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(12) United States Patent (10) Patent No.: US 8,916,513 B2 Anderson (45) Date of Patent: Dec USOO891 6513B2 (12) United States Patent (10) Patent No.: US 8,916,513 B2 Anderson (45) Date of Patent: Dec. 23, 2014 (54) DIOXIRANE COMPOUNDS AND USES OTHER PUBLICATIONS THEREOF Adam et al., “Dioxiranes—A New class of Powerful Oxidants.” Acc. (75) Inventor: Kraig Anderson, Burlingame, CA (US) Chem. Res., 1989, vol. 22, pp. 205-211. Curci et al., “Dioxirane oxidations—Taming the reactivity-selectiv (73) Assignee: Empire Technology Development LLC, ity principle.” Pure & Appl. Chem., 1995, vol. 67. No. 5, pp. 811-822. Wilmington, DE (US) Deary et al., “Evidence for cyclodextrin dioxiranes.” Carbohydrate Research, 1998, vol. 309, pp. 17-29. (*) Notice: Subject to any disclaimer, the term of this Deary et al., “Evidence for cyclodextrin dioxiranes. Part 2. Catalytic and enantioselective properties of cyclodextrin dioxiranes formed patent is extended or adjusted under 35 from keto-derivatised hydroxypropyl-cyclodextrins.” Carbohydrate U.S.C. 154(b) by 236 days. Research, 1999, vol. 317, pp. 10-18. Du et al., “Investigation of Physicochemical Properties of Lactam (21) Appl. No.: 13/554,633 Based Bronsted Acidic Ionic Liquids.” J. Phys. Chem. B., 2005, vol. 109, No. 41, pp. 19542-19546. (22) Filed: Jul. 20, 2012 International Search Report and Written Opinion for Intl. Pat. Applin. No. PCT/US2012/025211, mailed on Apr. 17, 2012, 9 pp. (65) Prior Publication Data JLA Limited, OTEX product description, 2011, webpage: http:// www.jla.com/otex, accessed on Jun. 13, 2012. US 2014/O187467 A1 Jul. 3, 2014 Murray et al., "Chemistry of Dioxiranes. 4. Oxygen Atom Insertion into Carbon-Hydrogen bonds by Dimethyldioxirane.” J. Am. Chem. (51) Int. Cl. Soc., 1986, vol. 108, pp. 2470-2472. C07D 317/02 (2006.01) Murray et al., “Dioxiranes—Synthesis and Reactions of CO7D 32L/00 (2006.01) Methyldioxiranes,” J. Org. Chem., 1985, vol. 50, pp. 2847-2853. CO7D 49 I/II3 (2006.01) Russo, A. et al., “Difluorodioxirane.” Angewandte Chemie interna CID 3/30 (2006.01) tional Edition in English, 1993, vol. 32, pp. 905-907. CID 3/20 (2006.01) Sawwan, N. et al., “Generation of mono- and bis-dioxiranes from CID 7/32 (2006.01) 2,3-butanedione.” Journal of Organic Chemistry, 2006, vol. 71, No. 15, pp. 5796-5799. CID 7/26 (2006.01) Singh et al., “Chemistry of Dioxiranes. 21. Thermal Reactions of CID 3/28 (2006.01) Dioxiranes.” J. Org. Chem., 1992, vol. 57, pp. 4263-4270. (52) U.S. Cl. Sung, K., “Substituent effects on stability of oxiranes, OXirenes, and CPC .......... C07D 321/00 (2013.01); C07D491/113 dioxiranes. Can. J. Chem., 2000, vol. 78,562-567. (2013.01); CIID3/30 (2013.01): CI ID3/2096 Wallace et al., “Use of In Situ-Generated Dimethyldioxirane for (2013.01); CI ID 7/3281 (2013.01): CIID Inactivation of Biological Agents.” Environ. Sci. Technol., 2005, vol. 7/3209 (2013.01): CI ID 7/267 (2013.01); 39, pp. 6288-6292. CI ID 3/28 (2013.01) Wilk, K.A. et al. “Synthesis and hydrolysis of chemodegradable USPC ........... 510/499; 510/500; 510/504; 510/505; cationic Surfactants containing the 1,3-dioxolane moiety.” Journal of the American Oil Chemists' Society Jan. 1994, vol. 71, Issue 1. pp. 549/2OO 81-85. (58) Field of Classification Search Wong et al., “Dioxiranes Generated in Situ from Pyruvates and CPC .......... C11D 3/2096; C11D 3/28: C11D 3/30; Oxone as Environmentally Friendly Oxidizing Agents for Disinfec C11D 7/267; C11D 7/3209; C11D 7/3281; tion.” Environ. Sci. Technol., 2006, vol. 40, No. 2, pp. 625-630. CO7D 321/OO USPC ................... 510/499, 500, 504,505; 549/200 * cited by examiner See application file for complete search history. Primary Examiner — Gregory R Delcotto (56) References Cited (74) Attorney, Agent, or Firm — Foley & Lardner LLP U.S. PATENT DOCUMENTS (57) ABSTRACT 5,525,121 A 6, 1996 Heffner et al. A dioxirane-containing compound has a first Substituent that 7.465,411 B2 12/2008 Martin is an alkyl, polyalkoxy, aryl, heteroaryl, or heterocyclyl 7,582,594 B2 9/2009 Delcomyn et al. group, and a second Substituent that is an electron withdraw 20O2/O122775 A1* 9/2002 Reinhardt et al. .............. 424/49 ing group, and where the first and second Substituents can 2007/0219108 A1 9, 2007 Martin optionally join to form a cycloalkyl or heterocyclyl group. FOREIGN PATENT DOCUMENTS The dioxirane-containing compound can be used as an oxi dant, Surfactant, and/or an ionic liquid. EP 1288283 * 3/2003 WO WO-2011/005630 1, 2011 18 Claims, 1 Drawing Sheet US 8,916,513 B2 1. 2 DOXRANE COMPOUNDS AND USES SUMMARY THEREOF The present technology provides for dioxirane oxidants CROSS-REFERENCE TO RELATED which are strong, stable, safe, selective, and effective under a APPLICATIONS broad range of conditions. This is achieved by configuring the dioxirane compounds to include Substituents that render the compound an effective surfactant and/or an ionic liquid. This application claims the benefit of International Appli Compared to conventional oxidants, including known diox cation Serial No. PCT/US2012/025211, filed on Feb. 15, 10 iranes, the present dioxirane oxidants are easier to control and 2012, the entire disclosure of which is hereby incorporated by do not generate undesirable byproducts such as chlorinated reference for all purposes in its entirety as if fully set forth organics. The present technology provides a dioxirane com herein. pounds, compositions including Such dioxirane compounds, and methods of making and using Such dioxirane compounds. FIELD 15 The present technology provides a dioxirane oxidant (Scheme 1) that includes a dioxirane moiety stabilized by an The present technology relates to dioxirane-containing electron withdrawing group (EWG), bonded to a solvating compounds and uses of Such compounds in consumer or group (SG), thus forming a Surfactant and/or an ionic solvent. industrial applications related to cleaning, disinfection, and The SG and EWG are optionally joined ---- as shown. The decontamination, as oxidants, chiral oxidants, Surfactants, dioxirane is readily generated (and regenerated) from a ionic liquids, and combinations thereof. ketone precursor by reaction with peroxymonosulfate (POMS). In certain embodiments, surfactant dioxiranes (e.g., BACKGROUND where the EWG is ionic or non-ionic, the SG is relatively 25 large and hydrophobic, e.g., Ca-C alkyl) provide highly effective oxidants, e.g., for hydrophobic contaminants in The following description is provided to assist the under washwater. In other embodiments, the Surfactant properties standing of the reader. None of the information provided or of these compounds concentrate the dioxirane at the contami references cited is admitted to be prior art to the present nants, even though the average dioxirane concentration in the technology. 30 washwater can remain quite low. In certain embodiments, A wide variety of oxidants are employed for bleaching, ionic liquid dioxiranes (e.g., where the EWG is ionic, the SG cleaning, disinfection, and decontamination, yet they suffer is relatively small, e.g., C-C alkyl) have relatively low vapor from various drawbacks. Some oxidants are harsh, Such as the pressures and large liquid ranges. hypochlorites used in household bleach. Other oxidants, such as hydrogen peroxide, are ineffective at low (i.e., safe) con 35 centrations. Still other oxidants, such as OZone, can be diffi Scheme 1 cult to control at low concentrations, or they can generate undesirable byproducts, such as chlorinated organics from O O- O the use of hypochlorites. 40 ls... ros. X A particularly strong class of oxidants, the peroxymono SG SG sulfate (POMS) salts, such as OxoneR), suffer from the above indicated drawbacks, but can be reacted with ketones to create the relatively selective dioxirane oxidants. Dioxiranes react with a variety of organic Substrates, e.g., by inserting oxygen 45 atoms into carbon-carbon double bonds, which provides a bleaching action and makes the oxidized substrate more Further, both the surfactant and ionic liquid dioxiranes are water-soluble and Susceptible to rinsing. Despite these prac optionally configured as chiral oxidants by selecting a chiral SG or EWG. Their specificity makes them useful in selective tical attributes, dioxiranes have found limited Success as chemical oxidations. The new compounds are useful for agents for cleaning, disinfection, and decontamination. How 50 ever, such dioxiranes, especially those which are volatile, bleaching, cleaning, disinfection and decontamination. may be inconvenient or incompatible for use with typical hot In one aspect, a compound represented by Formula I, or a water washing processes. For example, dimethyl dioxirane salt thereof, is provided: and its corresponding ketone, acetone, are readily Volatilized under typical hot water washing conditions, which may lead 55 to undesirable Volatile organic emissions, flammable vapors, difficulty ensuring sufficient concentrations of dimethyldiox irane for the desired oxidations, or the like. Moreover, high concentrations of volatile dioxiranes, which are effectively cyclic peroxides, are undesirable. As such, dioxiranes such as 60 dimethyldioxirane have not found practical use for consumer or industrial applications related to cleaning, disinfection, In the above Formula I, R' may be an alkyl, alkoxy, poly and decontamination. alkoxy, aryl, heteroaryl, or heterocyclyl group; R is an elec Therefore, there is a need for new dioxirane oxidants which tron withdrawing group; and R' and R can optionally join to are safer, more selective, and more effective under conditions 65 form a cycloalkyl or heterocyclyl group; provided that if R is Such as those required of consumer or industrial applications CF, CFC1, or COR'; then R' is not CH or CF; where R' related to cleaning, disinfection, and decontamination. is H, CH, CHCHCH, CH(CH), or CH-B-cyclodextrin. US 8,916,513 B2 3 4 In another aspect, a compound represented by Formula II, The foregoing Summary is illustrative only and is not or salt thereof, is provided: intended to be in any way limiting.
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