USOO8999419B2
`
`(12) Unlted States Patent
`(10) Patent No.:
`US 8,999,419 B2
`
`Knowles et al.
`(45) Date of Patent:
`Apr. 7, 2015
`
`(54) ENHANCEMENT OF POTATO TUBER
`SPROUTING INHIBITORS USING VARIOUS
`COMBINATIONS OF AGENTS
`_
`Inventors: Llsa Knowles, Pullman, WA (US);
`$31121“ R' Knowles, Pullman, WA
`
`(75)
`
`(52) US. Cl.
`CPC ................ A23B 7/154 (2013.01); A01N 35/02
`(2013.01)
`
`(58) Field of Classification Search
`USPC .................... 426/89, 102, 321, 615, 637, 654
`See application file for complete search history.
`
`(73) Assignee: Washington State University, Pullman,
`WA (US)
`
`(56)
`
`References Cited
`U.S. PATENT DOCUMENTS
`
`( * ) Notice:
`
`Subject to any disclaimer, the term of this
`patent is extended or adjusted under 35
`U.S.C. 15403) by Odays.
`
`.
`(21) APP1~ N°~~
`.
`PCT Filed:
`
`(22)
`
`13/820,183
`
`Sep. 2, 2011
`
`(86)
`
`PCT No.:
`
`PCT/US2011/050286
`
`§ 371 (0(1):
`(2), (4) Date: Mar. 19, 2013
`
`PCT P1111 N05 W02012/031174
`PCT Pub. Date: Mar. 8, 2012
`
`5,129,951 A *
`7/1992 Vaughn et al.
`................ 504/348
`5,139,562 A *
`8/1992 Vanghn et al.
`.
`504/292
`
`5,436,226 A *
`7/l995 Lulaiet al.
`............
`504/291
`5,580,596 A * 12/1996 Winkelmann et al.
`426/321
`
`..........
`5,622,912 A *
`4/1997 Riggle et al.
`504/143
`
`5,635,452 A *
`6/1997 Lulai et al.
`.....
`504/324
`.............. 504/348
`6,855,669 B2 *
`2/2005 Knowles et al.
`2007/0135307 A1
`6/2007 Olson et a1.
`2007/0290062 A1
`12/2007 Forsythe et al.
`2009/0062126 A1
`3/2009 Knowles et al.
`
`* cited by examiner
`
`Primary Examiner 7 Leslie Wong
`(74) Attorney,
`Agent,
`or
`Firm 7 Whitham Curtis
`Chfistofferson & Cooks PC
`
`(87)
`
`(65)
`
`(60)
`
`(51)
`
`Prior Publication Data
`
`(57)
`
`ABSTRACT
`
`US 2013/0183419A1
`
`Jul. 18,2013
`
`.
`
`Related U-S- Application Data
`Provisional application No. 61/379,473, filed on Sep.
`2 2010
`’
`Int. Cl.
`A233 7/154
`A23L 1/216
`A23L 3/34
`A01N 35/02
`
`(2006.01)
`(2006.01)
`(2006.01)
`(2006.01)
`
`Compositions and methods for inhibiting the sprouting of
`potato tubers are provided. The compositions comprise com-
`binations of i) ot,[3-unsaturated aliphatic aldehydes, and
`ketones, C3 to. C14 aliphatic aldehydes and ketones, and/or
`C3 to C7 saturated or unsaturated primary and secondary
`aliphatic alcohols; and 2) conventional sprout Inhibitors, The
`effect of the combinations is additive and/or synergistic, and
`less of the conventional inhibitor is required to achieve the
`same or improved levels of sprout inhibition.
`
`24 Claims, 2 Drawing Sheets
`
`1,4 GROUP, INC.
`1,4 GROUP, INC.
`Exhibit 1001
`Exhibit 1001
`Page 0001
`Page 0001
`
`

`

`US. Patent
`
`Apr. 7, 2015
`
`Sheet 1 012
`
`US 8,999,419 B2
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`1,4 GROUP, INC.
`1,4 GROUP, INC.
`Exhibit 1001
`Exhibit 1001
`Page 0002
`Page 0002
`
`

`

`US. Patent
`
`Apr. 7, 2015
`
`Sheet 2 of2
`
`US 8,999,419 B2
`
`2‘0 a
`a
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`i Ruggetaurbank
`18 "gm WWWWWWWWWWWWWWWW«W W W f
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`Days After Harvest (BAH)
`
`Figure 2A
`
`Russet Burbank Stored 319°C (48°F) from Ql2?/C§2«?l’§?103 {293 days)
`
`
`
`Figure 28
`
`1,4 GROUP, INC.
`1,4 GROUP, INC.
`Exhibit 1001
`Exhibit 1001
`Page 0003
`Page 0003
`
`

`

`1. Field of the Invention
`
`15
`
`SUMMARY OF THE INVENTION
`
`1
`ENHANCEMENT OF POTATO TUBER
`SPROUTING INHIBITORS USING VARIOUS
`COMBINATIONS OF AGENTS
`
`US 8,999,419 B2
`
`2
`
`BACKGROUND OF THE INVENTION
`
`inhibitors that are safe and effective, particularly
`sprout
`sprout inhibitors that are natural compounds, and that do not
`pose a threat to the environment or to the health of humans
`and other species.
`1,4SIGHT® (94.7% DMN:1,4-dimethylnaphthalene) is
`one such natural chemical agent that is also registered for
`sprout control, but it tends to be less effective than CIPC.
`The invention generally relates to using (x,[3-unsaturated
`DMN is naturally produced in potatoes. It is more volatile
`aliphatic aldehydes and ketones, C3 to C14 aliphatic alde-
`than CIPC and thus dissipates from tubers more rapidly than
`10 CIPC. Multiple applications ofDMN are requiredto maintain
`hydes and ketones, and C3 to C7 aliphatic primary and sec-
`season-long sprout inhibition. DMN is vaporized and applied
`ondary saturated and unsaturated alcohols in combination
`as an aerosol into bulk storages. It can be applied any time
`with conventional sprout inhibitors to inhibit sprouting of
`after tubers are placed in the bin but is usually applied later in
`potato tubers, thereby reducing the amount 0f conventional
`the fall or early winter when sprouting potential begins to
`inhibitor that is applied.
`increase. DMN is registered for use at a rate of 1 lb DMN/500
`2. Background of the Invention
`cwt (:20 ppm on a DMN to potato weight basis). Because of
`Following harvest, potato tubers undergo a natural period
`the need for multiple applications of DMN to achieve pro-
`of dormancy during WhiCh sprout growth is inhibited by
`longed inhibition of sprouting, DMN is more costly to use
`endogenous hormones.As tubers emerge from dormancy and
`than CIPC.
`begin to sprout, respiration increases, starch is catabolized to
`Other natural volatile sprout inhibitors have been identi-
`sugars, and weight loss increases. The result is a decrease in 20
`fied. Carvone (derived from caraway seed) is commercially
`quality of tubers destined for fresh and processing markets.
`available for use on potatoes in the Netherlands (Hartmans et
`Hence, inhibition of sprouting through Chemical or physical
`al 1995. The following US patents describe the use of various
`means preserves quality and prolongs the duration ofstorage.
`compounds for the inhibition ofpotato sprout formation: US.
`The sprout inhibitors registered for use on potatoes in the
`United States include ClPC (also known as chlorpropham, 25 Pat. No. 5,436,226 to Lulai, et al. (Jul. 25, 1995) describes the
`Sprout Nip®, etc.), maleic hydrazide (MH), DMN (also
`use of jasmonates, US. Pat. No. 5,635,452 to Lulai et al
`known as dimethylnaphthalene,
`l,4SlGHT®, 1,4SEED®,
`(1997) describes the use of aromatic acids, US. Pat. No.
`1,4SHIP®), DIPN (diisopropylnaphthalene, Amplify®), and
`6,855,669 to Knowles and Knowles (2005) describes the use
`Clove Oil (BiOX-C®; Sprout TorChTM). Except for MH, WhiCh
`of 0t,[3unsaturated aldehydes and ketones, US. Pat. No.
`is applied pre-harvest to actively growing plants, all inhibitors 30 5,580,596 to Winkelmann et al. (Dec. 3, 1996) describes the
`are applied post harvest When tubers are in the storage bin.
`use of rape seed oil and certain long-chain alcohols, either
`CIPC is the most effective and most Widely used potato
`alone or in combination; US. Pat. No. 5,139,562 to Vaughn et
`sprout inhibitor. This chemical agent is most often applied as
`al., (Aug. 16, 1992) describes the use of volatile monoterpe-
`a thermal aerosol fog into potato storages after wound-heal-
`nes (e.g. from eucalyptus, peppermint, spearmint, etc.); and
`ing and prior to sprouting. In the Pacific Northwest, this is 35 US. Pat. No. 5,129,951 to Vaughn et al., (Jul. 14, 1992)
`usually in November or December, before dormancy has
`describes the use of aromatic aldehydes and alcohols. In
`ended. The chemical is fogged into storage at the recom-
`addition, Vokou et al. (1993) have demonstrated that the
`mended rate of 1 lb chlorpropham/600 CWt. One gallon 0f
`essential oils from a multitude of herbs (e.g. sage and rose-
`CIPC aerosol grade will treat 4200 cwt (210 tons) ofpotatoes.
`mary) possess sprout inhibiting activity in potatoes.
`CIPC can inhibit sprouting and extend the storage life of 40
`Despite the promise of these diverse compounds, CIPC
`table-stock and processing potatoes for up to 1 year With two
`remains by far the most effective sprout inhibitor but the
`applications.
`presence of chemical residues on potatoes is of concern glo-
`CIPC is an effective sprout suppressant that has been used
`bally. Therefore, as an alternative to the complete replace-
`in the potato industry for about 40 years and the EPA consid-
`ment of CIPC, a reduction in application rate of CIPC would
`ers it as a group E Chemical (non-carcinogenic). ClPC was 45 be beneficial though this may lead to poor or erratic sprout
`originally registered in the United States as a pre- and pOSt-
`control. In US. Pat. No. 5,622,912 a method for decreasing
`emergence herbicide in 1962 and the EPA has set residue
`CIPC residue via combination with DIPN or DMN is
`limits for potato tubers. Notwithstanding its safety record, the
`described. Supporting data demonstrated that an application
`trend today is to reduce the use of synthetic pesticides in
`rate of 14 ppm CIPC in combination with 56 ppm DMN or
`agriculture in order to reduce residues in the world’s food 50 DIPN resulted in a greater percentage of marketable tubers
`supply. The chemical is continually being scrutinized by the
`compared to 14 or 22 ppm CIPC alone folloWing a storage
`EPA as it is among the three pesticides found in the highest
`period.
`concentrations in the average American diet and constitutes
`over 90% of the total synthetic residues found in US. pota-
`toes (Gartrell et al., 1986). In July 2008, the Environmental 55
`The invention provides compositions and methods which
`Protection Agency (EPA) lowered the residue level on pota-
`permit the use of lower amounts of conventional sprout
`toes from 50 ppm to 30 ppm. Among many European coun-
`inhibitors while maintaining the same, or improved, levels of
`tries, the residue level of potatoes is set at 10 ppm. The
`sprout inhibition. The methods involve the use of combina-
`economic importance of this chemical as a sprout inhibitor to
`the potato industry is illustrated by the fact that it accounts for 60 tions of inhibitors, at least one member of the combination
`amajority ofthe sprout suppressant treatments in many coun-
`being: a C3 to C14 (x,[3-unsaturated aliphatic aldehyde or
`tries and the registrants allocated considerable resources in
`ketone, a C3 to C14 saturated aliphatic aldehyde or ketone; or
`the re-registration of CIPC.While other potential sprout sup-
`a C3 to C7 saturated or unsaturated aliphatic primary or
`pressant agents have been identified (e.g. aromatic aldehydes
`secondary alcohol; and the other member of the combination
`and alcohols, methyl esters of rape oil, carvone, jasmonates,
`65 being a conventional sprout inhibitor.
`spearmint and peppermint oils), none appear as effective as
`According to the present invention (x,[3-unsaturated and
`saturated carbonyl compounds as well as saturated and unsat-
`CIPC. There remains an ongoing need to provide alternative
`1,4 GROUP, INC.
`1,4 GROUP, INC.
`Exhibit 1001
`Exhibit 1001
`Page 0004
`Page 0004
`
`

`

`US 8,999,419 B2
`
`3
`urated primary and secondary alcohols are used in combina-
`tion with reduced application rates of a conventional inhibitor
`such as CIPC to achieve long-term potato sprout control.
`Preliminary studies have shown that unexpectedly, the use of
`trans-2-nonenal followed by CIPC provided sprout control
`for a longer period compared to either compound used alone.
`Thus, the present invention provides methods for inhibiting
`potato tuber sprouts, the methods utilizing a lower dosage
`conventional inhibitor (e. g. CIPC) if one or more of the pres-
`ently disclosed sprout inhibitor compounds is used in various
`types of mixtures or sequential applications with the conven-
`tional inhibitor.
`
`BRIEF DESCRIPTION OF THE DRAWINGS
`
`FIG. 1. Effects of 3-nonen-2-one (3N2) in various combi-
`nations with 2-nonanone on sprouting of Russet Burbank
`tubers. The compounds were applied as described in Example
`1. Tubers were treated for 24 h, removed from treatment
`chambers, and placed at 220 C. to sprout for 3 weeks. Sprout
`fresh weight is expressed as a percentage of control (non-
`treated), which were 100% sprouted.
`FIGS. 2A and B. Treatment with combination of T2N and
`
`CIPC. A, sprout growth in “Russet Burbank” tubers treated as
`indicated with CIPC, trans -2 -nonenal, or trans -2 -nonenal and
`CIPC in sequence; fresh weight of sprouts (g/tuber) at the
`indicated time points. CIPC, 20 mg/kg; T2N, 0.75 mmol/kg;
`B, photo of tubers.
`
`DETAILED DESCRIPTION OF THE PREFERRED
`EMBODIMENTS OF THE INVENTION
`
`The present invention provides combinations of two cat-
`egories of agents to inhibit (e.g. prevent, forestall, slow,
`reverse, or otherwise hinder) sprouting of potato tubers. The
`first category of agents includes one or more of 1) a C3 to C14
`aliphatic aldehyde or ketone; and/or 2) a C3 to C7 aliphatic
`saturated or unsaturated primary and secondary alcohol; and/
`or 3) a C3 to C14 (x,[3-unsaturated aldehyde or ketone. The
`second category of agent
`includes known, conventional
`sprout inhibitors. Use of these two categories in combination
`allows the use of lower amounts of the conventional inhibitor
`
`while achieving substantially the same or improved levels of
`sprout inhibition.
`Suitable C3 to C14 (x,[3-unsaturated aldehydes and ketones
`are described in US. Past. No. 6,855,669, the complete con-
`tents of which are hereby incorporated by reference. Suitable
`C3 to C14 aliphatic aldehydes and ketones and C3 to C7
`aliphatic saturated or unsaturated primary and secondary
`alcohols (which are metabolites ofC3 to C14 (X, B-unsaturated
`aldehydes and ketones) are described in co-pending US.
`patent application Ser. No. 12/186,861 (published as US
`2009-0062126 the complete contents of which are hereby
`incorporated by reference) and are described in detail below.
`The metabolites may be applied directly to potato tubers as
`“first components”, or indirectly as a result of the application
`of C3 to C14 (x,[3-unsaturated aldehydes and ketones parent
`compounds, the metabolites appearing on the tubers as break-
`down products.
`The first category ofagents may be referred to herein e.g. as
`“the compounds described herein”, the “sprout inhibitors
`described herein”, or as the “first” agent, inhibitor, com-
`pound, etc. The second category of agents may be referred to
`e.g. as “known” or “conventional” or “additional” inhibitors,
`or as the “second” agent,
`inhibitor, compound, etc. The
`chemical structure and characteristics of the first inhibitor
`differ from those of the second, conventional inhibitor.
`
`5
`
`10
`
`15
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`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
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`60
`
`65
`
`4
`
`Conventional inhibitors that may be used in the practice of
`the invention include but are not limited to: chlorpropham
`(CIPC), dimethylnaphthalene (DMN), diisopropylnaphtha-
`lene (DIPN), carvone, clove oil, mint oil or other essential
`oils, ethylene gas, etc. Examples of some combinations of
`agents of the invention with conventional agents include but
`are not limited to: trans-2-nonenal plus CIPC; 2-nonanone
`plus MH, 3-decen-2-one plus CIPC, 3-decen-2-one plus
`DMN, 2-decanone plus DIPN, 3-decen-2-one plus clove oil,
`3-nonen-2-one plus CIPC, etc.
`Methods of applying the two categories of inhibitors are
`also provided. Such methods are generally carried out after
`the tubers are harvested, i.e. during storage, although this
`need not always be the case. In some embodiments, maleic
`hydrazide (MH), is also utilized although not as a component
`of a mixture per se. Rather, MH may be applied pre-harvest
`and prior to the post-harvest application of one or more ofthe
`compounds described herein, or prior to the application of a
`mixture of the two categories of inhibitors as described
`herein. In other words, MH may be used in methods involving
`the sequential application of inhibitors but not in e.g. single
`tank mixtures.
`The treatment of tubers with a combination of inhibitors
`
`may be carried out by any suitable method known to those of
`skill in the art. For example, at least one sprout inhibitor as
`described herein and at least one conventional inhibitor may
`be mixed together into a single composition for delivery to the
`tubers. The two are then applied simultaneously, e.g. as a
`single tank mixture. In this embodiment, the sprout inhibitors
`described herein are combined, e.g. with one or more of
`CIPC, DMN, DIPN, carvone, mint, clove, various essential
`oils (but not maleic hydrazide) in a ratio ranging from about
`1 to about 99% well before application.
`Formulations of the sprout inhibitors of the invention
`include but are not limited to: 1) “application mixtures” that
`are prepared by combining two or more inhibitors (e.g. two or
`more commercial products) before application; this embodi-
`ment may be a temporary, short-lived mixture that is made up
`“on the spot” at the time of application, i.e. just before or
`shortly before use; and 2) “pre-application mixtures” which
`are commercial products that are specifically formulated to
`contain two (or more) inhibitors (e.g. CIPC+3D2), and which
`can be purchased off-the-shelf as one product.
`Alternatively, separate preparations of the two categories
`of inhibitors are used and each type of inhibitor is applied to
`the tubers separately (solo application). Exposure of the
`tubers to the separate inhibitor preparations may occur simul-
`taneously or substantially simultaneously, e.g. by simulta-
`neous fogging from two or more sources (e. g. cold or thermal-
`electric, internal combustion or gas fired); by direct spraying;
`or by misting or humidification systems or other commer-
`cially available applications systems; or via tank mixed, co-
`injections from multiple or separate injection systems into the
`same applicator or application system, etc. In some embodi-
`ments, application is not strictly simultaneous, but is substan-
`tially so e.g. one inhibitor is applied and then the second
`inhibitor is applied immediately thereafter, or as soon as is
`practically possible or convenient. In this embodiment, the
`time interval between applications is minimal, e.g. on the
`order of minutes or hours, or at most a few days. Thus,
`exposure of the tubers to the two categories of inhibitors
`overlaps for at least a portion of the exposure period, and
`usually for most of the exposure period.
`Alternatively, the application ofthe two different inhibitors
`may be carried out sequentially, i.e., one inhibitor is applied,
`an interval of time is allowed to lapse, and then the second
`inhibitor is applied. Typically, the timing of the separate
`1,4 GROUP, INC.
`1,4 GROUP, INC.
`Exhibit 1001
`Exhibit 1001
`Page 0005
`Page 0005
`
`

`

`US 8,999,419 B2
`
`5
`
`6
`In some embodiments of the invention, the effect of com-
`bining inhibitors is additive. Alternatively, the effect of using
`a combination of inhibitors may be synergistic in a classical
`sense and the effect is non-additive, i.e. the result of using a
`combination of inhibitors causes a decrease in sprout devel-
`opment (or expressed conversely, an increase in the inhibition
`of sprout formation) that is greater than the sum of the
`decreases that are observed when the inhibitors are used
`
`5
`applications is spaced apart by a week to several weeks, or
`even months (e.g. 1-3 months). In some embodiments, appli-
`cations are planned so that the second application occurs
`approximately when the effects of the first application are
`waning,
`i.e. when sprouts begin to appear on the tubers.
`Alternatively, when the probable duration of the effect of an
`inhibitor is already known, application ofthe second inhibitor
`may be scheduled for a time before sprouting actually begins,
`separately. Generally, the increase in sprout inhibition is in
`e.g. for a time which is a few days or weeks prior to a date
`when sprouts are likely to appear, based on past experience. In 10 the range of from at least about 5 to 100% (or even more)
`some embodiments of sequential applications, a conventional
`greater than would be predicted or expected, based on the
`inhibitoris applied first andan inhibitor as described hereinis
`known level of sprout inhibition that is observed when the
`applied later. Advantages of this strategy include that, by the
`inhibitory agents are used separately. In some embodiments,
`end of storage, very little if any conventional inhibitor residue
`two agents are used, but the invention also encompasses the
`is still present. First category agents include several natural
`15 use ofthree or more (e.g. 4, 5, 6, 7, 8, 9, 10 or more) inhibitors
`products and are relatively non-toxic. Thus, even if residual
`together.
`first agent inhibitor remains, handling and consumption ofthe
`In some embodiments, the first sprout inhibiting agent is an
`tubers is safe. However, the order of application may be
`(x,[3-unsaturated aliphatic aldehyde or an (x,[3-unsaturated ali-
`reversed, i.e. inhibitors described herein are applied first and
`phatic ketone and metabolic breakdown products which
`the application of a conventional inhibitor follows. In either 20 inhibit potato tuber sprouting are formed therefrom. The
`case, the use of two different categories of inhibitors advan-
`metabolic breakdown products include C3 to C14 saturated
`tageously permits the use of lower quantities of conventional
`aliphatic aldehydes, C3 to C14 saturated aliphatic ketones,
`inhibitor.
`C3 to C7 saturated or unsaturated aliphatic primary alcohols;
`Generally, a total of two applications of inhibitor are car-
`and C3 to C7 saturated or unsaturated aliphatic secondary
`ried out. An exemplary embodiment would be utilizing a 25 alcohols. In other embodiments, the breakdown products
`thermal fogging system to apply a conventional inhibitor such
`themselves are used as the first agent.
`as CIPC at a low rate (e.g. 5-8 ppm) within a few weeks (e.g.
`Aliphatic C3 to C14 aldehydes that may be used in the
`2-8 weeks) after potatoes have been transferred post-harvest
`practice ofthe invention generally have the chemical formula
`into storage. After a time interval of from about 30-45 days,
`the agents described herein are applied also using a thermal 30
`fogging system. However, repetitive applications of one or
`both ofthe two categories of sprout inhibitor are also encom-
`passed, e.g. conventional inhibitor may be applied, followed
`by application of at least one inhibitor of the present inven-
`tion, followed by one or more additional applications of at 35
`where R1 is a C2 to C13 branched or unbranched, substi-
`least one inhibitor of the present invention, etc.
`tuted or unsubstituted saturated alkyl or a C2 to C13 branched
`In all embodiments ofthe invention, the first component of
`or unbranched, substituted or unsubstituted unsaturated alk-
`the combination and the second component of the combina-
`enyl. In some embodiments of the invention, the aldehyde is
`tion includes at least one, and may include more than one,
`agent. In other words, a mixture of “first” agents may be 40 110113111311:
`applied as the first component of the combination and a mix-
`ture of “second” agents may be applied as the second com-
`ponent. Ifa plurality ofeither category ofinhibitor is used, the
`plurality may be applied as a single preparation or individu-
`ally from separate preparations.
`According to the invention, when combinations of agents
`are used as described herein, the amount of conventional
`inhibitor that is employed to obtain the same or substantially
`the same level of sprout inhibition (or even greater levels of
`sprout inhibition) is lower than would otherwise be required. 50
`For example, the amount of CIPC that is normally applied WVW
`when used alone is in the range of from about 16 to about
`20'” mg OfCIPC per kg ofpotato tuber5; However, by using
`the methods 0f the invention and combimng the use Of CIPC
`with the use of one or more sprout inhibitors as described 55
`herein, (e. g. when a combination of CIPC and T2N is used),
`the amount of CIPC can be reduced (decreased) to an amount
`or level in the range of from about 1 to about 14 mg/kg; while
`achieving essentially the same level (or an even higher level)
`of sprout inhibition. The amount of e.g. trans-2-nonenal or 60
`3-decen-2-one or other sprout inhibitor described herein that
`where R2 and R3 are C1 to C12 branched or unbranched,
`is used in such combinations is generally in the range of from
`substituted or unsubstituted saturated alkyl or a C1 to C12
`about 0.1 to about 3 mmol/kg of tubers.
`branched or unbranched, substituted or unsubstituted unsat-
`In all embodiments described herein, additional surfac-
`tants or adjuvants which enhance or aid in application and 65 urated alkenyl. R2 and R3 may be the same or different. The
`sum of the carbons in R2+R3 does not exceed 13. In some
`deposition of the agents on the surface of potato tubers may
`embodiments of the invention, the ketone is 2-nonanone,
`also be employed.
`1,4 GROUP, INC.
`1,4 GROUP, INC.
`Exhibit 1001
`Exhibit 1001
`Page 0006
`Page 0006
`
`0
`CI
`Rl/ \H
`
`fi
`C
`45 W \H
`
`or decanal
`
`’
`
`O._
`
`Aliphatic C3 to C14 ketones that may be used in the prac-
`tice of the invention generally have the chemical formula
`
`0
`I
`R /C\R
`3
`
`2
`
`

`

`/\/\/\J\CH
`
`3
`
`or 2-decanone,
`
`US 8,999,419 B2
`
`8
`the breakdown of (x,[3-unsaturated aliphatic aldehydes and/or
`(x,[3-unsaturated aliphatic ketones as described herein. C8 to
`C14 primary alcohols have the general formula
`
`R7/I\H
`
`/\/\/\j\/
`
`10
`
`Aliphatic C3 to C7 primary alcohols that may be used in the
`practice of the invention generally have the chemical formula
`
`15
`
`Where R7 is a C7 to C13 branched or unbranched, substituted
`or unsubstituted saturated alkyl or a C7 to C13 branched or
`unbranched, substituted or unsubstituted unsaturated alkenyl.
`C8 to C14 secondary alcohols have the general formula
`
`OH
`
`A.
`
`R4
`
`where R4 is a C2 to C6 branched or unbranched, substituted or
`unsubstituted saturated alkyl or a C2 to C6 branched or
`unbranched, substituted or unsubstituted unsaturated alkenyl.
`In various embodiments of the invention, the unsaturated C3
`to C7 primary alcohol is
`
`VWOH,
`l-hexanol
`
`NWOH,
`l-heptanol
`
`WVOH, or
`trans-Z-hexen- 1 -ol
`
`WVOH"
`trans-Z-hepten- 1 -ol
`
`The aliphatic C3 to C7 secondary alcohols that may be used
`in the practice of the present invention generally have the
`chemical formula
`
`where R5 and R6 is a C1 to C5 branched or unbranched,
`substituted or unsubstituted i saturated alkyl or a C1 to C5
`branched or unbranched, substituted or unsubstituted unsat-
`urated alkenyl. The sum of the carbons in R5+R6 does not
`exceed 6, R5 and R6 may be the same or different. In one
`embodiment of the invention, the saturated C3 to C7 second-
`ary alcohol is 2-heptanol,
`
`OH
`
`W_
`
`In addition, various C8 to C14 primary and secondary
`alcohols may be used in the practice of the invention. These
`compounds may be provided directly or may be provided via
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`OH
`
`AR8
`
`R9
`
`where R8 is a C1 to C12 branched or unbranched, substituted
`or unsubstituted saturated alkyl or a C1 to C12 branched or
`unbranched, substituted or unsubstituted unsaturated alkenyl;
`and R9 is a C1 to C12 branched or unbranched, substituted or
`unsubstituted saturated alkyl or a C1 to C12 branched or
`unbranched, substituted or unsubstituted unsaturated alkenyl.
`The sum of R8 and R9 is not less than 7 and does not exceed
`13.
`
`Examples of additional compounds that may be used in the
`practice of the invention include but are not limited to the
`following:
`Aliphatic C3 to C14 aldehydes that may be used in the
`practice ofthe present invention include but are not limited to:
`propanal, butanal, pentanal, hexanal, heptanal, octanal,
`4-nonenal, 6-nonenal, decanal, undecanal, dodecanal, tride-
`canal, and tetradecanal.
`Aliphatic C3 to C14 ketones that may be used in the prac-
`tice of the present invention include but are not limited to:
`propanone, 2-butanone, 2-pentanone, 2-hexanone, 2-hep-
`tanone, 2-octanone, 3-octanone, 3-nonanone, 2-decanone,
`3-decanone, 2-undecanone, 2-dodecanone, 2-tridecanone,
`and 2-tetradecanone.
`
`Aliphatic C3 to C7 primary alcohols that may be used in the
`practice ofthe present invention include but are not limited to:
`1-propanol, 1-butanol, 2-buten-1-ol, 1-pentanol, 2-penten-1-
`ol, 1-hexanol, 2-hexen-1-ol, and 1-heptanol.
`Aliphatic C3 to C7 secondary alcohols that may be used in
`the practice of the present invention include but are not lim-
`ited to: 2-propanol, 2-butanol, 2-pentanol, and 2-hexanol.
`Aliphatic C8 to 14 primary alcohols that may be used in the
`practice ofthe present invention include but are not limited to:
`1-octanol, 1-decanol and 2-nonen-1-ol.
`Aliphatic C8 to C14 secondary alcohols that may be used in
`the practice of the present invention include but are not lim-
`ited to: 2-octanol, 2-nonanol, and 2-decanol
`By “substituted” we mean the replacement of hydrogen
`with a monovalent or divalent radical. Suitable substitution
`
`groups include but are not limited to, for example, hydroxyl,
`nitro, amino, imino, cyano, halo, thio, thioamido, amidino,
`imidino, oxo, oxamidino, methoxamidino, guanidino, sul-
`fonamido, carboxyl, formyl, lower alkyl, halo-lower alkyl,
`lower alkoxy, halo -lower alkoxy, lower alkoxyalkyl, alkylcar-
`bonyl, cycloalkyl, heterocycloalkyl, alkylthio, aminoalkyl,
`cyanoalkyl, and the like.
`The application of sprout inhibiting compounds to potato
`tubers is generally known to those of skill in the art. The
`1,4 GROUP, INC.
`1,4 GROUP, INC.
`Exhibit 1001
`Exhibit 1001
`Page 0007
`Page 0007
`
`

`

`US 8,999,419 B2
`
`9
`treatment of potato tubers is described, for example, in U.S.
`Pat. No. 6,855,669 (Knowles et al.), the complete contents of
`which are hereby incorporated by reference. Application is
`typically to bulk potatoes in storage bins, although this need
`not be the case as the compounds may be applied to potatoes
`stored or sorted in any manner, so long as sufficient contact is
`made between the compounds and the potato tubers to inhibit
`sprouting. Application of the compounds to the potatoes may
`be carried out by any of several methods. Generally, the
`compound(s) will be volatilized, e.g. by cold fogging, or at
`high temperature (which utilize various heat sources such as
`gasoline, propane, butane, natural gas, electric, etc.) to create
`a thermal fog, or by atomization, and introduced into storage
`bins e.g. Via the ventilation system. This introduction may be
`a discrete event that is carried out once or multiple times
`throughout the storage period. Alternatively, a slow-release
`mechanism or formulation may be employed in which the
`compound gradually enters the storage area over a longer
`period of time, for example by evaporation from a source
`impregnated with the compound(s). Further, the compounds
`may also be advantageously applied by spraying or misting a
`liquid form of the compound onto the potatoes, or by dipping
`or otherwise coating the potatoes with the compound, either
`prior to, during, or after the potatoes are stored (e.g. between
`storage and boxing or bagging for commercial purposes).
`Such compounds can also be used to coat or impregnate
`consumer containers (such as cardboard boxes, burlap bags,
`plastic bags etc) which typically hold potatoes coming out of
`storage sheds or bins for the express purpose of making
`available the precursor or metabolite compounds to delay
`sprouting in transit and at final destinations (e.g. homes,
`grocery stores, restaurants and other food establishments).
`For such applications, the compounds may also be mixed
`with various other agents known to facilitate the delivery of
`gases, liquids, or gels as appropriate (e.g. emulsifiers, slow
`release agents or matrices and the like). Other means of deliv-
`ering the sprout inhibitors include but are not limited to
`employing tank mixtures of the combination of inhibitors.
`Any delivery method known in the art may be used.
`The timing ofexposure ofthe potatoes to the compounds of
`the invention can be prior to or after emergence from dor-
`mancy.
`The application of the compounds (including mixtures)
`may be carried out only once as described above (i.e. early in
`the storage ofthe potatoes and even prior to sprouting). Alter-
`natively, depending on the factors such as the cultivar, the
`time of harvest of the potatoes, the length of storage of the
`potatoes, the intended use ofthe potatoes, etc. multiple appli-
`cations of the compounds may be made. For example, if the
`potatoes are to be used as seed potatoes, only one application
`may be necessary as the eventual sprouting of the potatoes
`will be desirable. However, if the potatoes are to be stored
`long term (e.g. over the entire winter for distribution in the
`spring or the following summer) multiple applications may be
`made. In this case, the first application will generally be made
`early in the storage process (e.g. at between 4 and 32 weeks
`following harvest