Patent Interference No. 105,995 (SGL), 2014, 39 pages.
Levin Reply 3—Paper 140, Patent Interference No. 105,995 (SGL), 2015, 13 pages.
Levin Reply 3—Paper 248, Patent Interference No. 105,995 (SGL), 2015, 42 pages.
Levin Reply 4 (Judgment Based on Invalidity [sic] of the Pastorio Claims over the Prior Art), filed on Nov. 10, 2015, in Interference No. 105,995 (Paper 251), IPR2016-00577, 41 pages (Exhibit 2009).
Levin Reply 4—Paper 251, Patent Interference No. 105,995 (SGL), 2015, 41 pages.
Levin Request for Rehearing (Regarding Levin Motion No. 4 and Judgment)—paper 261, Patent Interference No. 105,995 (SGL), 2016, 12 pages.
Levin Responsive Motion 2 (To Add Claim 11 Contingent Upon the Board Granting Pastorio Motion 1)—Paper 63, Patent Interference No. 105,995 (SGL), 2014, 29 pages.
Levin Substantive Motion 1 (for Judgment that Pastorio's involved Claims are Indefinite)—Paper 52, Patent Interference No. 105,995 (SGL), 2014, 28 pages.
Levin Substantive Motion 1, filed Jul. 18, 2014 in Patent Interference No. 105,995.
Mandate—Dkt. 57, Fed. Cir. Appeal No. 17-2195, 2018, 1 page.
Notice of Allowance filed on Jul. 12, 2012, in U.S. Appl. No. 13/498,245, 8 pages (Exhibit 2028).
Notice of Allowance, including Notice of Allowability issued in connection with U.S. Appl. No. 13/498,245, Patent Interference No. 105,995 (SGL), dated Jul. 12, 2012, 8 pages (Exhibit 1007).
Notice of Docketing—Dkt. 1, Fed. Cir. Appeal No. 17-2195, 2017, 29 pages.
Oct. 1, 2009 purchase order confirmation; English translation; certifications of Translation, Patent Interference No. 105,995 (SGL), 6 pages (Exhibit 2035).
Oct. 6, 2009 purchase order; Oct. 15, 2009 invoice with stamp of receipt, and Oct. 1, 2009 shipping document; English translations; certification of translation, Patent Interference No. 105,995 (SGL), 9 pages (Exhibit 2036).
Oda et al., "Some Researches on the Chemistry of Dimethyl Sulfoxide and Related Compounds," Bull. Inst. Chem. Res., Kyoto Univ., 47(5): 480-521 (1970) (Exhibit 2006).
Order Denying Petition for Panel Rehearing and Rehearing En Banc—Dkt. 55, Fed. Cir. Appeal No. 17-2195, 2018, 2 pages.
Order Modifying Scheduling Order—Paper 16, IPR2016-00577, 2016, 3 pages.
Order—Authorizing Motion—37 C.F.R. § 41.121(a), filed on Aug. 4, 2015, in Interference No. 105,995 (Paper 155), IPR2016-00577, 4 pages (Exhibit 2006).
Order—Authorizing Motion—37 C.F.R. § 41.121(a)—Paper 155, Patent Interference No. 105,995 (SGL), 2015, 4 pages.
Order—Authorizing Motion—Bd.R. 121(a)—Paper 76, Patent Interference No. 105,995 (SGL), 2014, 4 pages.
Order—Authorizing Opposition—Bd.R. 125(c)(4)—Paper 265, Patent Interference No. 105,995 (SGL), 2016, 4 pages.
Order—Authorizing Surreply—Bd. R. 104(a), filed on Nov. 19, 2015, in Interference No. 105,995 (Paper 252), IPR2016-00577, 6 pages (Exhibit 2014).
Order—Authorizing Surreply—Bd.R. 104(a)—Paper 252, Patent Interference No. 105,995 (SGL), 2015, 6 pages.
Order—Conduct of the Proceeding—37 CFR 42.5(a)—Paper 20, IPR2016-00577, 2016, 8 pages.
Order—Miscellaneous—Bd.R. 104(a)—Paper 114, Patent Interference No. 105,995 (SGL), 2014, 9 pages.
Order—Miscellaneous—Bd.R. 104(a)—Paper 141, Patent Interference No. 105,995 (SGL), 2015, 8 pages.
Order—Miscellaneous—Bd.R. 104(a)—Paper 19, Patent Interference No. 105,995 (SGL), 2014, 4 pages.
Order—Miscellaneous—Bd.R. 104(a)—Paper 20, Patent Interference No. 105,995 (SGL), 2014, 3 pages.
Order—Miscellaneous—Bd.R. 104(a)—Paper 80, Patent Interference No. 105,995 (SGL), 2014, 8 pages.
Order—Motion Times—Bd. R. 104(c), filed on May 30, 2014, in Interference No. 105,995 (Paper 38), IPR2016-00577, 12 pages (Exhibit 2004).
Order—Motion Times—Bd.R. 104(c)—Paper 24, Patent Interference No. 105,995 (SGL), 2014, 7 pages.
Order—Motion Times—Bd.R. 104(c)—Paper 38, Patent Interference No. 105,995 (SGL), 2014, 12 pages.
Order—Oral Argument—Bd. R. 124(a)—Paper 142, Patent Interference No. 105,995 (SGL), 2015, 3 pages.
Order—Oral Argument—Bd. R. 124(a)—Paper 143, Patent Interference No. 105,995 (SGL), 2015, 3 pages.
Order—Oral Argument—Paper 25, IPR2016-00577, 2017, 3 pages.
Order—Priority Times—Bd.R. 104(c)—Paper 146, Patent Interference No. 105,995 (SGL), 2015, 6 pages.
Organic Chemistry: An Advanced Treatise, vol. II, pp. 1726-1739 (Henry Gilman ed., John Wiley & Sons, Inc., 2d ed., 1943), 17 pages (Exhibit 2024).
Overberger et al., "Kinetics and Mechanism of the Oxidation of p,p'-Dichlorobenzyl Sulfide by Hydrogen Peroxide," J. Am. Chem. Soc., 1953, 75(19), 4783-4787 (Exhibit 2014).
Paper 116—Pastorio Reply 1 (for judgment based on no interference-in-fact) filed Dec. 19, 2014 in Interference No. 105,995, IPR2016-00577, 35 pages (Exhibit 1027).
Paper 144—Decision on Motions filed Jun. 26, 2015 in Interference No. 105,995, IPR2016-00577, 28 pages (Exhibit 1028).
Paper 155—Order Authorizing Motion filed Aug. 4, 2015 in Interference No. 105,995, IPR2016-00577, 4 pages (Exhibit 1029).
Paper 175—Levin Motion 4 (for judgment Based on Invalidity of the Pastorio Claims over the Prior Art) filed Aug. 17, 2015 in Interference No. 105,995, IPR2016-00577, 38 pages (Exhibit 1030).
Paper 177—Pastorio Motion 4 (for judgement based on priority) filed Aug. 25, 2015 in Interference No. 105,995, IPR2016-00577, 33 pages (Exhibit 1031).
Paper 1—Declaration of Interference filed Feb. 6, 2014 in Interference No. 105,995, IPR2016-00577, 7 pages (Exhibit 1022).
Paper 21—Levin List of Proposed Motions filed May 7, 2014 in Interference No. 105,995, IPR2016-00577, 6 pages (Exhibit 1023).
Paper 227—Pastorio Opposition 4 filed Oct. 6, 2015 in Interference No. 105,995, IPR2016-00577, 44 pages (Exhibit 1035).
Paper 251—Levin Reply 4 filed Nov. 10, 2015 in Interference No. 105,995, IPR2016-00577, 41 pages (Exhibit 1036).
Paper 25—Pastorio Motion 1 (for judgment based on no interference-in-fact) filed May 23, 2014 in Interference No. 105,995, IPR2016-00577, 25 pages (Exhibit 1024).
Paper 26—Statutory Disclaimer filed on May 23, 2014 in Interference No. 105,995, IPR2016-00577, 2 pages (Exhibit 1025).
Paper 38—Order—Motion Times filed May 30, 2014 in Interference No. 105,955, IPR2016-00577, 12 pages (Exhibit 1026).
Pastorio Contingent Motion 2 (to modify count and obtain benefit)—Paper 57, Patent Interference No. 105,995 (SGL), 2014, 20 pages.
Pastorio Contingent Motion 3 (to add reissue application claims)—Paper 73, Patent Interference No. 105,995 (Sgl), 2014, 36 pages.
Pastorio Contingent Motion 3, filed Jul. 25, 2014 in Patent Interference No. 105,995.
Pastorio et al., "Inter Parties Review Certificate" U.S. Pat. No. 8,304,559, Apr. 29, 2019, 2 pages.
Pastorio List of Proposed Motions—Paper 23, Patent Interference No. 105,995 (SGL), 2014, 3 pages.
Pastorio Miscellaneous Opposition 3—Paper 136, Patent Interference No. 105,995 (SGL), 2015, 10 pages.
Pastorio Motion 1 (for judgment based on no interference-in-fact)—Paper 25, Patent Interference No. 105,995 (SGL), 2014, 25 pages.
Pastorio Motion 4 (for judgment based on priority)—Paper 177, Patent Interference No. 105,995 (SGL), 2015, 33 pages.
Pastorio Opposition 1, filed Oct. 31, 2014 in Patent Interference No. 105,995.
Pastorio Opposition 1—Paper 81, Patent Interference No. 105,995 (SGL), 2014, 34 pages.
Pastorio Opposition 2—Paper 110, Patent Interference No. 105,995 (SGL), 2014, 35 pages.
Pastorio Opposition 3—Paper 229, Patent Interference No. 105,995 (SGL), 2015, 43 pages.
Pastorio Opposition 4, filed on Oct. 16, 2015, in Interference No. 105,995 (Paper 227), IPR2016-00577, 44 pages (Exhibit 2010).
Pastorio Opposition 4—Paper 227, Patent Interference No. 105,995 (SGL), 2015, 44 pages.
Pastorio Opposition to Levin Request for Rehearing—Paper 267, Patent Interference No. 105,995 (SGL), 2016, 11 pages.
Pastorio Reissue Patent Application—Paper 72, Patent Interference No. 105,995 (SGL), 2014, 17 pages.
Pastorio Reply 1—Paper 116, Patent Interference No. 105,995 (SGL), 2014, 35 pages.
Pastorio Reply 2, filed Dec. 19, 2014 in Patent Interference No. 105,995.
Pastorio Reply 2—Paper 117, Patent Interference No. 105,995 (SGL), 2014, 17 pages.
Pastorio Reply 3—Paper 123, Patent Interference No. 105,995 (SGL), 2014, 27 pages.
Pastorio Reply 4—Paper 249, Patent Interference No. 105,995 (SGL), 2015, 34 pages.
Pastorio Statutory Disclaimer in Patent Under 37 C.F.R. § 1.321(a)—Paper 26, Patent Interference No. 105,995 (SGL), 2014, 2 pages.
Pastorio Submission of Transcript of Sep. 29, 2015 Conference Call—Paper 217, Patent Interference No. 105,995 (SGL), 2015, 47 pages.
Pastorio Surreply 4, filed on Nov. 24, 2015, in Interference No. 105,995 (Paper 253), IPR2016-00577, 5 pages (Exhibit 2011).
Pastorio Surreply 4—Paper 253, Patent Interference No. 105,995 (SGL), 2015, 5 pages.
Pastorio's Designation of Real Party-In-Interest—Paper 8, Patent Interference No. 105,995 (SGL), 2014, 2 pages.
Patent Owner Preliminary Response to Petition for Inter Partes Review—Paper 6, IPR2016-00577, 2016, 35 pages.
Patent Owner Response—Paper 19, IPR2016-00577, 2016, 61 pages.
Patent Owner's Corrected Submission of Demonstrative Exhibits for Feb. 14, 2017 Oral Hearing—Paper 28, IPR2016-00577, 2017, 18 pages.
Patent Owner's Notice of Appeal—Paper 32, IPR2016-00577, 2017, 28 pages.
Patent Owner's Request for Partial Rehearing of the Board's Decision Instituting Inter Partes Review—Paper 9, IPR2016-00577, 2016, 18 pages.
Perry's Chemical Engineers' Handbook, Sixth Edition, R.H. Perry et al., eds. McGraw-Hill Book Co. (1984), pp. 4-4 to 4-5, Patent Interference No. 105,995 (SGL), 6 pages (Exhibit 1021).
Petitioner's Demonstratives for Oral Argument on Feb. 14, 2017—Paper 26, IPR2016-00577, 2017, 12 pages.
Petitioner's Reply to Patent Owner Response—Paper 22, IPR2016-00577, 2016, 38 pages.
Petitioner's Request for Partial Rehearing—Paper 10, IPR2016-00577, 2016, 10 pages.
Prosecution history for U.S. Appl. No. 13/498,245, filed Mar. 26, 2012, 450 pages (Exhibit 2027).
Ravikumar et al., "Role of Hexafluoro-2-propanol in Selective Oxidation of Sulfide to Sulfoxide: Efficient Preparation of Glycosyl Sulfoxides," Eur. J. Org. Chem., 1998, 2937-2940 (Exhibit 2020).
Redeclaration—Bd.R. 203(c)—Paper 15, Patent Interference No. 105,995 (SGL), 2014, 3 pages.
Renewed Request for Patent Prosecution Highway and Response to Decision to Dismiss Petition for Patent Prosecution Highway filed in connection with U.S. Appl. No. 13/498,245, Patent Interference No. 105,995 (SGL), Jun. 18, 2012, 5 pages (Exhibit 1004).
Scheduling Order—Paper 8, IPR2016-00577, 2016, 6 pages.
Second Declaration of Barry M. Trost, Ph.D., dated Oct. 31, 2014, filed Oct. 31, 2014 in Patent Interference No. 105,995.
Second Declaration of Barry M. Trost, Ph.D., Patent Interference No. 105,995 (SGL), Oct. 31, 2014, 22 pages (Exhibit 2018).
Second Declaration of Claudia Mora, Patent Interference No. 105,995 (SGL), Sep. 30, 2015, 3 pages (Exhibit 2082).
Second Declaration of Gordon W. Gribble, Ph.D., Patent Interference No. 105,995 (SGL), Jul. 25, 2014, 13 pages (Exhibit 1013).
Second Declaration of Roberto Pellegri, Patent Interference No. 105,995 (SGL), Sep. 30, 2015, 3 pages (Exhibit 2081).
Second Order Modifying Scheduling Order—Paper 18, IPR2016-00577, 2016, 7 pages.
Second Preliminary Amendment filed in connection with U.S. Appl. No. 13/498,245, Patent Interference No. 105,995 (SGL), Jun. 18, 2012, 5 pages (Exhibit 1006).
Second Redeclaration—Bd.R 203(c)—Paper 145, Patent Interference No. 105,995 (SGL), 2015, 4 pages.
Siddiqui et al., "Thiazoles: A Valuable Insight into the Recent Advances and Biological Activities," Int'l J. Pharm. Sci.& Drug Res., 2009; 1(3): 136-143, (Exhibit 2079).
Sigma-Aldrich Charges Summary, Patent Interference No. 105,995 (SGL), May 18, 2010, 1 page (Exhibit 1043).
Sigma-Aldrich Material Safety Data Sheet for Dichloroacetic acid IPR2016-00577, Jun. 19, 2015, 8 pages (Exhibit 2018).
Sigma-Aldrich Material Safety Data Sheet for Dichloromethane, IPR2016-00577, Jun. 28, 2016, 10 pages (Exhibit 2017).
Sixth Declaration of Gordon W. Gribble, Ph.D., filed in Interference No. 105,995 (Levin Exhibit 1044), IPR2016-00577, Aug. 17, 2015, 37 pages (Exhibit 2028).
Sixth Declaration of Gordon W. Gribble, Ph.D., Patent Interference No. 105,995 (SGL), Aug. 17, 2015, 36 pages (Exhibit 1044).
Substituent Effects, Chapter 12: Reactions of Arenes. Electrophilic Aromatic Substitution (McGraw Hill) found at: http://www.mhhe.com/physsci/chemistry/carey/student/olc/ch12substituenteffects.html, Sep. 16, 2015, 6 pages (Exhibit 2078).
Suggestion of Interference Pursuant to 37 C.F.R. § 41.202 filed on Jun. 25, 2013, in U.S. Appl. No. 13/926,389, 40 pages (Exhibit 2032).
Synopsys, Inc. v. Mentor Graphics Corp., No. 2014-1516, 2016 U.S. App. Lexis 2250 (Fed. Cir. Feb. 10, 2016), 26 pages. (Exhibit 2091).
The Merck Index—An Encyclopedia of Chemicals, Drugs, and Biologics, Merck & Co., Inc. p. 3043 (11th ed. 1989), 3 pages (Exhibit 2029).
Thermo Fisher Scientific, meta-Chloroperbenzoic Acid Technical Data Sheet, revision Sep. 26, 2012, 4 pages (Exhibit 1020).
Third Declaration of Gordon W. Gribble, Ph.D., Patent Interference No. 105,995 (SGL), Oct. 31, 2014, 20 pages (Exhibit 1018).
Transcript of Aug. 29, 2014 Deposition of Gordon W. Gribble, Ph.D., filed Oct. 31, 2014 in Patent Interference No. 105,995.
Transcript of Aug. 29, 2014 Deposition of Gordon W. Gribble, Ph.D., Patent Interference No. 105,995 (SGL), 93 pages (Exhibit 1020).
Transcript of Feb. 14, 2017 Oral Hearing—Paper 29, IPR2016-00577, 2017, 45 pages.
Transcript of Oct. 13, 2014 Deposition of Barry M. Trost, Ph.D., Patent Interference No. 105,995 (SGL), 98 pages (Exhibit 1017).
Transcript of Oct. 27, 2015 Deposition of Dennis P. Curran, Ph.D. submitted as Exhibit 1052 in Interference No. 105,995, IPR2016-00577, 158 pages (Exhibit 1037).
Transcript of Oct. 27, 2015 Deposition of Dennis P. Curran, Ph.D., Patent Interference No. 105,995 (SGL), 158 pages (Exhibit 1052).
Transcript of Oct. 27, 2016 Deposition of Dennis P. Curran, Ph.D., IPR2016-00577, 159 pages (Exhibit 1039).
Transcript of Sep. 17, 2015 Deposition of Gordon W. Gribble, Ph.D., Patent Interference No. 105,995 (SGL), 103 pages (Exhibit 1050).
U.S. Appl. No. 13/926,389, filed Jun. 25, 2013, Patent Interference No. 105,995 (SGL), 14 pages (Exhibit 1010).
U.S. Appl. No. 61/363,366, Patent Interference No. 105,995 (SGL), filed Jul. 12, 2019, 22 pages (Exhibit 1012).
Ullman's Encyclopedia of Industrial Chemistry, Chloroacetic Acids, pp. 473-490 (Koenig et al., John Wiley & Sons, Inc., 2014), 18 pages (Exhibit 2025).
Written Opinion of the International Searching Authority issued in connection with PCT International Application No. PCT/IB2011/052304 (the Pastorio PCT), Patent Interference No. 105,995 (SGL), dated Jul. 18, 2014, 8 pages (Exhibit 1005).

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BR112012007362A2 (pt) 2015-09-15
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CN102812009B (zh) 2015-05-13
CA2815338A1 (en) 2012-01-12
CA2815338C (en) 2018-07-31
CN102812009A (zh) 2012-12-05
US8304559B2 (en) 2012-11-06
IT1400666B1 (it) 2013-06-28
IL221005A (en) 2014-07-31
WO2012004692A1 (en) 2012-01-12
BR112012007362B1 (pt) 2017-12-12
EP2477971A1 (en) 2012-07-25
US20120184753A1 (en) 2012-07-19
ITBS20100118A1 (it) 2012-01-08
EP2477971B1 (en) 2014-05-28

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