US 2010O227009 A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2010/0227009 A1 Spooner-Hart et al. (43) Pub. Date: Sep. 9, 2010 (54) METHODS AND COMPOSITIONS FOR Publication Classification CONTROLLING PESTS (51) Int. Cl. AOIN 65/00 (2009.01) (75) Inventors: Robert Neil Spooner-Hart, AOIN 35/06 (2006.01) Kurrajong (AU); Albert Habib AOIN3L/4 (2006.01) Basta, Glenwood (AU) AOIN 37/42 (2006.01) AOIN 33/10 (2006.01) Correspondence Address: AOIN 33/24 (2006.01) KNOBBE MARTENS OLSON & BEAR LLP AOIN3L/6 (2006.01) 2040 MAINSTREET, FOURTEENTH FLOOR AOIN 6.5/22 (2009.01) AOIN 65/10 (2009.01) IRVINE, CA 92.614 (US) AOIN 65/12 (2009.01) AOIN 65/04 (2009.01) (73) Assignees: BIOPROSPECT LIMITED, Perth AOIN 65/48 (2009.01) (AU); UNIVERSITY OF AOIP5/00 (2006.01) WESTERN SYDNEY, South AOIP 7/00 (2006.01) Penrith DC (AU) AOIP 9/00 (2006.01) (52) U.S. Cl. ......... 424/742: 514/678; 514/690: 514/689; (21) Appl. No.: 12/782,125 514/685; 514/718; 514/576; 514/646; 514/644; 514/706: 424/725; 424/747; 424/756 (22) Filed: May 18, 2010 (57) ABSTRACT Related U.S. Application Data The present invention is directed to pest-controlling compo sitions comprising as active ingredients one or more f3-di (63) Continuation of application No. 12/134,035, filed on ones, particularly B-diketones and B-triketones, and to the use Jun. 5, 2008, which is a continuation of application No. of these compositions inter alia for preventing, eradicating, 10/477.057, filed on Sep. 23, 2004, now abandoned, destroying, repelling or mitigating harmful, annoying or filed as application No. PCT/AU02/00569 on May 8, undesired pests including insects, arachnids, helminths, mol 2002. luscs, protozoa and viruses. The present invention is further directed to processes of preparing B-diones by de novo syn thesis or from natural Sources Such as Volatile oil-bearing (30) Foreign Application Priority Data plants from families including Alliaceae, Apiaceae, Aster aceae, Cannabinaceae, Lamiaceae, Pteridaceae, Myrtaceae, May 8, 2001 (AU) ...................................... PR 4842 Myoporaceae, Proteaceae, Rutaceae and Zingiberaceae. O O C) O O O O O C) O or C) OCH tasman one angustione dehydroangsutione flawesome O o C) O O O O O O O O O OHC CHO OCHs. O O O leptosperm one isoleptosperm one Jense none agglomerone O O O O O O O O O O O O O C) OCH3 xanthostem one papuanone grandiflorone lateriticone HC) H O C) HCO OCH O O O Cha 3 3 H3CO OCH3 H H3C CH3 H3C CH3 OCH OCH3 OCH OCHs. torquatone isolateriticone O C) O HH OC OCCH3 H3CO OCH3 H3CO OCH3 O O H3C CH3 OCH3 CCH OCH3 O baecked conglomerone Patent Application Publication Sep. 9, 2010 Sheet 1 of 4 US 2010/0227009 A1 O O O O O O O O O O O O O OCH3 tasman one angustione dehydro angsutione flawesone O O O O O O O O O O O O OHC CHO OCH3 O O O leptosperm one isoleptospermone jense none agglomerone O O O O O O O O O O O O O CH O O 3 Xanthostem one papuanone grandiflorone lateriticone HO HO O O HCO O CH O O H3CO OCH 3 3 H3CO OCH3 HC CH H3C CH 3 O CH 3 H3C CH3 O CH OCH3 3. OCH3 3 torquatone isolateriticone O O O O HO OCH HCO OCH3 HCO OCH O O H3C H3C CH3 OCHs OCH3 O CHs O baeckeo conglomerone FIGURE I Patent Application Publication Sep. 9, 2010 Sheet 2 of 4 US 2010/0227009 A1 Abundance TC: 96O1 OO1 D 18OOOOO 17OOOOO 16OOOOO 15 OOOOO 14 OOOOO 13 OOOOO 12OOOOO 1 1 OOOOO 1 OOOOOO 9 OOOOO 8OOOOO 7OOOOO 6 OOOOO 5OOOOO 4OOOOO 3OOOOO 2OOOOO 6 5 1 OOOOO I I I I I I I I I I I I It I, II, A I I I I I I I I I I I I I illI I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I It 8 OO1 OOO12 OO14 OO16 O18O2OOO22 OC24 OC26 OC28 OOBOOCB2. OCB.4 OO Time --> FIGURE 2 Patent Application Publication Sep. 9, 2010 Sheet 3 of 4 US 2010/0227009 A1 H NMR Data (CDC13,500MHz) "H (see below) Signal (ppm) | Integral Signal (ppm) | Integral 19.18 O.89 1845 O.48 3.98 109 3.85 O55 3.96 2.75 3.87 155 1.97 3.00 192 172 134 6.43 1.46 352 115 6.13 117 3.48 FIGURE 3 Patent Application Publication Sep. 9, 2010 Sheet 4 of 4 US 2010/0227009 A1 os-- os HO-le-SeO Os-S-OH -a-e- - e -2 - O CH O CH 3 3 A B C FIGURE 4 US 2010/0227009 A1 Sep. 9, 2010 METHODS AND COMPOSITIONS FOR tones, such as those obtainable from Volatile oil-bearing CONTROLLING PESTS plants including plants from the families Alliaceae, Apiaceae, Asteraceae, Cannabinaceae, Lamiaceae, Pteridaceae, Myrta CROSS-REFERENCE TO RELATED ceae, Myoporaceae, Proteaceae, Rutaceae and Zingiber APPLICATIONS aceae, exhibit significant pesticidal, especially insecticidal, 0001. This application is a continuation of U.S. applica arachnicidal, helminthicidal and/or molluscicidal activity. tion Ser. No. 12/134,035, filed Jun. 5, 2008, which is a con This discovery has been reduced to practice in novel pest tinuation of U.S. application Ser. No. 10/477.057, filed Sep. controlling compositions and methods for their preparation 23, 2004. U.S. application Ser. No. 10/477,057 is the U.S. and use, as described hereinafter. National Phase under 35 U.S.C. S371 of International Appli cation No. PCT/AU02/00569, filed May 8, 2002 designating BRIEF DESCRIPTION OF THE DRAWINGS the U.S. and published in English as WO 02/089587, which 0005 FIG. 1 shows the structures relating to the major claims priority to Australian Patent Application PR 4842, constituents of the published Myrtaceae essential oils. filed May 8, 2001. This application incorporates herein by 0006 FIG. 2 is a representation of a GC-MS trace of E. reference U.S. application Ser. No. 12/134,035, U.S. appli cloeziana oil. cation Ser. No. 10/477.057, International Application No. 0007 FIG. 3 is a tabular and graphical representation PCT/AU02/00569 including the International Publication showing "H NMR data recorded on a fraction (F4) obtained No. WO 02/089587, and Australian Patent Application PR from silica gel chromatography of E. cloeziana oil and the 4842 in their entireties. structure of the major and minor isomers of the compound deduced from these data. FIELD OF THE INVENTION 0008 FIG. 4 is a diagrammatic representation showing 0002 This invention relates generally to methods and various tautomeric forms of an isolated B-triketone com compositions for controlling pests. More particularly, the pound in solution (CDC1). present invention relates to pest-controlling compositions comprising as active ingredients one or more f3-diones, par DETAILED DESCRIPTION OF THE INVENTION ticularly 3-diketones and B-triketones, and to the use of these 0009. One aspect of the present invention contemplates compositions inter alia for preventing, eradicating, destroy the use of a B-dione compound, particularly a 3-diketone or a ing, repelling or mitigating harmful, annoying or undesired B-triketone compound, in the preparation of a composition pests including insects, arachnids, helminths, molluscs, pro for controlling harmful, annoying or undesired pests, said tozoa and viruses. The present invention further relates to processes of preparing B-diones by de novo synthesis or from compound being represented by the general formula (I) natural sources such as Volatile oil-bearing plants from fami lies including Alliaceae, Apiaceae, Asteraceae, Cannabi (I) naceae, Lamiaceae, Pteridaceae, Myrtaceae, Myoporaceae, A B Proteaceae, Rutaceae and Zingiberaceae. Bibliographic details of various publications referred to in this specification are collected at the end of the description. Q BACKGROUND OF THE INVENTION 0003 Triketones have been used for many years as herbi wherein cides for the control of undesired vegetation. Herbicidal trike 0010) A is (C=O)R., (C=S)R, OR, SR (CRNRR), tones have been described, for example, in EP-A-33.8992, C(R)OR, NRRs (C=N Ra)R, N=O, N(EO), EP-A-336898, U.S. Pat. No. 4,869,748, EP-A-186118, EP NROR or SOR: A-186119, EP-A-186120, U.S. Pat. No. 4,202,840, U.S. Pat. 0011 R is selected from H. C-C alkyl, C-C aryla No. 4,695,673, U.S. Pat. No. 4,780,127, U.S. Pat. No. 4,921, lkyl, C-C cycloalkyl, C-Coalkenyl, C-Co heteroaryla 526, U.S. Pat. No. 5,006,150, U.S. Pat. No. 5,545,607, U.S. lkyl, C-C haloalkyl, C-Co dihaloalkyl, C-C triha Pat. No. 5,925,795, U.S. Pat. No. 5,990,046, U.S. Pat. No. loalkyl, C-Co haloalkoxy, C-Co hydroxyalkyl, C-Co 6,218,579, EP-A-249.150, EP-A-137963, EP-A-394889, EP thioalkyl and C-C nitroalkyl, OR, SR (CRNRRs), A-506907 or EP-B-135191. Examples of herbicidal trike NRRs (C=N-R)R N=O, N(=O), NROR, or tones are interalia Sulcotrione (MIKADOR) whose chemical SOR7; designation is 2-(2-chloro-4-methanesulfonylbenzoyl)-1,3- 0012 R is selected from H. C-C alkyl, C-C aryla cyclohexandione, 2-(4-methylsulfonyloxy-2-nitrobenzoyl)- lkyl, C-C cycloalkyl, C-Coalkenyl, C-Co heteroaryla 4,4,6,6-tetramethyl-1,3-cyclohexane dione: 3-(4-methylsul lkyl, C-C haloalkyl, C-Co dihaloalkyl, C-C triha fonyloxy-2-nitrobenzoyl)-bicyclo-3.2.1]octane-2,4-dione; loalkyl, (CRNRRs).