US009131719B2

(12) United States Patent (10) Patent No.: US 9,131,719 B2 Backes et al. (45) Date of Patent: *Sep. 15, 2015

(54) USE OF CERTAIN NEOFLAVONOIDS FOR (56) References Cited INTENSIFYING AND/OR PRODUCINGA SENSORY MIPRESSION OF SWEETNESS U.S. PATENT DOCUMENTS 7,005,146 B2* 2/2006 Lee ...... 424,725 (75) Inventors: Michael Backes, Holzminden (DE); 2008. O1769 12 A1 7/2008 Kuo et al. Tobias Vössing, Beverungen (DE); 2008/0305.052 A1 12/2008 Ley et al. Jakob Peter Ley, Holzminden (DE); 2010. 0233102 A1 9/2010 Krammer et al. Susanne Paetz, Höxter (DE) 2011 0160311 A1* 6/2011 Prakash et al...... 514,777 (73) Assignee: SYMRISE AG, Holzminden (DE) FOREIGN PATENT DOCUMENTS DE 27.01280 A1 7, 1978 (*) Notice: Subject to any disclaimer, the term of this EP 2298 084 A1 3, 2011 patent is extended or adjusted under 35 OTHER PUBLICATIONS U.S.C. 154(b) by 198 days. R.S.J. Keast and P.A.S. Breslin. An overview of binary taste-taste This patent is Subject to a terminal dis interactions. Food Quality and Preference 14 (2002) 111-124.* claimer. Li Hongfang, Ma Qingyun, Liu Yuqing, Qian Jinfu, Zhou Jun & Zhao Youxing. Chemical Constituents from Polygonum perfoliatum. Chin J Appl Environ Biol. 2009, 15(5): 615-620.* (21) Appl. No.: 13/616,134 Abu T.M. Serajuddin. Salt formation to improve drug solubility. Advanced Drug Delivery Reviews 59 (2007) 603-616.* (22) Filed: Sep. 14, 2012 Property prediction cpds 7 and 8 from “Drug Relevant Properties Predictor' found online Oct. 27, 2014 from the site: http://www. (65) Prior Publication Data rdchemicals.com/drug-relevant-properties.html. Roelens F. et al., “Regioselective synthesis and estrogenicity of (+/-)- US 2013/OO84252A1 Apr. 4, 2013 8-alkyl-5,7-dihydroxy-4-(4-hydroxyphenyl)-3,4- dihydrocoumarins”, European Journal of Medicinal Chemistry Edi tions Scientifique Elsevier, Paris, FR, vol. 40, No. 10, 2005, pp. 1042-1051, XPO27857667. Related U.S. Application Data European Search Report, European Application No. 11 181511.4. (60) Provisional application No. 61/535,127, filed on Sep. dated Jun. 13, 2012. 15, 2011. * cited by examiner (30) Foreign Application Priority Data Primary Examiner — Frederick Krass Assistant Examiner — Michael P Cohen Sep. 15, 2011 (EP) ...... 11 181511 (74) Attorney, Agent, or Firm — Novak Druce Connolly Bove + Quigg LLP (51) Int. Cl. A2.3L I/236 (2006.01) (57) ABSTRACT A6 IK 47/22 (2006.01) The present invention primarily relates to the use of one or a A6 IK 8/49 (2006.01) plurality of neoflavonoids of formula (I) and/or one or a A61O 19/00 (2006.01) plurality of physiologically acceptable salts of one or a plu A2.3L. I./22 (2006.01) rality of neoflavonoids of formula (I) for producing a sensory A2.3L. I./226 (2006.01) impression of Sweetness (i.e. an impression of Sweetness) in CO7D 3L/20 (2006.01) an orally consumable preparation or for intensifying the sen C07C 57/52 (2006.01) sory impression of Sweetness of an orally consumable prepa C07C 57/60 (2006.01) ration comprising at least one further Sweet-tasting and/or C07C 57/64 (2006.01) Sweet-smelling Substance. The present invention further (52) U.S. Cl. relates to certain semifinished products and certain orally CPC ...... A23L I/2363 (2013.01); A23L I/22091 consumable preparations containing one or a plurality of (2013.01); A23L I/22657 (2013.01); A23L neoflavonoids of formula (I) and/or one or a plurality of I/22671 (2013.01); A61K 8/498 (2013.01); physiologically acceptable salts of one or a plurality of A61K47/22 (2013.01); A61O 19/00 (2013.01); neoflavonoids of formula (I). Finally the invention also C07C 57/52 (2013.01); C07C 57/60 (2013.01); relates to a method of producing an orally consumable prepa C07C 57/64 (2013.01); C07D 311/20 (2013.01) ration and a method of producing and/or intensifying a sen (58) Field of Classification Search sory impression of Sweetness in/of an orally consumable None preparation. See application file for complete search history. 14 Claims, No Drawings US 9, 131,719 B2 1. 2 USE OF CERTAIN NEOFLAVONOIDS FOR Sweetness effect (strong Sweet aftertaste, e.g. saccharin, INTENSIFYING AND/OR PRODUCINGA Sucralose, Stevioside, rebaudioside, neotame, advantame, SENSORY IMPRESSION OF SWEETNESS Superaspartame). Therefore it is desirable to find (Sweet) substances that The present invention primarily relates to the use of one or 5 have or impart an intensive Sweet taste similar to cane Sugar a plurality of neoflavonoids of formula (I) defined hereunder and furthermore are stable and/or can be used widely, prefer and/or one or a plurality of physiologically acceptable salts of ably in orally consumable preparations. one or a plurality of neoflavonoids of formula (I) defined Another possibility for lowering the caloric content of hereunder for producing a sensory impression of Sweetness foodstuffs or beverages—without the use of normutritive (i.e. an impression of Sweetness) in an orally consumable 10 Sweeteners—consists of reducing the Sugar content of foods preparation or for intensifying the sensory impression of and/or semi-luxury food products and adding sensorily Sweetness of an orally consumable preparation comprising at weakly perceptible or imperceptible substances, which inten least one other Sweet-tasting Substance. The present invention Sify the Sweetness indirectly or directly, as described e.g. in further relates to certain semifinished products and certain 15 WO 2005/041684. orally consumable preparations containing one or a plurality Such substances of natural origin (pyridinium betaines) are of neoflavonoids of formula (I) and/or one or a plurality of described in EP 1 291 342; however, they do not influence physiologically acceptable salts of one or a plurality of Sweet taste selectively, but also other tastes such as umami or neoflavonoids of formula (I). Finally the invention also saltiness. Moreover, the Substances disclosed can only be relates to a method of producing an orally consumable prepa purified at high cost and/or are difficult to produce syntheti ration and a method of producing and/or intensifying a sen cally. sory impression of Sweetness in/of an orally consumable The use of hesperetin is recommended in WO 2007/ preparation. 014879 A1 and phloretin is recommended in WO 2007/ Foods and semi-luxury food products that have a high 107596 A1 as an intensifier of the sweet taste of reduced Sugar content (mainly Sucrose (Saccharose), lactose, glu 25 Sugar preparations used for nutrition or for pleasure. cose or fructose or mixtures thereof), are as a rule greatly However, the comparatively low level of intensification of preferred by consumers on account of their sweetness. How Sweetness in foods and semi-luxury food products that con ever, it is generally known that a high content of carbohy tain high proportions of proteins, in particular denatured pro drates that can be easily metabolized causes a large rise in teins or polysaccharides, e.g. yoghurt products, is sometimes blood Sugar level, leads to the formation offat depots and can 30 a disadvantage when using hesperetin and phloretin. More ultimately lead to health problems such as overweight, obe sity, insulin resistance, adult-onset diabetes and the sequelae over, hesperetin also has the drawback that it is not suffi thereof. In particular, a further complication is that many of ciently effective in very acidic and carbonized applications the aforementioned carbohydrates can additionally have an Such as lemonades or cola beverages. adverse effect on dental health, as they are degraded by cer 35 Therefore it is also desirable to find a possible way of tain types of bacteria in the oral cavity, for example to lactic lowering the content of Sweet compounds, in particular acid, and can attack the enamel of juvenile or adult teeth Sweet-tasting compounds in orally consumable preparations, (caries). while the impression of Sweetness remains the same, so that Therefore it has long been an aim to reduce the Sugar reduced-Sugar preparations are obtained. In particular, there content of foods and/or semi-luxury food products as much as 40 is a need for agents that intensify a given impression of possible, and the preferred aim is to achieve this reduction Sweetness, in particular even beyond a purely additive effect. with the minimum possible decrease in the impression of Accordingly, the primary aim of the present invention was Sweetness. A corresponding measure consists of the use of to find substances (individual substances or mixtures of sub Sweeteners: these are chemically homogeneous Substances, stances) that can produce an impression of Sweetness (i.e. which themselves have no or only a very slight calorific value 45 have intrinsic Sweetness) and/or can intensify the impression and at the same time produce a strong impression of Sweet of sweetness of other sweet substances. taste; the Substances are as a rule noncariogenic (a review is Furthermore, corresponding orally consumable prepara given e.g. in Journal of the American Dietetic Association tions should be provided, for which the impression of sweet 2004, 104 (2), 255-275). The so-called bulk sweeteners such ness is produced by these Substances or whose impression of as Sorbitol, mannitol or other Sugar alcohols are admittedly 50 sweetness is intensified by these substances while the con Sometimes excellent Sweeteners and can also partially replace centration of other Sweet compounds, in particular Sweet the other food-processing properties of Sugars, but ifingested tasting compounds, is largely unaltered, or for which, while too often, lead in a certain segment of the population to the impression of Sweetness remains the same, the content of osmotically-induced digestive problems. The normutritive, other compounds producing an impression of Sweet taste is highly intensive Sweeteners are very Suitable, owing to the 55 low concentration at which they are used, for imparting decreased, preferably with no or only slight negative sensory sweetness to foodstuffs. A number of these sweeteners are side-effects. not, however, of natural origin (sucralose, cyclamate, In particular, the Substances imparting the required impres acesulfame-K, saccharin, aspartame), display taste-related sion of Sweetness or intensifying the impression of Sweetness problems because of different time-intensity profiles com 60 should preferably be effective even at low concentrations. pared to Sugar (e.g. Sucralose, Stevioside, cyclamate), a bitter Moreover, the required substances should be usable as widely and/or astringent aftertaste (e.g. acesulfame-K, Saccharin, as possible, i.e. it should be possible to incorporate them in Stevioside, rebaudioside), pronounced additional flavor many different orally usable application forms and product impressions (e.g. glycerrhizinic acid ammonium salt). Some forms and should correspondingly be combinable and com of the Sweeteners are not particularly heat-resistant (e.g. thau 65 patible with many different orally consumable base sub matin, braZZein, monellin), are not stable in all applications stances, auxiliaries, carriers, additives and/or active Sub (e.g. aspartame) and are sometimes very long-lasting in their StanceS. US 9, 131,719 B2 3 4 The primary aim of the present invention is achieved by It was found, Surprisingly, that the neoflavonoids of for using one, two or a plurality of different compounds of for mula (I) to be used according to the invention, mixtures mula (I) thereof and/or salts thereof (in each case as defined above) can themselves produce an impression of Sweetness, for example in preparations intended (i.e. suitable) for direct

(I) consumption, or significantly and markedly intensify the impression of Sweetness of other Sweet-tasting Substances and of orally consumable preparations that contain one or a 10 plurality of Sweet-tasting Substances, for example an aqueous Sucrose solution. Surprisingly, it was also found that, even at very low con centrations, the neoflavonoids of formula (I) to be used 15 according to the invention, mixtures thereof and/or salts thereof (in each case as defined above) can greatly intensify the Sweet taste or the Sweet taste quality of Sweet-tasting (NOTE: The figures “5” and “7” indicate positions C5 or C7 Substances in orally consumable preparations according to of the compound.) the invention (preferably preparations to be used for nutrition, O oral hygiene or pleasure or cosmetic preparations for appli one, two or a plurality of different physiologically acceptable cation in the region of the head). salts of one, two or a plurality of different compounds of The neoflavonoids of formula (I) to be used according to formula (I), the invention, mixtures thereof and/or salts thereof (in each O 25 case as defined above) can in particular be used for influenc a mixture of one, two or a plurality of different compounds of ing the strength of taste impressions, wherein formula (I) with one, two or a plurality of different physi the impression of Sweet taste of a Sweet-tasting Substance or ologically acceptable salts of one, two or a plurality of mixture of Substances is intensified different compounds of formula (I), 30 and/or wherein the impression of Sweet taste of a Substance or mixture of E either denote in each case OH or both E together denote an Substances that is both Sweet and unpleasant tasting, in O, particular bitter tasting, is intensified and the unpleasant, in R1, independently of the other residue R1 in each case, 35 particular bitter, taste impression of the Substance or mix denotes hydrogen or OR, wherein R is hydrogen, C1-C5 ture of substances that is both Sweet and unpleasant tasting, alkyl or C2-C5 alkenyl, in particular bitter tasting is reduced or masked. R2, independently of the other residues R2, denotes hydrogen In our own research it has moreover been demonstrated or OR, wherein R is hydrogen, C1-C5 alkyl or C2-C5 that the meaning of the residue R3 and its position at C7 in alkenyl, 40 formula (I) is important for the effects found for the com wherein optionally two directly adjacent residues R1 and/or pounds to be used according to the invention, particularly for R2 together represent a group OCHO, the Sweetness intensifying action, in particular for the Sweet and ness intensifying action of a Sweet-tasting Substance or mix R3 denotes a residue OR, wherein R is C1-C5 alkyl or 45 ture of Substances. It was observed that compounds that are C2-C5 alkenyl, not to be used according to the invention, which have a resi for producing an impression of Sweetness in an orally con due corresponding to the residue R3 not at position C7, but Sumable preparation or for influencing the strength of the with otherwise identical structure for example at position C5, impression of Sweetness of Sweet Substances or mixtures of 50 display a significantly smaller Sweetness intensifying action Substances or of Substances or mixtures of Substances that than the neoflavonoids of formula (I) to be used according to are both, Sweet and unpleasant, preferably bitter, tasting. the invention (cf. practical example la-1 given below). A “sweet substance or mixture of Sweet substances' It was also found in our own research that the neofla means, in the context of the present invention, Substances and 55 vonoids of formula (I) to be used according to the invention, mixtures of Substances producing a sensory impression of mixtures thereof and/or salts thereof (in each case as defined Sweetness, in particular Sweet-tasting Substances or mixtures above) in addition can alter and mask unpleasant taste notes, of Substances. and in particular have bitterness-masking properties (cf. prac The present invention preferably relates to the use of the 60 tical example 1b given below). neoflavonoids of formula (I) to be used according to the "Mask or masking' means, in the context of the present invention, mixtures thereof and/or salts thereof (in each case text, a reduction, i.e. a decrease, or a complete Suppression. as defined above) for intensifying the Sweet taste of a Sweet The altering or masking of the unpleasant taste impression tasting Substance, in particular the impression of sweetness of 65 therefore regularly means in consequence an improvement of an orally consumable preparation comprising at least one taste, in particular with respect to bitter, astringent and/or other Sweet-tasting Substance. metallic taste impressions. US 9, 131,719 B2 5 6 The configuration on the chiral carbon atom of the com R3 is selected from the group consisting of pounds of formula (I) (i.e. at the position marked with 66: 1. the above formula (I)) can be (R) or (S). This also applies to w w w w the following account and to the structural formulas given 5 v O , O CH3 w O below of the compounds to be used according to the inven - NCH, ux N1 ux N-1Nchi, tion. The compounds of formula (I) can, in preferred configu j-N-n-"w cas" rations, be combined together as pure enantiomers or as mix 10 tures of enantiomers in any desired ratio to one another. In a CH3 CH w preferred configuration, the compounds of formula (I) are w , -O CH3 used in the form of racemic mixtures, i.e. as racemates. ->y O CH ux , SkCH3 Preferably R1 and R2 mean, independently of the respec 15 , CH3 tive other residue R1 and R2, hydrogen, hydroxyl or a residue selected from the group consisting of -> O n-N- CH3. w CH3 w w - O NCH, ux O N1 CH3 -w ... O N-1\ch, Preferred, according to the invention, is the aforemen

w tioned use, wherein one, two, a plurality of or all of the 3-N-N-" >N’" 25 compounds used are selected in each case from the group CH consisting of the compounds of formula (I) and physiologi cally acceptable salts thereof, CH w w , -O CH3 wherein ux-os-Ni CH - , K CH E each denote OH or both E together denote oxygen, y CH3 R1, independently of the other residue R1 in each case, denotes hydrogen or hydroxyl, O CH3, R2, independently of the other residues R2, denotes hydro -> n-N- gen, hydroxyl, methoxy, ethoxy, n-propoxy, iso-propoxy, w CH3 n-butoxy, iso-butoxy, tert-butoxy or OR, wherein R is C5-alkenyl, and in its turn R' preferably denotes prenyl, wherein the dashed line marks the bond that joins the residue to the adjacent carbon atom in formula (I). 40 wherein optionally two directly adjacent residues R2 together Preferably R3 means a residue selected from the group represent a group OCHO, consisting of R3 denotes methoxy, ethoxy, n-propoxy, iso-propoxy, n-bu toxy, iso-butoxy, tert-butoxy or OR, wherein R is 45 C5-alkenyl, and in its turn R preferably denotes prenyl, , O , O CH, , --O ux NCH, ux N1 ux N1)-chi, wherein preferably one or a plurality of the residues R1 or R2 denote a hydroxyl group.

w 50 The compounds to be used according to the invention of 3-N-N-" >N’" formula (I) can, depending on the meaning of E. correspond CH CH3 w to the following structural formulas (I-A) or (I-B), wherein W , -O CH3 R1,R2 and R3 in each case have the meaning given above: ->y O CH3 ux , SkCH3 55 y CH3 (I-A) -> O n-n CH3, w CH 60 R2 : wherein the dashed line marks the bond that joins the residue to the adjacent carbon atom in formula (I). R3 Preferably, for the compounds of formula (I): 65 R1 denotes H or OH, and US 9, 131,719 B2 8 -continued Another aspect of the present invention relates to the use of (I-B) a mixture of Substances comprising one or a plurality of O compounds of formula (I-A1) and one or a plurality of com HO pounds of formula (I-A2), and/or physiologically acceptable HO R1 salts thereof.

R2 : R2 In a particularly preferred configuration, the following applies to the compounds of formula (I) and (I-A): E each denote OH or both E together denote oxygen, R3 R2 R2 R1 10 R1 denotes H, R2 R2 R2, independently of the other residues R2, is selected from the group consisting of hydrogen, hydroxyl, methoxy, Depending on the pH, the lactone ring of the compound of ethoxy, n-propoxy, iso-propoxy, formula (I-A) can be opened and the compound of formula 15 wherein optionally two directly adjacent residues R2 together represent a group OCH2O, (I-A) can be in equilibrium with the corresponding “open R3 is selected from the group consisting of methoxy, ethoxy, chain compound of formula (I-B), as shown Schematically n-propoxy and iso-propoxy, 20 and wherein in some preferred compounds of formula (I) or below, wherein M" denotes a (preferably physiologically (I-A) one or a plurality of the residues R2 denote a acceptable) oppositely charged cation (and wherein the oppo hydroxyl group. sitely charged cation preferably has the meaning given In Some cases, the use of one or a plurality of compounds of formulas (1)–(4), physiologically acceptable salts and/or mix below): tures thereof, is preferred according to the invention.

O O M

O R1 OH O R2 : R2 R1 R2 : R2

R2 R2 R2 R1 R2 R2 R2 R2 (I) (Ic)

40 For the case when at least one of the two residues R1 in formula (I) denotes a hydroxyl group, depending on the (1) 45 (foodstuff) matrix and its pH in particularin media or matri O ces with weakly acid pH in most cases an equilibrium can be observed between the substances of formula (I-A1) and 50 No Cry o1 (I-A2).

O

O OH OH O :

R2 R2 R2 : R2

R3 R2 R2 R1 R3 R2 R2 R2 R2 (I-A1) (I-A2) US 9, 131,719 B2 9 10 -continued R3 denotes methoxy, ethoxy, n-propoxy, iso-propoxy, n-bu (2) toxy, iso-butoxy, tert-butoxy or OR, wherein R is O C5-alkenyl, and in its turn R preferably denotes prenyl, and physiologically acceptable salts thereof, O 5 wherein preferably one or a plurality of the residues R2 denote a hydroxyl group. Also preferable is the use of compounds of formula (II-A),

No o1 10 (II-A) (3) O

O 15

No O o1

(4) O O of a salt of a compound of formula (II-A) O O 25 of a mixture of two or a plurality of different compounds of formula (II-A), two or a plurality of different salts of compounds of formula (II-A) or of one or a plurality of No O o1 different compounds of formula (II-A) and one or a plurality of different salts of one or a plurality of differ 30 ent compounds of formula (II-A), wherein (1) (4S)-7-methoxy-4-(4-methoxyphenyl)chroman-2-one R2, independently of the other residues R2, denotes hydro (2) (4R)-7-methoxy-4-(4-methoxyphenyl)chroman-2-one gen, hydroxyl, methoxy, ethoxy, n-propoxy or iso-pro (3) (4S)-5,7-dimethoxy-4-(4-methoxyphenyl)chroman-2- 35 poxy, preferably H, OH, OCH or OCHCH O wherein optionally two directly adjacent residues R2 together (4) (4R)-5,7-dimethoxy-4-(4-methoxyphenyl)chroman-2- represent a group OCHO, O R3 denotes methoxy, ethoxy, n-propoxy, iso-propoxy, n-bu For the case when in an individual case there is a discrep ancy between the chemical nomenclature given above and the toxy, iso-butoxy, tert-butoxy or OR, wherein R is structural formula shown in each case for the compounds of 40 C5-alkenyl, and in its turn R preferably denotes prenyl, formulas (1) through (4) preferably to be used according to particularly preferably denotes methoxy, ethoxy and the invention, the structural formula applies. n-propoxy, In addition, generally compounds of formula (I) are pref wherein preferably one or a plurality of residues R2 denote a erably used according to the invention that are in each case hydroxyl group. selected from the group consisting of compounds of formula 45 The configuration on the chiral carbon atom (i.e. at the position marked with “*” in the above formulas (II) and (II) (II-A)) can in each case be (R) or (S). Preferably a compound of formula (II) or a compound of formula (II-A) has a total of one, two, three or four hydroxyl (II) 50 groups, particularly preferably a total of one or two hydroxyl groups. It is particularly preferable according to the invention to use one or a plurality of compounds of formulas (5)-(26) and/or physiologically acceptable salts thereof 55 (5)

60 wherein E each denote OH or both E together denote oxygen, R2, independently of the other residues R2, denotes hydro gen, hydroxyl, methoxy, ethoxy, n-propoxy or iso-pro OH poxy, preferably H, OH, OCH or OCHCH 65 wherein optionally two directly adjacent residues R2 together represent a group OCH2O, US 9, 131,719 B2 12 -continued -continued (6) (12) O O

O

'', F.

No O OH 10 N-1 no OH (13)

(7) 15 O

O 1No OH OH (14) No o1

25 (8) O 1No Ol OH O (15) 30 OH No O o1 35

(9) (16) O O

40 O O O O OH No o1 45 No '',OCOH (17) O (10) O O 50 O F. OH Crys No OH No O o1 55 (18) O (11) O 60 O O

65 US 9, 131,719 B2 13 14 -continued -continued (19) (26) O O

O O

* O '',OC N OCl. 10 1no OH (20) O (5) (4S)-5,7-dimethoxy-4-(4-methoxyphenyl)chroman-2- O O 15 (6) (4R)-5,7-dimethoxy-4-(4-methoxyphenyl)chroman-2- O '', (7) (4S)-4-(3-hydroxy-4-methoxyphenyl)-7-methoxy-chro man-2-one No OH (8) (4R)-4-(3-hydroxy-4-methoxyphenyl)-7-methoxy-chro (21) O man-2-one (9) (4S)-4-(3-hydroxy-4-methoxyphenyl)-5,7-dimethoxy O chroman-2-one 25 (10) (4R)-4-(3-hydroxy-4-methoxyphenyl)-5,7-dimethoxy chroman-2-one Crys (11) (4S)-4-(4-hydroxyphenyl)-7-propoxy-chroman-2-one N-1 no OH (12) (4R)-4-(4-hydroxyphenyl)-7-propoxy-chroman-2-one (22) 30 (13) (4S)-7-ethoxy-4-(4-hydroxyphenyl)chroman-2-one O (14) (4R)-7-ethoxy-4-(4-hydroxyphenyl)chroman-2-one

O (15) (4S)-4-(4-hydroxy-3-methoxyphenyl)-7-methoxy chroman-2-one '', On 35 (16) (4R)-4-(4-hydroxy-3-methoxyphenyl)-7-methoxy chroman-2-one N-1 no OH (17) (4S)-4-(4-hydroxy-3-methoxyphenyl)-5,7-dimethoxy chroman-2-one (23) O 40 (18) (4R)-4-(4-hydroxy-3-methoxyphenyl)-5,7-dimethoxy chroman-2-one O (19) (4S)-4-(4-hydroxyphenyl)-7-methoxy-chroman-2-one (20) (4R)-4-(4-hydroxyphenyl)-7-methoxy-chroman-2-one 45 (21) (4S)-4-(4-hydroxy-3-methoxyphenyl)-7-propoxy-chro Cryos man-2-one No OH OH (22) (4R)-4-(4-hydroxy-3-methoxyphenyl)-7-propoxy-chro (24) man-2-one O (23) (4S)-5-hydroxy-4-(4-hydroxy-3-methoxyphenyl)-7- 50 methoxy-chroman-2-one O (24) (4R)-5-hydroxy-4-(4-hydroxy-3-methoxyphenyl)-7- On methoxy-chroman-2-one (25) (4S)-7-ethoxy-4-(4-hydroxy-3-methoxyphenyl)chro 55 man-2-one No OH OH (26) (4R)-7-ethoxy-4-(4-hydroxy-3-methoxyphenyl)chro (25) O man-2-one Various neoflavonoids of formula (I) may also occur in 60 O certain plants or parts of plants. The neoflavonoids (27), (28), (29) and (30) that are covered O by general formula (I), and were found in Polygonum perfo liatum (see Planta Medica 1999, 65, 671-673; Chin. J. Appl. 65 Environ. Biol. 2009, 15, 615-620), and physiologically acceptable salts thereof, are also preferred in the context of the present invention. US 9, 131,719 B2 15 16 O (27) of a salt of a compound of formulas (1)–(30), preferably of a O compound of formulas (5)-(30), O O 5 of a mixture of two or a plurality of different compounds of formulas (1)–(30), preferably of a compound of formulas (5)-(30), O of a mixture of two or a plurality of different salts of com No OH o1 10 pounds of formulas (1)–(30), preferably of a compound of (28) formulas (5)-(30), O O of a mixture one or a plurality of different compounds of O formulas (1)–(30), preferably of a compound of formulas 15 (5)-(30), and one or a plurality of different salts of one or a plurality of different compounds of formulas (1)–(30), '. preferably of a compound of formulas (5)-(30), for producing an impression of Sweetness in an orally con No OH o1 Sumable preparation or for influencing the strength of the (29) impression of Sweetness of Sweet Substances or mixtures of O 2O Substances (in particular Sweet-tasting Substances or mix tures of Substances) or both Sweet and unpleasant, prefer O ably bitter, tasting Substances or mixtures of substances, in particular for intensifying the impression of Sweetness of 25 an orally consumable preparation comprising at least one other Sweet-tasting Substance. In a preferred embodiment of the present invention, R3 No OH OH denotes methoxy. This applies to all aspects of the present (30) O invention, in particular to the compounds of formulas (I), 30 (I-A), (I-A1), (I-A2). (I-B), (II) and (II-A) to be used accord ing to the invention. Compounds of formula (II-A) that are O particularly preferably to be used are therefore the com pounds (5), (6), (7), (8), (9), (10), (15), (16), (17), (18), (19), '', (20), (23), (24), (27), (28), (29) and (30). 35 The compounds of formulas (I), (I-A), (I-A1), (I-A2). (I-B), (II) and (II-A) to be used according to the invention can O OH OH preferably be in the form of monovalent, or (in particular in the case when a plurality of hydroxyl groups are present) polyvalent anions, wherein the cations with unipositive charge of the first main group and Subgroup, the ammonium (27) (4S)-5-hydroxy-7-methoxy-4-(4-methoxyphenyl)chro ion (NH), a trialkylammonium ion, the divalently charged man-2-one cations of the second Subgroup, and the trivalent cations of the (28) (4R)-5-hydroxy-7-methoxy-4-(4-methoxyphenyl)chro 3rd main group and Subgroup serve as oppositely charged man-2-one cation. Preferably one, a plurality of or all oppositely charged (29) (4S)-5-hydroxy-4-(4-hydroxyphenyl)-7-methoxy-chro 45 cations are selected from the group consisting of Na', K. man-2-one NH", Ca?", M?", Al" and Zn". (30) (4R)-5-hydroxy-4-(4-hydroxyphenyl)-7-methoxy-chro A chemist knows several routes for preparing the com man-2-one pounds of formula (I). A particularly preferred route is the acid-catalyzed reaction (classically, e.g. using Sulfuric acid or One or a plurality of the neoflavonoids of formula (I) to be 50 hydrochloric acid) of phenol derivatives of the following used according to the invention can, if they occur naturally, formula (A) with cinnamic acid derivatives of the following also be used according to the invention in the form of plant formula (B) or of the corresponding esters of the following extracts, in particular in the form of plant extracts of formula (C) to the compounds of formula (I) (as defined Polygonum perfoliatum. above), as outlined in the following scheme: For the case when in an individual case there is a discrep ancy between the chemical nomenclature given above and the 55 structural formula shown in each case for the compounds of OH O R1 formulas (5) through (30) preferably to be used according to the invention, the structural formula applies. R2 H HO a R2 - I - (I) Compounds (1) through (30) are preferred according to the 60 R3 R2 R1 R2 invention, compounds (5) through (30) are further preferred, and the mixtures and salts thereof defined above, wherein these can in each case be racemic mixtures, individual Sub (A) (B) stances or can be combined in any desired ratio to one another. Therefore in a preferred configuration the invention relates 65 to the use of a compound of formulas (1)–(30), preferably a compound of formulas (5)-(30), US 9, 131,719 B2 17 18 -continued (1) preparations to be used for nutrition, for food supple O ments, for oral hygiene or for pleasure, (2) cosmetic preparations, in particular for application in the O R1 region of the head, (3) pharmaceutical preparations intended to be taken orally, R2 R2 (4) semifinished products, preferably flavoring compositions, H for producing one of the preparations mentioned in (1) through (3). R3 R2 Semifinished products in the context of the present inven 10 tion are in particular in the form of flavoring compositions (C) and/or compositions of flavoring materials or as a mixture of Spices. If the compounds to be used according to the invention wherein in each case the residues R1, R2 and R3 have the 15 occur naturally, they can also be used in the form of a plant respective meanings given above with respect to formula (I). eXtract. For example, the synthesis of compounds of formula (I) Accordingly, the present invention also relates to the use of starting from 5-methoxyresorcinol is known from the litera a product obtainable or obtained from plant material by ture, as described in Synth. Commun. 2006, 36(8) 1117-1122. extraction, comprising Use of montmorillonite K-10 as catalyst is also conceivable, one, two or a plurality of different compounds of formula (I) similar to the synthesis route described in Synthesis 2001, 15, as defined above, 2247-2254. one, two or a plurality of different physiologically acceptable Moreover, the neoflavanoids to be used according to the salts of one, two or a plurality of different compounds of invention can also be prepared on the basis of the method formula (I) as defined above, described in Synth. Commun. 1987, 17(6) 723-727, as shown 25 O schematically below on the basis of the reaction of Mel a mixture of one, two or a plurality of different compounds of drums acid (E) with a corresponding ether of phloroglycinol formula (I) as defined above with one, two or a plurality of (D) (wherein R3 has the meaning given above) with addition different physiologically acceptable salts of one, two or a of an aldehyde (e.g. para-hydroxybenzaldehyde (F)) in the plurality of different compounds of formula (I) as defined presence of pyridine to produce a racemic mixture of com 30 above, pounds to be used according to the invention. for producing an impression of Sweetness in an orally con sumable preparation or for influencing the strength of the impression of Sweetness of Sweet Substances or mixtures of OH O Substances (in particular Sweet-tasting and/or Sweet-smell O 35 ing Substances or mixtures of Substances) or both Sweet and unpleasant, preferably bitter, tasting Substances or mixtures of Substances, in particular for intensifying the O impression of Sweetness of an orally consumable prepara R3 OH O tion comprising at least one other Sweet-tasting Substance. (D) 40 Said plant extract to be used according to the invention (E) preferably contains a total proportion of 50 wt % or more, preferably of 80 wt % or more, particularly preferably of 90 wt % or more of compounds of formula (I) and salts thereof, in each case relative to the dry matter of the plant extract, 45 wherein the compounds of formula (I) and/or salts thereofare either present as individual Substances or can be combined in any proportions. The term “dry matter in the broader sense means the OH water-free and extractant-free matter of an extract to be used (F) 50 according to the invention. Said matter can be obtained for example by completely removing the extractant by distilla tion or Some other evaporative technique (including the water that optionally originates from the plant material) after completion of the extraction step or steps. 55 The term “dry matter in the narrower sense means the total mass of all solids of the extract, referred to 20° C. at 1013 mbar. In the context of the present text, the “solid’ state or the term “solid material relates to 20° C. at 101.3 mbar. 60 The invention further relates to semifinished products com R3 OH OH prising or consisting of the following components: (a) one or a plurality of compounds of formula (I) and/or salts The present invention also relates to the use of the neofla thereofas defined above, preferably in one of the configu vonoids of formula (I), (I-A), (I-A1), (I-A2). (I-B), (II) and rations designated as preferred or particularly preferred, (II-A) to be used according to the invention, mixtures thereof 65 and and/or salts thereof (in each case as defined above) in a one, two, three or a plurality of Substances selected from preparation selected from the group consisting of the group consisting of the components (b) and (c) US 9, 131,719 B2 19 20 (b) one or a plurality of Sweet-tasting Substances, (d) of a semifinished product according to the invention com and/or prises or consists of one or a plurality of solid carriers fit for (c) one or a plurality of Substances that are both Sweet and consumption. unpleasant tasting, in particular bitter tasting, Semifinished products according to the invention in the and form of flavoring compositions in the sense of the present (d) optionally one or a plurality of carriers fit for consump invention contain, in addition to one or a plurality of com tion, pounds of formula (I) and/or one or a plurality of physiologi (e) optionally one or a plurality of further substances for cally acceptable salts of these compounds, at least (i) one, masking or reducing an unpleasant, in particular a bitter two, three, four, five, six, seven, eight, nine, ten or a plurality taste impression, 10 of (further) aromatic substances (preferably selected from group (A) defined below) and/or (ii) one, two, three, four, five, and six, seven or a plurality of (further) flavoring Substances. (f) optionally one or a plurality of further substances for A particularly preferred semifinished product according to intensifying an impression of Sweet taste, the invention is characterized in that the semifinished product wherein the components (b)-(f) neither are or contain a com 15 contains two, three, four, five, six, seven, eight, nine, ten or a pound of formula (I) nor are or containa salt of a compound plurality of further aromatic substances with a molar of formula (I). weight above 120 g/mol, preferably with a molar weight Semifinished products according to the invention, prefer above 125 g/mol, preferably with a molar weight in the ably flavoring compositions according to the invention, and range from 125 g/mol through 220 g/mol, in particular orally consumable preparations according to the invention preferably with a molar weight in the range from 130 g/mol can, in addition to the substances of formula (I) to be used through 210 g/mol. according to the invention and/or salts thereof (as defined A preferred semifinished product according to the inven above), contain one or a plurality of different (natural or tion preferably does not contain hexane and does not contain normatural) aromatic Substances and/or reactive aromas, aro methylene chloride, and preferably does not contain any hex matic preparations, other flavoring Substances, further flavor 25 ane, methylene chloride, acetone or methanol. modulating Substances, precursors, further aromatic Sub The invention also relates to a semifinished product, pref stances, additives, Sweeteners, colorants and acidifying erably in the form of an aromatic composition, for producing agents, stabilizers or solvents, auxiliaries and carriers. a preparation according to the invention (as defined above), A semifinished product is preferred according to the inven containing tion that additionally comprises one, two, three, four, five, six, 30 one, two or a plurality of different compounds of formula (I) as defined above, or seven, eight, nine, ten or a plurality of further Sweet-tasting one, two or a plurality of different physiologically accept and/or Sweet-smelling Substances, wherein these further able salts of one, two or a plurality of different com Sweet-tasting and/or Sweet-smelling Substances are prefer pounds of formula (I) as defined above, or ably selected from groups (b1) through (b5) defined below. 35 a mixture of one, two or a plurality of different compounds A semifinished product that is preferred according to the of formula (I) as defined above with one, two or a plu invention comprises a total amount of compounds of formula rality of different physiologically acceptable salts of (I) and physiologically acceptable salts thereof as defined one, two or a plurality of different compounds of for above (component (a)) in the range from 0.0001 through 90 mula (I) as defined above, wt %, preferably in the range from 0.001 through 50 wt %, 40 and more preferably in the range from 0.01 through 40 wt %, contains one, two, three, four, five, six, seven, eight, nine, ten particularly preferably in the range from 0.1 through 20 wt %, or a plurality of further aromatic substances with a molar most preferably in the range from 0.2 through 10 wt %, weight above 90 g/mol, preferably above 100 g/mol, pref relative to the total weight of the semifinished product. erably with a molar weight in the range from 110 g/mol Semifinished products according to the invention can be 45 through 300 g/mol, more preferably with a molar weight in used for intensifying the sensory impression of Sweetness, in the range from 120 g/mol through 250 g/mol, particularly particular the impression of Sweet taste, of orally consumable preferably with a molar weight in the range from 125 g/mol finished products (i.e. of preparations intended for direct con through 220 g/mol, in particular preferably with a molar Sumption), which are produced using the semifinished prod weight in the range from 130 g/mol through 210 g/mol. uct according to the invention. 50 and preferably one or a plurality of carriers fit for consump A preferred semifinished product according to the inven tion, preferably selected from the group consisting of etha tion contains one or a plurality of carriers fit for consumption nol, isopropanol, glycerol, 1.2-propylene glycol, diacetin, (component (d)) selected from the group consisting of etha triacetin, maltodextrin, gum arabic, silicon dioxide and nol, isopropanol, glycerol. 1,2-propylene glycol, diacetin, mixtures thereof. triacetin, edible fats, edible fatty oils, maltodextrin, gum ara 55 The configurations described above, in particular the con bic, silicon dioxide and mixtures thereof. figurations characterized above as preferred or particularly A further preferred semifinished product according to the preferred, with respect to the use according to the invention of invention contains one or a plurality of carriers fit for con the compounds of formulas (I), (I-A), (I-A1), (I-A2). (I-B). Sumption selected from the group consisting of glycerol, (II) and (II-A) apply correspondingly to a semifinished prod 1.2-propylene glycol, diacetin, triacetin, edible fatty oils, 60 uct according to the invention, in particular to a preferred or maltodextrin, gum arabic, silicon dioxide and mixtures particularly preferred semifinished product according to the thereof. invention. In a preferred embodiment, a semifinished product accord The present invention also relates to a preparation, prefer ing to the invention is characterized in that it is spray-dried. ably orally consumable preparation, selected from the group In a preferred embodiment, a semifinished product accord 65 consisting of ing to the invention is characterized in that it comprises one or (1) preparations to be used for nutrition, for food supple a plurality of solid carriers fit for consumption, i.e. constituent ments, for oral hygiene or for pleasure, US 9, 131,719 B2 21 22 (2) cosmetic preparations, in particular for application in the cal composition, comprises neither a compound of formula region of the head, (I) nor a salt of a compound of formula (I) as defined above, (3) pharmaceutical preparations intended to be taken orally, to impart an increase in the impression of Sweetness, to be comprising determined in sucrose equivalents, by 10% or more, prefer (i) one or a plurality of compounds of formula (I) and/or salts ably by 20% or more, preferably by 30% or more and par thereofas defined above, ticularly preferably 35% or more. and Surprisingly, it was also found that compounds of general (ii) one or a plurality of further Sweet-tasting Substances, one formula (I), mixtures and/or salts thereof (as defined above) or a plurality of Sweet-smelling Substances and/or one or a in particular in the form of the semifinished products accord plurality of Substances that are both Sweet and unpleasant 10 ing to the invention described above or hereunder, can reduce tasting, in particular bitter tasting, or even completely suppress the impression of a large number wherein the amount of constituent (i) in the preparation is of unpleasant, in particular bitter tasting Substances and orally Sufficient for sensorily intensifying the impression of consumable preparations that contain one or a plurality of Sweetness of the Sweet-tasting and/or Sweet-smelling Sub unpleasant, in particular bitter tasting Substances. stance or Substances of constituent (ii). 15 Substances causing unpleasant taste impressions in the A preferred preparation according to the invention, prefer context of this text are: ably an orally consumable preparation according to the inven Substances that taste bitter, astringent, Sticky, chalky, dusty, tion, comprises a semifinished product as defined above, pref dry, mealy, rancid and/or metallic and erably in one of the configurations designated as preferred or Substances that have a bitter, astringent, Sticky, chalky, particularly preferred. dusty, dry, mealy, rancid and/or metallic (optionally very A preferred orally consumable preparation according to persistent) aftertaste. the invention (as defined above) is selected from the group The aforementioned unpleasant tasting Substances can consisting of possess further, not unpleasant taste and/or odor qualities. (1) preparations to be used for nutrition, for food supple Bitter Substances that are to be masked according to the ments, for oral hygiene or for pleasure, 25 invention are preferably Xanthines (in particular caffeine, (2) cosmetic preparations for application in the region of the theobromine, theophylline), phenolic glycosides (in particu head, lar salicin, arbutin), flavanoid glycosides (in particular neo (3) pharmaceutical preparations intended to be taken orally, hesperedin, eriocitrin, neoeriocitrin, narirutin, hesperidin, wherein the orally consumable preparation (1), (2) or (3) naringin), chalcones or chalcone glycosides, dihydrochal comprises, relative to its total weight, 0.1 mg/kg (corre 30 cone glycosides (in particular phloridzin, trilobtain), hydro sponding to 0.1 ppm) through 1 wt %, preferably in the ly Zable tannins (in particular gallic or elagic acid esters of range from 0.5 through 1000 mg/kg, preferably in the carbohydrates, e.g. pentagalloylglucose), nonhydrolyzable range from 1 through 500 mg/kg, more preferably in the tannins (in particular galloylated catechins or epicatechins range from 3 through 300 mg/kg, particularly preferably in and oligomers thereof, e.g. proanthyocyanidins or procyani the range from 5 through 200 mg/kg, most preferably in the 35 dins, thearubigenin), flavones and glycosides thereof (in par range from 10 through 100 mg/kg, of compounds of for ticular quercetin, quercitrin, rutin, taxifolin, myricetin, mula (I) and/or salts thereofas defined above. myrictrin), caffeic acid oresters thereof, terpenoid bitter sub For determining the impression of Sweetness of a com stances (in particular limonin, nomilin, lupolones and humo pound of formula (I) to be used according to the invention, in lones), metallic salts (potassium chloride, Sodium sulfate, comparison with an aqueous Sucrose solution, an aqueous 40 magnesium salts, iron salts, aluminum salts, Zinc salts), active Solution of a compound of formula (I) is prepared at the same pharmaceutical ingredients (e.g. fluoroquinolone antibiotics, concentration as it is present in the orally consumable prepa paracetamol, aspirin, B-lactam antibiotics, ambroXol, propy ration to be investigated. This aqueous Solution is then com lthioracil PROP. guaifenesin), amino acids (e.g. leucine, pared and assigned with respect to taste by a group of at least isoleucine, Valine, tryptophan, proline, histidine, tyrosine, five persons against a comparative series of different Sucrose 45 lysine orphenylalanine), peptides (in particular peptides with concentrations in water. In this way the Sucrose equivalence is an amino acid from the group leucine, isoleucine, Valine, determined (given in Sucrose (Saccharose) equivalents), i.e. tryptophan, proline orphenylalanine at the N- or C-terminus). the concentration of the Sucrose Solution whose impression of Bitter Substances that are preferably masked according to Sweetness is equivalent to the impression of Sweetness of the the invention are selected from the group consisting of caf concentration of the compound of formula (I). A correspond 50 feine, theobromine, quinine, salicin, arbutin, neohesperedin, ing procedure is also followed for determining the impression eriocitrin, neoeriocitrin, narirutin, hesperidin, naringin, phlo of Sweetness of a physiologically acceptable salt of the com ridzin, catechin, epicatechin, epigallocatechin gallate pound of formula (I) or of mixtures (as defined above). (EGCG), gallocatechin, gallocatechin-3-gallate, procyanidin Preferred concentrations of the saccharose comparative B2, procyanidin B5, procyanidin C1, thearubigenin, rutin, solution are 0, 0.25, 0.5,0.75, 1, 1.5, 2, 3, 4 and 5 wt % of 55 taxifolin, myricetin, myrictrin, caffeic acid or esters thereof, saccharose in water. Optionally, other concentrations, in par limonin and nomilin, amino acids (e.g. leucine, isoleucine, ticular higher concentrations, can also be used for the com Valine, tryptophan, proline, histidine, tyrosine, lysine or phe parison series. The Sucrose equivalence determined is nylalanine), peptides with an amino acid from the group obtained from the mean value of the individual classifications leucine, isoleucine, Valine, tryptophan, proline or phenylala of the individual members of the panel. The members of the 60 nine on the N- or C-terminus, potassium chloride, paraceta panel are preferably persons who have experience in the area mol, aspirin and B-lactam antibiotics. of tasting, of varying age and sex and of varying origin. The compounds of formula (I) to be used according to the A preferred preparation according to the invention, prefer invention and the physiologically acceptable salts of the com ably orally consumable preparation, is characterized in that pounds of formula (I) do not have, in particular in the con the total amount of compounds of formula (I) and/or salts 65 centrations to be used preferably or particularly preferably thereof (as defined above) in the preparation is sufficient, in according to the invention, in (preferably orally consumable) comparison with a preparation which, with otherwise identi preparations according to the invention, any notable intrinsic US 9, 131,719 B2 23 24 taste, in particular in the (preferred or particularly preferred) inol, (24S)-ethylcholesta-33.5C,6C.-triol, quercetin, cucurbi concentrations used, they do not have any unpleasant or inter tacin IIa, cucurbitacin U, iotroridoside A, fering taste notes. pokeweedcerebroside 5, bonaroside, helonioside A, helonio In a preferred preparation according to the invention the side B, lapathoside D, vanicoside B. vanicoside C. vanicoside total amount of compounds of formula (I) as defined above F. asteryunnanoside, Saikosaponin M, hydropiperoside, quer and of physiologically acceptable salts of the compounds of cetin-3-O-B-D-glucuronide-6"-butyl ester and quercetin-3- formula (I) as defined above is in the range from 0.1 mg/kg O-B-D-glucuronide-6"-methyl ester. (corresponding to 0.1 ppm) through 1 wt %, preferably in the Here, with respect to the structural formulas corresponding range from 0.5 through 1000 mg/kg (corresponding to 0.5 to these compounds, reference is made to the literature source through 1000 ppm), preferably in the range from 1 through 10 Chin. J. Appl. Environ. Biol. 2009, 15, 615-620, which with 500 mg/kg, more preferably in the range from 3 through 300 respect to the corresponding compounds disclosed therein mg/kg, particularly preferably in the range from 5 through becomes part of the present application by reference. 200 mg/kg, most preferably in the range from 10 through 100 A preferred preparation or semifinished product according mg/kg, in each case relative to the total weight of the prepa to the invention is not a preparation or semifinished product ration. These ranges of amounts apply in particular to orally 15 that contains 4-dihydroxy-5,7-dihydroxy-4-(4-hydroxyphe consumable preparations according to the invention that are nyl)coumarin, C-tocopherol quinone, 7-dihydroxymataires intended for direct consumption. inol, (24S)-ethylcholesta-33.5C,6C.-triol, quercetin, cucurbi In our own research it was also found that at much higher tacin IIa, cucurbitacin U, iotroridoside A, total concentrations used of compounds of formula (I) as pokeweedcerebroside 5 and bonaroside in the proportions by defined above and of physiologically acceptable salts of the mass of 4.9:8:37:30:24:14:5:12:41. compounds of formula (I) as defined above, the Sweetness If a preparation or semifinished product according to the intensifying effect decreases or occurs to a lesser degree. Also invention contains 4-dihydroxy-5,7-dihydroxy-4-(4-hydrox to that extent the aforementioned total amount of compounds yphenyl)coumarin, one, a plurality of or all of the following of formula (I) as defined above and of physiologically accept conditions apply: able salts of the compounds of formula (I) as defined above is 25 the weight ratio of 4-dihydroxy-5,7-dihydroxy-4-(4-hy preferred, in particular in the preferred or particularly pre droxyphenyl)coumarin to quercetin is not equal to 4:30, ferred ranges of total amounts. the weight ratio of 4-dihydroxy-5,7-dihydroxy-4-(4-hy In particular the Sweetness intensifying action of the com droxyphenyl)coumarinto cucurbitacin IIa is not equal to pounds of formula (I) to be used according to the invention is 4:24, observed even at a total amount of compounds of formula (I) 30 the weight ratio of 4-dihydroxy-5,7-dihydroxy-4-(4-hy according to the invention of less than 0.01 wt % (correspond droxyphenyl)coumarin to cucurbitacin U is not equal to ing to 100 ppm) (ppm parts by weight per million), prefer 4:14, ably of less than 0.0050 wt % (corresponding to 50 ppm), in the weight ratio of 4-dihydroxy-5,7-dihydroxy-4-(4-hy each case relative to the total weight of an orally consumable droxyphenyl)coumarin to 7-dihydroxymatairesinol is preparation according to the invention. 35 not equal to 4:8. As already noted above, semifinished products according If a preparation or semifinished product according to the to the invention and orally consumable preparations accord invention contains 4-dihydroxy-5,7-dihydroxy-4-(4-hydrox ing to the invention are preferred that contain one or a plural yphenyl)coumarin, the mass ratio of 4-dihydroxy-5,7-dihy ity of the aforementioned compounds of formula (I) or salts droxy-4-(4-hydroxyphenyl)coumarin to the total mass of thereofthat are characterized as preferred or particularly pre 40 C-tocopherol quinone, 7-dihydroxymatairesinol, (24S)-eth ferred. ylcholesta-33.5C.6C-triol, quercetin, cucurbitacin IIa, cucur The ethanolic-aqueous extracts of the ground whole plant bitacin U, iotroridoside A, pokeweedcerebroside 5 and bon Polygonum perfoliatum described in Planta Medica 1999, 65, aroside is not 4:180. 671-673 and Chin. J. Appl. Environ. Biol. 2009, 15, 615-620, A preferred preparation or semifinished product according as well as the fractions and mixtures of Substances obtained 45 to the invention is not a preparation or semifinished product there from the ethanolic-aqueous extracts, are not an object of that contains C-tocopherol quinone, 7-dihydroxymataires the present invention. inol, (24S)-ethylcholesta-33.5C,6C.-triol, quercetin, cucurbi A preferred preparation or semifinished product according tacin IIa, cucurbitacin U, iotroridoside A, pokeweedcerebro to the invention is characterized in that the preparation or side 5, bonaroside, helonioside A, helonioside B, lapathoside semifinished product is not an extract that is obtainable by 50 D. Vanicoside B. Vanicoside C, Vanicoside F, asteryunnano extraction of the ground whole plant Polygonum perfoliatum side, Saikosaponin M, hydropiperoside, quercetin-3-O-B-D- with a mixture of extractants of ethanol and water in the glucuronide-6"-butyl ester and quercetin-3-O-B-D-glucu weight or volume ratio 90:10 or 95:5, and preferably is not an ronide-6"-methyl ester. extract that is obtainable by extraction of the whole plant A preferred preparation or semifinished product according Polygonum perfoliatum with a mixture of extractants of etha 55 to the invention is not a preparation or semifinished product nol and water with a volume ratio greater than 1:1, and pref that contains C-tocopherol quinone, (24S)-ethylcholesta-3?, erably is not an extract that is obtainable by extraction of the 5C,6O-triol, cucurbitacin IIa, cucurbitacin U, iotroridoside A, whole plant Polygonum perfoliatum with a mixture of extrac pokeweedcerebroside 5 and bonaroside. tants of ethanol and water. A preferred preparation or semifinished product according A preferred preparation or semifinished product according 60 to the invention does not contain cucurbitacin IIa, preferably to the invention preferably does not contain hexane and does does not contain cucurbitacin IIa and does not contain cucur not contain methylene chloride, and preferably does not con bitacin U, and preferably does not contain any cucurbitacins. tain hexane, methylene chloride, acetone or methanol. The configurations described above, in particular the con A preferred preparation or semifinished product according figurations characterized above as preferred or particularly to the invention is not a preparation or semifinished product 65 preferred, with respect to the use of the compounds of formu that contains 4-dihydroxy-5,7-dihydroxy-4-(4-hydroxyphe las (I), (I-A). (I-A1), (I-A2). (I-B), (II) and (II-A) according to nyl)coumarin, C-tocopherol quinone, 7-dihydroxymataires the invention, apply correspondingly to a preparation or semi US 9, 131,719 B2 25 26 finished product according to the invention, in particular to a The present invention also relates to a method for (a) preferred or particularly preferred preparation or semifin imparting an impression of Sweet taste and/or intensifying an ished product according to the invention. impression of Sweet taste of one, two or a plurality of Sweet Method of Production tasting Substances and/or (b) producing an orally consumable of a semifinished product according to the invention as preparation according to the invention, preferably in one of defined above or hereunder the configurations characterized as preferred, with the follow O ing steps: ofa preparation according to the invention as defined above a) providing a compound to be used according to the inven or hereunder, comprising the steps 10 tion, preferably in one of the configurations characterized (1) preparing or providing the following components: as preferred, or a physiologically acceptable salt of a com (a) one or a plurality of compounds of formula (I) and/or pound to be used according to the invention, preferably in salts thereofas defined above, one of the configurations characterized as preferred, a and semifinished product according to the invention, prefer one, two, three or a plurality of Substances selected from 15 ably in one of the configurations characterized as preferred, the group consisting of the components (b) and (c) and/or an extract to be used according to the invention, (b) one or a plurality of Sweet-tasting Substances, preferably in one of the configurations characterized as and/or preferred, (c) one or a plurality of Substances that are both Sweet and unpleasant tasting, in particular bitter tasting, b) providing an orally consumable preparation, preferably and comprising one, two or a plurality of further Sweet-tasting (d) optionally one or a plurality of carriers fit for consump Substances, tion, c) bringing in contact or mixing the constituents provided in (e) optionally one or a plurality of further substances for step a) and b). masking or reducing an unpleasant, in particular a bitter 25 Preparations to be consumed orally according to the inven taste impression, tion are preferred that comprise one or a plurality of com and pounds of formula (I) and/or one or a plurality of physiologi (f) optionally one or a plurality of further substances for cally acceptable salts of a compound of formula (I), in a total intensifying an impression of Sweet taste, amount that is Sufficient to produce a perception of Sweetness wherein the components (b)-(f) neither are or contain a 30 compound of formula (I) nor are or contain a salt of a in the preparations to be consumed orally that at least corre compound of formula (I), sponds to that of a comparative preparation that consists of a and 2 wt % solution of sucrose in water. (2) mixing component (a) with one or a plurality of the com Preparations to be consumed orally according to the inven ponents (b) and/or (c) and optionally (d) and optionally 35 tion are preferred that comprise one or a plurality of the component (e) and optionally component (f). compounds of formula (I) or one or a plurality of physiologi In another aspect, the present invention relates to a method cally acceptable salts of a compound of formula (I) to be used of influencing the strength of a sensory impression, in par according to the invention and at least one other Sweet-tasting ticular of the impression of Sweetness, of a Sweet-tasting Substance, wherein the latter is present at a concentration that and/or Sweet-smelling Substance or mixture of Substances or 40 is Sufficient to produce a perception of Sweetness in the prepa a Substance or mixture of Substances that is both Sweet and rations to be consumed orally that at least corresponds to that unpleasant tasting, in particular bitter tasting, with the fol of a comparative preparation that consists of a 2 wt % Solution lowing step: of Sucrose in water. mixing of component (a) The present invention also relates to a method of intensi (a) one or a plurality of compounds of formula (I) and/or salts 45 fying the impression of Sweetness of an orally consumable thereofas defined above with component (b) and/or (c) preparation that is formed during tasting (appraisal), com (b) one or a plurality of Sweet-tasting Substances, prising the steps: and/or a) providing an orally consumable preparation, comprising (c) one or a plurality of Substances that are both Sweet and one or a plurality of further Sweet-tasting Substances that unpleasant tasting, in particular bitter tasting, 50 and together impart an impression of Sweetness that is equal to (d) optionally one or a plurality of carriers fit for consump or stronger than that of an aqueous Sucrose solution with a tion, concentration of 2 wt % Sucrose, (e) optionally one or a plurality of further substances for b) providing one or a plurality of compounds of formula (I), masking or reducing an unpleasant, in particular a bitter 55 salts or mixtures thereof (as defined above), taste impression, and c) mixing the constituents provided in step a) and b). (f) optionally one or a plurality of further substances for The invention also relates to a method of intensifying the intensifying an impression of Sweet taste, Sweet taste of a Sweet-tasting Substance with the following wherein the components (b)-(f) neither are or contain a step: compound of formula (I) nor are or contain a salt of a 60 compound of formula (I), and mixing a Sweet-tasting Substance with an amount of one or wherein the total amount of component (a) in the mixture is a plurality of compounds of formula (I), salts or mixtures Sufficient to influence the strength of the sensory impres thereof (as defined above) that is sufficient for sensorily sion, in particular of the impression of Sweetness, of the intensifying the impression of Sweet taste of the Sweet Sweet-tasting Substance or Substances of component (b) or 65 tasting Substance or Substances, of the both Sweet and unpleasant tasting, in particular bitter wherein preferably the total amount of component (a) in the tasting Substance or Substances of component (c). mixture is sufficient US 9, 131,719 B2 27 28 to intensify, preferably synergistically intensify, the impres vanillinisobutyrate (3-ethoxy-4-isobutyryloxybenzalde sion of Sweet taste of a Sweet-tasting Substance or mixture hyde), Furaneol R (2,5-dimethyl-4-hydroxy-3(2H)-fura of Substances none) and its derivatives (preferably homofuraneol, and/or 2-ethyl-4-hydroxy-5-methyl-3(2H)-furanone), homofu to intensify the impression of sweet taste of a both sweet and ronol (2-ethyl-5-methyl-4-hydroxy-3 (2H)-furanone and unpleasant, in particular bitter tasting Substance or mixture 5-ethyl-2-methyl-4-hydroxy-3 (2H)-furanone), maltol and of Substances synergistically and to reduce or to mask the its derivatives (preferably ethylmaltol), coumarin, gamma unpleasant, in particular bitter, taste impression of the Sub lactones (preferably gamma-undecalactone, gamma-nona stance or mixture of Substances that is both Sweet and lactone), delta-lactones (preferably 4-methyldeltalactone, unpleasant tasting, in particular bitter tasting. 10 massoilactone, deltadecalactone, tuberolactone), methyl Further Sweet-tasting Substances in the sense of the inven sorbate, divanillin, 4-hydroxy-2(or 5)-ethyl-5(or 2)-me tion can be naturally occurring Sweet-tasting Substances or thyl-3(2H)furanone, 2-hydroxy-3-methyl-2-cyclopenten plant extracts or else synthetic Sweet-tasting Substances. one, 3-hydroxy-4,5-dimethyl-2(5H)-furanone, fruit esters Naturally occurring Sweet-tasting Substances (including and fruit lactones (preferably acetic acid-n-butyl ester, ace plant extracts) can for example be Sweet-tasting carbohy 15 tic acid isoamyl ester, propionic acid ethyl ester, butyric drates (e.g. Sucrose, trehalose, lactose, maltose, melezitose, acid ethyl ester, butyric acid-n-butyl ester, butyric acid melibiose, raffinose, Palatinose, lactulose, D-fructose, D-glu isoamyl ester, 3-methyl-butyric acid ethyl ester, n-hex cose, D-galactose, L-rhamnose, D-Sorbose, D-mannose, anoic acid ethyl ester, n-hexanoic acid allyl ester, n-hex D-tagatose, D-arabinose, L-arabinose, D-ribose, D-glyceral anoic acid-n-butyl ester, n-octanoic acid ethyl ester, ethyl dehyde, maltodextrins), Sugar alcohols (e.g. erythritol, threi 3-methyl-3-phenylglycidate, ethyl-2-trans-4-cis tol, arabitol, ribitol, xylitol, sorbitol, mannitol, maltitol, iso decadienoate), 4-(p-hydroxyphenyl)-2-butanone, 1,1- maltitol, dulcitol, lactitol), proteins (e.g. miraculin, pentadin, dimethoxy-2.2.5-trimethyl-4-hexane, 2,6-dimethyl-5- monellin, thaumatin, curculin, braZZein, mabinlin), D-amino hepten-1-al and phenyl acetaldehyde; acids (e.g. D-phenylalanine, D-tryptophan) or extracts or (b2) carbohydrates selected from the group consisting of fractions obtained from natural sources containing these 25 Sucrose, trehalose, lactose, maltose, melezitose, melibiose, amino acids and/or proteins, neohesperidin dihydrochalcone, raffinose, Palatinose, lactulose, O-fructose, D-glucose, naringin dihydrochalcone, Steviol glycoside, Stevioside, Ste D-galactose, L-rhamnose, D-Sorbose, D-mannose, D-taga violbioside, rebaudiosides, rebaudioside A, rebaudioside B, tose, D-arabinose, L-arabinose, D-ribose, D-glyceralde rebaudioside C, rebaudioside D, rebaudioside E, rebaudio hydes, maltodextrins and plant preparations containing side F, rebaudioside G, rebaudioside H, dulcoside, rubusos 30 one or a plurality of the aforementioned carbohydrates, ide, Suavioside A, Suavioside B, Suavioside G, Suavioside H. preferably in a proportion of at least 5 wt %, preferably at suavioside I, Suavioside J, baiyunoside 1, baiyunoside 2, least 15 wt %, wherein the carbohydrates can also be in the phlomisoside 1. phlomisoside 2, phlomisoside 3, and phlo form of a naturally occurring or artificially produced mix misoside 4, abrusoside A, abrusoside B, abrusoside C, abru ture, in particular as honey, invert-Sugar syrup or highly Soside D, cyclocaryoside A and cyclocaryoside I, oslandin, 35 enriched fructose syrup from corn starch, and the physi polypodoside A, strogin 1, Strogin2, Strogin 4, selligueaninA, ologically acceptable salts of these carbohydrates, in par dihydroquercetin-3-acetate, perillartin, telosmoside As ticular the Sodium, potassium, calcium or ammonium salts; periandrin I-V, pterocaryoside, cyclocaryoside, mukurozio (b3) Sugar alcohols, preferably naturally occurring Sugar side, trans-anethol, trans-cinnamaldehyde, bryoside, bryono alcohols selected from the group consisting of glycerol, side, bryonodulcoside, carnosifloSide, Scandenosides, gype 40 erythritol, threitol, arabitol, ribitol, xylitol, sorbitol, man nosides, trilobtain, phloridzin, dihydroflavanole, nitol, maltitol, isomaltitol, dulcitol, lactitol, and the physi hematoxylin, cyanin, chlorogenic acid, albiziasaponin, telos ologically acceptable salts of these Sugar alcohols, in par mosides, gaudichaudioside, mogrosides, mogroside V, her ticular the Sodium, potassium, calcium or ammonium salts; nandulcine, monatin, glycyrrhetin acid and derivatives (b4) naturally occurring sweeteners, preferably selected from thereof in particular glycyrrhizin (preferably as ammonium 45 the group consisting of salt), and phyllodulcin, wherein in the case of the naturally (b4-1) miraculin, monellin, mabinlin, thaumatin, curculin, occurring Sweeteners it is also possible to use extracts or braZZein, pentadin, D-phenylalanine, D-tryptophan, and enriched fractions of these extracts, e.g. Thaumatococcus extracts or fractions obtained from natural sources contain extracts (katemphe), extracts of Stevia ssp. (in particular Ste ing these amino acids and/or proteins, and the physiologi via rebaudiana), Swingle extract (Momordica or Siratia gros 50 cally acceptable salts of these amino acids and/or proteins, venorii, Luo-Han-Guo), extracts of Glycerrhyzia ssp. (espe in particular the Sodium, potassium, calcium or ammonium cially Glycerrhyzia glabra), Rubus ssp. (in particular Rubus salts; suavissimus), citrus extracts, extracts of Lippia dulcis, (b4-2) neohesperidin dihydrochalcone, naringin dihydroch extracts of Mycetia balansae (which preferably contain bal alcone, Stevioside, Steviolbioside, rebaudiosides, in par ansin A and/or balansin B), as disclosed in the European 55 ticular rebaudioside A, rebaudioside B, rebaudioside C, patent application with the application number 11 168468.4 rebaudioside D, rebaudioside E, rebaudioside F, rebaudio (Symrise), which with respect to this compound becomes part side G, rebaudioside H, dulcosides and rubusoside, Suavio of the present application by reference. side A, Suavioside B, Suavioside G, Suavioside H. Suavio A semifinished product or an orally consumable prepara side I, Suavioside J, baiyunoside 1, baiyunoside 2, tion is preferred according to the invention that additionally 60 phlomisoside 1. phlomisoside 2, phlomisoside 3, and phlo comprises one, two, three, four, five, six, seven, eight, nine, misoside 4, abrusoside A, abrusoside B, abrusoside C. ten or a plurality of further sweet substances, selected from abrusoside D, cyclocaryoside A and cyclocaryoside I, the following groups (b1) through (b5): oslandin, polypodoside A, strogin 1, Strogin 2, Strogin 4. (b1) Sweet aromatic Substances, wherein preferably one, two, selligueanin A, dihydroquercetin-3-acetate, perillartin, three, four, five or a plurality of the sweet aromatic sub 65 telosmoside A15, periandrin I-V, pterocaryoside, cyclo stances are selected from the group consisting of Vanillin, caryoside, mukurozioside, trans-anethol, trans-cinnamal ethylvanillin, 2-hydroxy-4-methoxybenzaldehyde, ethyl dehyde, bryoside, bryonoside, bryonodulcoside, carnosi US 9, 131,719 B2 29 30 floside, Scandenosides, gypenosides, trilobtain, phloridzin, pounds disclosed therein forms part of this application by dihydroflavanols, hematoxylin, cyanin, chlorogenic acid, reference); hydroxyphenylalkane dione, for example isogin albiziasaponin, telosmosides, gaudichaudioside, mogro gerdione-2 (in particular as described in WO 2007/003527, sides, mogroside V, hernandulcinen, monatin, phyllodul which with respect to the corresponding compounds dis cin, glycyrrhetin acid and derivatives thereof, in particular 5 closed therein forms part of this application by reference); glycosides thereof Such as glycyrrhizin, and the physi diacetyl trimers (in particular as described in WO 2006/ ologically acceptable salts of these compounds, in particu 058893, which with respect to the corresponding compounds lar the Sodium, potassium, calcium or ammonium salts; disclosed thereinforms part of this application by reference); (b4-3) extracts or enriched fractions of the extracts, selected divanillins (in particular as described in WO 2004/078302, from the group consisting of Thaumatococcus extracts 10 which with respect to the corresponding compounds dis (katemphe), extracts of Stevia ssp. (in particular Stevia closed therein forms part of this application by reference), rebaudiana), Swingle extracts (Momordica or Siratia gros hesperetin as disclosed in WO 2007/014879, which with venorii, Luo-Han-Guo), extracts of Glycerrhyzia ssp. (in respect to said compounds becomes part of the present appli particular Glycerrhyzia glabra), extracts of Rubus ssp. (in cation by reference, 4-hydroxydihydrochalcones, and in par particular Rubus suavissimus), citrus extracts and extracts 15 ticular phloretin, as disclosed in EP 1998636 B1, which with of Lippia dulcis; extracts of Mycetia balansae, respect to said compounds becomes part of the present appli (b5) synthetic sweet-tasting substances, preferably selected cation by reference, or propenylphenylglycosides (chavicol from the group consisting of magap, sodium cyclamate or glycosides) as described in EP 1955 601 A1, which with other physiologically acceptable salts of cyclamic acid, respect to said compounds becomes part of the present appli acesulfame-K or other physiologically acceptable salts, 20 cation by reference, hydroxyflavans as disclosed in EP 2 253 neohesperidin dihydrochalcone, naringin dihydrochal 226A1, which with respect to said compounds becomes part cone, Saccharin, Saccharin sodium salt, aspartame, of the present application by reference, certain extracts of Superaspartame, neotame, alitame, advantame, perillartin, Hydrangea macrophylla as disclosed in EP 2 298 084 A1, Sucralose, lugduname, carrelame. Sucrononate and which with respect to said compounds becomes part of the SuCrOOCtate. 25 present application by reference, 1-(2,4-dihydroxyphenyl)-3- The aromatic Substances of the above group (b1) are aro (3-hydroxy-4-methoxyphenyl)-propan-1-one as disclosed in matic Substances that produce a Sweet odor impression. The EP 2 353 403 A1, which with respect to this compound aromatic Substances of the above group (b1) do not actually becomes part of the present application by reference and taste Sweet in the narrower sense, but can suggest a Sweet taste triterpenes and triterpene glycosides (balansins) and extracts in the broader sense (including odor perception). 30 of Mycetia balansae (preferably containing balansin A and/or In a preferred configuration, the total amount of com balansin B) as disclosed in the European patent application pounds of formula (I) and the total amount of Sweet-tasting with the application number 11 168468.4 (Symrise), which substances of groups (b4) and (b5) defined above is in the with respect to this compound becomes part of the present range from 0.001 through 1 wt %, preferably in the range application by reference. from 0.001 through 0.5 wt %, more preferably in the range 35 Preferred Substances intensifying Sweet taste are in par from 0.003 through 0.1 wt %, relative to the total mass of the ticular hesperetin, phloretin, 3',7-dihydroxy-4'-methoxyfla orally consumable preparation intended for direct consump van and (S)-3',7-dihydroxy-4-methoxyflavan, certain tion. Hydrangea extracts or phyllodulcin, and 1-(2,4-dihydrox A semifinished product or an orally consumable prepara yphenyl)-3-(3-hydroxy-4-methoxyphenyl)-propan-1-one. tion is preferred according to the invention wherein the both 40 With the substances of the last-mentioned groups, further Sweet-tasting and unpleasant-tasting Substance or Substances intensifying effects with respect to the impression of Sweet of component (c) are selected from the group consisting of ness of the preparations according to the invention can be Steviol glycosides (in particular Stevioside and rebaudioside achieved. A), rubusoside, dulcoside, mogrosides, phyllodulcin, glycyr A preparation according to the invention comprising one or rhetin acid, extracts of Stevia ssp. (in particular Stevia rebau- 45 a plurality of further aromatizing plant extracts, flavoring diana), Luo Han Guo, Rubus suavissimus, Hydrangea dulcis, materials, auxiliaries or carriers is further preferred. Glycyrrhyza glabra, magap, sodium cyclamate, acesulfame Of course, preferred preparations according to the inven K, neohesperidin dihydrochalcone, maringin dihydrochal tion also comprise further usual foodstuff ingredients. cone, Saccharin, Saccharin Sodium salt, aspartame, Superas In a preferred configuration, an orally consumable prepa partame, neotame, alitame. Sucralose, lugduname, carrelame, 50 ration according to the invention comprises, as Sweet-tasting Sucrononate and Sucrooctate. Substance or Sweet-tasting Substances, one or a plurality of A preferred orally consumable preparation according to Sweet-tasting Sugars, wherein the amount of neoflavonoids of the invention comprises, in addition to a compound to be used formula (I), salts thereofand/or mixtures thereof (in each case according to the invention, in addition to a physiologically as defined above) is Sufficient to impart the same or an inten acceptable salt or in addition to a mixture to be used according 55 sified impression of Sweetness, in comparison with a prepa to the invention (as defined above), additionally one or a ration of otherwise identical composition containing neithera plurality of further Substances for intensifying an impression compound of formula (I) nor a salt of a compound of formula of Sweet taste. (I), but comprising at least 1.05 times the amount of Sugar. Further substances for intensifying the impression of sweet An orally consumable preparation intended for direct con taste—without limiting the present invention thereto-are 60 Sumption according to the invention is quite particularly pre preferably selected from the group consisting of hydrox ferred in which the total amount of the compounds of formula ydeoxybenzoins, for example 2-(4-hydroxy-3-methoxyphe (I) is in the range from 3 ppm through 250 ppm, preferably in nyl)-1-(2,4,6-trihydroxyphenyl)ethanone, 1-(2,4-dihydrox the range from 5 ppm through 175 ppm, particularly prefer yphenyl)-2-(4-hydroxy-3-methoxyphenyl)ethanone, 1-(2- ably in the range from 10 through 95 ppm, relative to the total hydroxy-4-methoxyphenyl)-2-(4-hydroxy-3- 65 weight of the preparation. methoxyphenyl)ethanone (in particular as described in WO An orally consumable preparation according to the inven 2006/106023, which with respect to the corresponding com tion is preferred, wherein it is selected from the group con US 9, 131,719 B2 31 32 sisting of pharmaceutical preparation, oral hygiene prepara Zylbenzoate, beta-ionone, butylbutyrate, butyl caproate, tion, liquid and solid foodstuff preparation to be used for butylidene phthalide, carvone, camphene, caryophyllene, nutrition or for pleasure, as well as cosmetic preparations for cineol, cinnamyl acetate, citral, citronellol, citronellal, cit application in the region of the head, wherein said cosmetic ronellyl acetate, cyclohexyl acetate, cymene, damascone, preparations may come in contact with the oral cavity. decalactone, dihydrocoumarin, dimethyl anthranilate, Orally consumable preparations can preferably be sweet dimethyl anthranilate, dodecalactone, ethoxyethyl acetate, tasting preparations to be used for nutrition, food Supple ethylbutyric acid, ethyl butyrate, ethyl caprate, ethyl ments, oral hygiene or pleasure, cosmetic preparations, pref caproate, ethyl crotonate, ethyl furaneol, ethyl guaiacol, erably for application in the region of the head, or oral ethyl isobutyrate, ethyl isovalerate, ethyl lactate, ethyl pharmaceutical preparations (i.e. pharmaceutical prepara 10 methyl butyrate, ethyl propionate, eucalyptol, eugenol, tions intended for oral administration). ethyl heptylate, 4-(p-hydroxyphenyl)-2-butanone, A preferred semifinished product or preparation according gamma-decalactone, geraniol, geranyl acetate, geranyl to the invention is characterized in that the semifinished prod acetate, grapefruit aldehyde, methyl dihydrojasmonate uct or preparation (e.g. Hedion(R), heliotropin, 2-heptanone, 3-heptanone, (i) contains one, two, three, four, five, six, seven, eight, nine, 15 4-heptanone, trans-2-heptenal, cis-4-heptenal, trans-2- ten or a plurality of further aromatic substances with a hexenal, cis-3-hexenol, trans-2-hexenoic acid, trans-3- molar weight above 90 g/mol, preferably above 100 g/mol, hexenoic acid, cis-2-hexenyl acetate, cis-3-hexenyl preferably with a molar weight in the range from 110 g/mol acetate, cis-3-hexenyl caproate, trans-2-hexenyl caproate, through 300 g/mol, more preferably with a molar weight in cis-3-hexenyl formate, cis-2-hexyl acetate, cis-3-hexyl the range from 120 g/mol through 250 g/mol, particularly acetate, trans-2-hexyl acetate, cis-3-hexyl formate, para preferably with a molar weight in the range from 125 g/mol hydroxybenzylacetone, isoamyl alcohol, isoamylisovaler through 220 g/mol, particularly preferably with a molar ate, isobutyl butyrate, isobutyraldehyde, isoeugenol weight in the range from 130 g/mol through 210 g/mol. methyl ether, isopropyl methylthiazole, lauric acid, and/or levulinic acid, linalool, linalool oxide, linallyl acetate, men (ii) the semifinished product or preparation does not contain 25 thol, menthofuran, methyl anthranilate, methylbutanol, one, two, three, four, five, six, seven, eight or all of the methyl butyric acid, 2-methyl butyl acetate, methyl following Substances: caproate, methylcinnamate, 5-methylfurfural, 3.2.2-meth tocopherol quinone, 7-dihydroxymatairesinol, (24S)-eth ylcyclopentenolone, 6.5.2-methylheptenone, methyldihy ylcholesta-33.5C.6C-triol, quercetin, cucurbitacin IIa, drojasmonate, methyl jasmonate, 2-methylmethyl cucurbitacin U, iotroridoside A, pokeweedcerebroside 5 30 butyrate, 2-methyl-2-pentenolic acid, methylthiobutyrate, and bonaroside, 3.1-methylthiohexanol, 3-methylthiohexyl acetate, nerol, and/or neryl acetate, trans,trans-2,4-nonadienal, 2.4-nonadienol, (iii) the semifinished product or preparation does not contain 2,6-nonadienol. 2,4-nonadienol, nootkatone, delta-octa any of the following Substances: lactone, gamma-octalactone, 2-octanol, 3-octanol. 1.3- (24S)-ethylcholesta-3?.5C.6O-triol, iotroridoside A, 35 octenol, 1-octyl acetate, 3-octyl acetate, palmitic acid, pokeweedcerebroside 5, bonaroside, helonioside A, paraldehyde, phellandrene, pentanedione, phenylethyl helonioside B, lapathoside D, vanicoside B. vanicoside acetate, phenylethyl alcohol, phenylethyl alcohol, phenyl C. vanicoside F, asteryunnanoside, hydropiperoside, ethyl isovalerate, piperonal, propionaldehyde, propyl and/or butyrate, pulegon, pulegol, sinensal, Sulfurol, terpinene, (iv) the semifinished product or preparation is free from fresh 40 terpineol, terpinols, 8.3-thiomenthanone, 4.4.2-thiometh or dried parts of plants, in particular is free from leaves and ylpentanone, thymol, delta-undecalactone, gamma-unde leaf parts, of Persicaria perfoliata ( Polygonum perfolia calactone, Valencene, Valeric acid, Vanillin, acetoin, ethyl tum). vanillin, ethylvanillin isobutyrate (3-ethoxy-4-isobutyry A particularly preferred semifinished product or prepara loxybenzaldehyde), 2,5-dimethyl-4-hydroxy-3(2H)-fura tion according to the invention is characterized in that the 45 none and its derivatives (here preferably homofuraneol semifinished product or preparation (=2-ethyl-4-hydroxy-5-methyl-3(2H)-furanone), homofu (i) contains two, three, four, five, six, seven, eight, nine, ten or ronol (=2-ethyl-5-methyl-4-hydroxy-3(2H)-furanone and a plurality of further aromatic substances with a molar 5-ethyl-2-methyl-4-hydroxy-3 (2H)-furanone), maltol and weight above 120 g/mol, preferably with a molar weight maltolderivatives (here preferably ethylmaltol), coumarin, above 125 g/mol, preferably with a molar weight in the 50 gamma-lactones (here preferably gamma-undecalactone, range from 125 g/mol through 220 g/mol, particularly pref gamma-nonalactone, gamma-decalactone), delta-lactones erably with a molar weight in the range from 130 g/mol (here preferably 4-methyldeltadecalactone, massoilac through 210 g/mol. tone, deltadecalactone, tuberolactone), methyl Sorbate, Preferably at least two of the conditions defined above divanillin, 4-hydroxy-2(or 5)-ethyl-5(or 2)-methyl-3(2H) apply, preferably condition (i) and (iv) or condition (i) and 55 furanone, 2-hydroxy-3-methyl-2-cyclopentenone, 3-hy (iii). droxy-4,5-dimethyl-2(5H)-furanone, acetic acid isoamyl Preferably at least three of the conditions defined above ester, butyric acid ethyl ester, butyric acid-n-butyl ester, apply, preferably condition (i), (ii) and (iv) or condition (i), butyric acid isoamyl ester, 3-methyl-butyric acid ethyl (ii) and (iii), or all the conditions (i) through (iv). ester, n-hexanoic acid ethyl ester, n-hexanoic acid allyl In the context of the present invention, (further) aromatic 60 ester, n-hexanoic acid-n-butyl ester, n-octanoic acid ethyl Substances to be used preferably (as constituent of a semifin ester, ethyl-3-methyl-3-phenylglycidate, ethyl-2-trans-4- ished product or preparation according to the invention) are cis-decadienoate, 4-(p-hydroxyphenyl)-2-butanone, 1,1- preferably selected from the following group (A) consisting dimethoxy-2.2.5-trimethyl-4-hexane, 2,6-dimethyl-5- of: hepten-1-al. phenylacetaldehyde, 2-methyl-3- acetophenone, allyl caproate, alpha-ionone, beta-ionone, 65 (methylthio) furan, 2-methyl-3-furanthiol, bis(2-methyl-3- anisaldehyde, anisyl acetate, anisyl formate, benzalde furyl)disulfide, furfurylmercaptan, methional, 2-acetyl-2- hyde, benzothiazole, benzyl acetate, benzyl alcohol, ben thiazoline, 3-mercapto-2-pentanone, 2,5-dimethyl-3- US 9, 131,719 B2 33 34 furanthiol. 2,4,5-trimethylthiazole, 2-acetylthiazole, 2,4- The preparations used for oral hygiene (oral hygiene prod dimethyl-5-ethylthiazole, 2-acetyl-1-pyrroline, 2-methyl ucts) in the sense of the present invention are in particular oral 3-ethylpyrazine, 2-ethyl-3,5-dimethylpyrazine, 2-ethyl-3, and/or dental hygiene products such as toothpastes, dental 6-dimethylpyrazine, 2,3-diethyl-5-methylpyrazine, gels, dental powders, mouthwash, chewing gums and other 3-isopropyl-2-methoxypyrazine, 3-isobutyl-2-methoxy oral hygiene products. pyrazine, 2-acetylpyrazine, 2-pentylpyridine, (E.E)-2,4- Oral pharmaceutical preparations in the sense of the inven decadienal. (E.E)-2,4-nonadienal, (E)-2-octenal, (E)-2- tion are preparations that are for example in the form of nonenal, 2-undecenal, 12-methyltridecanal, 1-penten-3- capsules, tablets (uncoated and coated tablets, e.g. enteric one, 4-hydroxy-2,5-dimethyl-3(2H)-furanone, guaiacol, coatings), Sugar-coated pills, granules, pellets, Solid mix 3-hydroxy-4,5-dimethyl-2(5H)-furanone, 3-hydroxy-4- 10 tures, dispersions in liquid phases, as emulsions, as powders, methyl-5-ethyl-2(5H)-furanone, cinnamaldehyde, cinna as Solutions, as pastes or as other preparations for Swallowing mon alcohol, methyl salicylate, isopulegol and (here not or chewing and are used as prescription-only medicines, explicitly named) Stereoisomers, enantiomers, positional pharmacy-only medicines or other medicinal products or as isomers, diastereomers, cis/trans isomers or epimers of food Supplements. these Substances. 15 Cosmetic preparations for application in the region of the In a preferred configuration, the total amount of a semifin head are in particular those that, when applied properly on the ished product according to the invention, preferably an aro skin, can come in contact with the oral cavity, for example— matic composition according to the invention, preferably as mentioned above-cosmetic preparations for application containing one, two, three, four, five or a plurality of the in the region of the head such as Soaps, other cleaning or care aromatic Substances from group (b1) defined above or from products for the facial Zone, face creams, lotions or oint group (A), is in the range from 0.01 through 2 wt %, prefer ments, Sunscreens, beard cleaning or care products, shaving ably in the range from 0.01 through 1 wt %, more preferably foams, soaps or gels, lipsticks or other lip cosmetics or lip in the range from 0.01 through 0.5 wt %, particularly prefer care products. ably in the range from 0.01 through 0.2 wt %, in each case Other usual active Substances, base Substances, auxiliaries relative to the total mass of the orally consumable preparation 25 and additives used for preparations to be used for nutrition, intended for direct consumption. for oral hygiene or for pleasure, cosmetic or oral pharmaceu The liquid and solid foodstuff preparations in the sense of tical preparations can be contained in amounts of up to the invention used for nutrition or pleasure are for example 99.9999999 wt %, relative to the total weight of the prepara baked products (e.g. bread, cookies, cakes, other baked tion. Moreover, the preparations can contain water in an goods), confectionery in the narrower sense (e.g. chocolates, 30 amount up to 99.99 wt %, preferably 5 through 90 wt %, chocolate bar products, other bar products, fruitgums, hard relative to the total weight of the preparation. and soft toffee, chewing gum), alcoholic or nonalcoholic The preparations according to the invention containing beverages (e.g. coffee, tea, wine, wine-containing beverages, compounds of formula (I) are, according to a preferred con beer, beer-containing beverages, liqueurs, spirits, brandies, figuration, produced by incorporating the compounds of for fruit-containing lemonades, isotonic beverages, refreshing 35 mula (I) preferably as an aromatic composition in the form of beverages, nectars, fruit and vegetable juices, fruit or Veg a mixture with a solidor liquid carrier in an orally consumable etable juice preparations), instant beverages (e.g. instant-co base preparation. Advantageously, preparations according to coa beverages, instant-tea beverages, instant-coffee bever the invention in the form of solution can also be transformed ages), meat products (e.g. ham, sausage or raw sausage by spray-drying into a solid preparation. preparations, spiced or marinated fresh or salted meat prod 40 According to another preferred embodiment, for produc ucts), eggs or egg products (dried egg, egg white, egg yolk)), ing orally consumable preparations according to the inven cereal products (e.g. breakfast cereals, muesli bars, pre tion, the compounds of formula (I) or flavoring compositions cooked prepared rice products), milk products (e.g. milk containing them are also incorporated beforehand in emul drinks, milk ices, yoghurt, kefir, fresh cheese, Soft cheese, sions, in liposomes, e.g. starting from phosphatidylcholine, in hard cheese, dried milk powder, whey, butter, buttermilk, 45 microspheres, in nanospheres or also in capsules, granules or partially or fully hydrolyzed lactoprotein-containing prod extrudates from a matrix for foodstuffs and semi-luxury food ucts), products from Soya protein or other soybean fractions products, e.g. from starch, starch derivatives, cellulose or (e.g. Soya milk and products prepared therefrom, soya leci cellulose derivatives (e.g. hydroxypropylcellulose), other thin-containing preparations, fermented products Such as polysaccharides (e.g. alginate), natural fats, natural waxes tofu or tempeh or products prepared therefrom, soy sauces), 50 (e.g. beeswax, carnauba wax) or from proteins, e.g. gelatins. fruit preparations (e.g. jellies, fruit ices, fruit sauces, fruit In another preferred method of production the compounds fillings), vegetable preparations (e.g. ketchup, sauces, dried of formula (I) or flavoring compositions containing them are Vegetables, frozen vegetables, precooked vegetables, Veg complexed beforehand with one or a plurality of suitable etables pickled in vinegar, preserved vegetables), nibbles complexing agents, for example with cyclodextrins or cyclo (e.g. baked or fried potato chips or potato dough products, 55 dextrin derivatives, preferably C- or B-cyclodextrin, and are bread dough products, extruded products based on maize or used in this complexed form. peanut), fat- and oil-based products or emulsions thereof (e.g. An orally consumable preparation according to the inven mayonnaise, remoulade, dressings, condiment preparations), tion, in which the matrix is selected so that the release of the other ready-meals and Soups (e.g. dried Soups, instant Soups, compounds of formula (I) from the matrix is delayed, thus precooked soups), Spices, condiment mixtures and in particu 60 giving a long-lasting action, is particularly preferred. lar seasonings, which for example find application for Snacks. As further constituents for orally consumable preparations The preparations in the sense of the invention can also be in according to the invention, it is possible to use usual base the form of capsules, tablets (uncoated and coated tablets, e.g. materials, auxiliaries and additives for foods and semi-luxury enteric coatings), Sugar-coated pills, granules, pellets, Solid food products, e.g. water, mixtures of fresh or processed, mixtures, dispersions in liquid phases, as emulsions, as pow 65 plant or animal basic or raw materials (e.g. raw, baked, dried, ders, as Solutions, as pastes or as other preparations for Swal fermented, Smoked and/or boiled meat, bone, cartilage, fish, lowing or chewing as food Supplements. Vegetables, fruit, herbs, nuts, vegetable or fruit juices or US 9, 131,719 B2 35 36 pastes or mixtures thereof), digestible or nondigestible, non adenosine monophosphate or other substances such as Sweet carbohydrates (e.g. dextrins, amylose, amylopectin, Sodium glutamate or 2-phenoxypropionic acid), humectants, inulin, Xylans, cellulose), natural or hardened fats (e.g. tallow, thickeners, emulsifiers, other flavoring materials and stabiliz lard, palm oil, coconut oil, hardened plant oil), oils (e.g. ers or odor correctants. Sunflower oil, peanut oil, corn oil, olive oil, fish oil, soybean 5 As ingredients for oral pharmaceutical preparations oil, Sesame oil), fatty acids or salts thereof (e.g. potassium according to the invention, it is possible to use all usual Stearate), proteinogenic or nonproteinogenic amino acids and further active Substances, base materials, excipients and addi related compounds (e.g. Y-aminobutyric acid, taurine), pep tives for oral pharmaceutical preparations. AS active Sub tides (e.g. glutathione), native or processed proteins (e.g. stances it is in particular also possible to use unpleasant gelatin), enzymes (e.g. peptidases), nucleic acids, nucle 10 tasting orally formulable active pharmaceutical ingredients. otides, other flavor correctants for unpleasant taste impres The active substances, base materials, excipients and addi sions, taste modulators for further, generally not unpleasant tives can be transformed in a manner known perse into the taste impressions, further flavor-modulating Substances (e.g. oral dosage form. This takes place regularly using inert, non inositol phosphate, nucleotides such as guanosine monophos toxic, pharmaceutically suitable excipients. These include, phate, adenosine monophosphate or other Substances such as 15 among others, carriers (e.g. microcrystalline cellulose), Sol Sodium glutamate or 2-phenoxypropionic acid), emulsifiers vents (e.g. liquid polyethylene glycols), emulsifiers (e.g. (e.g. lecithins, diacylglycerols, gum arabic), Stabilizers (e.g. Sodium dodecyl Sulfate), dispersing agents (e.g. polyvi carrageenan, alginate), preservatives (e.g. benzoic acid, Sor nylpyrrolidone), synthetic and natural biopolymers (e.g. bic acid), antioxidants (e.g. tocopherol, ascorbic acid), albumin), stabilizers (e.g. antioxidants such as ascorbic acid), chelating agents (e.g. citric acid), organic or inorganic acidi colorants (e.g. inorganic pigments such as iron oxides) and fying agents (e.g. malic acid, acetic acid, citric acid, tartaric odor correctants and flavor correctants that do not affect the acid, phosphoric acid), additional bitter Substances (e.g. qui bitter taste. nine, caffeine, limonin, amarogentin, humolones, lupolones, Preferably, the orally consumable preparations according catechins, tannins), mineral salts (e.g. sodium chloride, to the invention can also contain further aromatic Substances, potassium chloride, magnesium chloride, Sodium phos 25 to round off and to improve the taste and/or odor of the phates), Substances preventing enzymatic browning (e.g. preparation. Suitable flavoring compositions contain e.g. Syn Sulfite, ascorbic acid), essential oils, plant extracts, natural or thetic, natural or nature-identical aromas, odoriferous and/or synthetic dyes or colored pigments (e.g. carotenoids, fla flavoring materials and Suitable auxiliaries and carriers. It is vonoids, anthocyans, chlorophyll and derivatives thereof), regarded as especially advantageous that any bitter or metal spices, trigeminally effective Substances or plant extracts 30 lic taste impression present, which stems from the aromas, containing said trigeminally effective Substances, synthetic, odoriferous and/or flavoring materials contained in the prepa natural or nature-identical aromatic substances or odoriferous rations according to the invention, can be reduced or Sup Substances and odor correctants. pressed and thus the overall aroma or taste profile is Dental hygiene products (as an example of preparations improved. used for oral hygiene) generally comprise an abrasive system 35 As already described, one aspect of the present invention (abrasive or polishing medium), for example silicic acids, relates to the use of a compound of formula (I) to be used calcium carbonates, calcium phosphates, aluminum oxides according to the invention, a salt to be used according to the and/or hydroxyapatites, Surface-active Substances e.g. invention or a mixture to be used according to the invention Sodium lauryl Sulfate, sodium lauryl sarcosinate and/or coca (in each case as defined above), or a semifinished product midopropyl betaine, humectants e.g. glycerol and/or Sorbitol, 40 according to the invention (as defined above) thickening agents, e.g. carboxymethylcellulose, polyethyl to achieve an impression of Sweet taste, ene glycols, carrageenan and/or Laponite R, flavor cor to intensify an impression of Sweet taste, rectants for unpleasant taste impressions, flavor correctants and/or for further, as a rule not unpleasant taste impressions, flavor as flavor correctant. modulating Substances (e.g. inositol phosphate, nucleotides 45 In a particularly preferred embodiment of the invention, in Such as guanosine monophosphate, adenosine monophos addition to a compound of formula (I), a physiologically phate or other Substances such as Sodium glutamate or 2-phe acceptable salt of a compound of formula (I), a mixture to be noxypropionic acid), Substances with a cooling effect e.g. used according to the invention (in each case as defined menthol, mentholderivatives (e.g. L-menthol, L-menthyllac above), a preparation according to the invention additionally tate, L-menthyl alkyl carbonates, menthone ketals, men 50 comprises one or a plurality of further flavor correctants, i.e. thane-carboxylic acid amides), 2.2.2-trialkyl acetic acid one or a plurality of further Substances not corresponding to amides (e.g. 2.2-diisopropylpropionic acid methyl amide), formula (I) or a salt thereof, wherein the flavor correctant is icilin derivatives, stabilizers and active substances, for suitable or the flavor correctants are suitable for example sodium fluoride, Sodium monofluorophosphate, tin altering or masking (where masking means reducing or difluoride, quaternary ammonium fluorides, Zinc citrate, Zinc 55 completely suppressing) the unpleasant taste impression Sulfate, tin pyrophosphate, tin dichloride, mixtures of various of one or a plurality of unpleasant tasting Substances, or pyrophosphates, triclosan, cetylpyridinium chloride, alumi intensifying a pleasant taste impression, preferably another num lactate, potassium citrate, potassium nitrate, potassium taste impression additional to an impression of Sweet chloride, strontium chloride, hydrogen peroxide, flavoring taste, or materials and/or sodium bicarbonate or odor correctants. 60 intensifying a pleasant tasting Substance, preferably a Chewing gums (as a further example of preparations to be pleasant tasting Substance that in addition to an impres used for oral hygiene or pleasure) generally comprise a chew sion of Sweet taste, imparts another pleasant taste ing gum base, i.e. a chewing paste that becomes plastic as it is impression. chewed, other flavor correctants for unpleasant taste impres The additional flavor correctants can preferably be selected sions, taste modulators for further, as a rule not unpleasant 65 from the following list: nucleotides (e.g. adenosine-5'-mono taste impressions, flavor-modulating Substances (e.g. inositol phosphate, cytidine-5'-monophosphate) or pharmaceutically phosphate, nucleotides such as guanosine monophosphate, acceptable salts thereof, lactisole, sodium salts (e.g. sodium US 9, 131,719 B2 37 38 chloride, Sodium lactate, Sodium citrate, sodium acetate, cation by reference, umami compounds as described in WO Sodium gluconoate), hydroxyflavanones, for example eriod 2008/046895 A1 and EP 1989 944 A1, which in each case ictyol, sterubin (eriodictyol-7-methyl ether), homoeriodic with respect to these compounds form part of this application tyol, and Sodium, potassium, calcium, magnesium or Zinc by reference and umami compounds as described in EP2064 salts thereof (in particular as described in EP 1258 200 A2, 959 A1 or EP 2 135 516 A1, which with respect to the which with respect to the corresponding compounds dis corresponding compounds disclosed thereinform part of this closed therein forms part of this application by reference), application by reference, phyllodulcin or extracts of Hydran hydroxybenzoic acid amides, for example 2,4-dihydroxyben gea macrophylla var. Thunbergii makino and flavoring com Zoic acid vanillyl amide, 2,4-dihydroxybenzoic acid-N-(4- positions derived therefrom, as described in EP 2298 084A1 hydroxy-3-methoxybenzyl)amide, 2,4,6-trihydroxybenzoic 10 acid-N-(4-hydroxy-3-methoxybenzyl)amide, 2-hydroxy or US 2011/0076239A1, which with respect to these extracts benzoic acid-N-4-(hydroxy-3-methoxybenzyl)amide, 4-hy or phyllodulcin form part of this application by reference, droxybenzoic acid-N-(4-hydroxy-3-methoxybenzyl)amide, hydroxyflavan derivatives and flavoring compositions 2,4-dihydroxybenzoic acid-N-(4-hydroxy-3-methoxyben derived therefrom, as described in US 2010/0292175 A1, Zyl)amide-monosodium salt, 2,4-dihydroxybenzoic acid-N- 15 which with respect to these compounds and the flavoring 2-(4-hydroxy-3-methoxyphenyl)ethyl amide, 2,4-dihy compositions derived therefrom form part of this application droxybenzoic acid-N-(4-hydroxy-3-ethoxybenzyl)amide, by reference and certain neoflavonoids as disclosed in the 2,4-dihydroxybenzoic acid-N-(3,4-dihydroxybenzyl)amide European patent application with the application number EP and 2-hydroxy-5-methoxy-N-2-(4-hydroxy-3-methoxyphe 11 181 504.9 (Symrise). nyl)ethylamide: 4-hydroxybenzoic acid vanillyl amide (in If a preparation according to the invention for example particular as described in WO 2006/024587, which with contains a comparatively high concentration of a compound respect to the corresponding compounds disclosed therein of formula (I) to be used according to the invention, of a forms part of this application by reference); hydroxydeoxy physiologically acceptable salt of a compound of formula (I), benzoins, for example 2-(4-hydroxy-3-methoxyphenyl)-1- or of a mixture to be used according to the invention, it may (2,4,6-trihydroxyphenyl)ethanone, 1-(2,4-dihydroxyphe 25 happen that as well as the desired sensory effects described, nyl)-2-(4-hydroxy-3-methoxyphenyl)ethanone, 1-(2- additional undesirable taste impressions arise. These undesir hydroxy-4-methoxyphenyl)-2-(4-hydroxy-3- able taste impressions can be at least partially reduced or even methoxyphenyl)ethanone) (in particular as described in WO completely Suppressed with flavor correctants. In such a case, 2006/106023, which with respect to the corresponding com the flavor correctants are preferably selected from the group pounds disclosed therein forms part of this application by 30 consisting of Sodium salts (thereby preferably sodium chlo reference); hydroxyphenylalkane dione, for example ginger ride, Sodium lactate, sodium citrate, sodium acetate, sodium dione-2, gingerdione-3, gingerdione-4, dehydroginger gluconoate), homoeriodictyolor its sodium salts, eriodictyol. dione-2, dehydrogingerdione-3, dehydrogingerdione-4) trans-pellitorin and Rubus extracts, preferably Rubus extracts (in particular as described in WO 2007/003527, which with as described in the European patent application with the respect to the corresponding compounds disclosed therein 35 application number 11 165566.8 (Symrise). forms part of this application by reference); diacetyl trimers (in particular as described in WO 2006/058893, which with EXAMPLES respect to the corresponding compounds disclosed therein forms part of this application by reference); y-aminobutyric The following examples have the purpose of clarifying the acids (in particular as described in WO 2005/096841, which 40 invention, without limiting it thereby. Unless stated other with respect to the corresponding compounds disclosed wise, all data refer to weight. thereinforms part of this application by reference); divanil The extract of Mycetia balansae and the compounds bal lins (in particular as described in WO 2004/078302, which ansin A and balansin B used hereunder were obtained as with respect to the corresponding compounds disclosed described in the European patent application with the appli thereinforms part of this application by reference) and 4-hy 45 cation number 11 168468.4 (Symrise). droxydihydrochalcones, preferably as described in US 2008/ 227867 A1, which with respect to the corresponding com Examples pounds disclosed therein becomes part of the present application by reference, including in particular phloretin and The examples have the purpose of clarifying the invention, davidigenin, amino acids or mixtures of whey proteins with 50 without limiting it. Unless stated otherwise, all data refer to lecithins, hesperetinas disclosed in WO 2007/014879, which weight. with respect to said compounds becomes part of the present application by reference, 4-hydroxydihydrochalcone as dis Example 1 closed in WO 2007/107596, which with respect to said com (4S)-7-Methoxy-4-(4-methoxyphenyl)chroman-2- pounds becomes part of the present application by reference, 55 or propenylphenyl glycosides (chavicol glycosides) as one (1) and (4R)-7-methoxy-4-(4-methoxyphenyl) described in EP 1955 601 A1, which with respect to said chroman-2-one (2) compounds becomes part of the present application by refer (1) ence, pellitorin, in particular trans-pellitorin, and flavoring O compositions derived therefrom as described in EP 2008530 60 A1, which with respect to these compounds and flavoring O compositions form part of this application by reference, cer tain extracts of Rubus Suavissimus as described in U.S. pro visional application 61/333,435 (Symrise) and the patent applications based thereon (e.g. the European patent applica 65 tion with the application number 11 165566.8 (Symrise)). S-C O which with respect to these extracts form part of this appli US 9, 131,719 B2 39 40 -continued 30 mmol of 3,5-dimethoxyphenol and 30 mmol of 4-meth (2) oxycinnamic acid were put in 70 ml of 1,4-dioxane and 2.0 ml O of concentrated sulfuric acid and heated under reflux for 24 hours. The reaction mixture was poured into 600 ml of 5% O sodium bicarbonate solution and was extracted with 300 ml of methyl tert-butyl ether. The organic phase is then washed again with 100 ml of 5% sodium bicarbonate solution, dried over Sodium Sulfate and concentrated by evaporation. The solid obtained was recrystallized from hexane/acetone (5:2). No D No1 10 Yield: 12.0 mmol (40% of theor.) Analysis Data: 30 mmol of 3-methoxyphenol and 30 mmol of 4-methoxy 'H-NMR (400 MHz, CDC1): 2.98 (m, 2H); 3.75 (s, 6H): cinnamic acid were put in 70 ml of 1,4-dioxane and 2.0 ml of 3.81 (s.3H); 4.51 (t, J–4.4 Hz, 1H); 6.27 (d. J=6.3 Hz, 1H): concentrated sulfuric acid and heated under reflux for 24 6.32 (d. J=6.3 Hz, 1H); 6.79 (m, 2H); 7.02 (m, 2H) ppm. hours. The reaction mixture was poured into 600 ml of 5% 15 C-NMR (100 MHz, CDC1): 33.7 (CH); 37.3 (CH): sodium bicarbonate solution and was extracted with 300 ml of 55.2 (CH); 55.6 (CH); 55.8 (CH): 93.9 (CH): 95.1 (CH): methyl tert-butyl ether. The organic phase is then washed 106.4 (C); 114.2 (CH); 127.8 (CH); 133.6 (C); 153.0 (C); again with 100 ml of 5% sodium bicarbonate solution, dried 1574 (C); 158.6 (C); 160.6 (C); 167.8 (C=O) ppm. over Sodium Sulfate and concentrated by evaporation. The Mass spectrum (EI): m/z (%)=315 (20); 314 (M', 100); solid obtained was recrystallized from hexane/acetone (80: 286 (38): 272 (14); 271 (74); 257 (14); 241 (32); 207 (19); 121 45). (11); 69 (8). Yield: 4.2 mmol (14% of theor.) Example 3 Analysis Data: 'H-NMR (400 MHz, CDC1): 2.95 (dd, J=8.0/15.8 Hz, 25 (4S)-4-(4-Hydroxyphenyl)-5,7-dimethoxy-chroman 1H); 3.03 (dd, J=5.9/15.8 Hz, 1H); 3.79 (s.3H); 3.80 (s.3H): 2-one (5) and (4R)-4-(4-hydroxyphenyl)-5,7- 4.24 (dd, J=5.9/8.0 Hz, 1H); 6.63 (dd, J=2.6/8.5 Hz 1H); 6.68 dimethoxy-chroman-2-one (6) (d. J=2.6 Hz, 1H); 6.84-6.90 (kB, 3H); 7.04-7.09 (m, 2H) ppm. C-NMR (100 MHz, CDC1): 37.5 (CH.); 39.3 (CH); 30 55.3 (CH); 55.6 (CH); 102.5 (CH): 110.7 (CH); 114.5 (5) (CH); 118.1 (C); 128.6 (CH); 128.9 (CH); 132.7 (C); 152.4 (C); 158.9 (C); 160.0 (C); 167.8 (C=O) ppm. Mass spectrum (EI): m/z (%)=285 (19); 284 (M', 100); 256 (29): 253 (9): 242 (17): 241 (84); 227 (16); 212 (11): 211 35 (56); 128 (12). Example 2

(4S)-5,7-Dimethoxy-4-(4-methoxyphenyl)chroman 40 2-one (3) and (4R)-5,7-dimethoxy-4-(4-methoxyphe nyl)chroman-2-one (4) (6)

O 45 (3)

No O''',Ol OH 50

40 mmol of 3,5-dimethoxyphenol and 40 mmol of 4-hy droxycinnamic acid were put in 70 ml of 1,4-dioxane and 1.5 55 ml of concentrated sulfuric acid and heated under reflux for (4) 24 hours. The reaction mixture was poured into 600 ml of water, whereupon the product precipitates. The solid is fil tered off and washed with ethanol/water (1:1) and then recrystallized twice from ethanol/water (1:1). 60 Yield: 13.6 mmol (34% of theor.) Analysis Data: 'H-NMR (400 MHz, CDC1): 2.97 (m, 2H); 3.76 (s.3H): 3.82 (s, 3H); 4.50 (t, J–4.6 Hz, 1H); 4.87 (s, 1H); 6.28 (d. J=2.3 Hz, 1H); 6.32 (d. J=2.3 Hz, 1H); 6.71 (m, 2H); 7.97 (m, 65 2H) ppm. C-NMR (100 MHz, CDC1): 33.7 (CH); 37.3 (CH): 55.6 (CH); 55.8 (CH): 94.0 (CH): 95.2 (CH); 106.4 (C); US 9, 131,719 B2 41 42 115.6 (CH): 128.0 (CH); 133.7 (C); 153.0 (C); 154.6 (C); Mass spectrum (EI): m/z (%)=301 (23): 300 (M", 100); 157.4 (C); 160.6 (C); 168.0 (C=O) ppm. 282 (23); 267 (25): 257 (90); 243 (31); 241 (83): 227 (41): 176 Mass spectrum (EI): m/z (%)=301 (19); 300 (M", 100); (70): 133 (27). 272 (37): 258 (14); 257 (72); 241 (20): 207 (12): 154 (9): 153 (8): 69 (11). 5 Example 5

Example 4 (4S)-4-(3-Hydroxy-4-methoxyphenyl)-5,7- dimethoxy-chroman-2-one (9) and (4R)-4-(3-hy (4S)-4-(3-Hydroxy-4-methoxyphenyl)-7-methoxy 10 droxy-4-methoxyphenyl)-5,7-dimethoxy-chroman-2- chroman-2-one (7) and (4R)-4-(3-hydroxy-4-meth one (10) oxyphenyl)-7-methoxy-chroman-2-one (8)

15 (9) (7)

O O OH

No o1 25 C

(8) 30 (10)

O O ''. OH 35 '' OH No O 1. O No O O o1

40 mmol of 3-methoxyphenol and 40 mmol of isoferulic 40 acid were put in 70 ml of 1,4-dioxane and 2.0 ml of concen trated sulfuric acid and heated under reflux for 24 hours. The 40 mmol of 3,5-dimethoxyphenol and 40 mmol of isoferu reaction mixture was poured into 600 ml of 5% sodium bicar lic acid were put in 70 ml of 1,4-dioxane and 2.0 ml of concentrated sulfuric acid and heated under reflux for 24 bonate solution and was extracted with 300 ml of methyl 45 tert-butyl ether. The organic phase is then washed again with hours. The reaction mixture was poured into 600 ml of 5% 100 ml of 5% sodium bicarbonate solution, dried over sodium sodium bicarbonate solution and was extracted with 300 ml of Sulfate and concentrated by evaporation. The oily product methyl tert-butyl ether. The organic phase is then washed was purified by column chromatography (methyl tert-butyl 50 again with 100 ml of 5% sodium bicarbonate solution, dried ether/hexane, 1:1) and the resultant solid was recrystallized over Sodium Sulfate and concentrated by evaporation. The from ethanol/water (1:1). solid obtained was recrystallized from hexane/acetone (5:2). Yield: 4.1 mmol (10% of theor.) Yield: 7.1 mmol (18% of theor.) Analysis Data: 55 Analysis Data: 'H-NMR (400 MHz, CDC1): 2.94 (dd, J=5.7/15.8 Hz, 'H-NMR (400 MHz, CDC1): 2.94 (dd, J–7.7/15.8 Hz, 1H); 2.99 (dd, J=3.4/15.8 Hz, 1H); 3.75 (s.3H); 3.81 (s.3H): 1H); 3.02 (dd, J=5.9/15.8 Hz, 1H); 3.80 (s.3H); 3.86 (s.3H): 3.83 (s.3H); 4.47 (dd, J=3.2/5.7 Hz, 1H); 5.55 (s, 1H); 6.27 4.18 (m, 1H); 5.70 (s, 1H); 6.59-6.67 (kB,3H); 6.71 (d. J–2.2 (d. J=2.3 Hz, 1H); 6.31 (d. J=2.3 Hz, 1H); 6.56 (ddd, J=0.6/ HZ, 1H); 6.79 (d. J=8.3 Hz, 1H); 6.89 (m. 1H) ppm. 60 2.2/8.3 Hz, 1H); 6.70 (dd, J=0.3/2.2 Hz, 1H); 6.72 (d. J=8.4 'C-NMR (100 MHz, CDC1): 37.4 (CH), 39.5 (CH): HZ, 1H) ppm. C-NMR (100 MHz, CDC1): 33.9 (CH); 37.3 (CH): 55.6 (CH); 56.0 (CH); 102.5 (CH): 110.7 (CH): 111.0 55.6 (CH):55.85 (CH); 55.93 (CH): 94.0 (CH);95.1 (CH): (CH); 113.7 (CH); 117.8 (C); 119.0 (CH); 128.9 (CH); 133.9 65 106.2 (C); 110.9 (CH); 113.4 (CH): 117.9 (CH): 134.8 (C); (C); 145.9 (C); 146.0 (C); 152.4 (C); 159.9 (C); 167.8 (0–0) 145.6 (C); 145.7 (O): 153.1 (C); 157.4 (C); 160.6 (C); 167.7 ppm. (C=O) ppm. US 9, 131,719 B2 43 44 Mass spectrum (EI): m/z (%)=331 (20): 330 (M", 100); Mass spectrum (EI): m/z (%)=299 (19); 298 (M", 100); 302 (10);287 (41); 273 (12); 271 (17): 257 (10); 207 (11): 176 270 (13): 256 (25): 255(51): 239 (17): 228 (25): 214 (11); 213 (30): 154 (38); 137 (11). (39); 197 (15).

Example 6 Example 7

(4S)-4-(4-Hydroxyphenyl)-7-propoxy-chroman-2- (4S)-7-Ethoxy-4-(4-hydroxyphenyl)chroman-2-one one (11) and (4R)-4-(4-hydroxyphenyl)-7-propoxy 10 (13) and (4R)-7-ethoxy-4-(4-hydroxyphenyl)chro chroman-2-one (12) man-2-one (14)

(11) 15 (13)

O O

N-1\o OH 1No OH 25

(12) O (14) O

O O '', 35 N-1 no OH 1No OH

15 mmol of 3-propoxyphenol and 15 mmol of 4-hydroxy 15 mmol of 3-ethoxyphenol and 15 mmol of 4-hydroxy cinnamic acid were put in 70 ml of 1,4-dioxane and 1.0 ml of a cinnamic acid were put in 70 ml of 1,4-dioxane and 1.0 ml of concentrated sulfuric acid and heated under reflux for 24 concentrated sulfuric acid and heated under reflux for 24 hours. The reaction mixture was poured into 250 ml of 5% sodium bicarbonate solution and was extracted with 300 ml of hours. The reaction mixture was poured into 250 ml of 5% methyl tert-butyl ether. The organic phase is then washed 45 sodium bicarbonate solution and was extracted with 300 ml of methyl tert-butyl ether. The organic phase is then washed again with 50 ml of saturated sodium chloride solution, dried over Sodium Sulfate and concentrated by evaporation. The again with 50 ml of saturated sodium chloride solution, dried oily product was purified by column chromatography (methyl over Sodium Sulfate and concentrated by evaporation. The tert-butyl ether/hexane, 1:1). 50 oily product was purified by column chromatography (methyl tert-butyl ether/hexane, 1:1). Yield: 4.3 mmol (29% of theor.) Analysis Data: Yield: 4.5 mmol (30% of theor.) Analysis Data: 'H-NMR (400 MHz, CDC1): 1.03 (t, J=7.4 Hz, 3H); 1.81 55 (td, J=6.6/7.4 Hz, 2H); 2.95 (dd, J=7.6/15.7 Hz, 1H);3.03 (dd, 'H-NMR (400 MHz, CDC1): 1.42 (t, J–7.0 Hz, 3H); 2.94 J=5.9/15.7 Hz, 1H); 3.90 (t, J=6.6 Hz, 2H); 4.22 (dd, J=6.1/ (dd, J=7.8/15.8 Hz, 1H); 3.03 (dd, J=5.9/15.8 Hz, 1H); 4.02 7.5 Hz, 1H); 5.12 (bs, 1H); 6.63 (dd, J=2.5/8.4 Hz, 1H); 6.66 (q, J–7.0 Hz, 2H); 4.22 (dd, J=5.9/7.9 HZ, 1H); 4.87 (s, 1H): (d. J=2.5 Hz, 1H); 6.78 (m, 2H); 6.86 (ddd, J=0.4/0.9/8.4 Hz, 60 6.62 (dd, J=2.5/8.4 Hz, 1H); 6.67 (d. J=2.6 Hz, 1H); 6.79 (m, 1H); 7.0 (m. 2H) ppm. 2H); 6.86 (ddd, J=0.4/0.9/8.4 Hz, 1H); 7.01 (m, 2H) ppm. 'C-NMR (100 MHz, CDC1): 10.5 (CH); 22.5 (CH): 'C-NMR (100 MHz, CDC1): 14.7 (CH,); 37.6 (CH): 37.6 (CH); 39.3 (CH); 69.9 (CH); 103.0 (CH); 111.3 (CH): 65 39.3 (CH): 63.9 (CH); 103.0 (CH): 111.3 (CH); 115.9 (CH): 115.9 (CH); 117.7 (C); 128.7 (CH); 128.8 (C); 132.9 (C); 117.8 (C); 128.78 (CH): 128.81 (CH); 133.0 (C); 152.4 (C); 152.3 (C); 155.0 (C); 159.5 (C); 168.1 (C=O) ppm. 154.9 (C); 159.3 (C); 167.9 (C=O) ppm. US 9, 131,719 B2 45 46 Mass spectrum (EI): m/z (%)=285 (19); 284 (M', 100); Mass spectrum (EI): m/z (%)=301 (20): 300 (M", 100); 256 (26); 242 (16); 241 (74); 227 (8): 225 (23); 213 (21): 128 272 (11); 267 (11): 257 (46): 243 (9): 242 (13): 241 (29): 227 (9): 77 (8). (22): 176 (19).

Example 8 Example 9

(4S)-4-(4-Hydroxy-3-methoxyphenyl)-7-methoxy (4S)-4-(4-Hydroxy-3-methoxyphenyl)-5,7- chroman-2-one (15) and (4R)-4-(4-hydroxy-3-meth dimethoxy-chroman-2-one (17) and (4R)-4-(4-hy Oxyphenyl)-7-methoxy-chroman-2-one (16) droxy-3-methoxyphenyl)-5,7-dimethoxy-chroman-2- one (18)

15 (15) (17) O

O

No C c OHO No OH 25

(16) (18) O

O 30 O

O '' O

No O OH 35 No O O OH 40 mmol of 3-methoxyphenol and 40 mmol offerulic acid were put in 70 ml of 1,4-dioxane and 2.0 ml of concentrated 40 mmol of 3,5-dimethoxyphenol and 40 mmol of ferulic sulfuric acid and heated under reflux for 24 hours. The reac 40 acid were put in 70 ml of 1,4-dioxane and 2.0 ml of concen tion mixture was poured into 600 ml of 5% sodium bicarbon trated sulfuric acid and heated under reflux for 24 hours. The ate solution and was extracted with 300 ml of methyl tert reaction mixture was poured into 600 ml of 5% sodium bicar butyl ether. The organic phase is then washed again with 100 bonate solution and was extracted with 300 ml of methyl ml of saturated sodium bicarbonate solution, dried over 45 tert-butyl ether. The organic phase is then washed again with Sodium Sulfate and concentrated by evaporation. The crude 100 ml of 5% sodium bicarbonate solution, dried over sodium product was purified by column chromatography (methyl sulfate and concentrated by evaporation. The solid obtained tert-butyl ether/hexane, 1:1). 50 was recrystallized from methyl tert-butyl ether/hexane. Yield: 12.7 mmol (32% of theor.) Yield: 17.4 mmol (44% of theor.) Analysis Data: Analysis Data:

H-NMR (400 MHz, CDC1): 2.95 (dd, J=8.1/15.6 Hz, 55 H-NMR (400 MHz, CDC1): 2.97 (m, 2H); 3.76 (s.3H): 1H); 3.04 (dd, J=5.9/15.6 Hz, 1H); 3.81 (s.3H); 3.84 (d. J=0.2 3.81 (s.3H); 3.83 (s.3H); 4.49 (dd, J=4.5/5.3 Hz, 1H); 5.50 Hz, 3H); 4.21 (dd, J=5.9/8.2 Hz, 1H); 5.57 (d. J=0.3 Hz, 1H): (d. J=0.4 Hz, 1H); 6.28 (d. J–2.3 Hz, 1H); 6.32 (d. J=2.3 Hz, 6.61-6.69 (kB, 4H); 6.88 (d. J–8.1 Hz, 1H); 6.89 (ddd, J=0.3/ 1H); 6.59 (m. 1H); 6.62 (d. J=2.1 Hz, 1H); 6.78 (d. J=8.1 Hz, 0.8/8.4 Hz, 1H) ppm. 60 1H) ppm. C-NMR (100 MHz, CDC1): 37.6 (CH.); 39.9 (CH); 'C-NMR (100 MHz, CDC1): 34.2 (CH); 37.4 (CH): 55.6 (CH.); 55.9 (CH), 102.5 (CH); 109.7 (CH); 110.7 55.6 (CH):55.82 (CH):55.85 (CH,): 94.0 (CH);95.1 (CH): (CH); 114.8 (CH); 118.0 (C); 120.5 (CH); 128.9 (CH); 132.6 106.4 (C); 109.2 (CH); 114.5 (CH): 119.5 (CH); 133.5 (C); (C); 1450(C); 146.9 (C); 1524(C); 1600 (C); 1678 (C=O) “ 144.7 (C); 146.7 (C); 153.0 (C); 157.4 (C); 160.6 (C); 167.9 (C=O) ppm. US 9, 131,719 B2 47 48 Mass spectrum (EI): m/z (%)=331 (20): 330 (M", 100); Mass spectrum (EI): m/z (%)=271 (18): 270 (M", 100); 242 (29): 228 (20); 227 (97): 212 (9): 211 (37); 128 (9): 121 302(16): 287(41); 272 (10); 271 (17): 257 (14); 207 (10); 176 (9): 77 (10). (20): 154 (25). Example 11 Example 10 (4S)-4-(4-Hydroxy-3-methoxyphenyl)-7-propoxy chroman-2-one (21) and (4R)-4-(4-hydroxy-3-meth Oxyphenyl)-7-propoxy-chroman-2-one (22) (4S)-4-(4-Hydroxyphenyl)-7-methoxy-chroman-2- one (19) and (4R)-4-(4-hydroxyphenyl)-7-methoxy 10 chroman-2-one (20) (21)

15 O (19)

O ury O OH (22) O

No OH O 25 O

l O O OH (20) 30 15 mmol of 3-propoxyphenol and 15 mmol of ferulic acid were put in 70 ml of 1,4-dioxane and 1.0 ml of concentrated O sulfuric acid and heated under reflux for 24 hours. The reac tion mixture was poured into 250 ml of saturated sodium 35 bicarbonate solution and extracted with 300 ml of methyl tert-butyl ether. The organic phase is then washed with 50 ml of saturated sodium chloride solution, dried over sodium No Ol OH Sulfate and concentrated by evaporation. The crude product was purified by column chromatography (methyl tert-butyl ether/hexane, 1:1). 40 mmol of 3-methoxyphenol and 40 mmol of 4-hydroxy 40 Yield: 7.0 mmol (47% of theor.) cinnamic acid were put in 70 ml of 1,4-dioxane and 2.0 ml of Analysis Data: 'H-NMR (400 MHz, CDC1): 1.04 (t, J–74 Hz, 3H); 1.81 concentrated sulfuric acid and heated under reflux for 24 (td, J=6.5/7.4 Hz, 2H); 2.95 (dd, J=8.1/15.8 Hz, 1H);3.04 (dd. hours. The reaction mixture was poured into 600 ml of 5% J=5.9/15.8 Hz, 1H); 3.83 (s.3H); 3.91 (t, J=6.6 Hz, 2H); 4.21 sodium bicarbonate solution and was extracted with 300 ml of 45 (dd, J–5.8/8.2 Hz, 1H); 5.59 (d. J=0.3 Hz, 1H); 6.61-6.68 (m, 4H); 6.87 (ddd, J=0.4/0.9/8.4 Hz, 1H); 6.87 (d. J=8.1 Hz, 1H) methyl tert-butyl ether. The organic phase is then washed ppm. again with 100 ml of 5% sodium bicarbonate solution, dried 'C-NMR (100 MHz, CDC1): 10.5 (CH); 22.5 (CH): 37.6 (CH.); 39.9 (CH); 55.9 (CH.); 69.9 (CH,); 103.0 (CH): over Sodium Sulfate and concentrated by evaporation. The 50 109.7 (CH); 111.3 (CH); 114.8 (CH); 117.7 (C); 120.5 (CH): solid obtained was recrystallized from hexane/acetone. 128.8 (CH); 132.6 (C); 145.0 (C); 146.9 (C); 152.4(C); 159.5 (C); 167.9 (C=O) ppm. Yield: 4.4 mmol (11% of theor.) Mass spectrum (EI): m/z (%)=329 (22); 328 (M', 100); Analysis Data: 286 (15): 285 (32); 269 (20);255 (11): 243 (18): 227 (10); 213 55 (11): 176 (13). 'H-NMR (400 MHz, CDC1): 2.95 (dd, J–7.8/15.7 Hz, Example 12 1H); 3.03 (dd, J=6.0/15.7 Hz, 1H); 3.80 (s, 3H); 4.23 (dd, (4S)-5-Hydroxy-4-(4-hydroxy-3-methoxyphenyl)-7- J=6.2/73 Hz, 1H); 4.89 (bs, 1H); 6.64 (dd, J=2.3/8.3 Hz, 1H): methoxy-chroman-2-one (23) and (4R)-5-hydroxy-4- 6.68 (d. J=2.7 Hz, 1H); 6.79 (m,2H); 6.87 (ddd, J=0.3/0.8/8.8 60 (4-hydroxy-3-methoxyphenyl)-7-methoxy-chroman 2-one (24) plus (4S)-7-hydroxy-4-(4-hydroxy-3- HZ, 1H): 7.01 (m, 2H) ppm. methoxyphenyl)-5-methoxy-chroman-2-one (A) and C-NMR (100 MHz, CDC1): 37.5 (CH.); 39.3 (CH); (4R)-7-hydroxy-4-(4-hydroxy-3-methoxyphenyl)-5- 55.6 (CH,); 102.5 (CH): 110.8 (CH); 115.9 (CH): 117.9 (C); methoxy-chroman-2-one (B) 65 128.8 (CH): 128.9 (CH); 132.9 (C); 152.4 (C); 154.9 (C); 0.5 ml of concentrated sulfuric acid was added to a mixture 160.0 (C); 167.9 (C=O) ppm. of 17.5 mmol of trans-4-hydroxycinnamic acid and 17.5 US 9, 131,719 B2 49 50 mmol of 5-methylresorcinol in 40 ml of 1,4-dioxane and it Example 12b was heated under reflux for 12 hours. After cooling, the reac tion mixture was poured into 250 ml of demineralized water (4S)-7-Hydroxy-4-(4-hydroxy-3-methoxyphenyl)-5- and was extracted with 150 ml of ethyl acetate (EAc). The methoxy-chroman-2-one (A) and (4R)-7-hydroxy-4- organic phase was washed twice with 50 ml of demineralized (4-hydroxy-3-methoxyphenyl)-5-methoxy-chroman water and 50 ml of 5% sodium bicarbonate solution each 2-one (B) time, and was dried over Sodium sulfate. After removing the Solvent, the product was purified by silica-gel column chro 10 matography (solvent: ethyl acetate/hexane 2:3). According to O (A) NMR, the product consisted of two isomers, which were in the ratio 37:63 (23/24: A/B). Further separation was carried O out by preparative HPLC (Phenomenex Luna C18 (2), 5um, 15 150x21.5 mm; acetonitrile/water 75:25:25 ml/min: 105 bar). Yield: 9.8 mmol (56% of theor.) Cryos HO OH Example 12a O (B) (4S)-5-Hydroxy-4-(4-hydroxy-3-methoxyphenyl)-7- methoxy-chroman-2-one (23) and (4R)-5-hydroxy-4- O (4-hydroxy-3-methoxyphenyl)-7-methoxy-chroman 25 2-one (24)

HO O''',OC OH (23) 30 O

O Analysis Data: Retention time: 17.0 min-19.8 min 35 H-NMR (400 MHz, CDC1): 2.95-2.99 (kB, 2H); 3.76 (s, Cryos 3H); 3.81 (s.3H); 4.48 (dd, J=3.9/4.7 Hz, 1H); 5.19 (bs, 1H): 5.49 (bs, 1H); 6.25 (d. J=2.3 Hz, 1H); 6.27 (d. J=2.3 Hz, 1H): OH OH 6.59 (dd, J=2.1/7.9 Hz: 1H); 6.61 (d. J=2.1 Hz, 1H); 6.79 (d. J–7.9 HZ, 1H) ppm. (24) 40 O 'C-NMR (100 MHz, (CD) SO): 33.1 (CH); 38.8-40.1 (CH; masked by solvent signal); 55.5 (CH); 55.6 (CH): 95.4 (CH); 95.6 (CH); 104.3 (C); 111.1 (CH): 115.2 (CH): O 118.1 (CH); 132.7 (C); 145.3 (C); 147.5 (C); 152.5 (C); 157.0 45 (C); 158.2 (C); 167.7 (C=O) ppm. HRMS M-H, CH: calc.: 315.0874. found: 3150920. O OH'',OC OH 50 Example 13 Analysis Data: (4S)-7-Ethoxy-4-(4-hydroxy-3-methoxyphenyl)chro Retention time: 20.3 min-21.8 min man-2-one (25) and (4R)-7-ethoxy-4-(4-hydroxy-3- methoxyphenyl)chroman-2-one (26) 'H-NMR (400 MHz, CDC1): 2.97 (dd, J=3.6/15.8 Hz: 55 1H); 3.03 (dd, J=6.1/15.8 Hz: 1H); 3.79 (s.3H); 3.82 (s.3H): 4.44 (dd, J=3.6/6.1 Hz, 1H); 4.96 (bs, 1H); 5.53 (bs, 1H); 6.21 (d. J=2.3 Hz, 1H); 6.35 (d. J=2.3 Hz, 1H); 6.62 (d. J=2.0 Hz: (25) 1H); 6.64 (dd, J=2.0/8.6 Hz, 1H); 6.82 (d. J=8.6 Hz, 1H) ppm. 'C-NMR (100 MHz, (CD) SO): 33.2 (CH); 37.1 (CH): 60 55.1 (CH.); 55.5 (CH): 93.0 (CH), 97.5 (CH); 105.2 (C); O 111.3 (CH): 115.2 (CH); 118.2 (CH); 132.7 (C); 145.3 (C); O 147.5 (C); 1540 (C); 155.3 (C); 159.5 (C); 167.8 (C=O) 65 HRMS M-H, CHO: calc.: 315.0874. found: ls, OH 315.0902. US 9, 131,719 B2 51 52 -continued the Sucrose solution and of the respective sample to be inves (26) tigated containing the test Substance. The test Substances used were in each case a racemic mixture of the following com pounds to be used according to the invention.

Impression of Sweetness% intensification 1-10 of the impression O OH 10 Substance without with of Sweetness (1) + (2), ratio 1:1, 50 ppm 4.8 + 0.9 5.4 + 0.9 12% (p<0.08) 15 mmol of 3-ethoxyphenol and 15 mmol of ferulic acid (11) + (12), ratio 1:1, 25 ppm 5.8 + 1.1 6.6+ 1.5 14% (p<0.09) (15) + (16), ratio 1:1, 50 ppm 5.2 + 0.9 6.7 + 1.4 29% (p<0.001) were put in 70 ml of 1,4-dioxane and 1.0 ml of concentrated (17) + (18), ratio 1:1, 50 ppm 4.2 + 1.4 7.1 + 1.8 37% (p<0.002) sulfuric acid and heated under reflux for 24 hours. The reac 15 (19) + (20), ratio 1:1, 50 ppm 4.7 + 1.1 5.4 + 1.1 14% (p<0.09) (23) + (24), ratio 1:1, 50 ppm 4.2. O.8 7.6 1.5 47% tion mixture was poured into 250 ml of saturated sodium (p<0.00001) bicarbonate solution and extracted with 300 ml of methyl tert-butyl ether. The organic phase is then washed with 50 ml of saturated sodium chloride solution, dried over sodium Practical Example 1a-1 Sulfate and concentrated by evaporation. The crude product Intensification of the Impression of Sweetness of a was purified by column chromatography (methyl tert-butyl Sugar Solution ether/hexane, 1:1). 25 In order to quantify the intensification of the impression of Yield: 4.3 mmol (29% of theor.) Sweetness, the Sweetness of a 5 wt % Sucrose solution (con Analysis Data: sisting of 5 wt % Sucrose in water) and of a sample that 'H-NMR (400 MHz, CDC1): 1.42 (t, J–7.0 Hz, 3H); 2.95 consisted of water, 5 wt % Sucrose and a specified amount (i.e. (dd, J=5.9/15.6 Hz, 1H); 3.04 (dd, J=5.9/15.6 Hz, 1H); 3.83 30 given below in each case) of test Substance, was determined (s.3H); 4.01 (q, J–7.0 Hz, 2H); 4.21 (dd, J=5.8/8.1 Hz, 1H): by a panel of experts. The assessment was based on a scale 5.60(bs, 1H); 6.61-6.67 (m, 4H); 6.87 (ddd, J–0.4/0.9/8.4 Hz, from 1 not sweet through 10 extremely sweet. The inten 1H); 6.87 (d. J=8.0 Hz, 1H) ppm. sification of the impression of Sweetness (in '%) was calcu 'C-NMR (100 MHz, CDC1): 14.7 (CH); 37.6 (CH): 35 lated from the respective mean values of the assessments of 39.9 (CH); 55.9 (CH): 63.8 (CH); 103.0 (CH); 109.7 (CH): the Sucrose solution and of the respective sample to be inves 111.2 (CH); 114.8 (CH): 117.8 (C); 120.5 (CH): 128.8 (CH): tigated containing the test Substance. 132.6 (C); 145.0 (C); 146.9 (C); 152.4 (C); 159.3 (C); 167.9 40 (C=O) ppm. Impression of Sweetness% intensification Mass spectrum (EI): m/z (%)=315 (20); 314 (M', 100); 1-10 of the impression 286 (11); 272 (8): 271 (39): 257 (11): 255 (22); 243 (10); 241 Substance without with of Sweetness

(14); 176 (11). 45 (23) + (24), ratio 1:1, 50 ppm 4.2. O.8 7.6 1.5 47% (p<0.00001) Practical Example 1 (A) + (B), ratio 1:1, 50 ppm 54 - 1.6 5.8 + 1.4 8% (p<0.5) Mixture according to 5.1 1.5 7.4 + 1.5 44% (p<0.0002) Example 12 consisting of: Investigations of Intensification of the Impression of (23) + (24), ratio 1:1, 37ppm Sweetness or Masking of Bitterness 50 (A) + (B), ratio 1:1, 63 ppm Practical Example 1 a This example clearly shows that structurally similar com Intensification of the Impression of Sweetness of a pounds with a corresponding residue at position C5 (e.g. Sugar Solution 55 compounds (A) and (B)) instead of position C7 (e.g. com pounds (23) and (24)) have a much lower Sweetness intensi For quantifying the intensification of the impression of fying action than compounds to be used according to the Sweetness, the Sweetness of a 5 wt % Sucrose solution (con invention. sisting of 5 wt % Sucrose in water) and of a sample that 60 consisted of water, 5 wt % Sucrose and a specified amount (i.e. Practical Example 1b that given below in each case) of test Substance was deter Reduction of Bitterness of a Solution of Bitter mined by a panel of experts. The assessment was based on a Substance scale from 1 not sweet to 10 extremely sweet. The inten 65 sification of the impression of Sweetness (in '%) was calcu To quantify the reduction (i.e. the masking or decrease) of lated from the respective mean values of the assessments of the impression of bitterness in a sample, the bitterness of a US 9, 131,719 B2 53 54 Solution containing 500 ppm caffeine or 100 ppm naringin -continued was compared by a panel of experts, in each case against a sample that contained 500 ppm caffeine or 100 ppm naringin Preparation (amount used, wt % and additionally the amount stated in each case of a Substance ngredient A. B C D E F G H Extract of 25 25 to be assessed (with respect to capacity for reducing bitter Hydrangea dulcis ness) (assessment scale: 1 not bitter through 10 extremely containing 8% phyllodulcin, bitter). Evaluation, i.e. calculation of the reduction (in 96) of relative to the 10 otal weight the impression of bitterness, was based in each case on the of the extract mean values of the assessment of the panel of experts. Phloretin 3.5 O.O2 S Hesperetin O.O2 1 3',7- Dihydroxy-4'- 15 methoxyflavan Impression of % reduction of the according bitterness impression of O EP 2253 226 Bitter (1-10) bitterness Neohesperidin dihydrochalcone Homoeriodictyol, Test substance Substance without with (significance) Sodium salt Vanillin, natural 2 Sugar distillate 25 ppm (15) + (16) 500 ppm 42 1.6 3.2 - 1423.7% Ol C86 (ratio 1:1) caffeine (p<0.06) Sugar (e.g. Treatt) 50 ppm (19) + (20) 500 ppm 3.9 - 11 3:6 - 1.5 9.9% (ratio 1:1) caffeine (p < 0.6) 25 The ingredients are mixed in the proportions stated above 25 ppm (15) + (16) 100 ppm 4.1 18 32 1.920.5% and can then be used (further) in this form. The typical dosage (ratio 1:1) naringin (p < 0.2) of preparations A and G in the finished product is in the range 25 ppm (17) + (18) 100 ppm 6.12.2 4.8 2.5 9.9% from 7 through 15 wt %, relative to the total weight of the (ratio 1:1) naringin (p < 0.2) 30 finished product. The typical dosage of the other preparations from Practical example 5 is in the range from 0.01 through 0.1 wt %, preferably 0.03 through 0.06 wt %, relative to the total weight of the finished product. Practical Example 2 35 Practical Example 3 Semifinished Products Mixtures or Semifinished Products According to the Invention 40 Preparation (amount used, wt % Ingredient A. B C D E F G H Liquid Sugar, 99.85 99.80 - Preparation (amount used, wt % containing 80% Ingredient A. B C D E F G. H. SUCOS 45 Compound (15) + O.O2S 10 9 4 7 Compound (17) + (18) 80 20 25 2O 15 (16) (ratio 1:1) (ratio 1:1) Compound (23) + O.O2S 8 10 5 O.OS Compound (23) + (24) 2O 80 SO 20 20 20 15 (24) (ratio 1:1) (ratio 1:1) Rebaudioside 80 — — — 25 O.O1 68.5 Balansin A 25 5 A 98% 50 Balansin B 5 Stevioside 95% 70 Rebaudioside A 98% SO 25 2O Balansin A O.OS 5 - 70 7 O.O2 9 Stevioside 95% 25 Balansin B 5 15 — — 4 9 Saccharin (R) sodium salt 2O Extract of — — 21 Cyclamate (R) 75 Mycetia balansae Acesulfame (RK 2O containing 5 wt % 55 Aspartame (R) 2O balansin A Neotame (R) 5 and 5 wt % Thaumatin 2O balansin B, Sucralose (R) 8O relative to Glycyrrhizin ammonium 2O the total weight Salt of the extract Extract of Rubus — — 25 — 25 O.O7 - 60 Siavissiniis, containing 5 wt % The ingredients are mixed in the proportions stated above rubusoside, and used for Sweetening orally consumable preparations. The relative to the total weight typical dosage of mixtures A through H in the finished prod of the extract e.g. 65 uct is in the range from 0.001 through 0.5 wt %, preferably in from PlantExtract the range from 0.003 through 0.1 wt %, relative to the total weight of the finished product. US 9, 131,719 B2 55 56 Practical Example 4 The drinking water is put in a vessel and the maltodextrin Semifinished Products (with Calorie-Free Sugars and the gum arabic are dissolved therein. Then the aromatic and/or Sugar Alcohols) Substances are emulsified in the carrier Solution using a Tur

Preparation (amount used, wt % Ingredient A. B C D E F G H Preparation. A from O.OS O.OS O.OS practical example 3 Preparation C from O.OS O.OS practical example 3 Preparation H from O.OS O.OS practical example 3 Compound (23) + (24) O.OS (ratio 1:1) Maltitol 50 10 Mannitol 10 Sorbitol 2O 2O Erythritol 29.95 59.95 99.9S 99.95 50 50 99.95 Xylitol 49.95 Palatinose 50 Tagatose 49.95 49.9S

The Substances are mixed in the proportions stated above rax. The temperature of the spraying solution should not and used for Sweetening orally consumable preparations. The 25 exceed 30°C. The mixture is then spray-dried (required- inlet0 typical dosage of the semifinished products A through H in the finished product is in the range from 0.01 through 80 wt temperature: 185-195° C., required outlet temperature: %, preferably in the range from 0.1 through 50 wt %, particu- 70-75° C) larly preferably in the range from 0.1 through 10 wt %, in each case relative to the total weight of the finished product. The 30 semifinished products A through H can be used as a Sweet- Practical Example 6 ener, e.g. also directly for coffee or tea. Practical Example 5 Solutions of the Semifinished Products 35 Spray-Dried Preparation as Semifinished Product for The mixtures and semifinished products from the above Flavoring Finished Products Practical examples 5, 6 and 7 can also be taken up in water, propylene glycol, glycerol or ethanol or preferably in mix "tures of the aforementioned solvents (e.g. water-propylene Ingredient Amount used, wt % Preparation A. B C D E glylycol, water-glycerol,gly water-ethanol, glyglycerol-ethanol, glyglyc erol-propylene glycol, propylene glycol-ethanol) for Drinking water 60.8 60.8 60.8 60.8 60.8 Maltodextrin from wheat 24.3 24.3 24.3 24.3 24.3 as example as 1-20% solution, preferably 2-10%, particularly Gum arabic 6.1 6.1 6.1 6.1 6.1 Compound (17) + (18) 8.8 3.3 4.0 — preferably 5% solution and dissolved completely by heating (ratio 1:1) tl Compound (23) + (24) 33 1.5 33 4.4 genuy. (ratio 1:1) Hesperetin 2.2 1.1 50 Homoeriodictyol, Sodium salt 5.5 3.3 Practical Example 7 Phloretin 3.3 Reduced-Sugar Refreshing Lemon Drink

Ingredient Amount used, wt %

Preparation A. B C D E F Sugar 8 8 8 8 8 7 (Sucrose) Citric acid O.15 O.15 O.15 O.15 O.15 O.15 Lemon flavor O.1 O.1 O.1 O.1 O.1 O.1 Compound (17) + (18) O.OOS O.OO20 O.OO2S (ratio 1:1) Compound (23) + (24) O.OOS O.OO2O O.OO2S O.OOS (ratio 1:1) Balansin A O.OO1 O.OO1 Balansin B O.OO2 US 9, 131,719 B2 57 58 -continued

ngredient Amount used, wt %

Preparation A. B C D E F

Phloretin O.OO1 Hesperetin O.O10 3',7-Dihydroxy-4'- O.OO2S methoxyflavan according O EP 2253 226 Extract of Rubus O.O1O Suavissiniis, containing 5 wt % rubusosiderel. to the otal weight of the extract Extract of Hydrangea O.O10 duticis containing 8% phyllodulcin, relative to he total weight of the extract Water to 100

25 The ingredients were mixed in the orderstated and made up The ingredients were mixed in the order stated, filled in bottles and carbonated. to 100% with water. The mixtures are filled in glass bottles and carbonated. 30 Practical Example 9 Reduced-Sugar Refreshing Beverage of “Cola'. Type Practical Example 8 Preparation A: comparative preparation with 10 wt % sugar Preparation B-G: reduced-Sugar preparations according to Soft Drink of the “Cola Type the invention with 8 wt % Sugar

Preparation (amount used, wt %)

Ingredient A. B C D E F G

Sucrose O 8 7 7 7 Glucosef fructose corn Syrup, 8 7 containing 55 wt % fructose Aromatic composition A from 10 practical example 2 Aromatic composition B from O.OOS practical example 3 Aromatic composition C from O.O12S practical example 3 Aromatic composition D from O.O15 practical example 3 Aromatic composition E from O.O3 practical example 3 Aromatic composition F from O.O1 practical example 3 Aromatic composition H from O.O15 practical example 3 Phosphoric acid O.O7 O.O7 O.O7 O.O7 O.O7 O.O7 O.O7 Citric acid O.O6 OO6 O.O6 O.O6 O.O6 O.O6 O.O6 Caramel color O.14 O.14 O.14 O.14 O.14 O.14 O.14 Caffeine O.O1 OO1 O.O1 O.O1 O.O1 O.O1 O.O1 Beverage emulsion of “Cola O.OS O.OS O.OS O.OS O.OS O.OS O.OS type Water to 100 US 9, 131,719 B2 59 60

Preparation (amount used, wt % Ingredient A. B C D E F G

Sucrose 10 8 8 8 Glucosef fructose corn Syrup, — 8 8 8 containing 55 wt % fructose Compound (15) + (16) O.OO3 O.OO2S O.OO3 O.OO2S (ratio 1:1) Compound (23) + (24) O.OOS O.OO2S O.OOS O.OO2S (ratio 1:1) Phosphoric acid O.O7 O.O7 O.O7 O.O7 O.O7 O.O7 O.O7 Citric acid O.O6 OO6 O.O6 O.O6 O.O6 O.O6 O.O6 Caramel color O.14 O.14 O.14 O.14 O.14 O.14 O.14 Caffeine O.O1 OO1 O.O1 O.O1 O.O1 O.O1 O.O1 Beverage emulsion of “Cola' 0.05 0.05 O.OS O.OS O.OS O.OS O.OS type Water fill to 100%

The ingredients were mixed in the orderstated and made up Part C is premixed and added to A and B; D is added and the to 100% with water. The mixtures are filled in glass bottles mixture is stirred well at 25-30°C. for 30 min under vacuum. and carbonated. After returning to normal pressure, the toothpaste is ready and can be filled. Practical Example 12 Practical Example 14 Chewing Gum 25 Sugar-Free Hard Candy

Part Ingredient Amount used, wt % A Chewing gum base, company Jagum T. 30.95 30 Content (amounts in wt % B Sorbitol, powdered 39.00 Isomalt (R) (Palatinit GmbH) 9.50 Ingredient A. B C D Xylitol 2.OO Mannitol 3.00 Palatinit, type M 75.00 74.OO 75.50 75.00 Aspartame (R) O.10 Citric acid 1.O O.S Water 24.885 24.844 23.88 24.881S Acesulfame (R) K O.10 35 Emulgum (R) (Colloides Naturels, Inc.) O.30 Yellow dye O.O1 C Sorbitol, 70% 14.00 Red dye O.O1 Glycerol 1.OO Blue dye O.O1 O.O1 Peppermint flavor O.1 O.1 D Compound (23) + (24) (ratio 1:1) O.OS Lemon flavor O.1 Red fruit flavor O.1 40 Rebaudioside A 98% O.040 Parts A through Dare mixed and kneaded thoroughly. The Compound (15) + (16) O.O10 O.OOS raw mixture can be processed to chewing gums ready for (ratio 1:1) consumption, e.g. in the form of thin Strips. Compound (23) + (24) O.OOS O.OO2 (ratio 1:1) Hesperetin O.OO1 O.OO1 Practical Example 13 45 Phloretin O.OO2 3',7-Dihydroxy-4'- O.OO2S Toothpaste methoxyflavan according to EP 2253 226

50 Palatinit was mixed with water after optionally adding the Part Ingredient Amount used, wt % citric acid and the mixture was melted at 165° C. and then A. Demineralized water 23.08 cooled to 115° C. The flavorings and the other ingredients Sorbitol (70%) 45.00 were added and, after thorough mixing, were poured into Solbrol (R) M, sodium salt (Bayer AG, O.15 molds, removed from the molds after solidifying and then p-hydroxybenzoic acid alkyl ester) 55 wrapped individually. Trisodium phosphate O.10 Compound (15) + (16) (ratio 1:1) O.O2 Sodium monofluorophosphate 1.12 Practical Example 15 Polyethylene glycol 1500 S.OO B Sident 9 (abrasive silicon dioxide) 1O.OO Sident 22 S (thickening silicon dioxide) 8.00 Reduced-Sugar Boiled Pudding Sodium carboxymethylcellulose O.90 60 Titanium dioxide OSO C Demineralized water 4.53 Preparation A: comparative preparation with full Sugar Sodium lauryl Sulfate 1...SO COntent D Peppermint flavor O.1 Preparation B: comparative preparation with reduced 65 Sugar content The ingredients of parts A and B are each premixed and Preparation C-F: preparations according to the invention stirred well together under vacuum at 25-30°C. for 30 min. with reduced Sugar content US 9, 131,719 B2

Preparation (amounts in wt % Preparation (amounts in wt % Ingredient A. B C D E F ngredient A. B C D Sucrose 7.8 5.4 5.4 5.4 5.4 5.4 5. Sucrose 10 8 7 Starch 3.0 3.0 3.0 3.0 3.0 3.0 Fructose O.S Skim milk powder 1.5 1.S 1.5 1.5 1.5 1.5 Rebaudioside A 98% O.040 Aubygel MR50 O.S. O.S. O.S. O.S O.S O.S Compound (15) + (16) O.OOS O.OO2S O.OO2S Compound (17) + (18) - O.O1 O.OOS O.OOS O.OO3 (ratio 1:1) (ratio 1:1) Balansin A O.OO3 O.OO1 O.OO1 Extract (e.g. from O.O10 0.005 10 Extract of Rubus O.O10 PlantExtract) of Rubus Suavissiniis (e.g. from Siavissiniis, PlantExtract) containing containing 5 wt % 5 wt.% rubusoside, rubusoside, relative to relative to the total the total weight of the weight of the extract extract 15 Hesperetin O.OO3 O.OO2 O.OOS Hesperetin O.OO1 O.OO1 Phloretin O.OO2 Phloretin O.OO2 O.OO1 Homoeriodictyol, O.OO2 3',7-Dihydroxy-4'- O.OO1 Sodium salt methoxyflavan Vanilla flavor O.1 O.1 O.1 O.1 according to EP UHT milk, 1.5% fat to 100 2253 226 Vanilla pod extract, O.1 O.1 O.1 O.1 O.1 O.1 2O spray-dried (Symrise) The ingredients were mixed, milk was added, stirred well, Milk 1.5% fat to 100 filled in bottles and stored cold at 5° C. The solid ingredients were assembled and stirred with the Practical Example 18 milk. The mixture was heated to 95° C. for 2 min while stirring well, filled and cooled to 5-8°C. Reduced-Sugar Tomato Ketchup Practical Example 16 Comparative preparation with Sugar (A) Comparative preparation with reduced amount of sugar(B) Low-Fat Yoghurts 30 Preparations according to the invention (C-I) Preparation A: comparative preparation with full Sugar Preparation (amounts in wt % COntent Preparation B-D: preparations according to the invention is Ingredient A B C E F G H I Common salt 2 2 2 2 2 2 2 2 Starch, Farinex 1 1 1 1 1 1 1 1 - Preparation (announts in Wi o) WM 55 Sucrose 12 9.6 9.2 8.4 9.6 9.6 8.4 4.2 Ingredient A. B C D Tomato double 40 40 40 40 30 30 30 30 40 concentrate Sucrose 10 8 6 Glucose syrup 18 18 18 18 18 18 18 18 Fruit preparation, 10 10 10 10 80 Brix strawberry 0. Brandy 7 7 7 7 3 3 3 3 Rebaudioside A 98% O.OSO vinegar 10% Compound (15) + (16) O.OOS 0.0075 Rebaudioside O.OS (ratio 1:1) 45 A98% Compound (23) + (24) O.OOS Compound - O.O1 O.005 O.OOS O.O1 OOOS OO1 (ratio 1:1) (15) + (16) Extract of Rubus O.O10 (ratio 1:1) Suavissiniis (e.g. from Extract of 0.01 — PlantExtract) containing Rubus 5 wt % rubusoside, 50 Suavissimus relative to the total (e.g. from weight of the extract PintExtract) Hesperetin O.OO1 O.OO1 O.OO1 containing 5 wt Phloretin O.OO2 % rubusoside Hopmoeriodictyol, O.OOS relative to Sodium salt he total weight Natural strawberry O.1 O.1 O.1 O.1 of the extract flavor 0. Hesperetin O.1 O.1 Yoghurt, 0.1% fat to 100 2.5% in 1,2- propylene

The ingredients9. were mixed and cooled at 5°C glycolPhloretin — — — 0.2 O.2 — — 0.3 60 2.5% in Practical Example 17 ,2-propylene glycol Mixed Milk Drinks Water to 100 Preparation A: comparative preparation with full Sugar 65 The ingredients are mixed in the order stated and the fin COntent ished ketchup is homogenized with a stirrer, filled in bottles Preparation B-D: preparations according to the invention and sterilized. US 9, 131,719 B2 63 64 Practical Example 19 extract, Vanillin and a total of 3 wt % of compounds (15)+ (16) (ratio 1:1) and a total of 3 wt % of compounds (17)+ Reduced-Sugar Ice Cream (18) (ratio 1:1), relative to the total weight of the vanilla flavor). Comparative preparation with Sugar (A) 5 Nutritive value (per 100 g): Comparative preparation with reduced amount of sugar(B) protein 8 g. carbohydrates 43 g (including maltitol 34 g), fat Preparations according to the invention (C-F) 34 g.

Preparation (content in wt %) Ingredient A. B C D F Plant fat, melting range 35-40°C. 20.00 20.00 20.00 20.00 2O.OO 2O.OO Sugar (Sucrose) 12.00 8.00 8.OO 8.00 8.OO 8.00 Skim milk powder S.OO S.OO S.OO S.OO S.OO S.OO Glucose syrup 72% dry matter S.OO S.OO S.OO S.OO S.OO S.OO Emulsifier SE 30 (Grindstedt O.65 O.65 O.65 O.65 O.65 O.65 Products, Denmark) Flavoring, containing 0.1% O.20 O.20 O.2O O.20 O20 O.20 diacetyl and 1% vanillin Compound (23) + (24) (ratio 1:1) O.O1 0.0075 O.O1 O.OO3 Extract of Rubus suavissimus O.O10 (e.g. from Plant-Extract) containing 5 wt.% rubusoside, relative to the total weight of the extract Hesperetin 2.5% in 1,2-propylene O.10 O.10 glycol Phloretin 2.5% in 1,2-propylene O.OS O.OS glycol Skim milk to 100

The plant fat was heated to 58° C. Skim milk and glucose 30 Practical Example 22 syrup were heated to 55° C. and sugar, skim milk powder and emulsifier and flavoring were added and the mixture was Diet Chocolate Based on Fructose added to the plant fat. The mixture was homogenized using a flow-through high-pressure homogenizer (180/50 bar). The 35 Chocolate suitable for diabetics was made from the follow resultant mass was heat-treated for 1 min at 78° C., then ing ingredients and molded in rectangular slabs: cooled to 2-4°C. and incubated at this temperature for 10h for cocoa mass, fructose, skim milk powder, cocoa butter, inulin, maturation. Then the matured mass was filled and stored purified butterfat, soybean lecithin emulsifier, walnuts, frozen at -18°C. table salt, 0.1 wt % vanilla flavor (containing vanillin and a 40 total of 3 wt % of compound (23)+(24) (ratio 1:1), relative Practical Example 20 to the total weight of the vanilla flavor). Nutritive value (per 100 g): Ice Cream Suitable for Diabetics protein 8.8 g. carbohydrates 34 g (including fructose 23 g, lactose 7.5 g. Sucrose 1.4g), fat 36 g; ballast Substances 18.5 An ice cream suitable for diabetics was made from the 45 (including 12.2 g inulin); sodium: 0.10g. Proportion of cocoa following ingredients andfilled in 95-mL portions in beakers: at least 50 wt %. thickened skim milk, fructose syrup, Strawberry pieces and strawberry puree (15 wt %), plant fat, diet chocolate chips (3.5 wt %, with soybean lecithin emulsifier), whey product, Practical Example 23 beetroot juice, carob flour, guar flour, carrageenan, emul 50 sifier (E471), gelatin, citric acid acidifying agent, 0.1 wt % Reduced-Sugar Muesli Mixture strawberry flavor (containing a total of 5 wt % of com pounds (23)+(24) (ratio 1:1), relative to the total weight of Comparative preparation with Sugar (A) the strawberry flavor), carotene dye. Preparation according to the invention with reduced pro Nutritive value (per 95 mL): 55 portion of Sugar (B) protein 1.8 g. carbohydrates 13.3 g (including fructose 9.5 g), fat 4.2g. No. A (wt %) B (wt %) Practical Example 21 1 Rolled oats 17.00 19.00 60 2 Crunchy Rolled Oats Cluster 1O.OO 12.00 Diet Chocolate Based on Maltitol 3 Rice Crispies 16.90 17.8O 4 Cornflakes 16...SO 17.50 Chocolate suitable for diabetics was made from the follow 5 Currants 3.SO 3.SO 6 Hazelnuts, chopped 2.50 2.50 ing ingredients and molded in rectangular slabs: 7 Glucose syrup from wheat, DE 30 9.SO 9.SO maltitol, hazelnut paste, cocoa butter, skim milk powder, 65 8 Sucrose 2O.OO 14.00 cocoa mass, inulin, purified butterfat, soybean lecithin 9 Water 4.OO 4.03 emulsifier, 0.1 wt % vanilla flavor (containing vanilla pod US 9, 131,719 B2 66 -continued (a) a compound of Formula (I), or a physiologically accept able Salt thereof, in an amount Sufficient to impart or No. A (wt %) B (wt %) enhance Sweetness in the orally consumable composi 10 Citric acid powder, anhydrous O.10 O.10 tion: 11 Aromatic composition D from O.O7 practical example 2 (I) O Mix each of the ingredients No. 1 through 6 in a rotating drum mixer (Mix 1). Heat each of the ingredients No. 7 E through 9 and add ingredient No. 10 (and in Recipe B, also 10 E R1 addingredient No. 11) (Mix 2). In each case add Mix 2 to Mix R2 R2 1 and mix well. Finally put the resultant muesli mixture on a baking tray and dry in an oven at 130°C. for 8 minutes. 15 R3 R2, Practical Example 24 R2 R1 R2 R2 Reduced-Sugar Fruit Gums Comparative preparation with Sugar (A) wherein Preparation according to the invention with reduced pro E denotes in each case OH or both E together denote portion of Sugar (B) O, R1, independently of one another, denotes hydrogen or ORa, wherein Ra is hydrogen, C1-C5 alkyl or A (wt %) B (wt %) C2-C5 alkenyl, 25 R2, independently of one another, denotes hydrogen Water 23.70 25.70 Sucrose 34.50 8.20 or ORb, wherein Rb is hydrogen, C1-C5 alkyl or Glucose syrup, DE 40 31.89 29.89 C2-C5 alkenyl, wherein optionally two directly Iso Syrup C* Tru Sweet 01750 1...SO 2.10 adjacent residues R1 and/or R2 together representa (Cerestar GmbH) group OCH2O, and Gelatin 240 Bloom 8.2O 9.40 30 Polydextrose (Litesse (R) Ultra, Danisco Cultor 24-40 R3 denotes a residue ORX, wherein RX is C1-C5 alkyl or GmbH) C2-C5 alkenyl: Yellow and red dye O.O1 O.O1 thereby imparting or enhancing the Sweetness of the orally Citric acid O.20 O.2 consumable composition. Cherry flavor, containing a total of 4 wt % of O.10 compounds (23) + (24) (ratio 1:1), and 0.3 wt % 2. The method according to claim 1, wherein: phloretin, relative to the cherry flavor 35 R1, independently of one another, denotes hydrogen or hydroxyl, R2, independently of one another, denotes hydrogen, Polydextrose is a polysaccharide with low calorific value, hydroxyl, methoxy, ethoxy, n-propoxy, iso-propoxy, which itself is not Sweet-tasting. n-butoxy, iso-butoxy, tert-butoxy or ORb, wherein Rb is 40 C5-alkenyl, wherein optionally two directly adjacent Practical Example 25 residues R2 together represent a group OCH2O, R3 denotes methoxy, ethoxy, n-propoxy, iso-propoxy, Chocolate-Cappuccino Ice Cream n-butoxy, iso-butoxy, tert-butoxy or ORc, wherein Rc is Comparative preparation with Sugar (A) C5-alkenyl. 45 3. The method according to claim 1, wherein the compound Preparation according to the invention with reduced pro of formula (I) is a compound of formula (II), a physiologi portion of Sugar (B) cally acceptable salt thereof:

A (wt %) B (wt %) 50 (II) Glucose-fructose-syrup 14.30 14.30 Sucrose 1O.OO 7.50 Skim milk powder S.OO S.OO Cream (36% fat) 24.00 24.00 Emulsifier and stabilizer Cremodan (R) OSO OSO 709 VEG (Danisco) 55 Cocoa powder 5.975 5.975 Carrageenan O.O2S O.O2S Water 40.2O 42.50 Cappuccino flavor, containing a total of 2 O.2O R3 R2 wt % of compounds (15) + (16) (ratio 1:1) and 1 wt % homoeriodictyol, sodium salt, relative 60 to the total flavoring material wherein E denotes in each case OH or both E together denote O. The invention claimed is: R2, independently of one another, denotes hydrogen, 1. A method of imparting or enhancing Sweetness in an 65 hydroxyl, methoxy, ethoxy, n-propoxy or iso-propoxy, orally consumable composition comprising adding to the wherein optionally two directly adjacent residues R2 orally consumable composition: together represent a group OCH2O, and US 9, 131,719 B2 67 R3 denotes methoxy, ethoxy, n-propoxy, iso-propoxy, -continued n-butoxy, iso-butoxy, tert-butoxy or ORc, wherein Rc is (7) C5-alkenyl. O 4. The method according to claim 1, wherein the compound 5 of Formula (I) is selected from the group consisting of: O

(1) O O O OH 10 No o1 (8) O O

O No o1 OH (2) O No O o1 (9) O 2O O

O No ''',Ol o1 25 (3) O No O O OHo1 O 30 (10) O

O No O o1 35 OH (4) O No O o1 O 40 (11) O

O No O Ol o1 45 (5) O N-1\o OH (12) O 50 O

O

No O OH 55 (6) O N-1 no Ol OH (13) O O 60 O

65 US 9, 131,719 B2 70 -continued -continued (14) (21) O O

O O

O

1No OH 10 N-1 no C C OHN (15) O (22) O O 15 O O

O N No O O OHN (16) O N-1 no OH (23) O O

O 25 O O No O OHN (17) O No C OH O OHN 30 (24) O O

O O 35 O No O O OHN N

(18) No OH OH O 40 (25) O O O w O O 45 No O '',OC OHN 1No O O OHN (26) (19) O O 50

O O O 55 No . OH 1No '',OC OHN (20) (27) O O 60 O O

65 US 9, 131,719 B2 71 72 -continued ester, a fruit lactone, 4-(p-hydroxyphenyl)-2-butanone, 1,1- (28) dimethoxy -2.2.5-trimethyl-4-hexane, 2,6-dimethyl-5-hep O ten-l-al, and phenyl acetaldehyde. 9. The method according to claim 8, wherein the orally O consumable composition comprises (c), a Substance that is both Sweet and bitter tasting, which is not a compound of '', formula (I) or a physiologically acceptable salt thereof, selected from the group consisting of a Steviol glycoside, rubusoside, a dulcoside, a mogroside, phyllodulcin, glycyr No OH o1 10 (29) rhetin acid, extracts of Stevia ssp., Luo Han Guo, Rubus O Suavissimus, Hydrangea dulcis, GlycyrrhyZaglabra, magap, Sodium cyclamate, acesulfame-K, neohesperidin dihydroch O alcone, naringin dihydrochalcone, saccharin, Saccharin 15 Sodium salt, aspartame, Superaspartame, neotame, alitame, Sucralose, lugduname, carrelame. Sucrononate and Sucrooc tate. 10. The method according to claim 7, wherein the orally No OH OH and consumable composition comprises (b2), a carbohydrate, (30) O selected from the group consisting of Sucrose, trehalose, lac tose, maltose, melezitose, melibiose, raffinose, Palatinose, lactulose, D-fructose, D-glucose, D-galactose, L-rhamnose, O D-Sorbose, D-mannose, D-tagatose, D-arabinose, L-arabi nose, D-ribose, D-glyceraldehydes, and a maltodextrin. 25 11. The method according to claim 10, wherein the carbo hydrate is Sucrose. O OH OH, 12. The method according to claim 7, wherein the orally consumable composition comprises (b3), a Sugar alcohol, selected from the group consisting of glycerol, erythritol, 30 threitol, arabitol, ribitol, xylitol, sorbitol, mannitol, maltitol, or a physiologically acceptable salts thereof. isomaltitol, dulcitol, and lactitol. 5. The method according to claim 1, wherein an oppositely 13. The method according to claim 7, wherein the orally charged cation of the physiologically acceptable salt is consumable composition comprises (b4), a naturally occur present in the composition and selected from the group con 35 ring Sweetener, selected from the group consisting of mira sisting of Na+, K+, NH4+.Ca2+, Mg2+. Al3+and Zn2+. culin, monellin, mabinlin, thaumatin, curculin, braZZein, pen 6. The method according to claim 1, wherein the orally tadin, D-phenylalanine, D-tryptophan, neohesperidin consumable composition comprises: dihydrochalcone, naringin dihydrochalcone, Stevioside, Ste (b) a Sweet tasting or Smelling Substance, which is not a violbioside, rebaudiosides, rebaudioside B, rebaudioside C, compound of formula (I) or a physiologically acceptable 40 rebaudioside D, rebaudioside E, rebaudioside F, rebaudioside salt thereof, and/or G, rebaudioside H, dulcosides, rubusoside, Suavioside A, Sua (c) a Substance that is both Sweet and bitter tasting, which vioside B, Suavioside G, Suavioside H. Suavioside I, Suavio is not a compound of formula (I) or a physiologically side J. baiyunoside 1 baiyunoside 2, phlomisoside 1. phlomi acceptable salt thereof. Soside 2, phlomisoside 3, and phlomisoside 4, abrusoside A, 7. The method according to claim 6, wherein the orally 45 abrusoside B, abrusoside C, abrusoside D, cyclocaryoside A consumable composition comprises (b), a Sweet tasting or and cyclocaryoside I, oslandin, polypodoside A, strogin 1, Smelling Substance, which is not a compound of formula (I), strogin 2, Strogin 4, selligueanin A, dihydroquercetin-3-ac or a physiologically acceptable salt thereof, selected from the etate, perillartin, telosmoside As periandrin I-V, pterocaryo group consisting of sides, cyclocaryosides, mukuroziosides, trans-anethole, (b1) a Sweet aromatic Substance, 50 trans-cinnamaldehydes, bryosides, bryonosides, bryonodul (b2) a carbohydrate, cosides, carnosiflosidenes, Scandenosides, gypenosides, tri (b3) a Sugar alcohol, lobatin, phloridzin, dihydroflavanols, hematoxylin, cyanin, (b4) a naturally occurring Sweetener, and chlorogenic acid, albiziasaponin, telosmosides, gaudichau (b5) a synthetic Sweet-tasting Substance. dioside, mogrosides, mogroside V, hernandulcines, monatin, 8. The method according to claim 7, wherein the orally 55 consumable composition comprises (b1), a Sweet aromatic phyllodulcin, glycyrrhetin acid, and the physiologically Substance, selected from the group consisting of Vanillin, acceptable salts of these compounds, extracts of Thaumato ethylvanillin, 2-hydroxy-4-methoxybenzaldehyde, ethylvan coccus (katemphe), Stevia ssp., Swingle (Momordica or Sira illinisobutyrate (3-ethoxy-4-isobutyryloxybenzaldehyde), tia grosvenorii, Luo-Han-Guo), Glycerrhyzia ssp., Rubus 2,5-dimethyl-4-hydroxy-3 (2H)-furanone, homofuraneol, 60 ssp., Lippia dulcis, and Mycetia balansae. 2-ethyl-5-methyl-4-hydroxy-5-methyl-3(2H)-furanone, 14. The method according to claim 7, wherein the orally homofuronol (2-ethyl-5-methyl-4-hydroxy-3(2H)-furanone consumable composition comprises (b5), a synthetic Sweet and 5-ethyl-2-methyl-4-hydroxy-3 (2H)-furanone), maltol, tasting Substance, selected from the group consisting of ethylmaltol, coumarin, a gamma-lactone, a delta-lactone, magap, sodium cyclamate or other physiologically accept methyl sorbate, divanillin, 4-hydroxy-2(or 5)-ethyl-5(or 65 able salts of cyclamic acid, acesulfame-Korother physiologi 2)-methyl-3(2H)furanone, 2-hydroxy-3-methyl-2-cyclopen cally acceptable salts, neohesperidin dihydrochalcone, narin tenone, 3-hydroxy-4,5-dimethyl-2(5H) -furanone, a fruit gin dihydrochalcone, Saccharin, Saccharin sodium salt, US 9, 131,719 B2 73 74 aspartame, Superaspartame, neotame, alitame, advantame, perillartin, Sucralose, lugduname, carrelame. Sucrononate and Sucrooctate.