( 12 ) United States Patent

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( 12 ) United States Patent US010294500B2 (12 ) United States Patent ( 10 ) Patent No. : US 10 ,294 , 500 B2 Sato et al. (45 ) Date of Patent: * May 21, 2019 ( 54 ) METHOD FOR PRODUCING (58 ) Field of Classification Search METHACRYLIC ACID AND /OR ESTER None THEREOF See application file for complete search history . (71 ) Applicant: Mitsubishi Chemical Corporation , ( 56 ) References Cited Tokyo ( JP ) U . S . PATENT DOCUMENTS (72 ) Inventors: Eiji Sato , Kanagawa ( JP ) ; Michiko 8 ,241 , 877 B2 * 8 /2012 Burgard C12P 7 / 40 Yamazaki, Kanagawa ( JP ) ; Eiji 435 / 136 Nakajima, Kanagawa ( JP ) ; Fujio Yu , 8 , 501, 455 B2 8 / 2013 Gokarn et al. Kanagawa ( JP ); Toshio Fujita , 203014881 8 / 2003 DiCosimo et al. 2004 / 0076982 Al 4 / 2004 Gokarn et al . Kanagawa (JP ) ; Wataru Mizunashi, 2007 / 0184524 Al 8 / 2007 Gokarn et al . Kanagawa ( JP ) 2008 / 0076167 A1 3 / 2008 Gokarn et al. 2009 /0053783 Al 2 /2009 Gokarn et al . (73 ) Assignee : Mitsubishi Chemical Corporation , 2009 /0130729 A1 * 5 / 2009 Symes .. .. C12P 7 /62 Tokyo ( JP ) 435 / 135 2009 /0275096 AL 11 /2009 Burgard et al . 2010 / 0035314 A1 2 / 2010 Mueller et al. ( * ) Notice : Subject to any disclaimer, the term of this 2011/ 0165640 A17 / 2011 Mueller et al. patent is extended or adjusted under 35 2012 /0077236 AL 3 /2012 Gokarn et al. U . S . C . 154 (b ) by 252 days . 2012 /0276604 AL 11 / 2012 Burgard et al . 2012 /0276605 Al 11/ 2012 Burgard et al . This patent is subject to a terminal dis 2013/ 0065279 A1* 3 / 2013 Burk . C12P 19 / 32 claimer . 435 / 88 (21 ) Appl. No. : 14 /419 ,575 FOREIGN PATENT DOCUMENTS ( 22 ) PCT Filed : Sep. 10 , 2013 CA 2688292 A1 12 /2008 EP 0187680 A2 7 / 1986 0502476 A2 9 / 1992 ( 86 ) PCT No. : PCT/ JP2013/ 005359 2868648 A1 5 / 2015 $ 371 ( c ) ( 1 ) , 54 - 046887 4 / 1979 ( 2 ) Date : Feb . 4 , 2015 ??HE 61- 162191 A 7 / 1986 ( Continued ) ( 87) PCT Pub . No. : WO2014 /038216 PCT Pub. Date : Mar. 13 , 2014 OTHER PUBLICATIONS Office Action dated Jun . 28 , 2016 in Japanese Patent Application (65 ) Prior Publication Data No . 2013 -546110 . US 2015 /0191756 A1 Jul. 9 , 2015 Edwige J . F . Souleyre, et al ., " An alcohol acyl transferase from apple (cv . Royal Gala ) , MPAAT1 , produces esters involved in apple ( 30 ) Foreign Application Priority Data fruit flavor ” , FEBS Journal, vol. 272, No . 12 , 2005 , pp . 3132 -3144 . Sep . 10 , 2012 ( JP ) 2012 - 198840 (Continued ) Sep . 10 , 2012 ( JP ) . 2012 - 198841 Primary Examiner — Suzanne M Noakes Jan . 31 , 2013 ( JP ) 2013 -016947 ( 74 ) Attorney , Agent, or Firm — Oblon , McClelland , Jul. 30 , 2013 ( JP ) . .. .. 2013 - 157306 Aug . 1 , 2013 ( JP ) 2013 - 160300 Maier & Neustadt, L .L . P . Aug . 1 , 2013 ( JP ) .. .. .. .. 2013 - 160301 (57 ) ABSTRACT Aug . 20 , 2013 ( JP ) . .. .. .. .. .. 2013 - 170404 To provide a method for directly and efficiently producing ( 51 ) Int. Cl. methacrylic acid in a single step from renewable raw mate C12P 7 /62 ( 2006 .01 ) rials and / or biomass arising from the utilization of the C12N 9 / 10 ( 2006 . 01 ) renewable raw materials . Further provided is a method for C12N 9 /00 ( 2006 . 01 ) producing methacrylic acid using microbes having the abil C07C 57 / 04 ( 2006 . 01 ) ity to produce methacrylic acid , from renewable raw mate C07C 69 /54 ( 2006 . 01 ) rials and / or biomass arising from the utilization of the C12P 7740 ( 2006 . 01 ) renewable raw materials , as a carbon source and / or energy C12N 9 / 02 ( 2006 .01 ) source . The method for producing methacrylic acid enables (52 ) U . S . CI. methacrylic acid to be safely and easily produced from CPC . .. C12P 7762 ( 2013 .01 ) ; C07C 57 /04 biomass , without using petroleum - derived raw materials , by ( 2013 . 01 ) ; C07C 69 / 54 (2013 .01 ) ; C12N 9 /001 utilizing microbes having the ability to produce methacrylic ( 2013 .01 ) ; C12N 9 / 1029 (2013 . 01) ; C12P 7 /40 acid . (2013 .01 ) ; C12Y 103 /99 (2013 .01 ) ; C12Y 103 / 99003 (2013 . 01) ; C12Y 203 /01084 5 Claims, 7 Drawing Sheets ( 2013 .01 ) Specification includes a Sequence Listing . US 10 ,294 ,500 B2 Page 2 References Cited Database UniProt [ online ] , Accession No . G2UBR1, Definition : ( 56 ) Probable acyl - CoA dehydrogenase, http : // www . uniprot . org / uniprot / GRUBR1, Nov . 16 , 2011 uploaded [retrieved Nov . 27 , 2013 ], pp . FOREIGN PATENT DOCUMENTS 1 - 3 Database UniProt [online ], Accession No . C3J12 , Definition : Isobutyryl 62 -014788 1187 COA dehydrogenase , http : // www .uniprot . org / uniprot / C3J112 , Jun . 01 - 132392 5 / 1989 16 , 2009 uploaded [retrieved on Nov . 27 , 2013 ], pp . 1 - 3 . 5 - 64589 3 / 1993 Database UniProt [ online ] , Accession No . M2XPW5, Definition : 10 - 337185 A 12 / 1998 Acyl- CoA dehydrogenase , http : / /www .uniprot .org / uniprot / 11 - 243957 A 9 / 1999 2004 - 514431 A 5 /2004 M2XPW5, May 1 , 2013 uploaded [ retrieved Nov . 27 , 2013 ] , pp . 2005 - 516622 A 6 / 2005 1 - 3 . 2007 - 54011 A 3 / 2007 Sang -Hyun Pyo , et al. , “ A new route for the synthesis of methacrylic 2009 - 538118 11 / 2009 acid from 2 -methyl - 1 , 3 - propanediol by integrating biotransforma 2010 - 528597 A 8 / 2010 tion and catalytic dehydration ," Green Chemistry , vol . 14 , 2012 , pp . 2011 -519561 A 7 / 2011 1942 - 1948 2011 / 200133 A 10 / 2011 Mark R . Smith , et al . , “ The Utilization of 3 -Mercapto - 2 wo 00 / 32789 A1 6 / 2000 Methylpropionate as Sulphur Source by a Phototropic Bacterium , " WO 2002 /42418 A2 5 /2002 Bioorganic & Medicinal Chemistry , vol. 2 , No . 7 , 1994 , pp . 589 WO 2003 /066872 A1 8 / 2003 593 . WO 2007 /039415 A1 4 / 2007 WO 2007 / 110394 A2 10 / 2007 Jerry Vockley , et al. , “ Mammalian Branched - Chain Acyl -COA WO 2008 / 145737 Al 12 / 2008 Dehydrogenases :Molecular Cloning and Characterization of Recom WO 2009 / 135074 A2 11 / 2009 binant Enzymes, ” Methods in Enzymology, vol. 324 , 2000 , pp . WO 2011 /031897 Al 3 / 2011 241 - 258 WO 2012 / 135789 A2 10 / 2012 Lori A . Maggio - Hall, et al. , “ A Single Acyl- CoA Dehydrogenase Is WO 2013 / 044076 Al 3 / 2013 Required for Catabolism of Isoleucine , Valine and Short - Chain WO WO 2014 / 071289 Al 5 / 2014 Fatty Acids in Aspergillus nidulans, " Fungal Genet Biology , vol . 45 ( 3 ) , Mar . 2008 , pp . 180 - 189 . Ying -Xin Zhang , et al. , “ Genes encoding acyl- CoA dehydrogenase OTHER PUBLICATIONS ( AcdH ) homologues from Streptomyces coelicolor and Streptomyces avermitilis provide insights into the metabolism of small branched J . Michael Shaw , et al. , “ Phosphatidylmonoglucosyl Diacylglycerol chain fatty acids and macrolide antibiotic production ,” Microbiol of Pseudomonas diminuta ATCC 11568” , Journal of Biological ogy , vol . 145 , 1999 , pp . 2323 -2334 . Chemistry , vol. 252 , No. 12 , 1977 , pp . 4395 -4401 . Linda K . Massey , et al. , “ Branched - Chain Amino Acid Catabolism Takashi Yamada, et al. , “ Biodegradation of 2 , 4 ,6 - Tribromophenol in Bacteria ,” Bacteriological Reviews , vol. 40 , No . 1 ., Mar. 1976 , by Ochrobactrum sp . Strain TB01 " , Biosci Biotechnol Biochem , pp . 42 -54 . vol. 72 , No. 5 , 2008 , p . 1264 - p . 1271 . Zuzana Swigonova, et al. , “ Acyl- CoA Dehydrogenases : Dynamic Database Uniprot [online ] , Accession No . Q91513 , < http : / /www . History of Protein Family Evolution , " J . Mol . Evol. , vol. 69 , 2009 , uniprot. org /uniprot / Q91513 .txt ?version = 72) , uploaded on May 29 , pp . 176 - 193 . 2013 , [ retrieved on Jun . 20 , 2016 ] . Kathryn L . Hester , et al . , " Purification of Pseudomonas putida Database Uniprot [online ] , Accession No . G7EWVO , <http : // www . Branched - Chain Keto Acid Dehydrogenase El Component, ” Meth uniprot. org /uniprot /G7EWVO . txt ?version = 7 > , up loaded on Apr. 3 , ods in Enzymology , vol . 324 , 2000 , pp . 129 - 138 . 2013 , [ retrieved on Jun . 20 , 2016 ] . Naoki Kato , “ Progress and Prospect of Bio - process by Metabolic Database Uniprot [online ], Accession No. C1A227 , < http : / /www . Engineering, ” Bio Industry , vol. 29 , No. 5 , 2012 , pp . 17 - 21 . uniprot. org /uniprot / C1A227 . txt? version = 31 > , up loaded on Jul. 24 , U . S . Office Action , U . S . Appl. No. 14 / 405 ,593 , dated Mar . 8 , 2018 , 2013 , [ retrieved on Jun . 20 , 2016 ] . 19 pages . Database Uniprot [online ] , Accession No . J2JOW5, < http : / /www . Cristian Balbontin , et al . , “ VPAAT1 , a Gene Encoding an Alcohol uniprot .org /uniprot / J2JOW5. txt ? version = 5 > , up loaded on Apr. 3 , Acyltransferase , Is involved in Ester Biosynthesis during Ripening 2013 , [ retrieved on Jun . 20 , 2016 ) . of mountain Papaya Fruit " , J . Agric . Food Chem . 2010 , 58 , 5114 Partial Supplementary Search Report dated Jul. 23 , 2015 in Euro 5121 . pean Patent Application No. 13835104 . 4 , filed Sep . 10 , 2013 . Luis Morales - Quintana , et al ., “ Molecular docking simulation analy Natalia Korotkova , et al . , “ Glyoxylate Regeneration Pathway in the sis of alcohol acyltransferases from two related fruit species explains Methylotroph Methylobacterium extorquens AM1” , Journal of Bac their different substrate selectivities ” Molecular Simulation , 38 , 11 , teriology , vol . 184 , No . 6 , Mar . 1 , 2002 , pp . 1750 - 1758 . 912 - 921 . International Search Report dated Dec . 10 , 2013 in PCT / JP2013 / Office Action dated May 15 , 2018 in Chinese Patent Application No . 005359 filed Sep . 10 , 2013 . 201380047196 . 3 with English translation . Toru Nagasawa, et al ., “ Production of acrylic acid and methacrylic Office Action dated Aug. 27 , 2018 in Indian Patent Application No. acid using Rhodococcus rhodochrous J1 nitrilase , ” Applied Micro 595
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