US0093.76569B2 (12) United States Patent (10) Patent No.: US 9,376,569 B2 Cano et al. (45) Date of Patent: Jun. 28, 2016 (54) COLORANT COMPOUNDS DERIVED FROM USPC ........ 514/772.7: 426/540: 524/879; 528/321, GENPIN OR GENPIN CONTAINING 528/327; 435/267 MATERLALS See application file for complete search history. (71) Applicant: ECOFLORA S.A.S., Sabaneta, Antioquia (CO) (56) References Cited U.S. PATENT DOCUMENTS (72) Inventors: Esteban Vargas Cano, Itagui (CO); Luis Fernando Echeverri Lopez, 4,247,698 A 1/1981 Toyama et al. Medellin (CO); Juan Fernando Gil 4,347,356 A 8/1982 Touyama et al. Romero, Medellin (CO); Edwin Andrés (Continued) Correa Garcés, Medellin (CO); Sandra Patricia Zapata Porras, Medellin (CO) FOREIGN PATENT DOCUMENTS CN 101104745 1, 2008 (73) Assignee: ECOFLORA S.A.S., Sabaneta (CO) JP 52-053932 4, 1977 (*) Notice: Subject to any disclaimer, the term of this (Continued) patent is extended or adjusted under 35 U.S.C. 154(b) by 0 days. OTHER PUBLICATIONS (21) Appl. No.: 14/285,325 Paik; J. Agric. Food Chem. 2001, 49, 430-432.* (Continued) (22) Filed: May 22, 2014 Prior Publication Data Primary Examiner — Janet L. Andres (65) Assistant Examiner — Daniel Carcanague US 2014/O35O127 A1 Nov. 27, 2014 (74) Attorney, Agent, or Firm — Sterne, Kessler, Goldstein & FOX PLLC Related U.S. Application Data (60) Provisional application No. 61/826.391, filed on May (57) ABSTRACT 22, 2013, provisional application No. 61/836,072, filed on Jun. 17, 2013. The present disclosure provides colorant compounds and methods of isolation of the colorant compounds derived from (51) Int. C. a reaction of genipin and an amine. The colorant composi C09B 67/54 (2006.01) tions comprise purified compounds (e.g., a purified polymer C09B 23/04 (2006.01) or a purified dimer) obtained from multiple fractioning by C09B 67/22 (2006.01) chromatography of the reaction resulting material. The puri (52) U.S. C. fied polymer or dimer can be used as a colorant by itself or in CPC ............. C09B 23/04 (2013.01); C09B 67/0034 combination with another colorant for imparting color to a (2013.01); C09B 67/0096 (2013.01) food, a drug, a cosmetic, a medical device, and textile prod (58) Field of Classification Search uctS. CPC ........ C09B 67/54; C09B 23/04; C09B 67/22: C09B 67/0034; C09B 67/0096 24 Claims, 38 Drawing Sheets US 9,376,569 B2 Page 2 (56) References Cited ters 28(40):4699-4700, Pergamon Journals Ltd., United Kingdom (1987). U.S. PATENT DOCUMENTS Fujikawa, S., et al., "Brilliant Skyblue Pigment Formation from Gardenia Fruits.” J. Ferment. Technol. 65(4):419-424. 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Juice.” AnalytiCon Discovery, Nov. 14, 2010, 28 pages. Pino, Chala. “Handmade extraction of coloring natural, an alternative FOREIGN PATENT DOCUMENTS ofuse of the biological diversity of Choco, Columbia.” Acta Biologica Colombiana 8(2):95-98, (2003) Abstract. JP 52-053934 4, 1977 Touyama, R., et al., “Studies on the Blue Pigments Produced from JP 55-164625 12, 1980 Genipin and Methylamine. I. Structures of the Brownish-Red Pig JP 57-81466 5, 1982 ments, Intermediates Leading to the Blue Pigments.” Chem. Pharm. JP 57-209958 12/1982 Bull. 42(3):668-673, Pharmaceutical Society of Japan, Japan (1994). JP 61-47167 3, 1986 International Search Report for International Application PCT/ JP 64-22820 1, 1989 IB2013/001854, Eurpean Patent Office, Netherlands, mailed on Oct. JP 5-339134 12/1993 JP T-310O23 11, 1995 24, 2013. JP 8-301739 11, 1996 STN Database Registry Record: CAS Registry No. 1313734-13-2, WO WO 2009/120579 A1 10/2009 entered STN Jul 26, 2011. WO WO 2014/OO1910 A1 1, 2014 STN Database Registry Record: CAS Registry No. 1313734-14-3, WO WO 2014, 188275 A2 11/2014 entered STN Jul 26, 2011. International Search Report for International Patent Application No. OTHER PUBLICATIONS PCT/IB2014/001735, European Patent Office, Rijswijk, Nether lands, mailed Jan. 7, 2015. Park; Agric. Chem. Biotechnol. 2001, 44, 190-193.* Office Action mailed Oct. 1, 2014, from co-pending U.S. Appl. No. Yang; Modern Food Science and Technology, 2008, 24, 352-356.* 13/532,757, inventors, Echeverry, L.F., et al., filed Jun. 25, 2012. Djerassi, C., et al., “Naturally Occurring Oxygen Heterocyclics. IX. STN Database Registry Record: CAS Registry No. 1314879-21-4. Isolation and Characterization of Genipin.” Journal of Organic entered STNAug. 4, 2011. Chemistry 25:2174-2177. American Chemical Society, United States Office Action mailed Apr. 30, 2015, front co-pending U.S. Appl. No. (1960). 13/532,757, inventors, Echeverry, L.F., et al., filed Jun. 25, 2012. Fujikawa, S., et al., "Structure of Genipocyanin G, A Spontaneous Reaction Product Between Genipin and Glycine.” Tetrahedron Let * cited by examiner U.S. Patent Jun. 28, 2016 Sheet 1 of 38 US 9,376,569 B2 U.S. Patent Jun. 28, 2016 Sheet 2 of 38 US 9,376,569 B2 U.S. Patent Jun. 28, 2016 Sheet 3 of 38 US 9,376,569 B2 89"SOI U.S. Patent Jun. 28, 2016 Sheet 4 of 38 US 9,376,569 B2 U.S. Patent US 9,376,569 B2 szogsuookszuosisauudd tw) U.S. Patent Jun. 28, 2016 Sheet 6 of 38 US 9,376,569 B2 00: 09: U.S. Patent Jun. 28, 2016 Sheet 7 Of 38 US 9,376,569 B2 s |-|--|--|--|-- U.S. Patent Jun. 28, 2016 Sheet 8 of 38 US 9,376,569 B2 F.G. 8 U.S. Patent Jun. 28, 2016 Sheet 10 of 38 US 9,376,569 B2 sagie: A342 , w -xxis'' 8 S is: 3 8 6. i: 3C part ses irg gaixa 8: i. 'S 8 : 6) i 2 8 S3 i 3C opin gigstycs R::::: RC:C: Fis - (sig-Eig- side C iša-Šs scia C is 88 -: AES38 -88. eiercaroratic lysoxy:E-3- -SSR Castoxylic acid RC Sri Ri: C-8 sets CR sexide Suitone C-SC-R C-C-R ise RCORs Aikyne R&CS E. 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