Smoking article comprising a flavourant

Abstract

The present invention relates to a novel smoking article including a flavoring agent, and more particularly, to a smoking article including a flavoring agent including, in a basic skeleton thereof, a moiety derived from a sugar compound and a moiety derived from a flavor compound, which is a novel compound decomposed into a lactone compound, a sugar compound, and a flavor compound upon thermal decomposition.

Description

Technical Field

[0001] This invention relates to smoking articles containing novel flavoring agents that can release flavor components through heating. Background Technology

[0002] Flavoring agents can be added to smoking products to further improve the taste. The smoke or aerosol produced in a smoking product is delivered downstream to the smoker, thus providing the satisfaction of smoking. Many factors determine the satisfaction of smoking, the most important of which is the taste of the cigarette perceived by the smoker. Smokers desire to enjoy multiple tobacco flavors from a single smoking product; therefore, tobacco manufacturers add flavoring substances (such as flavoring agents) to meet smokers' needs, allowing them to experience different aromas or flavors.

[0003] Existing flavorings are prone to decomposition at room temperature during long-term storage of smoking media, leading to the volatilization of flavor components. This results in insufficient aroma production to enhance the taste of cigarettes during smoking, or the aroma persistence weakens or the tobacco flavor changes over time. Therefore, it is necessary to develop a flavoring agent that can improve smoking satisfaction. Furthermore, flavorings often decompose or evaporate during cigarette manufacturing and / or storage. Therefore, it is necessary to develop a flavoring agent that can prevent or delay the release of volatile flavorings, thereby extending shelf life, and fully release the aroma when the user uses the cigarette (e.g., while smoking). Summary of the Invention

[0004] The problem the invention aims to solve

[0005] Existing flavoring compounds exhibit poor chemical stability at room temperature (rt) or near room temperature, leading to structural transformations or decomposition and the volatilization of flavor components. To address this issue, this invention provides a smoking product comprising a novel flavoring agent, which releases its flavor components through thermal decomposition upon heating.

[0006] However, the technical problem to be solved by the present invention is not limited to the above-mentioned problems, and other problems not mentioned will be clearly understood by those skilled in the art through the following description.

[0007] means for solving problems

[0008] According to one embodiment of the present invention, a smoking article comprising a flavoring agent is provided, said flavoring agent being a compound represented by the following chemical formula 1:

[0009] [Chemical Formula 1]

[0010]

[0011] In the chemical formula 1,

[0012] n is an integer of 1 or 2.

[0013] R is a straight-chain or branched alkyl group having 1 to 30 carbon atoms.

[0014] Moiety A' is a moiety derived from a fragrance compound containing at least one of an aromatic ring, an aliphatic ring, and an aliphatic chain having a hydroxyl group (-OH), wherein the hydroxyl group participates in a carbonate bond ( A' is a fragrance compound other than the hydroxyl group involved in the carbonate bond.

[0015] Part G' is a portion derived from a sugar compound, wherein at least one of the hydroxyl groups (-OH) bonded to the ring of the sugar compound participates in an ester bond ( G' is a sugar compound other than the hydroxyl group involved in the ester bond, and m is partially bonded to G' via the ester bond. The number of is an integer from 1 to 8.

[0016] Invention Effects

[0017] According to one embodiment of the present invention, the flavoring agent of the smoking article of the present invention can improve the pungent taste in the sideflow smoke by producing a flavoring component when smoking, and the flavoring agent releases the flavoring component through thermal decomposition during heating, thereby improving the taste of the cigarette and maintaining a constant taste.

[0018] According to one embodiment of the present invention, smoking articles including the flavoring agent of the present invention can be used in various ways, at various locations and / or with various modifications, thereby controlling and improving the tobacco flavor, atmosphere, etc. Attached Figure Description

[0019] Figure 1 The results are NMR analysis of ethyl 4-hydroxyheptanate (2a) prepared in the example according to an embodiment of the present invention.

[0020] Figure 2 The results are NMR analysis of ethyl 4-(mentholylcarbonyloxy)heptanate (3a) according to an embodiment of the present invention.

[0021] Figure 3 The results are NMR analysis of 4-(mentholylcarbonyloxy)heptanoic acid (4a).

[0022] Figure 4 The results are NMR analysis of glucosyl-(4-menthylcarbonyloxy)heptanoate (5a) prepared in an embodiment of the present invention.

[0023] Figure 5The results are NMR analysis of glucosyl-(4-menthylcarbonyloxy)heptanoate (5a) prepared in an embodiment of the present invention.

[0024] Figure 6 The results are NMR analysis of 4-(mentholylcarbonyloxy)nonanoic acid (4b) prepared in an embodiment according to an embodiment of the present invention.

[0025] Figure 7 The results are NMR analysis of glucosyl-(4-menthylcarbonyloxy)nonanoate (5b) prepared in an embodiment of the present invention.

[0026] Figure 8 The results are NMR analysis of glucosyl-(4-menthylcarbonyloxy)nonanoate (5b) prepared in an embodiment of the present invention.

[0027] Figure 9 The results are NMR analysis of ethyl 5-(mentholylcarbonyloxy)decanoate (3c) prepared in an embodiment of the present invention.

[0028] Figure 10 The results are NMR analysis of ethyl 5-(mentholylcarbonyloxy)decanoate (3c) prepared in an embodiment of the present invention.

[0029] Figure 11 The results are NMR analysis of 5-(mentholylcarbonyloxy)decanoic acid (4c) prepared in an embodiment of the present invention.

[0030] Figure 12 The results are NMR analysis of 5-(mentholylcarbonyloxy)decanoic acid (4c) prepared in an embodiment of the present invention.

[0031] Figure 13 The NMR analysis results are for 5-isopropyl-2-methylcyclohexyl-(1-oxo-1-(2-thiothiazolin-3-yl)decyl-5-yl) carbonate (5c) prepared in an embodiment of the present invention.

[0032] Figure 14 The results are NMR analysis of glucosyl-(5-menthylcarbonyloxy)decanoate (6c) prepared in an embodiment of the present invention.

[0033] Figure 15 The results are NMR analysis of glucosyl-(5-menthylcarbonyloxy)decanoate (6c) prepared in an embodiment of the present invention.

[0034] Figure 16The results are NMR analysis of ethyl 4-hydroxyundecanoate (2d) prepared in an embodiment of the present invention.

[0035] Figure 17 The results are NMR analysis of ethyl 4-hydroxyundecanoate (2d) prepared in an embodiment of the present invention.

[0036] Figure 18 The results are NMR analysis of ethyl 4-(mentholylcarbonyloxy)undecanoate (3d) prepared in an embodiment of the present invention.

[0037] Figure 19 The results are NMR analysis of 4-(mentholylcarbonyloxy)undecanoic acid (4d) prepared in an embodiment according to an embodiment of the present invention.

[0038] Figure 20 The results are NMR analysis of 4-(mentholylcarbonyloxy)undecanoic acid (4d) prepared in an embodiment according to an embodiment of the present invention.

[0039] Figure 21 The results are NMR analysis of glucosyl-(4-menthylcarbonyloxy)undecanoate (6d) prepared in an embodiment of the present invention.

[0040] Figure 22 The results are NMR analysis of glucosyl-(4-menthylcarbonyloxy)undecanoate (6d) prepared in an embodiment of the present invention.

[0041] Figure 23 The results are NMR analysis of ethyl 4-(benzyloxycarbonyloxy)undecanoate (3e) prepared in an embodiment of the present invention.

[0042] Figure 24 The NMR analysis results are for glucosyl-(4-benzyloxycarbonyloxy)nonanoate (5e) prepared in an embodiment of the present invention.

[0043] Figure 25 The results are thermal analysis results of compounds prepared in the embodiments according to an embodiment of the present invention.

[0044] Figure 26 This refers to the component distribution of a compound prepared according to an embodiment of the present invention as a function of thermal decomposition temperature.

[0045] Figure 27 This refers to the component distribution of a compound prepared according to an embodiment of the present invention as a function of thermal decomposition temperature.

[0046] Figure 28The accompanying drawings are example drawings illustrating the combustion of a smoking product according to an embodiment of the present invention and the decomposition and realization process of aroma components during smoking.

[0047] Figure 29a This is an accompanying drawing of the flavoring coating area in a cigarette rod according to Embodiment 4 of the present invention.

[0048] Figure 29b This is an accompanying drawing of the flavoring coating area in a cigarette rod according to Embodiment 4 of the present invention.

[0049] Figure 30 This is an attached drawing showing the flavoring coating area in a cigarette product according to Embodiment 5 of the present invention.

[0050] Figure 31 This is an attached drawing showing the flavoring coating area in a cigarette of Example 6 of a cigarette product according to an embodiment of the present invention. Detailed Implementation

[0051] Embodiments of the present invention will now be described in detail with reference to the accompanying drawings. In describing the present invention, detailed descriptions of well-known functions or structures are omitted where it would unnecessarily obscure the spirit of the invention. Furthermore, the terminology used in this specification to accurately describe embodiments may vary depending on the intent of the user or operator, or the conventions of the technical field to which this invention pertains. Therefore, the definitions of terminology should be based on the overall content of the specification. The same reference numerals in the accompanying drawings denote the same components.

[0052] Throughout the specification, when it is stated that a component is "on" another component, this includes not only the case where one component is in contact with another component, but also the case where another component exists between the two components.

[0053] Throughout the specification, when a section “includes” a component, it means that other components may be included, rather than excluding other components.

[0054] The following detailed description of the smoking article including the novel flavoring agent of the present invention is provided with reference to the embodiments and accompanying drawings. However, the present invention is not limited to the embodiments and accompanying drawings.

[0055] This invention relates to smoking articles comprising novel flavoring agents that release flavor components upon thermal decomposition. According to one embodiment of the invention, the flavoring agent releases volatile flavor components through thermal decomposition when heated, thereby improving the flavor and persistence of cigarettes.

[0056] In other words, when synthetic compounds that release aroma components upon thermal decomposition (such as flavoring agents) are applied to the components of cigarettes (such as cigarette paper) and the cigarette is burned, especially during smoke production, the heat expresses the aroma components (such as lactones and / or menthol), thus improving the pungent odor in the sidestream smoke. Furthermore, when applied to the medium of heated cigarette sticks, it can make the aroma components last longer. For example, in heated cigarettes, static heating causes the aroma components contained in the medium to be consumed during the initial puff, but synthetic compounds that express aroma components upon thermal decomposition are only expressed during thermal decomposition. Therefore, even with continuous puffing, aroma components will be produced on the last puff, thus maintaining a constant tobacco flavor.

[0057] According to one embodiment of the present invention, the fragrance agent may be a compound represented by the following chemical formula 1.

[0058] [Chemical Formula 1]

[0059]

[0060] In one example of the invention, Formula 1 comprises a portion (G') derived from a sugar compound and a portion (A') derived from a flavoring compound, wherein in Formula 1, the flavoring compound is covalently bonded via carbonate bonds and the sugar compound is covalently bonded via ester bonds. The compound of Formula 1 undergoes thermal decomposition upon heating, releasing aroma components from sugar compounds, fragrance compounds, and lactone compounds. For example, the compound of Formula 1 reacts with the hydroxyl group (-OH) of the sugar compound via a ring-opening mechanism of the lactone compound, thereby forming an ester bond, and reacts with the hydroxyl group of the fragrance compound via a carbonate bond. The synthesis is achieved through a series of bonds. Specifically, the compound of Formula 1 is structurally stable at or near room temperature and has low volatility. When heated, the carbonate and ester bonds break through a dead-cycle mechanism, decomposing into sugar compounds (G), lactone compounds, and fragrance compounds (A), releasing the aroma. Harmless carbon dioxide is produced during the decomposition process. During heating, the carbonate bonds break, decomposing into fragrance compounds and generating carbon dioxide. Then, through ring closure, the ester bonds break, decomposing into sugar and lactone compounds, thereby releasing the aroma.

[0061] According to one embodiment of the present invention, moiety A' in Formula 1 may be a moiety derived from a fragrance compound comprising at least one of an aromatic ring having a hydroxyl group, an aliphatic ring having a hydroxyl group, and an aliphatic chain having a hydroxyl group. The hydroxyl group comprises at least one of a ring, a chain, or both (e.g., one or both), which may correspond to a substituent having a hydroxyl group, a basic skeleton, and / or a portion thereof. The hydroxyl group participates in the covalent bonding of a carbonate bond in Formula 1, and moiety A' corresponds to a fragrance compound other than the hydroxyl group. That is, the hydroxyl group of the fragrance compound in moiety A' is protected by a carbonate bond, preventing ring-closure-based decomposition reactions at room temperature.

[0062] According to one embodiment of the present invention, the fragrance compound may be selected from cyclic monoterpenoids having hydroxyl groups, acyclic monoterpenoids having hydroxyl groups, aromatic compounds having 6 to 10 carbon atoms having hydroxyl groups, and non-aromatic rings having 5 to 10 or 5 to 6 carbon atoms having hydroxyl groups, and their isomers. For example, the fragrance compound may be selected from the following compounds, which are compounds produced by the breaking of carbonate bonds during the thermal decomposition of the chemical formula 1:

[0063] , , , , , , , , , , , , , , , , , , , , , , , , , as well as .

[0064] According to an embodiment of the present invention, part A' can be selected from the following chemical formula, wherein * represents an oxygen site within the carbonate bond:

[0065] , , ,

[0066] , , , , , , , , , , , , , , , , , , , , , , as well as .

[0067] According to one embodiment of the invention, a portion G' is derived from a sugar compound and participates in an ester bond via a hydroxyl group bonded to the ring of the sugar compound. The compound of Formula 1 is generated by bonding sugar compounds, and part of G' can be a sugar compound other than the hydroxyl group. The compounds of Formula 1 can reduce volatility at room temperature, maintain structural stability, and improve solubility in organic solvents through the bonding of sugar compounds. This can improve compatibility and / or processability in a variety of substrates (or matrices) of the compounds of Formula 1, expanding their applicability as food and smoking products.

[0068] According to one embodiment of the present invention, the sugar compound comprises a six-membered ring, a five-membered ring, or both, and at least one, at least two, at least three, or all of the hydroxyl groups constituting the ring of the sugar compound can participate in the ester bond of Formula 1. For example, the ester bond is formed by one or more hydroxyl groups, such that the "[ ]" portion in Formula 1, i.e., one or more, It can be bonded to a portion of G'.

[0069] According to one embodiment of the present invention, m refers to the "[ ]" portion of G' bonded to the ester bond, i.e. The number of can be an integer from 1 to 8, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 to 2.

[0070] According to one embodiment of the present invention, the sugar compound may be from tagatose, trehalose, galactose, rhamnose, cyclodextrin, maltodextrin, dextran, sucrose, glucose, ribulose, fructose, threose, arabinose, xylose, lysose, arose, azoose, mannose, idoleose, lactose, maltose, invert sugar, isotrehalose, neotrehalose, palaginose, or isomaltulose, erythrose, deoxyribose, glucose, idoleose, or tarose. The sugar can be selected from erythritol, xylulose, allulose, menobiose, cellobiose, amylopectin, glucosamine, mannosamine, fucose, glucuronic acid, gluconic acid, gluconolactone, abigolose, galactosamine, isomaltoligosaccharide, xylooligosaccharide, gentiooligosaccharide, sorbitol, Aspergillus niger oligosaccharide, paraglucose oligosaccharide, fructooligosaccharide, maltodextrin, maltotriol, maltooligosaccharide, lactulose, melibiose, raffinose, rhamnose, and ribose. Preferably, it can be glucose, lactose, maltose, galactose, sucrose, D-fructose, gulose, tarose, and idole.

[0071] In one embodiment of the present invention, the fragrance agent may be selected from the following chemical formulas 1-1 to 1-9.

[0072] [Chemical Formula 1-1]

[0073]

[0074] [Chemical Formula 1-2]

[0075]

[0076] [Chemical Formulas 1-3]

[0077]

[0078] [Chemical Formulas 1-4]

[0079]

[0080] [Chemical Formulas 1-5]

[0081]

[0082] In one example of the present invention, R in chemical formulas 1-1 to 1-5 1 To R 5 It can be derived from hydroxyl (-OH) and (n, R, and A' are selected as defined in the chemical formula 1).

[0083] Preferably, It can be R 1 To R 5 At least one, at least two, at least three, at least four, or all of them, more preferably, can be R1 and R 5 At least one of them, R 1 and R 4 At least one of them, and / or R 3 and R 4 At least one of them.

[0084] [Chemical Formulas 1-6]

[0085]

[0086] In one example of the present invention, R in chemical formulas 1-6 1 To R 4 It can be derived from hydroxyl (-OH) and (n, R, and A' are selected as defined in the chemical formula 1).

[0087] Preferably, It can be R 1 To R 4 At least one, at least two, at least three, or all of them, more preferably, can be R 1 and R 4 At least one of them, R 2 and R 3 At least one of them, and / or R 1 and R 3 At least one of them.

[0088] [Chemical Formulas 1-7]

[0089]

[0090] [Chemical Formulas 1-8]

[0091]

[0092] [Chemical Formulas 1-9]

[0093]

[0094] In one example of the invention, R in chemical formulas 1-7 to 1-9 1 To R 8 It can be derived from hydroxyl (-OH) and (n, R, and A' are selected as defined in the chemical formula 1).

[0095] Preferably, It can be R 1 To R 8 At least one, at least two, at least three, at least four, or all of them, more preferably, can be R 1To R 3 At least one of them, and / or R 5 and R 8 At least one of them, most preferably, can be R 1 To R 2 At least one of them, R 1 and R 3 At least one of them, R 6 and R 8 At least one of them, and / or R 7 and R 5 At least one of them.

[0096] According to one embodiment of the present invention, the fragrance agent may be selected from the following chemical formulas 1-1-a to 1-9-a.

[0097] [Chemical formula 1-1-a]

[0098]

[0099] [Chemical Formula 1-2-a]

[0100]

[0101] [Chemical formula 1-3-a]

[0102]

[0103] [Chemical formula 1-4-a]

[0104]

[0105] [Chemical Formula 1-5-a]

[0106]

[0107] [Chemical formula 1-6-a]

[0108]

[0109] [Chemical Formula 1-7-a]

[0110]

[0111] [Chemical formula 1-8-a]

[0112]

[0113] [Chemical Formula 1-9-a]

[0114]

[0115] Wherein, n, R and A' are as defined in the chemical formula 1.

[0116] According to one embodiment of the present invention, n in the chemical formula 1 is an integer of 1 or 2. R can be a straight-chain or branched alkyl group having 1 to 30 carbon atoms; preferably, it can be a straight-chain or branched alkyl group having 2 to 10 carbon atoms.

[0117] According to one embodiment of the present invention, the lactone compound may be a γ-lactone of chemical formula 2 or a δ-lactone of chemical formula 3.

[0118] [Chemical Formula 2]

[0119]

[0120] [Chemical Formula 3]

[0121]

[0122] In one example of the present invention, R in both Formula 1 and Formula 2 is a straight-chain or branched alkyl group having 1 to 30 carbon atoms, preferably a straight-chain or branched alkyl group having 2 to 10 carbon atoms.

[0123] For example, the lactone compound can be selected from the following chemical formulas:

[0124] , , ,

[0125] , , , , , , , , as well as .

[0126] According to one embodiment of the present invention, the thermal decomposition temperature of the compound can be above 70°C, above 80°C, above 90°C, or above 100°C; preferably, it can be above 120°C, above 150°C, or above 200°C; or more preferably, it can be between 200°C and 300°C. Furthermore, it can undergo thermal decomposition in an environment including oxygen and / or moisture.

[0127] According to one embodiment of the present invention, the smoking article may include at least one flavoring compound represented by Chemical Formula 1 of the present invention. When the smoking article is heated and / or burned, the flavoring compound provides flavor through thermal decomposition. For example, when the smoking article is heated and / or burned, the mainstream smoke and / or sidestream smoke release flavor, which has the effect of improving the mainstream smoke and / or sidestream smoke. For example, Figure 28 The process of transferring the aroma components of the present invention is illustrated, which can be performed in... Figure 28 The flavoring compound is applied to the heated and / or burned portion and / or the portion near and / or affected by heat of the smoking article. When the flavoring compound is applied, it can improve the sidestream smoke as the flavor components transfer through the sidestream / mainstream smoke.

[0128] exist Figure 28 A burning con is formed in parts (a) and (b), and then sidestream smoke is generated during combustion, in which added flavoring components are generated. This is because the heat from the burning con causes the synthetic flavorings coated on the cigarette paper to improve the sidestream smoke to undergo thermal decomposition, thereby releasing flavoring components (such as undecalactone).

[0129] exist Figure 28 In part (b), as outside air flows in during smoking, some of the thermally decomposed aroma components can be inhaled into the mainstream smoke.

[0130] According to one embodiment of the present invention, the compound represented by chemical formula 1, in the smoking article, may be 0.0001 parts by weight or more, 0.001 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 1 to 5 parts by weight, 1 to 10 parts by weight, or 1 to 20 parts by weight relative to 100 parts by weight of the smoking medium. This can provide the effect of controlling and improving the flavor, atmosphere, etc. of the sidestream smoke and / or mainstream smoke during smoking.

[0131] According to one embodiment of the present invention, when smoking, the amount of flavor components such as lactones emitted by the compound represented by Chemical Formula 1 in the smoking article may be 0.00001 parts by weight or more, 0.0001 parts by weight or more, 0.001 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 1 to 5 parts by weight, 1 to 10 parts by weight, or 1 to 20 parts by weight relative to 100 parts by weight of the smoking medium. This provides an effect of controlling and improving the flavor, atmosphere, etc. of the sidestream smoke and / or mainstream smoke during smoking.

[0132] According to one embodiment of the present invention, the smoking article may include a slurry, paste, liquid, gel, powder, microbeads, sheet, film, fiber or molded body containing a compound represented by the chemical formula 1.

[0133] According to one embodiment of the present invention, the smoking article may be made by applying a compound represented by the chemical formula 1 or a composition comprising thereof, or by manufacturing thereof. For example, it may be a component and / or accessory of the smoking article. Preferably, it may be a component and / or accessory of the heated area in the smoking article. For example, it may be a smoking medium (e.g., liquid, gel, solid, slurry, paste), paper tube, tube, filter (e.g., tubular filter, fiber filter, woven filter, paper filter, capsule filter), rolling paper, cigarette paper, mouthpiece paper, packaging paper, cartridge (e.g., heated cartridge), etc., and may include components known in the technical field of the present invention without departing from the purpose of the present invention, which will not be specifically described here.

[0134] According to one embodiment of the present invention, the composition includes the flavoring agent of the present invention (i.e., the flavoring compound represented by the chemical formula 1), and may also include a carrier, an additive, or both, depending on the intended use. The carrier and additive are carriers and additives permitted for use in food or smoking articles, and may include, for example, solvents, binders, diluents, disintegrants, lubricants, flavoring agents, coloring agents, preservatives, antioxidants, emulsifiers, stabilizers, flavor enhancers, sweeteners, etc., but are not limited thereto.

[0135] According to one embodiment of the present invention, the composition may further include a substrate (or matrix) component, which may be, for example, paper, pulp, wood, polymer resin (e.g., cellulose), fiber, vegetable oil, petroleum (e.g., paraffin), animal oil, wax, fatty acids (e.g., animal fats, vegetable fats, saturated fatty acids, unsaturated fatty acids (e.g., monounsaturated or polyunsaturated fatty acids) having 1 to 50 carbon atoms). The substrate component may further contain organic and / or inorganic substances or ceramic powders (e.g., chalk, perlite, vermiculite, diatomaceous earth, colloidal silica, magnesium oxide, magnesium sulfate, magnesium carbonate), wetting agents (e.g., glycerol or propylene glycol), and acetate compounds.

[0136] According to one embodiment of the present invention, the composition may also close the ring of tobacco components depending on the intended use. When used in smoking articles, the composition can generate aroma in mainstream smoke and / or sidestream smoke under smoking conditions. The tobacco components may be solid substances based on tobacco raw materials such as reconstituted tobacco, raw-cut tobacco, and recycled tobacco, and may be selected from tobacco leaves, extruded tobacco, and bandcast tobacco. Furthermore, the composition may also close the ring of an aerosol generator used as a cigarette medium. Non-limiting examples of such aerosol generators include sorbitol, glycerol, propylene glycol, triethylene glycol, lactic acid, diacetate, triacetate, triethylene glycol diacetate, triethyl citrate, ethyl myristate, isopropyl myristate, methyl stearate, dimethyl dodecanoate, and dimethyl tetradecanoate.

[0137] According to one embodiment of the present invention, the flavoring agent may be 0.0001% or more by weight, 0.001% or more by weight, 0.01% or more by weight, 0.1% to 80% by weight, 0.0001% to 60% by weight, 0.001% to 50% by weight, 0.1% to 30% by weight, 1% to 20% by weight, 5% to 20% by weight, or 5% to 10% by weight in the composition. When included within the range, the flavor can be expressed through the thermal decomposition of the flavoring agent, which can improve the taste of cigarettes when used in smoking articles.

[0138] According to one embodiment of the present invention, the composition can be prepared into various phases, such as solids (e.g., powders, crystals, flakes, pulverized material), suspensions, slurries, pastes, gels, liquids, emulsions, or aerosols. For example, the composition can be molded, mixed with a desired product, or used by methods known in the art such as printing, dipping, spraying, and / or coating, which will not be specifically described here.

[0139] According to one embodiment of the present invention, the "smoking article" can refer to tobacco, tobacco derivatives, expanded tobacco, reconstituted tobacco, or any product that can be inhaled like smoking or provides a smoking experience, regardless of whether it is based on a tobacco substitute. For example, the smoking article can refer to aerosol-generating smoking articles such as cigarettes, cigars, cigarillos, and e-cigarettes. The smoking article may include aerosol-generating substances or aerosol-generating matrices. Alternatively, the smoking article may include solid materials based on tobacco raw materials such as reconstituted tobacco, raw-cut tobacco, and reconstituted tobacco. The smoking article may include volatile compounds.

[0140] According to one embodiment of the present invention, the smoking product may be a cigarette, a liquid cigarette, or a blended cigarette, and may be a combustible cigarette or a heated cigarette. Alternatively, it may be an electronic cigarette (e.g., an electronic heated cigarette).

[0141] According to one embodiment of the present invention, the smoking article may include at least one of a sheet, a film, and a filter tip having a compound represented by chemical formula 1 partially printed or coated on the entire surface or at least a portion of at least one surface. Furthermore, the compound represented by chemical formula 1 may be printed or coated on one or both surfaces.

[0142] According to one embodiment of the present invention, the compound represented by Chemical Formula 1 is printed as a pattern along the axial, transverse, or both directions of a smoking article. The pattern can be partially printed on the entire surface of at least one surface or on at least a portion of the smoking article. For example, the smoking article may include one or more patterned areas along the axial, transverse, or both directions of the rod, which can control the flavor and atmosphere of the sidestream smoke and / or mainstream smoke during smoking. For example, the pattern can be arranged in at least one shape selected from straight lines, dashed lines, grids, polygons, dots, circles, and ellipses. For example, the size of the pattern can be 0.01 mm or more, 0.1 mm or more, 1 mm to 10 mm, or 1 mm to 5 mm. The size can refer to thickness, length, diameter, etc., and in dotted patterns, it can be spacing, intervals, etc. For example, the spacing can be 0.01 mm to 1 mm.

[0143] According to one embodiment of the present invention, the smoking article may include a smoking medium portion and a filter portion. The smoking medium portion may include cigarette paper containing a compound represented by Chemical Formula 1, a smoking medium, or both.

[0144] According to one embodiment of the present invention, when the flavoring agent is applied to the cigarette paper of a cigarette and the cigarette is heated and / or burned, especially when smoke is generated, the flavoring components (e.g., lactones and / or flavoring components) are expressed by heat, thereby improving the pungent odor in the sideflow smoke.

[0145] According to one embodiment of the present invention, when applied to a medium for heated cigarette sticks, the aroma components can be made to retain their aroma for a longer period of time. That is, for heated cigarettes, static heating causes the aroma components contained in the medium to be consumed during the initial puff, but the aroma agent is only expressed when it is decomposed by heat, so even if it is continuously puffed until the last puff, the aroma components can still be produced, thereby maintaining a constant tobacco flavor.

[0146] According to one embodiment of the present invention, in manufacturing the smoking article, the flavoring agent itself may be mixed with a matrix or substrate, or the composition containing the flavoring agent may be mixed with, printed, impregnated (or impregnated), coated and / or sprayed with a matrix or substrate.

[0147] According to one embodiment of the present invention, the compound represented by the chemical formula 1 can be coated on cigarette paper or added to a smoking medium (e.g., tobacco medium).

[0148] As an example of the present invention, the method of adding the compound represented by Chemical Formula 1 to a smoking medium (e.g., tobacco medium) is the same as the method of adding other flavorings during the tobacco manufacturing process. The compound represented by Chemical Formula 1 is dissolved in a solvent for dilution and then added to the tobacco medium (e.g., raw cut tobacco) by spraying. Furthermore, it is soluble in water during the tobacco sheet manufacturing process, thereby being added in various ways during the manufacture of tobacco sheets.

[0149] As an example of the present invention, there are many methods for coating the cigarette paper. It can be applied to the entire cigarette stem or partially to at least a portion of the cigarette stem. It can be applied to the cigarette paper of a cigarette or added during the production process of the cigarette paper (paper).

[0150] For example, the entire surface of the cigarette paper may be distributed with patterned areas of compounds represented by chemical formula 1, or patterned areas of compounds represented by chemical formula 1 may be locally distributed with reference to the transverse and / or axial direction of the smoking article rod. The cigarette flavor and atmosphere of the sideflow smoke can be controlled by the position of the patterned areas.

[0151] For example, the cigarette paper may have one or more patterned areas and may be formed at different locations on the cigarette rod, such as near the far end of the cigarette rod (e.g., the end of the cigarette or the lighting position), near the filter, or in the middle section. For example, the pattern may be formed in the cigarette rod as a line (or transverse), a band (or axial), or a pattern based on both.

[0152] For example, in the cigarette paper, the patterned area may be distributed at 5%, 10%, 20%, 30%, 50%, 70%, 90%, and 95% of the length of the cigarette paper (or the bar, i.e., from the far end).

[0153] As an example of the present invention, when applied to cigarette paper, during the manufacturing process of cigarette paper, such as raw material peeling → removal of black skin → screening → soaking → cooking → washing / screening → bleaching → pulping → pulp preparation → stirring → papermaking → pressing → drying → finished product, a compound represented by chemical formula 1 is added during the soaking or papermaking stage.

[0154] As an example of the present invention, the compound represented by the chemical formula 1 is mixed or dissolved in a solvent, which may include an organic solvent and / or water that can disperse and / or dissolve the compound. By having solubility, it can be easily added in the papermaking process by water or alcohol when manufacturing cigarette paper.

[0155] For example, when cigarettes are being produced at a cigarette manufacturing plant (high speed), ink can be added to the cigarette stem, much like ink can be applied to a stamp.

[0156] For example, during cigarette manufacturing, it can be added by spraying it onto the rod.

[0157] For example, the amount of the compound relative to 100 parts by weight of the smoking medium (or tobacco portion) is 0.0001 parts by weight or more, 1 part by weight or more, 5 parts by weight or more, or 1 to 20 parts by weight.

[0158] According to one embodiment of the present invention, the smoking medium may further include flavoring agents and tobacco raw materials (e.g., medium raw materials, tobacco leaves), or may further include additives. As another example, when manufacturing the components and / or parts of a smoking article, the flavoring agent may be added as a flavoring agent and mixed with a base material, solvent, flavoring material, smoking medium material, etc., suitable for the smoking article. Furthermore, the smoking medium may be a liquid, gel, or solid.

[0159] The present invention will be described in more detail below through embodiments and comparative examples, but the following embodiments are only used to illustrate the present invention, and the content of the present invention is not limited to the following embodiments.

[0160] Example 1

[0161] [Option 1]

[0162]

[0163] (1-1) Synthesis of ethyl 4-hydroxyheptanoate (2a)

[0164] 20 g of γ-heptalactone (0.15 mol) was dissolved in 100 mL of methanol. While stirring, 11.17 g of KOH (0.16 mol, 1.05 eq.) was slowly added, and the reaction was allowed to proceed at room temperature for 12 hours. After concentrating the reaction solution under reduced pressure, 80 mL of DMF was added, followed by the addition of 17 g of bromoethane (0.15 mol, 1 eq.) while stirring, and the reaction was allowed to proceed for another 12 hours. 100 mL of water was added to the reaction solution, and the mixture was extracted with ethyl acetate, followed by washing with water and brine. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain 18.1 g of the target product 2a (66.7%, 2 steps).

[0165] 1 ¹H NMR (CDCl₃, 400.13 MHz); δ 8.01 (s, 1H, -OH), 4.12 (q, 2H, J = 8 Hz, COO-CH₂-), 3.63 (m, 1H, CH-O), 2.42 (m, 2H, CO-CH₂), 1.81 ~ 0.92 (m, 12H, alkyl)

[0166] (1-2) Synthesis of ethyl 4-(mentylcarbonyloxy)heptanoate [3a]

[0167] 18 g of ethyl 4-hydroxyheptaate (2a, 0.1 mol) was dissolved in 120 mL of THF, then 16 g of pyridine (0.2 mol, 2 eq.) was added and the mixture was cooled with ice water while stirring. Simultaneously, 23 g of mentyl chloroformate (0.1 mol, 1 eq.) and 20 mL of THF solution were slowly dropped in. After one hour, the reaction mixture was heated to room temperature and reacted overnight. Water was then added and the mixture was extracted with ethyl acetate. The organic layer was washed with dilute hydrochloric acid, a saturated sodium bicarbonate solution, and brine, respectively, and then dried over MgSO4. After concentration under reduced pressure, 30 g (yield 81%) of the target product 3a, a yellow liquid, was obtained.

[0168] 1H NMR (CDCl3, 400.13MHz); δ 4.74 (7tet, 1H, J = 4 Hz, -COOCH-), 4.51 (td, 1H, J = 9, 4 Hz, COO-CH-), 4.12 (q, 2H, J = 8 Hz, COO-CH2-), 2.36 (m, 2H, CO-CH2-), 1.93 ~ 0.79 (m, 30H, alkyl)

[0169] (1-3) Synthesis of 4-(mentylcarbonyloxy)heptanoic acid, 4a

[0170] 25 g of ethyl 4-(mentholylcarbonyloxy)heptanate (3a, 68.5 mmol) was dissolved in 100 mL of THF and 30 mL of distilled water, and 4.2 g of lithium hydroxide monohydrate (102.4 mmol, 1.5 eq.) was added. The mixture was reacted at room temperature for 12 hours. 50 mL of distilled water was added, and extraction was performed using ether. The aqueous layer was adjusted to pH 3 with concentrated hydrochloric acid and then extracted with ethyl acetate. The organic layer was washed with brine and dried over MgSO4. After concentration under reduced pressure, 21.8 g (81% yield) of the target product 4a, a yellow liquid, was obtained.

[0171] 1 H NMR (CDCl3, 400.13MHz); δ 4.76 (m, 1H, -COOCH-), 4.52 (td, 1H, J = 9, 4 Hz, COO-CH-), 4.11 (q, 2H, J = 8 Hz, COO-CH2-), 2.42 (m, 2H, CO-CH2-), 1.99 ~ 0.82 (m, 27H, alkyl)

[0172] (1-4) Synthesis of glucosyl-(4-mentylcarbonyloxy)heptanoate, 5a

[0173] 3 g of 4-(mentholylcarbonyloxy)heptanic acid (4a, 9.1 mmol) was dissolved in 20 mL of DMF, and then 3.7 g of glucose (20.5 mmol, 2.2 eq.) was added. While stirring at room temperature, 1.7 g of diisopropylcarbodiimide (13.4 mmol, 1.5 eq.) and 0.05 g of DMAP (cat.) were added sequentially, and the mixture was reacted at room temperature for 12 hours. Distilled water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with dilute hydrochloric acid, saturated sodium bicarbonate solution, and brine, respectively, dried over MgSO4, and concentrated under reduced pressure. The mixture was subjected to silica gel column chromatography (6:1) to obtain 0.6 g (13% yield) of the target product 5a.

[0174] 1 ¹H NMR (CDCl₃, 400.13 MHz); δ 5.30 ~ 3.54 (m, 13H, glucose, -COOCH, -COOCH), 2.45 (m, 2H, CO-CH₂-), 2.03 ~ 0.78 (m, 27H, alkyl).

[0175] 2. Synthesis of glucosyl-(4-mentylcarbonyloxy)nonanoate, 5b

[0176] [Option 2]

[0177]

[0178] (2-1) Synthesis of ethyl 4-hydroxynonanoate [2b]

[0179] 20 g of γ-nonalactone (0.13 mol) was dissolved in 100 mL of methanol. While stirring, 9.18 g of KOH (0.14 mol, 1.05 eq.) was slowly added, and the reaction was carried out at room temperature for 12 hours. The reaction solution was concentrated under reduced pressure, and 80 mL of DMF was added with stirring. While stirring, 14 g of bromoethane (0.13 mol, 1 eq.) was added, and the reaction was carried out for 12 hours. 100 mL of water was added to the reaction solution, and the mixture was extracted with ethyl acetate, followed by washing with water and brine. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain 24 g (93%, 2 steps) of the target product 2b.

[0180] (2-2) Synthesis of ethyl 4-(mentylcarbonyloxy)nonanoate [3b]

[0181] 24 g of ethyl 4-hydroxynonanoate (2, 0.12 mol) was dissolved in 120 mL of THF. 18 g of pyridine (0.42 mol, 2 eq.) was added, and the mixture was cooled with ice water. While stirring, 26 g of menthyl chloroformate (0.12 mol, 1 eq.) was slowly dropped into 30 mL of THF solution. After one hour, the reaction mixture was heated to room temperature and reacted overnight. Water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with dilute hydrochloric acid, saturated sodium bicarbonate solution, and brine, respectively, and dried over MgSO4. The solution was then concentrated under reduced pressure to obtain 34 g (74.5% yield) of a yellow liquid, the target product 3.

[0182] 1 H NMR (CDCl3, 400.13MHz); δ 4.74 (7tet, 1H, J = 4 Hz, -COOCH-), 4.51 (td, 1H, J = 9, 4 Hz, COO-CH-), 4.12 (q, 2H, J = 8 Hz, COO-CH2-), 2.36 (m, 2H, CO-CH2-), 1.93 ~ 0.79 (m, 23H, alkyl)

[0183] (2-3) Synthesis of 4-(mentylcarbonyloxy)nonanoic acid [4b]

[0184] 11.5 g of ethyl 4-(mentholylcarbonyloxy)nonanoate (3, 29.9 mmol) was dissolved in 50 mL of THF and 20 mL of distilled water, and 2 g of lithium hydroxide monohydrate (48.7 mmol, 1.6 eq.) was added. The mixture was reacted at room temperature for 12 hours. 50 mL of distilled water was added, and extraction was performed using ether. The aqueous layer was adjusted to pH 3 with concentrated hydrochloric acid and then extracted with ethyl acetate. The organic layer was washed with brine and dried over MgSO4. After concentration under reduced pressure, 8.6 g (80% yield) of the target product 4b in a yellow liquid was obtained.

[0185] 1 ¹H NMR (CDCl₃, 400.13 MHz); δ 4.75 (m, 1H, -COOCH-), 4.49 (m, 1H, COO-CH-), 2.04 (m, 2H, CO-CH₂-), 1.93 ~ 0.79 (m, 31H, alkyl)

[0186] (2-4) Synthesis of glucosyl-(4-mentylcarbonyloxy)nonanoate [5b]

[0187] 6.6 g of 4-(mentholylcarbonyloxy)nonanoic acid (4b, 24.1 mmol) was dissolved in 30 mL of DMF, followed by the addition of 13 g of glucose (72.1 mmol, 3 eq.). While stirring at room temperature, 3.4 g of diisopropylcarbodiimide (26.9 mmol, 1.2 eq.) and 0.05 g of DMAP (cat.) were added sequentially, and the mixture was reacted at room temperature for 12 hours. Distilled water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with dilute hydrochloric acid, saturated sodium bicarbonate solution, and brine, respectively, dried over MgSO4, and concentrated under reduced pressure. The mixture was subjected to silica gel column chromatography using a dichloromethane and methanol mixture (8:1) to obtain 2 g (yield 16%) of the target product 5b.

[0188] 1 ¹H NMR (CDCl₃, 400.13 MHz); δ 5.57 ~ 3.35 (m, 13H, glucose, -COOCH, -COOCH), 2.43 (m, 2H, CO-CH₂-), 2.03 ~ 0.78 (m, 31H, alkyl).

[0189] 3. Synthesis of glucosyl-(5-mentylcarbonyloxy)decanoate, 6c

[0190] [Option 3]

[0191]

[0192] (3-1) Synthesis of ethyl 5-hydroxydecanoate (2c)

[0193] 10 g of δ-Decalactone (58.7 mmol) was dissolved in 50 mL of methanol. While stirring, 4.2 g of KOH (64.7 mmol, 1.05 eq.) was slowly added, and the reaction was carried out at room temperature for 12 hours. The reaction solution was concentrated under reduced pressure, and 40 mL of DMF was added. While stirring, 6.4 g of bromoethane (58.7 mmol, 1 eq.) was added, and the reaction was carried out for 12 hours.

[0194] 100 mL of water was added to the reaction solution and the mixture was extracted with ethyl acetate, followed by washing with water and brine. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain 7.6 g (60%, 2 steps) of the target product 2c.

[0195] (3-2) Synthesis of ethyl 5-(mentylcarbonyloxy)decanoate [3c]

[0196] 7.5 g of ethyl 4-hydroxynonanoate (3c, 34.6 mmol) was dissolved in 50 mL of THF. 5.3 g of pyridine (69.2 mmol, 2 eq.) was added, and the mixture was cooled with ice water. Then, while stirring, 8.3 g of menthyl chloroformate (37.9 mmol, 1.1 eq.) was slowly dropped into 20 mL of THF solution. After one hour, the reaction mixture was heated to room temperature and reacted overnight. Water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with dilute hydrochloric acid, saturated sodium bicarbonate solution, and brine, respectively, dried over MgSO4, and concentrated under reduced pressure. The mixture was subjected to silica gel column chromatography (7:1) using a mixture of n-hexane and ethyl acetate to obtain 4.5 g (32.6% yield) of the target product 3c.

[0197] 1 H NMR (CDCl3, 400.13MHz); δ 4.72 (m, 1H, -COOCH-), 4.52 (m, 1H, COO-CH-), 4.12 (q, 2H, J = 8 Hz, COO-CH2-), 2.31 (t, 2H, J = 8 Hz, CO-CH2-), 2.08 ~ 0.86 (m, 27H, alkyl), 0.79 (d, 6H, J = 8 Hz, -CH3)

[0198] (3-3) Synthesis of 5-(mentylcarbonyloxy)decanoic acid [4c]

[0199] 2.7 g of ethyl 4-(mentholylcarbonyloxy)nonanoate (3, 6.8 mmol) was dissolved in 20 mL of THF and 10 mL of distilled water, and 0.42 g of lithium hydroxide monohydrate (10.2 mmol, 1.5 eq.) was added. The mixture was reacted at room temperature for 12 hours. 10 mL of distilled water was added, and extraction was performed using ether. The aqueous layer was adjusted to pH 3 with concentrated hydrochloric acid and then extracted with ethyl acetate. The organic layer was washed with brine, dried over MgSO4, and concentrated under reduced pressure to give 2.1 g (78% yield) of the target product 4b as a yellow liquid.

[0200] 1 ¹H NMR (CDCl₃, 400.13 MHz); δ 4.72 (m, 1H, -COOCH⁻), 4.51 (td, 1H, J = 8, 4 Hz, COO-CH⁻), 4.11 (q, 2H, J = 8 Hz, COO-CH₂⁻), 2.38 (m, 2H, CO-CH₂⁻), 2.06 ~ 0.78 (m, 33H, alkyl)

[0201] (3-4) Synthesis of 5-isopropyl-2-methylcyclohexyl(1-oxo-1-(2-thioxothiazolidin-3-yl)decan-5-yl)carbonate, 5c

[0202] 1.9 g of 5-(mentholylcarbonyloxy)decanoic acid (4c, 5.1 mmol) was dissolved in 20 mL of dried dichloromethane. 0.73 g of 2-mercaptothiazoline (6.1 mmol, 1.2 eq.) was added, and the mixture was cooled with ice water. Then, while stirring, 1.2 g of EDC·HCl (6.1 mmol, 1.2 eq.) and 50 mg of DMAP were slowly added separately. After one hour, the reaction mixture was heated to room temperature and reacted overnight. Water was added, and the mixture was extracted with dichloromethane. The organic layer was washed with dilute hydrochloric acid, saturated sodium bicarbonate solution, and brine, respectively, dried over MgSO4, and concentrated under reduced pressure. The mixture was subjected to silica gel column chromatography in a 3:1 mixture of n-hexane and ethyl acetate to obtain 2.1 g (yield 87.5%) of the target product 5c.

[0203] 1 H NMR (CDCl3, 400.13MHz); δ 4.71 (m, 1H, -COOCH-), 4.57 (t, 2H, J = 8 Hz, N -CH2), 4.51 (m, 1H, COO-CH-), 4.11 (q, 2H, J = 8 Hz, COO-CH2-), 3.28 (t, 2H, J = 8 Hz, S -CH2), 3.21 (m, 2H, CO-CH2-), 2.04 ~ 0.79 (m, 33H, alkyl).

[0204] (3-5) Synthesis of glucosyl-(5-mentylcarbonyloxy)decanoate, 6c

[0205] 2.2 g of 5-isopropyl-2-methylcyclohexyl(1-oxo-1-(2-thiothiazolin-3-yl)decyl-5-yl) carbonate (5c, 4.7 mmol) was dissolved in 20 mL of pyridine, followed by the addition of 2.5 g of glucose (14.1 mmol, 3 eq.). While stirring at room temperature, 93 mg of sodium hydride (60%, 2.4 mmol, 0.5 eq.) and 0.03 g of DMAP (cat.) were added sequentially, and the reaction was allowed to proceed for 12 hours at room temperature. 0.5 mL of acetic acid was added to the reaction mixture, followed by the addition of saturated brine and extraction with ethyl acetate. The organic layer was dried over MgSO4 and concentrated under reduced pressure. The mixture was subjected to silica gel column chromatography in a dichloromethane and methanol mixture (8:1) to obtain 0.55 g (22% yield) of the target product 6c.

[0206] 1 ¹H NMR (CDCl₃, 400.13 MHz); δ 5.57 ~ 3.15 (m, 13H, glucose, -COOCH, -COOCH), 2.36 (m, 2H, CO-CH₂-), 2.05 ~ 0.80 (m, 33H, alkyl)

[0207] 4. Synthesis of glucosyl-(4-mentylcarbonyloxy)undecanoate, 6d

[0208] [Option 4]

[0209]

[0210] (4-1) Synthesis of ethyl 4-hydroxyundecanoate (2d)

[0211] 10 g of γ-undecyl lactone (54.2 mmol) was dissolved in 50 mL of methanol. While stirring, 3.9 g of KOH (56.9 mmol, 1.05 eq.) was slowly added, and the reaction was carried out at room temperature for 12 hours. The reaction solution was concentrated under reduced pressure, and 50 mL of DMF was added. While stirring, 5.9 g of bromoethane (54.2 mmol, 1 eq.) was added, and the reaction was carried out for 12 hours.

[0212] 80 mL of water was added to the reaction solution and the mixture was extracted with ethyl acetate, followed by washing with water and brine. The organic layer was dried with MgSO4 and concentrated under reduced pressure to obtain 10.7 g (85.6%, 2 steps) of the target product 2d.

[0213] 1 ¹H NMR (CDCl₃, 400.13 MHz); δ 4.12 (q, 2H, J = 8 Hz, COO-CH₂-), 3.59 (m, 1H, CH-O), 2.43 (m, 2H, CO-CH₂), 1.81 ~ 0.92 (m, 20H, alkyl)

[0214] (4-2) Synthesis of ethyl 4-(mentylcarbonyloxy)undecanoate [Ethyl 4-(mentylcarbonyloxy)undecanoate, 3d]

[0215] 11 g of ethyl 4-hydroxyundecanoate (2d, 47.7 mmol) was dissolved in 60 mL of THF, and 6.8 g of pyridine (95.5 mmol, 2 eq.) was added. The mixture was cooled with ice water, and then 10.5 g of menthyl chloroformate (47.7 mmol, 1 eq.) was slowly dropped into 20 mL of THF solution while stirring. After one hour, the reaction mixture was heated to room temperature and reacted overnight. Water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with dilute hydrochloric acid, saturated sodium bicarbonate solution, and brine, respectively, and dried over MgSO4. After concentration under reduced pressure, 8.3 g (yield 42.1%) of the target product 3d, a yellow liquid, was obtained.

[0216] 1 H NMR (CDCl3, 400.13MHz); δ 4.74 (7tet, 1H, J = 4 Hz, -COOCH-), 4.51 (td, 1H, J = 9, 4 Hz, COO-CH-), 4.12 (q, 2H, J = 8 Hz, COO-CH2-), 2.36 (m, 2H, CO-CH2-), 1.93 ~ 0.79 (m, 23H, alkyl)

[0217] (4-3) Synthesis of 4-(mentylcarbonyloxy)undecanoic acid, 4d

[0218] 8.3 g of ethyl 4-(mentholylcarbonyloxy)undecanoate (3d, 19.4 mmol) was dissolved in 30 mL of THF and 20 mL of distilled water, and 1.2 g of lithium hydroxide monohydrate (29.1 mmol, 1.5 eq.) was added. The mixture was reacted at room temperature for 12 h. 20 mL of distilled water was added, and extraction was performed using ether. The aqueous layer was adjusted to pH 3 with concentrated hydrochloric acid and then extracted with ethyl acetate. The organic layer was washed with brine, dried over MgSO4, and concentrated under reduced pressure. The mixture was subjected to silica gel column chromatography in a hexane and ethyl acetate mixture (8:1) to obtain 6.8 g (91.8% yield) of the target product 4d.

[0219] 1 ¹H NMR (CDCl₃, 400.13 MHz); δ 4.75 (m, 1H, -COOCH-), 4.51 (m, 1H, COO-CH-), 2.43 (m, 2H, CO-CH₂-), 2.17 ~ 0.78 (m, 35H, alkyl)

[0220] (4-4) Synthesis of 5-isopropyl-2-methylcyclohexyl(1-oxo-1-(2-thioxothiazolidin-3-yl)dodecan-5-yl)carbonate, 5d

[0221] 9.1 g of 5-(mentholylcarbonyloxy)undecanoic acid (4d, 23.6 mmol) was dissolved in 50 mL of dried dichloromethane. 3 g of 2-mercaptothiazoline (24.8 mmol, 1.05 eq.) was added, and the mixture was cooled with ice water. Then, while stirring, 5 g of EDC·HCl (25.9 mmol, 1.1 eq.) and 20 mg of DMAP were slowly added separately. After one hour, the reaction mixture was heated to room temperature and reacted overnight. Water was then added, and the mixture was extracted with dichloromethane. The organic layer was washed with dilute hydrochloric acid, saturated sodium bicarbonate solution, and brine, respectively, and dried over MgSO4. After concentration under reduced pressure, 10.9 g (92% yield) of the target product 5d was obtained.

[0222] 1 H NMR (CDCl3, 400.13MHz); δ 4.71 (m, 1H, -COOCH-), 4.57 (t, 2H, J = 8 Hz, N-CH2), 4.51 (m, 1H, COO-CH-), 4.11 (q, 2H, J = 8 Hz, COO-CH2-), 3.28 (t, 2H, J = 8 Hz, S -CH2), 3.21 (m, 2H, CO-CH2-), 2.04 ~ 0.79 (m, 33H, alkyl)

[0223] (4-5) Synthesis of glucosyl-(4-mentylcarbonyloxy)undecanoate, 6d

[0224] 4.9 g of 4-(mentholylcarbonyloxy)undecanoic acid (12.7 mmol) was dissolved in 30 mL of dichloromethane, and then 3 g of thionyl chloride (25.2 mmol, 2 eq) was added and refluxed for two hours. In another flask, 6.9 g of glucose (3 eq) and 4.9 g of pyridine (5 eq) were added to DMF solvent and stirred at room temperature while the above reaction solution was slowly dropped in, and the reaction was carried out for 12 hours. Water was added to the reaction solution and the mixture was extracted with dichloromethane. The organic layer was washed with dilute hydrochloric acid, saturated sodium bicarbonate solution, and brine, respectively, and dried over MgSO4. After concentration under reduced pressure, 2.6 g of the target product (6d) was obtained by silica gel column chromatography (MC / MeOH, 10:1) (yield 37.7%).

[0225] 1 ¹H NMR (CDCl₃, 400.13 MHz); δ 5.23 ~ 3.35 (m, 13H, glucose, -COOCH, -COOCH), 2.43 (m, 2H, CO-CH₂-), 2.03 ~ 0.78 (m, 35H, alkyl)

[0226] 5. Synthesis of glucosyl-(4-benzyloxycarbonyloxy)undecanoate, 5e

[0227] [Option 5]

[0228]

[0229] (5-1) Synthesis of ethyl 4-hydroxyundecanoate [2d]

[0230] 10 g of γ-undecyl lactone (54.2 mmol) was dissolved in 50 mL of methanol. While stirring, 3.9 g of KOH (56.9 mmol, 1.05 eq.) was slowly added, and the reaction was carried out at room temperature for 12 hours. The reaction solution was concentrated under reduced pressure, and 50 mL of DMF was added. While stirring, 5.9 g of bromoethane (54.2 mmol, 1 eq.) was added, and the reaction was carried out for 12 hours.

[0231] 80 mL of water was added to the reaction solution and the mixture was extracted with ethyl acetate, followed by washing with water and brine. The organic layer was dried with MgSO4 and concentrated under reduced pressure to obtain 10.7 g (85.6%, 2 steps) of the target product 2d.

[0232] 1 ¹H NMR (CDCl₃, 400.13 MHz); δ 4.12 (q, 2H, J = 8 Hz, COO-CH₂-), 3.59 (m, 1H, CH-O), 2.43 (m, 2H, CO-CH₂), 1.81 ~ 0.92 (m, 20H, alkyl)

[0233] (5-2) Synthesis of ethyl 4-(benzyloxycarbonyloxy)undecanoate [Ethyl 4-(benzyloxycarbonyloxy)undecanoate, 3e]

[0234] 8.3 g of ethyl 4-hydroxyundecanoate (2d, 36 mmol) was dissolved in 50 mL of THF. 5.5 g of pyridine (72.3 mmol, 2 eq.) was added, and the mixture was cooled with ice water. Then, while stirring, 6.1 g of benzylchloroformate (35.3 mmol, 1 eq.) was slowly dropped into 20 mL of THF solution. After one hour, the reaction mixture was heated to room temperature and reacted overnight. Water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with dilute hydrochloric acid, saturated sodium bicarbonate solution, and brine, respectively, and dried over MgSO4. After concentration under reduced pressure, 9.9 g (75.6% yield) of the target product 3e, a yellow liquid, was obtained.

[0235] 1 H NMR (CDCl3, 400.13MHz); δ 7.37 ~ 7.34 (m, 5H, ph), 5.14 (m, 2H, O-CH2-Ph), 4.12 (brs, 1H, O-CH-), 2.42 (m, 2H, CO-CH2-), 1.90 ~ 0.79 (m, 21H, alkyl) ( Figure 24 )

[0236] (5-3) Synthesis of 4-(Benzyloxycarbonyloxy)undecanoic acid, 4e

[0237] 10 g of ethyl 4-(beryloxycarbonyloxy)undecanoate (3e, 27.5 mmol) was dissolved in 30 mL of THF and 20 mL of distilled water, and 1.7 g of lithium hydroxide monohydrate (41.4 mmol, 1.5 eq.) was added. The mixture was reacted at room temperature for 12 hours. 20 mL of distilled water was added, and extraction was performed using ether. The aqueous layer was adjusted to pH 3 with concentrated hydrochloric acid and then extracted with ethyl acetate. The organic layer was washed with brine and dried over MgSO4. After concentration under reduced pressure, 8.2 g (89% yield) of the target product 4e was obtained.

[0238] 1 ¹H NMR (CDCl₃, 400.13 MHz); δ 7.37 ~ 7.35 (m, 5H, ph), 5.14 (m, 2H, O-CH₂-Ph), 4.48 (m, 1H, O-CH⁻), 2.47 (m, 2H, CO-CH₂-), 1.90 ~ 0.79 (m, 21H, alkyl)

[0239] (5-4) Synthesis of glucosyl-(4-benzyloxycarbonyloxy)nonanoate [5e]

[0240] 8 g of 4-(benzyloxycarbonyloxy)undecanoic acid (4e, 23.8 mmol) was dissolved in 30 mL of DMF, and then 13 g of glucose (72.1 mmol, 3 eq.) was added. While stirring at room temperature, 3.4 g of diisopropylcarbodiimide (26.9 mmol, 1.1 eq.) and 0.05 g of DMAP (cat.) were added sequentially, and the mixture was reacted at room temperature for 12 hours. Distilled water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with dilute hydrochloric acid, saturated sodium bicarbonate solution, and brine, respectively, dried over MgSO4, and concentrated under reduced pressure. The mixture was subjected to silica gel column chromatography in a dichloromethane and methanol mixture (8:1) to obtain 0.3 g (yield 2.5%) of the target product 5e.

[0241] 1¹H NMR (CDCl₃, 400.13 MHz); δ 7.37 ~ 7.34 (m, 5H, ph), 5.30 ~ 3.37 (m, 13H, glucose, -COOCH, -COOCH), 2.39 (m, 2H, CO-CH₂-), 1.92 ~ 0.84 (m, 17H, alkyl)

[0242] Experimental Example

[0243] Pyrolysis tests were performed to confirm the pyrolytic behavior of compound 6d (2C) upon exposure to heat. This test utilized a well-known pyrolysis-gas-chromatography / mass-spectroscopy (Py-GC / MS) method. The pyrolyzer was used in a system connected to a Double-Shot Pyrolyzer 2020iD (Frontier Lab, Japan) and a GC / MS instrument (Agilent 6890 GC, USA / Aginelt 7890mSD, USA). After diluting 2C to a concentration of 2.5% in ethanol, 10 μL was added to the pyrolyzer sample cup for pyrolysis. The pyrolysis temperature experienced by the sample was controlled by specifying the furnace temperature of the Double-Shot Pyrolyzer. The initial pyrolysis temperature was 80 °C. The sample cup containing the sample was exposed to the furnace at 80 °C for 30 seconds, causing the target compound (2C) within the sample cup to pyrolyze. The thermally generated or volatilized components were immediately injected into the GC / MS injector and separated. During GC / MS analysis after pyrolysis, the sample cup was removed from the furnace to avoid exposure to the pyrolysis temperature. After the first pyrolysis GC / MS analysis, the initially used sample cup was pyrolyzed again at 90 °C (10 °C higher) for 30 seconds without injecting new compounds. Again, the sample cup was removed from the furnace after pyrolysis to avoid exposure to the pyrolysis temperature. The initial sample was placed into a sample cup in this manner, and the thermal decomposition temperature was increased from 80 °C, 90 °C, 100 °C, and finally to 320 °C to perform the thermal decomposition experiment. This allowed observation of the pyrolysis characteristics of the compound as the thermal decomposition temperature increased at different temperatures. The results are as follows... Figures 25 to 27 As shown.

[0244] [Decomposition Mechanism]

[0245]

[0246] Reference Figures 25 to 27 The results of the thermal decomposition experiment of the 2C compound show that menthol and γ-undecyl lactone decompose at a temperature of 120°C.

[0247] In the aforementioned decomposition mechanism, the lactone [1C, γ-undecaprolactone] undergoes ring opening, and the hydroxyl group bonds with L-menthol via a carbonate linkage, subsequently esterifying to a sugar (glucose) to prepare the [2C] compound. When the [2C] compound is applied to a product substrate, heating generates L-menthol ([3C]) and CO2, simultaneously forming a [4C] compound with exposed hydroxyl groups. The [4C] compound also undergoes ring-closing (intramolecular esterification) via heat, thereby generating γ-undecaprolactone [5C]. In the [2C] state, the hydroxyl group is protected by the menthyl carbonate group, thus inhibiting ring-closing (intramolecular esterification) at room temperature. Furthermore, as a result of thermal decomposition experiments, it was confirmed that a lactone ring was generated simultaneously with the thermal decomposition of menthol.

[0248] The compound of the present invention that releases aroma components through thermal decomposition is as follows. The temperature range for the production of lactones can be determined through such pyrolytic behavior. Therefore, when used in heated cigarettes, the degree and rate of release of menthol and lactones from compound 2C added to the medium can be adjusted by appropriately adjusting the heating temperature, thereby maintaining a uniform taste and aroma during continuous smoking under optimal temperature conditions.

[0249] Example 2

[0250] The target product of the preparation example (synthesized glucosyl-(4-menthylcarbonyloxy)heptanoate, 5b, 0.01 to 5 wt%), matrix (pulp, 95 to 99 wt%), and other additives (balance) were mixed and rolled into sheets (2 mm thick) using a roll-to-roll method and dried at room temperature. The sheets were smelled at room temperature and no odor of the flavoring compounds used in the synthesis of the target product was observed. The sheets were then used as cigarette paper to manufacture ordinary cigarettes and smoked, confirming the production of flavors (e.g., lactone and menthol flavors used in the synthesis of the target product) upon smoking.

[0251] Example 3

[0252] The target product of the preparation example (synthesized glucosyl-(5-menthylcarbonyloxy)decanoate, 6c, 0.003 wt% to 0.02 wt%), tobacco powder (tobacco powder, 90 wt% to 99 wt%, average particle size of 0.03 mm to about 0.12 mm), and other additives (balance) are mixed and a tobacco composition is manufactured in a conventional manner. The tobacco composition is then wrapped in cigarette paper as a smoking medium to form a filter and rolling paper to prepare a conventional cigarette. Smoking the cigarette confirms that aroma is produced in both the mainstream and sidestream smoke.

[0253] Example 4

[0254] An ink composition was prepared by mixing the target product (synthetic glucosyl-(4-menthylcarbonyloxy)heptanoate, 5a) and solvents (water and ethanol). One or more dashed lines of 0.1 mm to 1 mm thickness (line thickness) of the ink composition were printed onto one side of cigarette paper using an embossing method. The amount of synthetic flavoring used in each sample was g of target product per 100 kg of tobacco. (See table...) Figure 29a and Figure 29b As shown, when applied to cigarette paper, it can impart different effects depending on the part of the application, and it can be used on different parts of the cigarette holder.

[0255] Example 5

[0256] The ink composition (using compound 6d) was applied to multiple locations on cigarette paper in the same manner as in Example 4, and the effect was evaluated based on the different application locations of the synthetic flavoring (fragrance agent) used to improve sideflow smoke in the smoking article.

[0257] exist Figure 30 In the sample 5-1, γ-undecyl lactone was released during thermal decomposition, with a release amount of 2.56 g / 100 kg of tobacco. The following evaluation can be made:

[0258] Appearance and aroma: No difference from the control group (no odor). Mainstream smoke: The odor of lactone is faint but can be barely detected. From the user's perspective, there is no obvious difference, giving a mild feeling.

[0259] Sideflow smoke: The pungent smell of the sideflow smoke from the control group was slightly reduced, but there was no significant difference. It provides a milder feel to the user.

[0260] Sample 5-2 contains γ-undecyl lactone released during thermal decomposition, with a release amount of 12.51 g / 100 kg of tobacco. The following evaluation can be made:

[0261] Appearance and aroma: No difference from the control group (no odor).

[0262] Mainstream smoke: When smoking, it emits a faint lactone aroma, and the menthol aroma becomes stronger closer to the coated area (strip). When the coated area burns, it releases more aroma, without any nauseating or greasy feeling.

[0263] Sidestream smoke: The coating area releases a large amount of aroma, resulting in a strong but not unpleasant flavor. It's necessary to move the coating area from the end to the middle to provide a more rapid change in flavor by altering the coating position. Sidestream smoke releases more aroma and can also reduce the smell of smoke on your fingers.

[0264] Example 6

[0265] The ink composition (using compound 6d) was applied to multiple locations on cigarette paper in the same manner as in Example 4, and the effect was evaluated based on the different application locations of the synthetic flavoring agent (flavoring agent) for improving sideflow smoke in the cigarette product. The application locations of the synthetic flavoring agent (flavoring agent) for improving sideflow smoke in the cigarette product are shown below. Figure 31 As shown.

[0266] In this invention, by applying a novel compound that releases aroma components upon thermal decomposition to the cigarette paper of a conventional cigarette, the aroma components (such as lactones or menthol) are released through heat during cigarette combustion, particularly during smoke smouldering, thereby providing an effect that improves the pungent odor of sideflow smoke. Furthermore, it can also be applied to conventional cigarette tobacco media such as raw-cut tobacco to enhance the persistence of the aroma.

[0267] This invention, when applied to the medium of a heated tobacco stick (NGP), enables the aroma components to remain for a longer period. For heated cigarettes, static heating causes the aroma components in the medium to be consumed during the initial puff. However, the aroma agents are only expressed upon thermal decomposition; therefore, even with continuous puffing, aroma components are produced on the last puff, thus maintaining a consistent tobacco flavor.

[0268] In summary, embodiments have been described with reference to the limited accompanying drawings. Those skilled in the art can make various modifications and variations based on the description. Suitable results can also be obtained if the described techniques are performed in a different order, and / or if the described constituent elements are combined or arranged in different forms, or substituted by other constituent elements or equivalents. Therefore, other embodiments, other examples, and the scope of the claims and their equivalents should be interpreted as including within the scope of this invention.

Claims

1. A smoking product, characterized in that, Includes a fragrance agent, which is a compound represented by the following chemical formula 1: [Chemical Formula 1] In the chemical formula 1, n is an integer of 1 or 2. R is a straight-chain or branched alkyl group having 1 to 30 carbon atoms. Part A' is a portion derived from a fragrance compound containing at least one of an aromatic ring, an aliphatic ring, and an aliphatic chain having a hydroxyl group (-OH), wherein the hydroxyl group participates in a carbonate bond ( A' is a fragrance compound other than the hydroxyl group involved in the carbonate bond. Part G' is a portion derived from a sugar compound, wherein at least one of the hydroxyl groups (-OH) bonded to the ring of the sugar compound participates in an ester bond. G' is a sugar compound other than the hydroxyl group involved in the ester bond, and m is partially bonded to G' via the ester bond. The number of, where m is an integer from 1 to 8. The compound represented by the chemical formula 1 is 0.0001 parts by weight or more relative to 100 parts by weight of the smoking medium.

2. The smoking product according to claim 1, characterized in that, The fragrance compound is selected from cyclic monoterpenoids with hydroxyl groups, acyclic monoterpenoids with hydroxyl groups, aromatic compounds with 6 to 10 carbon atoms having hydroxyl groups, and non-aromatic ring compounds with 5 to 6 carbon atoms having hydroxyl groups.

3. The smoking product according to claim 1, characterized in that, The fragrance compound is selected from the following chemical formulas: , , , , , , , , , , , , , , , , , , , , , , , , , as well as .

4. The smoking article according to claim 1, characterized in that, The portion A' is selected from the following chemical formulas. Wherein, * represents the oxygen bonding site within the carbonate bond in chemical formula 1: , , , , , , , , , , , , , , , , , , , , , , , , , as well as .

5. The smoking article according to claim 1, characterized in that, The sugar compound is selected from tagatose, trehalose, galactose, cyclodextrin, maltodextrin, dextran, sucrose, ribulose, fructose, threose, arabinose, xylose, lysolose, allose, azoose, mannose, lactose, maltose, isotrehalose, neotrehalose, palaginose or isomaltulose, erythrose, deoxyribose, glucose, idole, tarose, erythritol, xylulose, allulose, mesobiose, cellobiose, amylopectin, glucosamine, mannosamine, fucose, glucuronic acid, gluconic acid, gluconolactone, apicoolose, galactosamine, isomaltoligosaccharide, xylooligosaccharide, gentiooligosaccharide, sorbose, Aspergillus niger oligosaccharide, palaginose oligosaccharide, fructooligosaccharide, maltooligosaccharide, lactulose, melibiose, raffinose, rhamnose, and ribose.

6. The smoking article according to claim 1, characterized in that, The fragrance agent is selected from the following chemical formulas 1-1 to 1-9: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formulas 1-3] [Chemical Formulas 1-4] [Chemical Formulas 1-5] Among them, R in chemical formulas 1-1 to 1-5 1 To R 5 These are from the hydroxyl group (-OH) and In the selection, n, R, and A' are as defined in the chemical formula 1; [Chemical Formulas 1-6] Among them, R 1 To R 4 These are from the hydroxyl group (-OH) and In the selection, n, R, and A' are as defined in the chemical formula 1; [Chemical Formulas 1-7] [Chemical Formulas 1-8] [Chemical Formulas 1-9] Among them, R in chemical formulas 1-7 to 1-9 1 To R 8 These are from the hydroxyl group (-OH) and Choose from, n, R, and A' as defined in the chemical formula 1.

7. The smoking article according to claim 1, characterized in that, The flavoring agent is selected from the following chemical formulas 1-1-a to 1-9-a: [Chemical formula 1-1-a] [Chemical Formula 1-2-a] [Chemical formula 1-3-a] [Chemical formula 1-4-a] [Chemical Formula 1-5-a] [Chemical formula 1-6-a] [Chemical Formula 1-7-a] [Chemical formula 1-8-a] [Chemical Formula 1-9-a] 。 8. The smoking article according to claim 1, characterized in that, The flavoring agent produces a fragrance upon thermal decomposition. Upon thermal decomposition, it decomposes into the sugar compound, the flavoring compound, the lactone compound, and carbon dioxide.

9. The smoking article according to claim 1, characterized in that, The fragrance decomposes thermally at temperatures above 80°C.

10. The smoking article according to claim 8, characterized in that, The lactone compound decomposes into either γ-lactone of Formula 2 or δ-lactone of Formula 3: [Chemical Formula 2] [Chemical Formula 3] R is a straight-chain or branched alkyl group having 1 to 30 carbon atoms.

11. The smoking article according to claim 8, characterized in that, The lactone compound is selected from the following chemical formulas: 、 、 、 , , , , , , , , as well as .

12. The smoking article according to claim 1, characterized in that, The smoking articles include liquids, gels, powders, films, or fibers containing compounds represented by the chemical formula 1.

13. The smoking article according to claim 1, characterized in that, The smoking article includes at least one of a film and a filter, wherein the entire surface or at least a portion thereof of the film and the filter is printed or coated with a compound represented by the chemical formula 1.

14. The smoking article according to claim 1, characterized in that, The compound represented by chemical formula 1 is printed as a pattern along the axial direction, transverse direction, or both of the shaft of the smoking article. The pattern is arranged in at least one shape selected from straight lines, dashed lines, grids, polygons, dots, circles, and ellipses.

15. The smoking article according to claim 1, characterized in that, The smoking product includes a filter and a smoking medium. The smoking medium portion includes cigarette paper containing a compound represented by the chemical formula 1, a smoking medium, or both.

16. The smoking article according to claim 15, characterized in that, The cigarette paper includes patterned regions of compounds represented by the chemical formula 1, distributed at least on the entire surface or partially distributed based on the axial, transverse, or both of the smoking article rod, and the position of the patterned regions controls the cigarette flavor and atmosphere contained in the sideflow smoke.

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