Compounds for controlled releasing active molecules

FIELD: organic chemistry, perfumery.

SUBSTANCE: invention relates to an aromatizing composition containing at least compound of the formula (I): as an active component wherein values w, m, P, X, G, Q and n are given in claim 1 of the invention description, and one or more aromatizing component. Also, invention relates to a method for improving, enhancing or modifying odor, to a method for aromatizing surface, method for enhancing or prolonging the diffusion effect of component on surface and to novel compounds of the formula (I) with exception of compounds enumerated in claim 10 of the invention description and to invention relating to aromatizing article using compounds of the formula (I).

EFFECT: valuable cosmetic properties of compounds.

13 cl, 14 ex

 

The present invention relates to the field of perfumery. In particular, it concerns compounds containing at least one β-hydroxy or β-thiocarbonyl residue capable of releasing the active molecules, such as, for example, α, β-unsaturated ketone, aldehyde or ester of carboxylic acid. The present invention also concerns the use of these compounds in perfumes as well as fragrance or perfume compositions or perfumed articles containing compounds according to the invention.

The level of technology

The perfume industry has a special interest in compounds that are capable of extending the effect of the active ingredients within a certain period of time, for example, in order to overcome the problems faced when using fragrances that are too volatile or having insufficient stability. These compounds can be used in various applications, for example, fine or functional perfumery. Washing of textiles is one of the specific areas in which there have been numerous developments in order to ensure the effectiveness of the active substances, in particular flavours that are valid for a certain period of time after washing and drying. Indeed, megavista, possessing the odor and which is particularly suitable for this type of application, actually known as losing stability in the wash or they are not saved after propulsive, as a result, their effect as fragrance lasts longer, and is not strong. Given the importance of this type of application for the perfume industry, was supported by the research in this field, in particular with the purpose of discovering new and more effective solutions to the aforementioned problems.

Among the compounds of the present invention known a few of the prior art. These compounds are 3-(phenylmethoxy)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1-butanone (With Fehr et al. in HeIv. Chim. Acta (1992), 75, 1023), 4-(phenylsulfonyl)-4-(2,6,6-trimethyl-1,3-cyclohexadiene-1-yl)-2-butanone (S. Torii et al. in Bull. Chem. Soc. Jpn. (1978), 51, 949), 4-(phenylthio)-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butanone (I. Kuwajima et al. in Synthesis (1976), 602), 4-(phenylsulfonyl)-4-(2,6,6-trimethyl-1 or 2-cyclohexen-1-yl)-2-butanone (S. Torii et al. in Chem. Lett. (1975), 479), 2-methyl-5-(1-methylethenyl)-3-[(4-were)sulfonyl]-cyclohexanone (Sayed A. et al. in Curr. Sci. (1999), 77, 818), 2-methyl-5-(1-methylethenyl)-3-(phenylmethoxy)-cyclohexanone (G. Hareau et al. in J.Am.Chem. Soc.(1999), 121, 3640), 2-methyl-5-(1-methylethenyl)-3-(octylthio)-cyclohexanone (Niyazymbetov M. et al. in Tetrahedron Lett. (1994), 35, 3037), 3,3'-THIOBIS[2-methyl-5-(1-methylethenyl)-cyclohexanone (Hargreaves M et al. in Z. Natwforsch., B: Anorg. Chem., Org. Chem. (1978), 33B, 155), 2-methyl-5-(1-methylethenyl)-3-(phenylthio)-cyclohexanone and its optical isomers (for example, Bakuzis, P. et al. in J.Org.Chem. (1981), 46, 235), 4-(phenylsulfonyl)-4-(2,5,6,6-tetramethyl-1 or 2-cyclohexen-1-yl)-2-butanone and its optical isomers (S. Torii et al. in J.Org.Chem. (1980), 45, 16), beta-[(4-were)thio]-benzoylpropionate ( G. Manickam et al. Tetrahedron (1999), 55, 2721), beta-[4-(trifluoromethyl)phenoxy]-benzoylpropionate (in ES 2103680), beta(phenylsulfonyl)-benzoylpropionate (J. Vidal et al. in Tetrahedron Lett. (1986), 27, 3733), beta(phenylmethoxy)-benzoylpropionate (Brickmann, K. et al. in Chem. Ber. (1993), 126. 1227), beta-[[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]thio]-benzoylpropionate (in EP 140298), beta-[(4-bromo-3-were)thio]-benzoylpropionate (P. Loiseau et al. in Pharm. Acta HeIv. (1983), 58, 115), beta-[(4-chlorophenyl)thio]-benzoylpropionate (in FR 2509725), beta-[(4-were)sulfonyl]-benzoylpropionate (in WO 00/000198) and beta(phenylthio)-benzoylpropionate (for example, Tilak C. et al. in Indian J.Chem. (1969), 7, 191).

However, all the compounds mentioned above, was used as a synthetic intermediate compounds, and not as flavorings. In addition, in the documents mentioned above, there is no mention or suggestion on the potential use of these compounds as fragrance and more specifically on the use of these compounds for the control release of the active molecules, such as molecules of compounds having the smell.

Disclosure of inventions

Was who discovered the existence of Monomeric, oligomeric or even polymeric compounds on a substrate, containing at least one β-hydroxy or β-thiocarbonyl residue capable of releasing the active molecules, namely northward. The term "active molecule" in the present invention, means any molecule that can bring gains in the smell or affect the environment and, in particular, an aromatic molecule, that is, flavouring, such as α, β-unsaturated ketone, aldehyde or ester of carboxylic acid. Compounds of the present invention have the formula

where (a) w is an integer from 1 to 10000;

b) n has a value of 1 or 0;

c) m is an integer from 1 to 4;

d) P represents a hydrogen atom or a radical that allow for the formation of aromatic α, β-unsaturated ketone, aldehyde or ester of carboxylic acid represented by the formula

where the wavy line indicates the position relationship between P and X;

R1represents a hydrogen atom, a C1-C6CNS radical or a C1-C15linear, cyclic or branched alkyl, alkanniny or akadeemiline radical, possibly substituted C1-C4alkyl groups;

R2, R3and 4represent a hydrogen atom, an aromatic ring or a C1-C15linear, cyclic or branched alkyl, alkanniny or akadeemiline radical, possibly substituted C1-C4alkyl groups; or two or three groups of R1-R4linked together to form a saturated or unsaturated ring having from 6 to 20 carbon atoms including the carbon atom that is attached to the specified R1, R2, R3or R4group, while this ring may be substituted C1-C8linear, branched or cyclic alkyl or alkenylamine groups; and provided that at least one R group has the formula (II) as defined above;

e) X is a functional group selected from the group comprising formulas (i) to xiii):

where in the above formulae the wavy lines have the meanings as defined above, and the bold lines show the position relationship between X and G, and R5represents a hydrogen atom, a C1-C22saturated or unsaturated alkyl group or aryl group, possibly substituted C1-C6alkyl or CNS groups or halogen atoms; and provided that X may be absent when P is an atom in Dorada;

f) G is a polyvalent radical (m+1 valence) derived from aryl radical, possibly substituted, or a divalent cyclic, linear or branched alkyl, alkanniny, akadeemiline or alkylbenzene hydrocarbon radical having from 6 to 22 carbon atoms, or three, four or pentavalent cyclic, linear or branched alkyl, alkanniny, akadeemiline or alkylbenzene hydrocarbon radical having from 1 to 22 carbon atoms specified hydrocarbon radical may be samemanner and containing from 1 to 10 functional groups selected from the group consisting of a simple ester, of ester, ketone, amine, Quaternary amines and amides; the possible substituents G are atoms of halogen, NO2, OR6, NR62, COOR6or R6group, R6represents a C1-C15alkyl or alkenylphenol group;

g) Q is a hydrogen atom (in this case w=1 and n=1) or is a group of [[P-X]m[G]n] where R, X, G, n and m are as defined above (in this case, w=1 or dendrimer selected from the group consisting of polyalkylene dendrimers, amino acids (e.g. lysine) dendrimers, mixed amino/ether dendrimers and mixed amino/amide dendrimers or polysacharide is, selected from the group consisting of cellulose, cyclodextrin and starch or cationic quarternizing silicone polymer, such as Abilquat® (source: Goldsmith, USA) or another polymer skeleton, derived from the monomer of element selected from the group comprising formulas (A) to (E) and mixtures thereof:

where the dashed lines show the position relationship between the specified monomer link and G;

z is an integer from 1 to 5;

n defined above;

R7represent simultaneously or independently a hydrogen atom, a C1-C15alkyl or alkenylphenol group4-C20polyalkyleneglycols or aromatic group;

R8represent simultaneously or independently a hydrogen atom or oxygen, C1-C5alkyl or glycol or missing;

Z represents a functional group selected from the group comprising formulas from 1) to 8), branched chains of formulas of 9) to 11) and mixtures thereof:

where the value of the dashed lines defined above, the dotted arrows show the position relationship between the specified Z and the rest of the unit link and arrows show the position relationship between the specified Z and either G or the remaining part of the monomer level, R7is how the definition is prohibited above; and provided that Z is not a group of formula 1), 3) and (7), if Monomeric link has the formula).

The phrase "sweet α, β-unsaturated ketone, aldehyde or ester of carboxylic acid"used in the definition of R, mean α, β-unsaturated ketone, aldehyde or ester of carboxylic acid, which is an average specialist in this field of knowledge is defined as used in perfumery as a flavouring ingredient (odorants). In the General case, the flavouring α, β-unsaturated ketone, aldehyde or ester of carboxylic acid is a compound having from 8 to 20 carbon atoms or more, preferably 10 to 15 carbon atoms. Preferred compounds of formula (I) are those in which:

a) w is an integer from 1 to 10000;

b) n has a value of 1 or 0;

c) m is 1 or 2;

d) R represents a hydrogen atom or a radical of the formulae (P-1) to (P-11), in the form of any one of its isomers:

where the wavy line have the meanings indicated above, and the dotted lines represent a single or double bond, R9means a methyl or ethyl group, and R10represents a C6-C9linear or branched alkyl, alkenylphenol or akadeemiline group; and priruslovye, that at least one R group has the formula (P-1) to (P-11)as defined above;

e) X is a functional group selected from the group comprising the formula:

where oily or wavy line have the meanings indicated above; and provided that X may be absent when R represents a hydrogen atom;

f) G represents a divalent or trivalent radical derived from an aryl radical, possibly substituted, or a divalent cyclic, linear or branched alkyl, alkanniny, akadeemiline or alkylbenzene hydrocarbon radical having from 8 to 22 carbon atoms or trivalent cyclic, linear or branched alkyl or alkanniny hydrocarbon radical having from 1 to 22 carbon atoms specified hydrocarbon radical may be substituted, containing from 1 to 5 functional groups selected from the group consisting of a simple ester, complex ester, ketone, amine, Quaternary amines and amides; the possible substituents G are atoms of halogen, NO2, OR6, NR62, COOR6or R6group, R6represents a C1-C15alkyl or alkenylphenol group;

g) Q is a hydrogen atom (in this case w=1 and n=1) or is the way the nd group [[P-X] m[G]n]where R, X, G, n and m are as defined above (in this case, w=1) or the polymer skeleton, derived from the monomer of element selected from the group comprising formulas (A), (C), (D), (E) and mixtures thereof:

where the dashed line, z and n are as defined above;

R7represent simultaneously or independently a hydrogen atom, a C1-C10alkyl group or a C4-C14polyalkyleneglycol group;

R8represent simultaneously or independently a hydrogen atom or oxygen, C1-C4alkyl or glycol or missing;

Z represents a functional group selected from the group comprising formulas from 1) to 5), 7), branched chains of formulas 9 and 10) and mixtures thereof:

where the dashed lines, dotted arrows and the arrows are defined above, R7have the meanings as defined above.

In the most preferred embodiment of the invention the compounds of formula (I) are those in which:

a) w is an integer from 1 to 10000;

b) n has a value of 1 or 0;

c) m is 1 or 2;

d) R is a radical of the formulae (P-1) to (P-11)as defined above;

e) X is a functional group selected from the group comprising formulas

where values in bold or wavy lines defined above;

f) G represents a divalent or trivalent radical derived from an aryl radical, possibly substituted, or a linear or branched alkyl, alkanniny, akadeemiline or alkylbenzene hydrocarbon radical having from 8 to 22 carbon atoms specified hydrocarbon radical may be substituted, containing from 1 to 5 functional groups selected from the group consisting of a simple ester, ketone and amine; possible substituents G groups are halogen atoms, NO2, OR6, NR62, COOR6or R6group, R6represents a C1-C6alkyl or alkenylphenol group;

g) Q is a hydrogen atom (in this case w=1 and n=1) or is a group of [[P-X]m[G]], where R, X, G, n and m are as defined above (in this case, w=1) or the polymer skeleton, derived from the monomer of element selected from the group comprising formulas (A), (C), (E) and mixtures thereof:

where the dashed line, z and n are as defined above;

R7represent simultaneously or independently a hydrogen atom, a C1-C5alkyl group or a C4-C10polyalkyleneglycol group;

R8represents about is simultaneously or independently a hydrogen atom or oxygen, C1-C4alkyl or glycol or missing;

Z represents a functional group selected from the group comprising formulas from 1) to 5), branched chains of formulas 9 and 10) and mixtures thereof:

where the dashed lines, dotted arrows and the arrows are defined above, R7defined above.

An alternative, in this most preferred embodiment of the invention, m is 2, X represents a functional group of formula (iii), as defined above, and G represents a trivalent linear or branched alkyl or alkanniny hydrocarbon radical having from 1 to 7 carbon atoms specified hydrocarbon radical may contain from 1 to 5 functional groups selected from the group consisting of a simple ester, ketone and amine.

In another specified alternative preferred embodiment of the invention m is 1 or 2, X represents a functional group selected from the group consisting of formulas

where values in bold or wavy lines are defined above; and G represents a divalent radical derived from a linear or branched alkyl or alkenylphenol hydrocarbon radical having from 8 to 20 carbon atoms, such uglevodorov the hydrated organic radical can be substituted, containing from 1 to 5 functional groups, selected from the group consisting of a simple ester, ketone and amine; possible substituents G groups are halogen atoms, NO2, OR6, NR62, COOR6or R6group, R6represents a C1-C6alkyl or alkenylphenol group.

It should be clear that when m or w in the compound of formula (I) is an integer greater than 1, then each of the different R can be the same or different, just as each of X or G.

In an even more preferred embodiment of the present invention represented by the compound of the formula (I'):

where m has a value of 1 or 2;

Q represents a hydrogen atom;

R represents a radical of the formulae (P-1) to (P-7), in the form of any one of its isomers:

where the values of wavy lines and dotted lines are as defined above;

X represents a functional group selected from the group consisting of formulas

where values in bold or wavy lines are defined above; and G represents a divalent or trivalent arene radical, possibly substituted by halogen atoms, NO2, OR6, NR62, COOR6and R6group, R6represents a C -C6alkyl or alkenylphenol group. Alternatively, these compounds of formula (I') are those in which

where R, m and Q are as defined above;

X represents a functional group of formula (iii) or x), as defined above, and

G represents a divalent radical derived from a linear or branched alkyl or alkenylphenol hydrocarbon radical having from 8 to 15 carbon atoms; or G represents a trivalent radical derived from a linear or branched alkyl hydrocarbon radical having from 2 to 10 carbon atoms.

Another alternative is represented by a compound of the formula (I'):

where R, m and Q are as defined above;

X represents a functional group selected from the group comprising formulas (ii), (viii) or (ix)as defined above;

G represents a divalent or trivalent radical derived from a linear or branched alkyl or alkenylphenol hydrocarbon radical having from 8 to 15 carbon atoms.

The compound of formula (I) represents an even more preferred embodiment of the invention:

where Q and R have the meanings given in the formula (I'); and G Ave dstanley a trivalent radical, derived from a linear or branched alkyl or alkenylphenol hydrocarbon radical having from 3 to 6 carbon atoms.

When m in the formula (I') has the value 2, then each of the different R can be the same or different, just as each of X.

The compounds of formula (I) can be synthesized from commercially available compounds using conventional methods. In General, compounds according to the invention are obtained by reaction of accession [1, 4] between sweet α, β-unsaturated ketone, aldehyde or carboxylic ester of formula (II')

where the configuration of the carbon-carbon double bond may be E or Z-type and R1, R2, R3and R4have the values given in the formula (I); and the compound of the formula Q[(-G-)n[X-H]m]wwhere all the symbols have the meanings given in the formula (I). For practical purposes and in accordance with nature and the nucleophilicity of the functional group X in the compounds according to the invention can be obtained more predominantly by the reaction between the compound of formula (II'), which is alcaline derived aromatic compounds of the formula (II'),

where R1, R2, R3and R4have the values given in the formula (I); and the derived Q[(-G-)n [X-H]m]wsuch as the acid chloride acid, sulphonylchloride or alkylchlorosilanes derived.

Use Algologie derived is of particular interest for the synthesis of all compounds of formula (I)in which X represents, for example, carboxyl, sulphonate, sulphate, carbonate, phosphate, borate and silicate functional group. On the other hand, the direct use of aromatic molecules as the source of the product is of particular interest for the synthesis of all compounds of formula (I), where X represents, for example, ether, thioester or even dicarboxylate derived.

Polymer products can be obtained by polymerization of one monomer, in which the residue (-G-)n[X-P]mpre-inoculated. This polymerization can also be carried out in the presence of other monomer units carrying different (-G-)n[X-P]mthe residue.

Common examples of this approach are presented in the following diagram for the specific cases of obtaining compounds of formula (I):

Although it was not possible to provide an exhaustive list of compounds of the formula Q[(-G-)n[X-H]m]wthat can be used for the synthesis of compounds according to the invention, it is possible to define the following, preferred is entrusted examples: benzoic acid, 4 - or 3-methylbenzoic acid, 3 - or 4-(N,N-dimethylamino)-benzoic acid, tasilova acid, benzolsulfonat acid, isophthalic acid, phthalic acid, terephthalic acid, benzene-1,2,3-tricarboxylic acid, Ethylenediamine-tetraoxane acid, nitryltriacetic acid, alkylenedioxy acid (where alkyl represents a C1-C10alkyl group), 10-undecenoate acid, undecanoate acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, dodecandioic acid, 1-octadecanethiol and CH3(CH2)11S(O)andN (where a represents 0, 1 or 2). As the polymer compounds of the formula Q[(-G-)n[X-H]m]wcan be given various polymers or copolymers based on polymethacrylates or polystyrene. As derivatives of the compounds of the formula Q[(-G-)n[X-H]m]wcan be given its alkaline salts, acid anhydrides (if X=MEO), sulphonylchloride and sulfochloride (if X=SO2or SO4and chloroformate derivatives (if X=LLC).

Similarly, it is also impossible to give an exhaustive list of the currently known aromatic compounds of the formula (II'), which can be used in the synthesis of compounds according to the invention, and then released. However, may the be following named compounds as preferred examples: α -Damasco, β-Damasco, γ-Damasco, Δ-Damasco, α-ionon, β-ionon, γ-ionon, Δ-ionon, β-damascenone, 3-methyl-5-propyl-2-cyclohexen-1-it, 1(6), 8-P pentadien-2-it, 2,5-dimethyl-5-phenyl-1-HEXEN-3-one, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-it, 8 or 10-methyl-alpha-ionon, 2-octanol, 1-(2,2,3,6-tetramethyl-1-cyclohexyl)-2-butene-1-he, 4-(2,2,3,6-tetramethyl-1-cyclohexyl)-3-butene-2-it, 2-cyclopentadien-1-he, nootkatone, cinnamic aldehyde, 2,6,6-trimethylbicyclo[3.1.1]heptane-3-Spiro-2'-cyclohexen-4'-he, ethyl-2,4-decadienoate, ethyl-2-octenoate, methyl-2-nonanoate, ethyl-2,4-undecadienal and methyl-5,9-dimethyl-2,4,8 - decadienoate. Undoubtedly, algaline derivatives of the formula (II), the latter compounds are also useful for the synthesis of compounds according to the invention.

Among the aromatic compounds contained in the above list, are preferred: damascone, ionone, beta-damascenone, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-it, 1(6),8-P pentadien-2-it, 2-cyclopentadien-1-it, 1-(2,2,3,6-tetramethyl-1-cyclohexyl)-2-butene-1-he, 4-(2,2,3,6-tetramethyl-1-cyclohexyl)-3-butene-2-it 2-cyclopentadien-1-it.

As you can see from the formula (I), compounds according to the invention consist of three main parts, namely releasing residue R-h, fragment G and the terminal group Q.

A characteristic feature of the invention relates to the structure of the releasing remainder R of Agricultural Bliod the OC special chemical structure of the specified residue of the compounds of formula (I) have the ability to escape through the reaction of the decomposition residue and aromatic molecules, such as, for example, α, β-unsaturated ketone, aldehyde or ester of carboxylic acid of the formula (II').

An example of the specified decomposition reaction represented by the following diagram:

Connection Q[(-G-)n[X-H]m]wthat is also the residue obtained in the reaction of decomposition itself can be odorless compound or flavoring ingredient; preferably the specified residue represents a connection that does not have a smell. Similarly, the compound of formula (I) is preferably a compound odorless.

The nature of X plays an important role in the kinetics of release of fragrant with the odor molecules. Accordingly, careful selection of nature X it is possible to configure the properties of the compounds of formula (I), associated with the release of odor.

The second part of the compounds according to the invention is a fragment of G. in Addition to its role as a connecting link between the release of P's and Q specified G residue may also influence the properties of the compounds of formula (I), associated with the release. Certainly, the careful choice of the chemical nature of the specified fragment, such as electron-donor/acceptor or hydrophobic/hydrophilic fragments, may be able to improve the harmonization of properties associated with a release preparations is the group of smell.

The third component compounds according to the invention is a terminal group of Q. Since Q is not hydrogen or a group of [[P-X]m[G]n]specified end group can play the role of the media, which can be joined by a few released links R-X. moreover, depending on its specific nature, it can also play an important role in the effective deposition surface and the presence of molecules of the compounds according to the invention on the surface, which is used for the application, especially on fabrics and hair. Specified the role of the media in the effective deposition is well known to specialists in this field of knowledge.

The reaction of the decomposition, which leads to the release of odoriferous or flavoring molecules, as it turns out, is affected by changes in pH or heating, but can also be caused by other types of mechanism.

Since the compounds according to the invention are useful ingredients for flavoring various products, the present invention also applies to all the different forms of the compounds according to the invention, which can be successfully used in perfumery. Such forms include a composition consisting of compounds of the formula (I) and a solvent commonly used in perfumery. As examples of these solvents can generally determine the connection type dipropyleneglycol, diethylphthalate, isopropylmyristate, benzyl benzoate, 2-(2-ethoxyethoxy)-1-ethanol or utilitate, which is mainly used.

In addition, the present invention relates to a fragrance composition comprising at least one compound of formula (I). In General, under "fragrance composition" means a mixture containing at least two aromatic ingredient in any of its forms, and possibly one or more of the solvents customarily used in perfume compositions. Therefore, flavoring compositions in accordance with the invention contain at least one of the compounds according to the invention together with one or more flavouring congregate and possibly one or more solvents.

The nature and type of these flavouring congregants not require a more detailed description of the present invention, which in any case would not be exhaustive, the average person skilled in the art are able to choose them on the basis of General knowledge and according to the nature of the product, which is the flavor, and depending on the desired effect. In General, these aromatic cogredient belong to chemical classes, such as various alcohols, aldehydes, ketones, esters, ethers, acetates, NITRILES, terpene hydrocarbons, nitrogen or ser is containing heterocyclic compounds and essential oils of natural or synthetic origin. Many of these ingredients, in any case, are listed in the book, which is a reference to S.Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its more recent re-issues, or in other works of a similar nature, as well as in a variety of available literature in the field of perfumery.

Similarly, a detailed description of the nature and type of solvents commonly used in flavouring compositions, may not be exhaustive. The average person skilled in the art are able to choose them based on the nature of the product, which should be flavored. However, as non-limiting examples of such solvents, it is possible to cite, in addition to the solvents mentioned above, ethanol, a mixture of water/ethyl alcohol, limonene or other terpenes, ISO, known under the trademark Isopar® (origin: Exxon Chemical) or glycol ethers and esters of glycol ether, known under the trademark Dowanol® (origin: Dow Chemical Company).

As mentioned above, the compound of formula (I), in any of its forms, or flavoring composition containing specified compound of formula (I), is useful flavouring ingredient, which can be used with success in all fields of modern perfumery, type of fine or functional perfumery perfumery, as it is able to regulate the SQL release of odoriferous molecules.

Indeed, the compounds according to the invention can be used with success in fine or functional perfumery, in order to achieve a more controlled deposition and then release aromatic compounds. For example, flavoring ingredients are present as such in detergents or flavoring compositions, may have slight effect of retention on the surface and, therefore, can often be chipped off, for example, when the rinsing water or dries to a given surface. This problem can be solved using the connection formula (I), which, as can be shown, has an amazing storage stability and strength retention or resistance on surfaces such as textile fabrics. Therefore, the compounds according to the invention, due to their good stability, low volatility and a controlled release of fragrance molecules can be included in any application requiring rapid or prolonged release of the flavouring component, as defined above, and, in addition, can make the smell and freshness of the processed surface, which will be retained after rinsing and/or drying. Suitable surfaces are, in particular, textiles, hard surfaces, hair and skin.

Thus, in perfumery, one of the main advantages of izobreteny what is the compounds of formula (I) give an intense smell of the processed surface, which provides a fragrant molecule, which would not be detected at the surface for a long enough period, if used flavouring α, β-unsaturated carbonyl derivative such as, without predecessor.

This behavior makes the compounds of formula (I) are particularly suitable for use as precursors flavouring ingredients for applications associated with functional or subtle perfumes. Consequently, the use of the compounds according to the invention as a flavouring ingredient is another object of the present invention. Moreover, perfumed articles containing at least one compound according to the invention, in any of its forms or flavoring composition containing specified compound of formula (I), are also an object of the present invention.

Suitable aromatic products include solid or liquid detergents and fabric softeners, as well as all other products, the usual perfumery, namely perfumes, colognes or aftershaves, scented soap, scented bath salts or soul, foams, oils or gels or hygiene or care products for your hair type is anuna, tools, body care, deodorants or antiperspirants, air fresheners and cosmetic preparations. As detergents are designed for applications such as detergent compositions or cleaning products for washing or cleaning of various surfaces, for example intended for cloth, utensils or processing of solid surfaces, in any case, they are designed for home or industrial use. Other scented products are fabric fresheners, water for Ironing, paper, wipers or bleach.

Preferred fragrance compositions or flavouring products are perfumes, detergents for cloth or grounds for bating.

Typical examples of detergents for cloth or softening compositions, which can be included compound according to the invention described in WO 97/34986 or US 4137180 and 5236615 or EP 799885. Other typical detergent and softening compositions which can be used are described in works such as Ullman''s Encyclopedia of Industrial Chemistry, vol.A8, pages 315 - 448 (1987) and vol.A25, pages 747-817 (1994); Flick, Advanced Cleaning Product Formulations, Noye Publication, Park Ridge, New Jersey (1989); Showell, in Surfactant Science Series, vol.71: Powdered Detergents, Marcel Dekker, New York (1988); Proceedings World Conference on Detergents (4th, 1998, Montreux, Switzerland), AOCS print.

Some of the above products can present a hostile environment for soybeans is inane according to the invention, thus, it is necessary, in order to be able to protect them from premature decomposition, for example, by using encapsulation.

For clarity it should be mentioned that under the "aromatic product" means in the present invention ready for use, the product or part of the specified product for consumption, are able to enhance the moisturising action. Thus, flavoured product in accordance with the invention, includes at least a portion of the entire composition corresponding to the desired product, for example cleaning tool, or part of it and at least the connection according to the invention possibly together with one or more flavouring congregants and possibly one or more solvents.

The nature and type of the component parts of the product are not discussed in more detail in the present invention, which in any case may not be exhaustive, the average person skilled in the art are able to choose them on the basis of General knowledge and according to the nature and the desired effect in relation to the specified item.

The proportions in which the compounds according to the invention can be incorporated into the various aforementioned articles or compositions vary within wide limits. These values depend on the nature of the product or product should be and what somatizirovanne, and depending on the olfactory effect, as well as from the nature of congregants in a given composition when the compounds according to the invention is mixed with the aromatic congregate, solvents or additives commonly used in this field.

For example, typical concentrations are in the range from 0.001 to 5% by weight or more compounds according to the invention based on the weight of the composition in which they are included. Can be used in concentrations lower than the order of from 0.01% to 1% by weight, when these compounds are used directly for flavoring various consumer products mentioned above.

Another object of the present invention is a method of flavoring a surface or a way to enhance or extend the effect of the diffusion characteristic odor of fragrance on the surface, namely, that the specified surface is treated in the presence of the compounds of formula (I). Suitable surfaces are, in particular, textiles, hard surfaces, hair and skin.

The invention is described below in detail using the following examples, in which the abbreviations have the usual meaning in the art, the temperatures are indicated in degrees Celsius (°C); the NMR spectral data recorded in CDCl3(unless stated otherwise) with a frequency of 360 or 400 MG is for 1H and13With the chemical shift δ recognize in parts per million relative to TMS as standard, the binding constant of the J are expressed in Hz. Helpanimals chromatography carried out on a column (Macherey-Nagel Nucleogel GPC 500-5 (300×7.7 mm diameter in inches), THF elution at 0.5 ml/min and calibrated with commercially available standards (origin: Fluka).

Example 1

The synthesis of compounds of formula (I), when using Algologie derived α-damascone as the original product

The original product, namely 3-hydroxy-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1-butanone obtained in accordance with .H.Schulte-Elte et al. in Helv. Chim. Acta 1973, 56, 310.

a) Synthesis of 1-methyl-3-oxo-3-(2,6,6-trimethyl-2-cyclohexen-1-yl)propylbenzoate

To a solution of 3-hydroxy-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1-butanone (4,00 g with a purity of 92%, 17.5 mmol), NEt3(3.2 ml, 22,85 mmol) and dimethylaminopyridine (DMAP) (400 mg) in CH2Cl2(100 ml) was added benzoyl chloride (2,43 ml, 20,94 mmol). The reaction mass is stirred for 65 hours at room temperature. The mixture is then acidified with 5% HCl solution and extracted twice with ether and washed with water, saturated solution of NaHCO3and then a saturated solution of Nad. Finally, the organic phase is dried over Na2SO4concentrate at 50-60°/0.03 mbar) and purified using flash chromatography on SiO2(the cycle is hexane/AcOEt=97:3). Accordingly gain of 4.25 g of product (yield: 73%). MS: 192 (52), 123 (22), 105 (100), 81 (13), 77 (20), 69 (45).

1H-NMR: 0.92/0.93/0.94 (3, 6N); 1.12-1.23 (m, 1H); 1.39/1.42 (d, J=6; 3H); 1.59 (s, 3H); 1.65-1.80 (m, 1H); 1.95-2.20 (m, 2H); 2.60-2.83 (m, 2H); 3.02-3.20 (m, 1H); 5.50-5.63 (m, 2H), 7.36-7.45 (m, 2 H), 7.48-7.57 (m, 1H), 7.96-8.04 (m, 2 H).

13C-NMR: 210.1 (C), 165.7 (C), 132.8 (d); 130.5 (C), 129.9 (C), 129.5 (2 d); 128.2 (2 d); 123.8 (d); 67.4/6 (d); 63.6/8 (d); 51.1 (t); 32.5 (C); 30.7/8 (t); 27.9 (kV); 27.8 (kV); 23.5 (kV); 22.6 (t); 20.0/1 (kV).

b) Synthesis of 1-methyl-3-oxo-3-(2,6,6-trimethyl-2-cyclohexen-1-yl)propyl 3-(dimethyl-amino)benzoate

To a solution of 3-hydroxy-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1-butanone (4,00 g, 92% purity, 17.5 mmol), 3-N,N-diethylaminobenzoic acid (3.13 g, 19.0 mmol) and DMAP (1.85 g, of 15.2 mmol) in CH2Cl2(50 ml) is added N,N-dicyclohexylcarbodiimide (DCC) (or 4.31 g of 20.9 mmol) in CH2Cl2(15 ml). The reaction mass was stirred at room temperature for 70 hours. The mixture is then acidified with concentrated HCl and extracted twice with ether and washed with water, saturated solution of NaHCO3and then a saturated solution of NaCl. Finally, the organic phase is dried over Na2SO4concentrate when (50-60°/0.03 mbar) and purified using flash chromatography on SiO2(cyclohexane/AcOEt=97:3). Accordingly receive 4,20 g of product (yield: 68%).

MS: 357 (M+, 19), 218 (8), 203 (28), 192 (13), 185 (10), 165 (19), 148 (100); 69 (36), 57 (19), 40 (51).

1H-NMR: 0.92/0.93/0.94 3, 6N); 1.12-1.23 (m, 1H); 1.38/1.40 (d, J=6; 3H); 1.60 (s, 3H); 1.65-1.80 (m, 1H); 1.95-2.20 (m, 2H); 2.60-2.80 (m, 2H); 2.97 (s, 6N); 3.01-3.20 (m, 1H); 5.49-5.62 (m, 2H), 6.85-6.91 (m, 1H); 7.21-7.27 (m, 1H), 7.30-7.38 (m, 2H).

13C-NMR: 210.0/2 (C), 166.3 (C); 150.4 (C), 131.1 (C), 129.9 (C), 128.9 (d); 123.8 (d); 117.5 (d); 116.7 (d); 113.3 (e); 67.3/5 (d); 63.6/8 (d); 51.1/2 (t); 40.6 (2 kV); 32.4 (C); 30.7/8 (t); 28.0 (kV); 27.8 (q; 23.5 (kV); 22.6 (t); 20.0/1 (kV).

c) Synthesis of bis[1-methyl-3-oxo-3-(2,6,6-trimethyl-2-cyclohexen-1-yl)propyl]terephthalate

A solution of 3-hydroxy-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1-butanone (3.55 g, 92% purity, of 15.5 mmol) in CH2Cl2(10 ml) are added to a solution of terephthaloylchloride (1,99 g of 9.80 mmol) and NEt3(2,12 g, 21.1 mmol) in CH2Cl2(15 ml). The reaction mass is heated at boiling point for 3 hours. The mixture is then acidified with 5% HCl solution and extracted twice with ether and washed with water, 5% NaOH solution, again with water and then saturated NaCl solution. Finally, the organic phase is dried over Na2SO4concentrate when (50-60°/0.03 mbar) and purified using flash chromatography on SiO2(cyclohexane/AcOEt=9:1). Accordingly gain of 2.54 g of product (yield: 60%).

1H-NMR: 0.91/0.94 (2, N); 1.12-1.23 (m, 2H); 1.40/1.43 (d, J=6; 6N); 1.58 (s, 6N); 1.65-1.80 (m, 2H); 1.95-2.20 (m, 4H); 2.63-2.84 (m, 4H); 3.02-3.23 (m, 2H); 5.53-5.64 (m, 4H); 8.02 (s, 4 H).

13C-NMR: 209.9/210.0 (C), 164.9 (C), 134.2 (C), 129.7/8 (C), 129.4 (2 d); 123.9 (e); 67.9/68.1 (d); 63.6/8 (d); 51.0 (t); 32.5 (C); 30.7/8 (t); 28.0 (kV); 27.8 (kV); 23.5 (kV); 22.6 (t); 2.0/1 (kV).

d) Synthesis of 1-methyl-3-oxo-3-(2,6,6-trimethyl-2-cyclohexen-]-yl)propyl 4-methylbenzenesulfonate

To a solution of 3-hydroxy-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1-butanone (1,00 g, 92% purity, to 4.38 mmol), DMAP (100 mg) and NEt3(1.0 ml, 7.2 mmol) in CH2Cl2(20 ml) is added, at a temperature of 0°, taillored (2.02 g, 10.56 mmol). The reaction mass was stirred at room temperature for 4 days. The mixture is then acidified with concentrated HCl and extracted twice with ether and washed with water, saturated solution of NaHCO3and then a saturated solution of NaCl. Finally, the organic phase is dried over Na2SO4concentrate when (50-60°/0.03 mbar). Accordingly receive from 0.76 g of product (yield: 50%). MS (electrospray): 365 (M++1, 100), 353 (20), 279 (5), 228 (19), 193 (22).

1H-NMR: 0.75/0.79/0.86/0.87 (4, 6N); 1.06-1.18 (m, 1H); 1.27/1.33 (d, J=6; 3H); 1.49 (broadened, 3H); 1.52-1.65 (m, 1H); 1.93-2.15 (m, 2H); 2.43 (s, 3H); 2.55-3.08 (m, 3H); 4.92-5.05 (m, 1H), 5.56 (broadened, 1H), 7.33 (d J=8; 2H), 7.77 (d, J=8; 2H).

13C-NMR: 209.5/6 (C); 144.6/7 (C), 133.6 (C), 129.7/8 (d); 129.4/6 (C), 127.9 (2 d); 124.0/1 (d); 75.6 (d); 63.5/8 (d); 51.3/6 (t); 32.3/4 (C); 30.6 (t); 27.7/8 (kV); 27.7 (kV); 23.3 (kV); 22.5 (t); 21.6 (kV); 21.0/1 (kV).

e) Synthesis of 1-methyl-3-oxo-3-(2,6,6-trimethyl-2-cyclohexen-1-yl)propylacetate

Using a similar experimental procedure as described in example 1.a), and using dodecanethiol instead of benzoyl chloride. Connection receive 8% of the output.

1H-NMR: 0.82-0.95 (m, N); 1.17 (m, 1H); 1.20-1.35 (m, N); 1.59 (m, 5H); 1.79 (m, 1H); 1.95-2.18 (m, 2H); 2.22 (t, J=7,2H); 2.46-2.66 (m, 1H); 2.70 (m, 1H); 2.83-3.03 (m, 1H); 5.32 (m, 1H); 5.59 (b, 1 N).

13C-NMR: 210.0 (); 173.0 (C); 129.9 (C), 123.8 (d); 66.6 (d)63.7 (e); 50.9 (t); 34.6 (t); 32.5 (C); 31.9 (t); 30.7 (t); 29.1-29.6 (several t); 27.8/9 (kV); 25.0 (t); 23.4 (kV); 22.6/7 (t); 19.9/20.0 (kV); 14.1 (kV).

f) Synthesis of bis-[1-methyl-3-oxo-3-(2,6,6-trimethyl-2-cyclohexen-1-yl)propyl]succinate

Using a similar experimental procedure as described in example 1.b), and using succinic acid instead of 3-N,N-diethylaminobenzoic acid. Connection receive from 51% yield.

1H-NMR: 0.85-0.95 (m, 6N); 1.17 (m, 1H); 1.27 (t, J=8, 3H); 1.58 (s, 3H); 1.70 (m, 1H); 1.95-2.20 (m, 2H); 2.22 (t, J=7, 2H); 2.44-2.68 (m, 1H); 2.53 (s, 2H); 2.73 (b, 1H); 2.84-3.04 (m, 1H); 5.32 (m,, 1H); 5.60 (b, 1 H).

13C-NMR: 210.1 (C), 171.4 (C); 129.8 (C), 123.8 (d); 66.2 (d)63.7 (e); 50.8 (t); 32.4 (C), 30.7 (t); 29.8 (t); 27.8 (kV); 23.4 (kV); 22.6 (t); 19.9 (kV).

g) 1-Methyl-3-oxo-3-(2,6,6-trimethyl-2-cyclohexen-1-yl)propyl 10-undecenoate

Using a similar experimental procedure as described in example 1.b), and using 10-undecenoate instead of 3-N,N-diethylaminobenzoic acid. Connection receive 64% yield.

1H-NMR: 0.83-0.96 (4, 6N); 1.17 (m, 1H); 1.20-1.45 (m, 15 NM); 1.58 (b, 3H); 1.70 (m, 1H); 1.95-2.17 (m, 4H); 2.22 (t, J=7; 2H); 2.45-2.65 (m, 1H); 2.72 (m, 1H); 2.83-3.03 (m, 1H); 4.92 (m, 1H); 4.97 (m, 1H); 5.30 (m, 1H); 5.59 (m, 1H); 5.80 (m, 1 H).

13C-NMR: 210.0 (); 172.9 (C), 139.2 (d); 129.8 (C), 123.8 (d); 114.1 (t); 66.6 (d)63.7 (e);50.95 (t); 34.5 (t); 33.8 (t); 32.4 (C), 30.7 (t); 28.9-29.3 (several t); 27.9 (kV); 27.8 (kV); 24.9 (t); 23.4 (kV); 22.6 (t); 19.95 (kV).

Example 2

The synthesis of compounds of formula (I) when using α-damascone as the original product

a) Synthesis of 3-[2-(dimethylamino)ethoxy]-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1-butanone

Solution α-damascone (6,44 g; and 33.5 mmol), N,N-dimethylaminoethanol (30,25 ml, 301 mmol) and tetramethylguanidine (TMG) (0,77 g; 6,70 mmol) is heated at a temperature of 70°C for 15 hours. Then the excess N,N-dimethylaminoethanol is distilled at a temperature of about 60°With/at pressures from 10 to 2 mbar. The crude product was diluted in diethyl ether (Et2O) and the resulting mixture is extracted with 5% HCl solution, washed with water and saturated NaCl solution. The combined aqueous phase is alkalinized using an aqueous solution of NaOH and extracted twice with ether to obtain the crude product in the organic phase. These organic phase is again washed with water and brine, then dried over Na2SO4and concentrate. Distilled from a flask into the flask crude product (100-125°/0,05 mbar) gives 2,94 g of the product of the desired purity (yield: 32%). MS: 281 (M+, 3), 192 (2), 123 (7), 73 (17), 72 (17), 58 (100).

1H-NMR: 0.90/0.92/0.93 (3, 6N); 1.10-1.20 (m, 1H); 1.15/1.18 (d, J=6; 3H); 1.58 (s, 3H); 1.65-1.77 (m, 1H); 1.95-2.20 (m, 2H); 2.23 (s, 6N); 2.37-2.56 (m, 3H); 2.70/2.75 (broadened, 1H); 2.82-3.00 (m, 1H); 3.40-3.50 (m, 1H); 3.55-3.4 (m, 1H); 3.86-3.99 (m, 1H); 5.58 (broadened, 1H).

13C-NMR: 211.7/212.0 (); 130.2 (C), 123.6 (d); 71.4/8 (d); 66.8/9 (t); 64.0/1 (d); 59.2 (t); 52.4/6 (t); 45.9 (2 kV); 32.4 (C); 30.7/9 (t); 28.0 (kV); 27.9 (kV); 23.4/5 (kV); 22.7 (t); 19.6/8 (kV).

b) Synthesis of 3-(octadecylamino)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1-butanone

Solution α-damascone (1,00 g; 5,20 mmol), n-octadecylsilane (0,76 g; of 2.66 mmol) and TMG (0,65 ml; 5,20 mmol) in THF (20 ml) was stirred at room temperature for 5 days. Then the reaction mass is treated with 5% aqueous HCl solution, extracted twice with ether and washed with water, 5% aqueous NaOH solution, and then brine. Finally, the organic phase is dried over Na2SO4concentrate at a temperature/pressure 90°/0,04 mbar. Accordingly gain of 1.30 g of crude product (yield: 100%, based on n-octadecylsilane). MS (electrospray): 479 (M++1, 100), 401 (27), 356 (17), 313 (19).

1H-NMR: 0.84-0.95 (4 peaks N); 1.10-1.40 (m, approximately 34N); 1.50-1.62 (m, 5H); 1.67-1.80 (m, 1H); 1.95-2.18 (m, 2H); 2.48-2.95 (m, 5H); 3.27 (m, 1H); 5.59 (broadened, 1H).

13C-NMR: 211.1/3 (C); 130.0 (C), 123.7 (d); 63.6/7 (d); 53.1/4 (t); 34.3/5 (d); 32.4/7 (C); 31.9 (t); 30.9/40.0 (t); 29.1-29.7 (lot t); 27.8/28.0 (kV); 27.8 (kV); 23.5 (kV); 22.6/7 (t); 21.6 (kV); 14.1 (kV).

Example 3

The synthesis of compounds of formula (I) when using Algologie derived δ-damascone as the original product

The original product, namely 3-hydroxy-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butano is, receive accordance with US 4334098.

General procedure: a solution of 3-hydroxy-1-(2,6,6,-trimethyl-3-cyclohexen-1-yl)-1-butanone (124 mmol), NEt3(16,26 g (22,40 ml, 161 mmol) and DMAP (2 g) in CH2Cl2(200 ml) is treated at room temperature derivative of the acid chloride of the carboxylic acid (136 mmol). The reaction solution is stirred for 15 hours, treated with 5% HCl solution and extracted twice with ether, washed with H2O, a saturated solution of NaHCO3, then brine, dried over Na2SO4and concentrate at the temperature/pressure of 65-75°/0.01 mbar. The oil is purified using flash chromatography (cyclohexane/AcOEt=95:5)using the SiO2(500 g).

a) 1-Methyl-3-oxo-3-(2,6,6-trimethyl-3-cyclohexen-1-yl)propylbenzoate

From benzoyl chloride, with 76% yield. MS: 192 (42), 122 (33), 105 (90), 77 (45), 69 (100).

1H-NMR: 0.90 (2 d, 3H); 0.93-1.05 (4, 6N); 1.42 (2 d, 3H); 1.65-1.75 (m, 1H); 1.95-2.02 (2 b, 1H); 2.22-2.30 (m, 1H); 2.52 (m, 1H); 2.60-2.83 (m, 1H); 2.95-3.20 (m, 1H); 5.40-5.61 (m, 3H), 7.38-7.45 (m, 2H), 7.53 (m, 1H), 7.96-8.04 (m, 2H).

13C-NMR: 211.4 (C), 165.7 (C), 132.8 (d); 131.7 (d); 130.5(C); 129.5 (2D); 128.3 (2D); 124.1 (d); 67.3 (d); 63.0 (d); 53.3 (t); 41.7 (t); 33.1 (C); 31.6 (d); 29.8 (q); 20.7 (q); 20.1 (kV); 19.9 (kV).

b) 1-Methyl-3-oxo-3-(2,6,6-trimethyl-3-cyclohexen-1-yl)propyl 10-undecenoate

10-undecenoate, with 63% yield.

1H-NMR: 0.88 (2 d, 3H); 0.98 (4, 6N); 1.22-1.42 (m, 13H); 1.58 (m, 2H); 1.65-1.75 (m, 1H); 1.92-2.05 (m, 3H); 2.22 (m, 3H); 2.50 (m, 1H); 2.42-2.58 (m, 1H); 278-3 .02 (m, 1H); 4.92 (m, 1H); 4.97 (m, 1H); 5.33 (m, 1H); 5.45 (m, 1H); 5.53 (m, 1H); 5.80 (m, 1H).

13C-NMR: 211.4 (C); 172.9 (C), 139.2 (d); 131.7 (d); 124.1 (d); 114.1 (t); 66.3 (d); 63.0 (d); 53.2 (t); 41.7 (t); 31.6-28.9 (a combination of signals); 20.7 (q); 20.0 (kV); 19.8 (kV).

c) Tris-[1-Methyl-3-oxo-3-(2,6,6-trimethyl-3-cyclohexen-1-yl)propyl]1,3,5-benzotrichloride

From 1,3,5-benzotrichloride using ClCH2CH2Cl as solvent, with 54% yield,

1H-NMR (number N: ×3): 0.87-1.10 (4 +2 d, N); 1.38-1.4.7. (m, 3H); 1.65-1.75 (m, 1H); 1.93-2.04 (m, 1H); 2.28 (m, 1H); 2.52 (m, 1H); 2.60-2.88 (m, 1H); 2.95-3.23 (m, 1H); 5.45 (m, 1H); 5.54 (m, 1H), 5.66 (m, 1H); 8.72-8.78 (m, 1H).

13C-NMR: 211.3 (C), 164.1 (C), 134.3 (d); 131.6 (d); 131.4 (C), 124.2 (d); 68.2 (d)63.1 (e); 53.2 (t); 41.7 (t); 33.1 (C); 31.6 (d); 29.8 (kV); 20.1 (kV); 20.0 (kV); 19.9 (kV).

d) Bis-[1-Methyl-3-oxo-3-(2,6,6-trimethyl-3-cyclohexen-1-yl)propyl]oxalate

From oxalicacid, with 80% yield.

1H-NMR (number N: ×2): 0.90 (d, J=7, 3H); 0.90-1.06 (4, 6N); 1.36 (2 d, 3H); 1.64-1.74 (m, 1H); 1.92-2.02 (2 b, 1H); 2.22 (m, 1H); 2.51 (m, 1H); 2.52-2.62 (m, 1H); 2.85-3.15 (m, 1H); 5.40-5.58 (m, 3H).

13C-NMR: 210.7-211.1 (5 signals, C), 156.9 (C); 131.6 (d); 124.1 (d); 69.95 (d)63.1 (e); 52.7 (t); 41.6 (t); 33.1 (C); 31.6 (d); 29.7 (kV); 20.7 (q); 19.8 (kV); 19.5 (kV).

(e) Bis-[1-Methyl-3-oxo-3-(2,6,6-trimethyl-3-cyclohexen-1-yl)propyl]dodecanoate

From the acid chloride of decollate of dodecanoate, with 59% yield.

1H-NMR (number N: ×2): 0.87/0.90 (d, J=7, 3H); 0.92-1.03 (4, 6N); 1.27 (m, N); 1.58 (m, 2H); 1.70 (m, 1H); 1.96 (2 b, 1H); 2.22 (m, 3H); 2.43-3.02(m, 3H); 5.34 (m, 1H); 5.45 (m, 1H); 5.53 (m, 1H).

13C-NMR: 211.4 (C); 172.9 (C); 131.7 (d); 124.1 (d); 66.3 (d); 63.0 (d); 53.2 (t); 41.7 (t); 34.5 (t); 33.0 (C); 31.5 (d); 29.7 (kV); 29.1-29.4 (several t); 25.0 (t); 20.7 (q); 19.9 (kV); 19.8 (kV).

(f) Ethyl-1-methyl-3-oxo-3-(2,6,6-trimethyl-3-cyclohexen-1-yl)propylmalonate

A solution of 3-hydroxy-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone (8.0 mmol) in pyridine (1.85 g, and 23.4 mmol) is treated at a temperature of 0°etelcharge.com (1.24 g, and 23.4 mmol). The reaction solution was stirred at room temperature for 36 hours, treated with 5% HCl solution and extracted twice with ether, washed (H2O, a saturated solution of NaHCO3, then brine), dried over Na2SO4and concentrate. Oil (2.38 g) purified using flash chromatography (cyclohexane/AcOEt=98:2)using the SiO2(100 g). Output: of 2.06 g (78%). MS: 192(47); 177(10); 151(11); 123(55); 122(41); 107(45); 91(11); 81(22); 69(100).

1H-NMR: 0.89 (d, J=7, 3H); 0.92-1.03 (4, 6N); 1.23-1.37 (m, 6N); 1.70 (m, 1H); 1.96 (m, 1H); 2.18-2.28 (m, 1H); 2.50 (m, N); 2.67 (m, N); 2.87 (m, N); 3.03 (m, N); 4.18 (m, 2H); 5.21 (m, 1H); 5.42-5.48 (m, 1H); 5.54 (m, 1H).

13C-NMR: 211.4 (C), 154.4 (C); 131.7 (d); 124.2 (d); 70.5 (e); 63.8 (t); 63.1 (e); 53.1 (t); 41.7 (t); 33.1 (C); 31.6 (d); 29.7 (kV); 20.7 (q); 20.0 (kV); 19.8 (kV); 14.3 (kV).

Example 4

The synthesis of compounds of formula (I) when using δ-damascone as the original product

a) Synthesis of 3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone

Dissolve the δ -damascone (10.0 g; of 52.1 mmol) and 1-dodecanethiol (8,42 g of 41.7 mmol) in THF (150 ml) is treated with DBU (7,92 g; of 52.1 mmol) and stirred at a temperature of 45°C for 90 minutes. The reaction solution is treated with 5% HCl solution, extracted twice with ether, washed with N2Oh, a saturated solution of NaHCO3, then brine, dried over Na2SO4and concentrate at a temperature/pressure 70°C/0.01 mbar. Crude yield: 16.2 g (99%).

1H-NMR: 0.84-0.92 (m, 6N); 0.93-1.02 (4, 6N); 1.26 (m, N); 1.29 (m, 3H); 1.36 (m, 2H); 1.58 (m, 2H); 1.69 (m, 1H); 1.96 (2 b, 1H); 2.22 (m, 1H); 2.50 (m, N); 2.70 (m, 1H); 2.90 (m, N); 3.30 (m, 1H); 5.43 (m, 1H); 5.53 (m, 1H).

13C-NMR: 212.4/5 (C); 131.8/9 (d); 124.1/2 (d); 62.9/63.0 (d); 55.2/3 (t); 41.7 (t); 34.1 (d); 33.0/2 (C); 31.9 (t); 31.6/8 (d); 30.9 (t); 29.8 (q); 29.0-29.8 (several t); 22.7 (t); 21.6/8 (kV); 20.7 (kV); 19.9 (kV); 14.1 (kV).

b) Synthesis of 3-(dodecyloxyphenyl)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone

A solution of 3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone (2.00 g; 5,10 mmol) in Meon (20 ml) is added at a temperature of 0°With the solution NaJO4(1,14 g, and 5.30 mmol) in H2O (11 ml). The temperature is brought to room temperature and added EtOH (30 ml). The suspension is stirred for 15 hours and the named compound is extracted (ether/brine). The organic phase is washed with solutions of NaHCO3N2Oh, a saturated solution of NaHCO3, then brine, dried Na 2SO4and concentrate (16.2 g). Flash chromatography (cyclohexane/ethyl acetate =7:3, then 1:1) on SiO2(40 g) gives 803 mg of the titled compound (38%).

1H-NMR: 0.85-0.94 (m, 6N); 0.95-1.03 (4, 6N); 1.25 (m, N); 1.45 (m, 2H); 1.65-1.83 (m, 3H); 1.97 (2 b, 1H); 2.28 (m, 1H); 2.46-2.62 (m N); 2.67 (m, 1H); 2.78 (m, N); 2.98 (m, N); 3.15-3.27 (m N); 5.45 (m, 1H); 5.54 (m, 1H).

13C-NMR: 211.8 (C), 131.5 (d); 124.3 (d); 62.9 (d); 49.1 (t); 48.0 (d); 41.6 (t); 33.2 (C); 31.9 (t); 31.8 (d); 29.8 (q); 29.0-29.8 (several t); 23.2 (t); 22.7 (t); 21.7 (q); 20.7 (q); 19.9 (kV); 14.1 (q); 10.3/4 (kV).

C) Synthesis of 3-(dodecylsulfonate)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone

A solution of KHSO4(62,1 mmol) in N2About (50 ml) is added to cooled with ice to a solution of 3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone (5,00 g; 12.7 mmol) in Meon (100 ml). Temperatures give the opportunity to reach 40°C. the Suspension is stirred for 2 hours and the named compound is extracted with a mixture of ether/brine. The organic phase is washed with N2Oh, a saturated solution of NaHCO3, then brine, dried over Na2SO4and concentrate. Flash chromatography (cyclohexane/ethyl acetate =95:5) on SiO2(130 g) gives 2,59 g of product (48%).

1H-NMR: 0.84-0.92 (m, 6N); 0.95-1.02 (3, 6N); 1.26 (m, N); 1.38 (m, 3H); 1.43 (m, 2H); 1.72 (m, 1H); 1.85 (m, 2H); 1.98 (2 b, 1H); 2.29 (m, 1H); 2.52 (m, 1H); 2.60 (m, N); 2.83 (m, N); 2.95 (t, J=8, 2H); 3.12 (m, N); 3.35 (m, N); 3.63 (m, 1H); 5.46 (m, 1H); 5.55 (m, 1 H).

13C-NMR: 210.7 (C); 131.4 (d), 124.4 (d); 63.1 (e); 52.1 (d); 50.2 (t); 45.8 (t); 41.6 (t); 33.2 (C); 28.6-32.1 (several signals); 22.7 (t); 21.6 (t); 20.7 (q); 19.9 (kV); 14.5/6 (kV); 14.1 (kV).

Example 5

The synthesis of compounds of formula (I) with other flavouring ingredients as the original product

a) Synthesis of CIS-4,4-dimethyl-2-(4-pentenyl)cyclohexyl benzoate

Ethylenically ester (10.5 g) slowly and dropwise added to 50 ml of Et2O, containing 6 carbomethoxy-4,4-dimethylcyclohexane-1-ol (25 g) at a temperature of 0°C in nitrogen atmosphere. After 30 minutes the mixture was washed with a saturated solution of NaHCO3. After distillation (boiling temperature/barometric pressure of 110-120° C/10 Torr; 1 Torr =1 mm Hg) to obtain 34 g of 2-carbomethoxy-4,4-dimethyl-1-(2-methyl-1,3-dissapont-1-yl)diclohexal (yield 98%)

1H-NMR: 0.87-2.10 (M); 2.35-2.80 (1H); 3.20-3.80 (5H); 4.00-4.30 (1H); 4.50-4.90 (1H).

A solution of 2-carbomethoxy-4,4-dimethyl-1-(2-methyl-1,3-dissapont-1-yl) cyclohexane (5,16 g) in 10 ml of THF is added dropwise over 15 minutes to a solution of vinylmania (1.2 g) and vinylboronic (5.35 g) in 20 ml THF at a temperature of 65°C. After 4 hours the mixture is cooled and poured into a chilled 20% aqueous HCl (40 ml). The extraction mixture Et2O, removal of solvent and chromatography on SiO2(CH2Cl2/AcOEt) to get pure 1-(2-hydroxy-5,5-dimethyl-1-cyclohexyl)-4-penten-1-29 she (yield 60%).

1H-NMR: 0.96 (6N);1.00-1.95 (6N); 2.20-2.80 (5H); 3.36 (1H); 4.19 (1H); 4.83-5.20 (2H); 5.83 (m, 1H)

The benzoyl chloride (12.8 g, 91 mmol) is added dropwise to a stirred solution of 1-(2-hydroxy-5,5-dimethyl-1-cyclohexyl)-4-penten-1-it (16 g, 75 mmol), Et3N (10 g, 99 mmol) and DMAP (1.8 g, 15 mmol) in CH2Cl2(380 ml) at a temperature of 20°and in nitrogen atmosphere. The solution is heated at a temperature of 45°C for 22 hours, cooled to room temperature and washed successively with 5% HCl solution, a 10% solution of Na2CO3and again with water. The organic phase is dried over Na2SO4and concentrated to obtain a brown oil. Chromatography (SiO2, AcOEt/cyclohexane 1:9) and gives 6.7 g of the named compound (yield =28%). MS (electrospray): 314 (M++1,1), 259 (5), 192 (14), 137 (39), 105 (100).

1H-NMR: 0.96 (s, 3H); 1.06 (s, 3H); 1.25 (m, 1H); 1.50 (m, 2H); 1.82 (m, 1H); 1.90 (Shostakovich, J=15.2 Hz, 1H); 2.05 (m, 1H); 2.27 (m, 2H); 2.59 (m, 2H); 2.74 (m, 1H); 4.86 (broadened D., J=10 Hz, 1H); 4.95 (broadened D., J=17 Hz, 1H); 5.68-5.78 (2H); 7.40 (m, 2H); 7.55 (m, JH); 7.97 (m, 2H).

13C-NMR: 209.1 (C); 165.6 (C); 137.1 (d); 133.0 (d); 130.3 (C), 129.6 (d); 128.4 (d); 115.2 (t); 69.5 (d); 49.5 (d); 39.6 (t); 34.8 (t); 33.0 (kV); 32.8 (t); 29.9 (C), 27.6 (t); 26.7 (t); 23.9 (kV).

b) Synthesis of 1-methyl-2-oxo-3-(2,2, C-3, T-6-tetramethyl-R-1-cyclohexyl)propylbenzoate

3-(Benzyloxy)-1-(2,2, C-3, T-6-tetramethyl-R-1-cyclohexyl)-1-butanone receive in accordance with a known method (S. Fehr, Acting Guntem, Helv. Chim. Acta 1992, 75,1023), with 56% yield. MS: 210 (30). 167 (7), 139 (55), 124 (76), 91 (100), 83 (69), 69 (35).

1H-NMR: 0.70-1.04 (m, 13H); 1.15-1.45 (m, 5H); 1.67 (m, 1H); 1.84 (m, 1 H), 2.02 (m, 1H); 2.37 (m, N); 2.62 (m, N); 2.82 (m, N); 3.00 (m, N); 3.05 (c, 1H); 4.10 (m, 1H); 4.52 (m, 2 H); 7.20-7.38 (m, 5 H).

The treated suspension of benzyl ether 82% purity (2,82 g, 7,30 mmol) and 10% Pd/C (282 mg) in EtOH (23 ml) is shaken in N2-the atmosphere. After 5 hours the reaction mixture is filtered on celite and concentrate. 3-Hydroxy-1-(2,2, C-3, T-6-tetramethyl-R-1-cyclohexyl)-1-butanone purified using flash chromatography (cyclohexane/AcOEt =98:2, then 9:1)using the SiO2(80 g). Output: 969 mg (56%). MS: 226 (5), 167 (18), 139 (57), 124 (28), 87 (25), 83 (100), 69 (55), 55 (26), 43 (26).

1H-NMR: 0.73-1.04 (m, 13H); 1.15-1.45 (m, 6H); 1.70 (m, 1H); 1.85 (m, 1H), 2.03 (m, 1H); 2.41 (m, N); 2.53 (m, N); 2.64 (m, N); 2.74 (m, N); 3.30-3.65 (m, 1H); 4.22 (m, 1H).

The named compound is obtained from 3-hydroxy-1-(2,2, C-3, T-6-tetramethyl-R-1-cyclohexyl)-1-butanone and benzoyl chloride, using a similar experimental procedure as described in example 1.a) with 51% yield. MS: 208 (18), 191 (17); 167 (32), 124 (44), 105 (100), 83 (81), 77 (28), 69 (84), 55 (23).

1H-NMR: 0.73-0.86 (m, N); 0.93 (s, 3H); 0.93-1.05 (m, 1H); 1.15-1.35 (m, 2H); 1.41 (m, 4H); 1.66 (m, 1H); 1.84 (m, 1 H), 2.05 (m, 1H); 2.79 (m, 1H); 2.96 (m, 1H); 5.57 (m, 1H); 7.40 (m, 2H); 7.53 (m, 1H); 8.00 (m, 2 H).

C) Synthesis of 3-oxocyclopentanecarboxylate

Using a similar experimental procedure as described in example 1.a), 3-oxocyclopentanecarboxylate obtained from 3-hydroxycyclopent is on and benzoyl chloride with 80% yield. MS: 344 (track). 239 (7), 222 (47), 122 (36), 105 (100), 96 (26), 77 (34).

1H-NMR: 1.18-1.48 (m, N); 1.55-1.88 (m, 4H); 2.50 (m, 2H); 2.86 (m, 2H); 5.48 (m, 1H); 7.43 (m, 2H); 7.55 (m, 1H); 8.03 (m, 2 H)

13C-NMR: 208.4 (C); 133.0 (d); 130.4 (C); 129.6 (2 d); 128.4 (2 d); 70.8 (d); 47.2 (t); 42.4 (t); 32.6 (t); 27.7 (t); 26.2-26.8 (t); 23.1 (t); 23.0 (t).

d) Synthesis of 1-methyl-3-oxo-3-(2,6,6-trimethyl-1,3-cyclohexadiene-1-yl)propylbenzoate

Using a similar experimental procedure as described in example 1.a), the title compound is obtained from 3-hydroxy-1-(2,6,6-trimethyl-1,3-cyclohexadiene-1-yl)-1-butanone and benzoyl chloride with 60% yield.

1H-NMR: 1.08 (2, 6N); 1.45 (d, 3H); 1.75 (s, 3H); 2.08 (m, 2H); 2.79 (m, 1H); 3.20 (m, 1H); 5.66 (m, 1H); 5.79 (m, 1H); 5.84 (m, 1H); 7.42 (m, 2 H), 7.53 (m, 1 H), 8.02 (m, 2H).

13C-NMR: 206.4 (C), 165.7 (C), 141.5 (C), 132.8 (d); 130.5 (C), 129.5 (2 d); 128.3 (2 d); 128.1 (d); 127.9 (d); 127.8 (d); 67.5 (d); 51.2 (t); 39.7 (t); 33.9 (); 26.2 (kV); 26.1 (kV); 20.2 (kV); 19.1 (kV).

Example 6

Synthesis of polymers of the compounds of formula (I) when using derivatives δ-damascone as the original product

a) Synthesis of 1-methyl-3-oxo-3-(2,6,6-trimethyl-3-cyclohexen-1-yl)propyl-4-vinylbenzoate

A solution of DCC (of 3.60 g, 17.5 mmol) in 10 ml of CH2Cl2add to cooled with ice to a solution of 4-vinylbenzoic acid (2.35 g, 15.9 mmol), DMAP (1.55 g, 12.7 mmol) and 3-hydroxy-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone (of 4.00 g of 19.1 mmol) in 30 ml of CH2Cl2. The reaction mixture was stirred at room temperature is 5 days. The precipitate is filtered off and the filtrate is placed in CH2Cl2, washed twice with 10% HCl solution, a saturated solution of Na2CO3and saturated NaCl solution. The organic phase is dried over Na2SO4and concentrate. Flash chromatography on SiO2(heptane/ether 9:1) gives as 4.02 g of the desired compound (yield: 74%). MS: 193 (11), 192 (72), 177 (10), 149 (6), 148 (12), 135 (5), 132 (10), 131 (100), 124 (5), 123 (29), 122 (24), 121 (5), 108 (6), 107 (23), 103 (19), 102 (5), 91 (6), 81 (13), 79 (5), 77 (15), 69 (52), 41 (7).

1H-NMR: 0.89 (d, J=7, 3H); 0.93 (s, 3H); 1.02 (s, 3H); 1.41 (2 d, J=7, 6, 3H); 1.70 (m, 1H); 1.98 (m, 1H); 2.27 (t, J=10, 1H); 2.50 (m, 1H); 2.63/3.00 (DD, J=18, 6, 1H); 2.79/3.15 (DD, J=18, 7,1H); 5.37 (d, J=10, 1H); 5.44 (m, 1H); 5.55 (m, 2H); 5.85 (d, J=17, 1H); 6.74 (DD. J=18, 11, 1H); 7.44 (d, J=9, 2H); 7.95 (d, J=8, 2H).

13C-NMR: 211.5 (C), 165.4 (C), 141.8 (C), 136.0 (d); 131.8 (d); 129.8 (d); 129.7 (C), 126.0 (d); 124.2 (d); 116.4 (t); 67.4/2 (d); 63.0 (d); 53.3 (t); 41.7 (2 t); 33.1 (2); 31.6 (2 d); 29.8 (q); 20.7 (q); 20.1 (kV); 19.9 (kV).

b) Synthesis of statistical copolymers of 1-methyl-3-oxo-3-(2,6,6-trimethyl-3-cyclohexen-1-yl)propyl-4-vinylbenzoate and 4-vinylbenzoic acid (approximately 1:3)

A solution of 1-methyl-3-oxo-3-(2,6,6-trimethyl-3-cyclohexen-1-yl)propyl-4-vinylbenzoate (1,00 g, 2.9 mmol), 4-vinylbenzoic acid (1.30 grams, 8,8 mmol) and 2,2'-azobisisobutyronitrile (AIBN) (0.10 g, 0.6 mmol) in 20 ml of dry THF is heated in an atmosphere of N2at a temperature of 80°C for 2 days add an additional 0.10 g AIBN and after 2 days the reaction mixture is concentrated and the cheese is th product re-dissolved in 3 ml of THF and precipitated with 4 ml of heptane (3). Drying in an atmosphere of high vacuum (0.3 mbar) gives of 1.93 g of the desired compound (yield: 84%).

The average molecular weight (helpanimals chromatography): approximately 1700 g/mol

IR(pure): 2925m (broadened), V, V (broadened), V (broadened), s, s, m, W, V, m, m, m, s (broadened)5S, m, m, m, W, V, m, 800m, s, s, W, 670v.

13C-NMR in THF-D8: 211.6 (C, extended); 167.6 (s, extended); 165.7 (C, extended); 150.6 (C, extended); 132.7 (d); 130.6 (d, extended); 129.8 (s, extended); 128.4 (d, extended); 125.0 (d); 124.9 (d); 63.3 (d); 54.0 (t); 44.5 (t, spread); 42.5 (t); 41.7 (d, extended); 33.7 (C); 32.6 (d)30.0 (kV); 21.1 (kV); 20.2 (kV, extended).

C) Synthesis of 2-[2-(2-methoxyethoxy)ethoxy]ethyl-4-vinylbenzoate

As described in example 6A), the connection is produced by joint reaction DCC (3.1 g, 14.9 mmol), 4-vinylbenzoic acid (2.0 g, 13.5 mmol), DMAP (1.3 g, a 10.8 mmol) and 2-[2-(2-methoxyethoxy)ethoxy]ethanol (3,3 g, 20.3 mmol) in 2 days. Flash chromatography on SiO2(heptane/ether gradient) and drying in a high vacuum atmosphere gives 3.1 g of a yellowish oil (yield: 78%). MS: 176 (8), 175 (63), 174 (5), 148 (13), 132 (11), 131 (100), 103 (26), 102 (8), 89 (7), 87 (7), 77 (16), 59 (24), 58 (15). 45 (7).

1H-NMR: 3.36 (s, 3H); 3.53 (m, 2H); 3.66 (m, 4H); 3.71 (m, 2H); 3.83 (m, 2H); 4.48 (m, 2H); 5.38 (d, J=11, 1H); 5.86 (d, J=17, 1H); 6.75 (DD, J=11, 18, 1H); 7.45 (d, J=9, 2H); 8.01 (d, J=8, 2H).

13C-NMR: 166.3 (C), 142.0 (C), 136.0 (d); 130.0 (d); 129.3 (C), 126.1(d); 116.5 (t); 71.9 (t); 70.7 (t); 70.6 (t); 70.6 (t); 69.2 (t); 64.1 (t); 59.0 (kV).

d) Synthesis of statistical copolymers of 1-methyl-3-oxo-3-(2,6,6-trimethyl-3-cyclohexen-1-yl)propyl-4-vinylbenzoate and 2-[2-(2-methoxyethoxy)ethoxy]ethyl-4-vinylbenzoate (approximately 1:2)

A solution of 1-methyl-3-oxo-3-(2,6,6-trimethyl-3-cyclohexen-1-yl)propyl-4-vinylbenzoate (to 0.29 g, 0.85 mmol) and 2-[2-(2-methoxyethoxy)ethoxy]ethyl 4-vinylbenzoate (0.50 g, 1.7 mmol) in 5 ml dry THF quickly add to the mix a solution of 0.05 g (0.3 mmol) of AIBN in 5 ml of dry THF in an atmosphere of N2. The reaction mixture is heated at a temperature of 80°C for 90 hours. After cooling to room temperature, add 1 ml of methanol and the mixture concentrated. The crude product is placed in 2 ml of THF and extracted with 4-6 ml of heptane. Phase hexane decanted and the process repeated twice. The concentration of heptane phase and drying in a high vacuum atmosphere gives of 0.53 g of a very viscous oil (yield: 67%). The average molecular weight (GPC): approximately 8000 g/mol.

IR (pure): 3013w, 2922m, 2870m, 1710s, 1651w, 1607m, 1573w. 1507w, 1451m, t, t, t, t, t, 1270s, 1197m, 1179m, 1135m, 1098s, 1029m, t, 999w, 986w, 940m, 826w, 852m, 771m, 707s, 682m.

13C-NMR: 211.7 (C, extended); 166.1 (C); 165.3 (C), 149.2 (s, extended); 131.7 (d); 129.6 (d, extended); 128.6 (d, extended); 128.1 (d, extended); 127.4 (d, extended); 124.3 (d); 124.2 (d); 71.9 (t); 70.6 (t); 70.6 (t); 69.2 (t); 67.3 (d, extended); 64.0 (t); 62.9 (d); 59.0 (kV); 53.3 (t); 41.7 t); 40.7 (d, extended); 33.1 (C); 31.6 (d); 29.8 (q); 20.7 (q); 20.1 (kV); 19.9 (kV).

e) Synthesis of statistical copolymers of 1-methyl-3-oxo-3-(2,6,6-trimethyl-3-cyclohexen-1-yl)propyl-4-vinylbenzoate and 2-[2-(2-methoxyethoxy)ethoxy]ethyl-4-vinylbenzoate (approximately 1:3)

As described in example 6C), the polymer is produced by joint response to 0.19 g (or 0.57 mmol) of 1-methyl-3-oxo-3-(2,6,6-trimethyl-3-cyclohexen-1-yl)propyl-4-vinylbenzoate, 2-[2-(2-methoxyethoxy)ethoxy]ethyl-4-vinylbenzoate (0.50 g, 1.7 mmol) and AIBN (0.3 mmol), which give 0.39 g of a very viscous oil (yield: 56%). The average molecular weight (GPC): approximately 6100 g/mol

IR (pure): 2927m, 2869m, 1711s, 1650w, 1607m, 1573w, 1507w, 1451m, 1418m, 1373m, 1366m, 1352m, 1307m, 1270s, 1197m, 1179m, 1098s, 1029m, 1016m, 998 w, 985 w, 940m, 853m, 772m, 707m, 683m.

13C-NMR: 166.1 (C); 165.3 (C); 149.3 (C, extended); 131.7 (d); 129.6 (d, extended); 128.2 (d, extended); 124.3 (d); 71.9 (t); 70.6 (t); 70.6 (t); 69.2 (t); 68.0 (t); 64.0 (t); 62.9 (d); 59.0 (kV); 53.3 (t); 41.7 (t); 40.7 (d, broadened); 33.1 (C); 21.6 (d); 29.8 (q); 20.7 (q); 20.1(kV); 19,9 (kV).

Example 7

The release of flavouring ingredient of an aqueous buffer solution containing non-ionic surfactant and a polymer in accordance with the invention

Alkaline buffer solution containing 1% by weight nonionic surfactant obtained by dissolving two tablets borate buffer pH 9.2 and 2.24 g Triton® X100 (origin: Union Carbide) in a mixture of 160 ml of water and 4 ml of acetonitrile. To determine the exact pH of the final reaction solution to 10 ml of buffer was diluted with 2 ml of acetonitrile (which gives a mixture of water/acetonitrile 2:1) and the pH value is defined as 10.5.

50 μl of a 0.25 M solution of the test compound in THF is added to 5 ml of the above-mentioned alkaline buffer (water/acetonitrile 4:1) and diluted with 1 ml of acetonitrile (giving a final mixture of water/acetonitrile 2:1). The sample give the opportunity to mix at room temperature for 3 days, then extracted with 1 ml of heptane and leave for desantirovaniya within 30 minutes. Heptane phase (0,5 µl) was injected three times into the gas chromatograph Carlo Erba MFC 500, equipped with a Fisons AS 800 autosampler and J&W Scientific DB1 capillary column (30 m, 0.32 mm diameter in inches) at a temperature of 70°C for 10 minutes, and then to a temperature of 260° (10°C/minute), a helium pressure of 50 kPa, the temperature of the injection, 250°C, detector temperature 280°C. the Number Veselinovo damascone determined using standard surface calibration of five different concentrations in heptane, using the average of the five spasciani for each calibration point. The results are summarized in the following table:

Example of connectionsThe number of allocated damascone (in mol.%)
6b)/td> 9
6d)9
6E)15

Despite the fact that as defined, the compounds listed in the table are stable in the acidic environment, δ-damascan stood out in all the experiments in alkaline conditions. The results show that the rate of release of damascone can be adapted to the specific needs of the final application by small changes of the previous patterns, such as increasing the number of hydrophilic co monomer included in the base polymer.

Example 8

The basis for softening fabrics, containing the compound of formula (I)

The basis for softening fabric obtained by mixing the following ingredients:

IngredientsWeight parts
Stepantex VK 90 diester quat1)16,5
Calcium chloride0,2
Divisioona water81,8
Only100
1) origin: Stepan Europe, France

The test compound is added to 35 g of the base to soften the fabric prepared above taken in an amount in the range between 0.15 and 1 mmol.

After vigorous stirring the mixture was poured in from the bookmark for fabric softener Miele Novotronic W900-79 SN washing machine. Then wash at a temperature of 40°17 small Terry towels (18×18 cm, about 30 g each) and 2.3 kg large cotton towels (11 towels 50×70 cm)using a short cycle and 136 g Henkel "ECE Colour fastness Test Detergent 77" detergent without perfumes (fragrances).

At the end of the washing 17 small Terry towels dried in the drying room within 24 hours, and then loosely wrapped in aluminum foil and determine the quality within 24 hours, 3 days and 7 days after washing with 20 experts.

Each expert was asked to evaluate various test cotton towels in the scale of 1 to 7 (1: lack of flavor, 2: weak aroma, 3: slightly weak aroma, 4: medium aroma, 5: slightly strong flavor, 6: strong aroma, 7: very strong flavor).

As recommendation used the basis for softening fabrics, containing 1 mmol of pure alpha damascone tested through the same process.

The results are summarized in the following tables for different aromatic enones:

1) α-gamescon in comparison with its derivatives of formula (I):

The test moleculeThe number of1)mmol2)The average intensity3)
< / br>
link
0.55

0.2
1.0

0.365
2.8

2.7
0.90

0.30

0.15
1.0

0.334

0.167
4.7

4.4

4.1
0.790.55.0
1.021.03.9
1.041.04.5
0.801.03.3
1.371.03.4
1.081.04.5
1.121.04.1
0.720.54.0
1) the quantity added to 35 g of the base to soften the tissue, in parts by weight

2) mmol add 35 g grounds to reduce tissue

3) the average intensity of the aroma of the dry fabric in the period, within about

one day to seven d is it after washing

2) δ-gamescon in comparison with its derivatives of formula (I)

The test moleculeThe number of1)mmol2)The average intensity3)
< / br>
link
0.55%1.03.2
0.90%1.04.5
1.131.04.5
1.171.04.6
1.221.04.2

3) Dynascone® (origin: Firmenich SA, Switzerland) in comparison with the derived formula (I):

The test moleculeThe number of1)mmol2)The average intensity3)
< / br>
link
0.551.03.3
0.891.0 5.4

4) 1-(2,2,3,6-tetramethyl-1-cyclohexyl)-2-butene-1-he (origin: Firmenich SA, Switzerland) in comparison with the derived formula (I):

The test moleculeThe number of1)mmol2)The average intensity3)
< / br>
Link
0.591.03.3
0.540.583.8

5) 1-(2,2,3-trimethyl-1,3-cyclohexadiene-1 yl)-2-butene-1-he is in comparison with a derivative of formula(I):

The test moleculeThe number of1)mmol2)The average intensity3)
< / br>
Link
0.541.03.4
0.921.04.1

Example 9

Granular surface-active basis for tissue containing the compound of formula (I)

2 mmol of the tested compounds (or 0.001 mol of terephthalic derived) are added to 100 g Henkel "ECEColour fastness Test Detergent 77" detergent without perfumes (fragrance). After mixing, a new surface-active basis is poured into the compartment for powder Miele Novotronic W900-79 SN washing machine. The fabric softner is not used. Then wash at a temperature of 40°17 small Terry towels (18 cm ×18 cm, about 30 g each) and 2.3 kg large cotton towels (11 towels 50×70 cm) using a short cycle of washing, stockpiling and evaluation of aroma performed as described in example 8), the results are summarize in the following tables:

1) α-gamescon in comparison with its derivatives of formula (I):

The test moleculeThe number of1)mmol2)The average intensity3)
0.382.02.3
0.632.04.6
0.551.03.2
0.562.02.8
0.752.04.6
0.78%2.0 4.0
0.501.04.6
1) the quantity added to 35 g of surface-active base fabric, in parts by weight

2) mmol add 35 g of surface-active basis for tissue

3) the average intensity of the aroma of the dry fabric in the period lying in the range from one day to seven days after washing

2) δ-gamescon in comparison with its derivatives of formula (I):

The test moleculeThe number of1)mmol2)The average intensity3)
0.392.02.6
0.632.04.4
0.792.03.2
0.531,253.6

Additional examples of compounds of formula (I):

a) the functional group of formula (iv) in the value X:

Preparation of TRANS-S-[1-methyl-3-oxo-3-(2,6,6-trimethyl-3-cyclohexyl-1-yl)propyl]benzylarbutin is and

Solution δ-damascone (2.00 g; 10.4 mmol) and thiobenzoic acid (7,18 g, with 52.0 mmol) is heated at 85°C for 15 hours. The reaction solution was poured into saturated aqueous NaHCO3and extracted (simple ether). Washed (H2Oh, then saturated aqueous NaCl, dried (Na2SO4and concentrate, receiving 3.74 g of crude product, which was purified using flash chromatography (cyclohexane/AcOEt=9:1)using the SiO2(200). Yield: 1.70 g (50%) oil pink color.

MS: 207 (5), 192 (19), 123 (16), 105 (100), 77 (27), 69 (17).

1H-NMR: 0.89/0.93 (2 d, J=7, 3H); 0.95-1.03 (3 s, 6H); 1.45 (2 d, 3H); 1.69 (m, 1H); 1.95 (2 b, 1H); 2.23 (m, 1H); 2.53 (m, 1H); 2.65-3.15 (m, 2H); 4.18 (m, 1H); 5.45 (m, 1H); 5.53 (m. 1H), 7.43 (m, 2H); rate of 7.54 (m, 1H); 7.94 (m, 2H).

13C-NMR: 211.9 (s); 191.6 (s); 137.2 (s); 133.3 (d); 131.8/9 (d); 128.5 (2 d); 127.1 (2 d); 124.1/3 (d); 62.6/7 (d); 53.9 (t); 41.7 (t); 34.1/2 (d); 33.1/2 (s); 31.7/8 (d); 29.7 (q); 20.7 (q); 20.5 (q); 19.9(q).

b) possible substituents G are NO2, OR6, NR62, COOR6or R6group, R6represents a C1-C15alkyl or alkenylphenol group" in the definition of G-values in paragraph 1:

Deputy NO2:

Preparation of TRANS-1-methyl-3-oxo-3-(2,6,6-trimethyl-3-cyclohexen-1-yl)propyl-4-nitrobenzene

The solution 6,09 g of 80% pure TRANS-3-hydroxy-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone (23.2 mmol) and NEt3(5,38 ml, 38 mmol) in CH2Cl2 (40 ml) is treated at 0° p-nitrobenzylamine (of 5.92 g, 32 mmol) in CH2Cl2(10 ml). The reaction solution is stirred at room temperature for 5 hours, treated with 5% HCl and extracted with ether (2x), washed (H2Oh, saturated aqueous NaHCO3then saturated aqueous NaCl, dried (Na2SO4) and concentrate when 65-7570 .01 mbar. The oil obtained (7,70 d) purified using flash chromatography (cyclohexane/AcOEt=95:5)using the SiO2(100 g). Output: 6,55 g (79%).

1H-NMR: 0,85-1.08 (9H); 1.40-1.48 (3H); 1.72 (m, 1H); 1.98 (2 b, 1H); 2.27 (m, 1H); 2.51 (m, 1H); 2.62-3.22 (m, 2H); 5.45 (m, 1H); 5.54 (m, 1H); 5.66 (m, 1); 8.16 (m, 2H); 8.27 (m, 2H).

13C-NMR: 211.0/3 (s); 163.8 (s); 150.5 (s); 136.0 (s); 131.6 (d); 130.6 (2 d); 124.2 (d); 123.5 (2d); 68.4/5 (d); 63.0/1 (d); 53.1 (t); 41.7 (t); 33.1/2 (s); 31.6/7 (d); 29.8 (q); 20.7 (q); 20.0 (q); 19.9(q).

Deputy OR6:

Preparation of rac-1-methyl-3-oxo-3-(2,2, C-3, T-6-tetramethyl-R-1-cyclohexyl)propyl-4-methoxybenzoate:

A solution of para-Antillid (1,67 g 9.8 mmol) in CH2Cl2(2 ml) are added dropwise at 20° in a solution of 3-hydroxy-1-(2,2,C-3, T-6-tetramethyl-R-1-cyclohexyl)-1-butanone (2.0 g, 8.9 mol) and Et3N (0,99 g, 9.8 mmol) in CH2Cl2(20 ml). After 40 minutes add DMAP (76 mg, of 0.62 mmol). After 72 hours at 20°this mixture is extracted with N2Oh, the aqueous phase is washed with CH2Cl2(3×30 ml). The organic phase is dried (Na2SO4), concentrate, and PTS who participate using flash chromatography (SiO 2, toluene/AcOEt 9:1) and pure rac-1-methyl-3-oxo-3-(2,2, C-3, T-6-tetramethyl-R-1-cyclohexyl)propyl-4-methoxybenzoate in the form of mixtures of the stereoisomers of 3:1.

1R: 2914, 1777, 1705, 1604, 1510, 1457, 1376, 1314, 1250, 1220, 1165, 1139, 1100, 1026, 845, 770.

1H-NMR: 0.79 (d, J=7, 3H); 0.80 (s, 3H); 0.85 (d, J=7, 3H); from 0.90 (m, 1H); 0.99 (s, 3H); 1.25 (m, 3H); 1.39 (d, J=7, 3H); 1.68 (m, 1H); 1.88 (m, 1H); 2.04 (m, 1H); 2.58 (dd, J - 7, 16, 1H); 3.14 (dd, J - 7. 16, 1H); 3.82 (s, 3H); 5.55 (m, 1H); 6.9 (d, J - 8, 2H); 7.98 (d, J - 8, 3H).

13C-NMR; 14.2q, 15.6q, 20.2q, 20.8q, 28.0q, 30.4t, 30.8d, 35.2t, 37.1s, 42.0d, 54,0t, 55.4q, 66.9d, 67.6d, 113.52d, 123.0s, 131.5 2d, 163.2s, 165.4s, 211.7s.

Deputy COOR6:

Preparation of TRANS-1-methyl-3-oxo-3-(2,6,6-trimethyl-3-cyclohexen-1-yl)propyl-2-(Sooma)-benzoate

Phthalate (R=H; main diast.):

A solution of TRANS-3-hydroxy-1-(2,6,6-trimethyl-3-cyclohexane-1-yl)-1-butanone (5,00 g of 23.8 mmol) in CH2Cl2(40 ml) is treated at room temperature phthalic anhydride (3,17 g, with 21.4 mmol), N(iPr)2Et (8,30 ml, or 47.6 mmol) and DMAP (dimethylaminopyridine) (0.29 grams). This reaction solution is stirred for 15 hours, treated with 5% HCl and extracted with ether, washed (H2Oh, then saturated aqueous NaCl, dried (Na2SO4) and concentrated at 70°/0.01 mbar. The output solids: rate of 7.54 g (98%).

1H-NMR: 0.85 (d, J=7, 3H); 0.94 (s, 3H); 0.96 (s, 3H); 1.42 (d, J 6.5, 3H); 1.68 (m, 1H); 1.93 (2 b, 1H); 2.26 (d, J - 10, 1H); 2.50 (m, 1H); 2.78 (dd, J - 7, 18, 1H); 3.01 (dd, J 5.5, 18, 1H); 5.42 (m, 1H); 5.52 (m, 1H), 5.59 (m, 1H); 7.50-7.66 (m, 3H); 7.93 (m, 1H); 8.50-9.50 (b, 1H).

13C-NMR: 211.7 (s); 172.0 (s); 167.4 (s); 134.1 (s); 132.4-128.7 (6d); 129.4 (s); 68.6 (d); 63.0 (d); 52.9 (t); 41.6 (t); 33.1 (s); 31.7 (d); 29.7 (q); 20.5 (q); 19.8 (q); 19.5 (q).

Phthalate (R=Me: the main diast.):

A suspension of the above acid (1.80 g, 5.0 mmol), K2CO3(828 mg, 6.0 mmol), and MeI (0,374 ml, 6.0 mmol) in DMF (25 ml) was gently stirred at 25° for 2 h, treated with 5% HCl and extracted with pentane (2x), washed (H2Oh, saturated aqueous NaHCO3then saturated aqueous NaCl, dried (Na2SO4) and concentrated at 70°/0.01 mbar. Output overdevelop oil: 1.29 g (69%).

1H-NMR: 0.85 (d, J=7, 3H); 0.95 (s, 3H); 0.98 (s, 3H); 1.42 (d, J=6.5, 3H); 1.70 (m, 1H); 1.96 (2 b, 1H); 2.25 (d, J=10, 1H); 2.50 (m, 1H); 2.77 (dd, J=7, 18, 1H); 2.97 (dd, J 5.5, 18, 1H); 3.91 (s, 3H); 5.43 (m, 1H); 5.52 (m, 1H), 5.55 (m, 1H); 7.50 (m, 2H); 7.65 (m, 1H); 7.72 (m, 1H).

13C-NMR: 211.5 (s); 167.9 (s); 166.8 (s); 132.7 (s); 131.8-128.6 (5d); 131.5 (s); 124.1 (d); 68.3 (d); 63.1 (d); 53.0 (t); 52.5 (q); 41.7 (t); 33.1 (s); 31.6 (d); 29.7 (q); of 20.7 (q); 19.8 (2q).

G represents a trivalent radical, Q is a hydrogen atom, R is one group of the formula R and one hydrogen atom

A solution of TRANS-3-hydroxy-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone (5,00 g of 23.8 mmol) in CH2Cl2(40 ml) is treated at room temperature glutaric anhydride (2,43 g, with 21.4 mmol), N(iPr)2Et (8,30 ml, or 47.6 mmol) and DMAP (dimethylaminopyridine) (0.29 grams). This reaction solution is stirred for 15 hours, treated with 5% HCl and extracted with ether, washed (H2 Oh, then saturated aqueous NaCl, dried (Na2SO4) and concentrated at 70°/0.01 mbar. The output solids: 6,74 g (97%).

1H-NMR; 0.89 (d, J=7, 3H); 0.94 (s, 3H); 0.97 (s, 3H); 1.26 (d, J - 6.5. 3H); 1.70 (m, 1H); 1.88-2.04 (m, 3H); 2.20-2.55 (m, 6H); 2.66 (dd, J=6, 18, 1H); 2.82 (dd, J=6.5, 18, 1H); 5.34 (m, 1H); 5.45 (m, 1H), 5.53 (m, 1H).

13C-NMR: 211.6 (s); 178.7 (s); 172,0 (s); 131.8 (d); 124.2 (d); 66.9 (d); 63.3 (d); 53.1 (t); 41.7 (t); 33.4 (t); 33.2 (s); 33.1 (t); 32.9 (t); 31.7 (d); 29.7 (q); 20.7 (q); 20.0 (q); 19.8 (q).

R1represents a C1-C6;

A solution of ethyl-3-hydroxy-3-phenylpropanoate (3.00 g, a 15.5 mmol) (M. W. Rathke, A. Lindert, J. Org. Chem. 1970, 35, 3966) in CH2Cl2(30 ml) is treated at 0° Net3(2,40 ml of 17.1 mmol) and DMAP (dimethylaminopyridine) (0,19 g) and benzoyl chloride (2.25 g, a 15.5 mmol) in CH2Cl2(10 ml). This reaction solution was stirred at room temperature for 15 hours, treated with 5% HCl and extracted with ether, washed (H2O, saturated aqueous NaHCO3then saturated aqueous NaCl, dried (Na2SO4) and concentrated at 50°/0.01 mbar. Output: 4,50 g (97%).

1H.NMR: 1.17 (t, J - 7, 3H); 2.88 (dd. J=15. 4, 1H); 3.12 (dd, J - 15, 9, 1H); 4.12(q, J=7, 2H); 6.42 (dd, J of 9.4, 1H); 7.25-7.48 (m, 8H); 8.05 (d, J=7, 2H).

13C-NMR: 169.7 (s); 165.3 (s); 139.3 (s); 133.1 (d); 130,0 (s); 129.7-128.4 (4 d); 126.5 (d); 72.9 (d); 60.8 (t); 41.8 (t); a 14.1 (q).

R1is a hydrogen atom;

Sieberiana diacetylene acid (11.4 g) as regards the NML add (£ )-2-geksenal (9.8 g, 0.1 mol) in 7°C for 30 minutes the solution is stirred for 16 hours At room temperature. This crude mixture is extracted with pentane (3×100 ml) and washed with a solution of saturated aqueous NaHCO3. The organic phase is dried over MgSO4filter and concentrate under vacuum, the crude oil distil (clean) Vigreux column, at 0.5 mbar. 57-62°and poluchaut of 15.3 g of the target product (yield 88%).

1H-NMR: 9,7 (t, J=0.8. 1H), 3.90-4.00 (m, 1H); 2,70-2.75 (m, 2H); 2,31 ('s. 3H); 1.59-of 1.65 (m, 2H), 1.30-1.50 (m, 2H); 0.91 (t, 7=7, 3H).

13C-NMR; 200 (d), 195 (s), 48 (t), 38 (d), 36 (t), 31 (q), 20 (t), 14 (q))

An example of a copolymer (±)-1-Methyl-3-oxo-3-(TRANS-2,6,6-trimethyl-3-cyclohexen-1-yl)propyl 2-methacrylate and methacrylic acid (CA. 1:5) (3A):

stage a): Preparation of (±)-1-methyl-1-3-oxo-3-(TRANS-2,6,6-trimethyl-3-cyclohexen-1-yl)l 2-methacrylate (1):

Pre-cooled to 0°With a fresh solution of methacrylic acid (2,87 g, 33.3 mmol), 4-dimethylaminopyridine (OMAR, 3.25 g, to 26.6 mmol) and (±)-TRANS-3-hydroxy-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone (7,00 g, 33.3 mmol) in CH2Cl2(35 ml) drops in for 20 minutes, add a solution of N,N'-dicyclohexylcarbodiimide (DCC, rate of 7.54 g, 36.6 mmol) in CH2Cl2(15 ml). This reaction mixture is stirred at room temperature for 5 is it. The formed precipitate is filtered off and the filtrate is placed in CH2Cl2, washed with HCl (10%, 2), a saturated solution of Na2CO3(2x) and saturated solution of Nad (2x, pH about 7). The organic layer is dried (Na2SO4) and concentrate. After the multi-layer column chromatography (SiO2, heptane/ether 9:1)get of 4.67 g (63%) slightly yellow oil.

IR (neat): 3017w, 2956m, 2929m, 2872m, 2829w, 1709s, 1652w, 1636m, 1451m, 1399m, 1375s, 1352m, 1317s, 1296s, 1266w, 1250w, 1225w, 1211w, 1164s, 1136s, 1115m, 1077m, 1062m, 1030s, 1008m, 998m, 987w, 937s, 911m, 900w, 885w, 862m, 848m, 813m, 787m, 752m, 699s, 682s.

1H-NMR: 6.06-6.02 (m, 1H); 5.58-5.49 (m, 2H); 5.48-5.35 (m, 2H); 3.05 and 2.89 (dd, J 17.9, 6.7, 1H); 2.71 and 2.54 (dd, J 17.9, 6.1, 1H); of 2.58-2.46 (m, 1H); 2.29-2.21 (m, 1H); 2.02-1.93 (m, 1H); 1.92 (m, 3H); 1.75-1.66 (m, 1H); 1.32 (d (2x), J=6.1, 3H); 1.02 and 0.99 (s, 3H); 0.95 and 0.93 (s, 3H); 0.89 and 0.88 (d, J=7.2 and 6.7, 3H).

13C-NMR:211.50 (s); 211.20 (s); 166.55 (s); 136.63 (s); 136.60 (s); 131.80 (d); 131,73 (d); 125.15 (t); 125.10 (t); 124.19 (d); 124.13 (d); 67.03 (d); 66.79 (d); at 63.04 (d); 62.87 (d); 53.21 (t); 41.75 (I); 41.71 (t); 33,12 (s); 33.09 (s); 31.63 (d); 31.53 (d); 29.75 (q); 20.69 (q); 19.96 (q); 19.93 (q); 19.84 (q); 18.34 (q); 18.31 (q).

MS (E1): 193 (6), 192 (40), 177 (7), 155 (5), 149 (3), 135 (5), 124 (5), 123 (34), 122 (24), 121

(5), 109 (4), 108 (8), 107 (31), 95 (5), 93 (5), 91 (7), 87 (3), 83 (5), 82 (3), 81 (17), 79 (6), 77 (4), 70 (5), 69 (100), 67 (6), 55 (5), 53 (3), 43 (7), 42 (3), 41 (21), 39 (6).

stage b): preparation of copolymer (±)-1-methyl-3-oxo-3-(TRANS-2,6,6-trimethyl-3-cyclohexen-1-yl)propyl-2-methacrylate and tert-butylmethacrylate (ca. 1:5) (2A);

tert-butylmethacrylate (0,90 g, 6.3 mmol) and 1 (0.35 g, 1.3 mmol) dissolved in anhydrous anisole (4 ml), then the solution in an atmosphere of N 2added dropwise 2,2'-azobisisobutyronitrile (AIBN, and 12.4 mg, 0.08 mmol). This mixture Tegaserod for 6 h using two cycles of freezing and heating to 90°C. the resulting polymer is dissolved in TMF and precipitated in cold methanol (twice)to give 0.95 g (76%) of white solid product.

IR (neat); 2975w, 2933w, 2873w, 2830w, 1717m, 1474w, 1457w, 1391w, 1366m, 1248m, 1133s, 1029w, 967w, 874w, 846m, 751m, 699w, 682w, 667w.

1H-NMR: of 5.53 (m, 1H); 5.45 (m, 1H); 5.10 (m, 1H); 3.06 (m, 1H); 2.86 (m, 1H); 2.72 (m, 1H); 2.50 each (m, 3H); 2.36 (m, 1H); 2.30-1.65 (m, 16H); 1.42 (m, 45H); 1.31 (m, 6H); 1.20-0.74 (m, 25H).

13C-NMR:211.32 (s, br.); 177.47 (s, br.); 176.66 (s, br.); 131.73 (d, br.); 124.28 (d, br.); 80.91 (s, br.); 80.82 (s, br.); 67,84 (d, br); 63.05 (d, br.); 52.89 (t, br.); 46.23 (s, br.); At 45.34 (s, br.); 41.72 (t); 33.05 (s, br.); 31.65 (d, br.); 29.76 (q, br.); 27.81 (d); 20.73 (q, br.); 19.89 (q, br.); 19.62 (q, br.); 17.82 (q, br.); 17.63 (q, br.).

Average molecular weight (SEC, PMMA): Mw- 47000 Yes, Mn=18000 Yes.

stage C): preparation of copolymer (±)-1-methyl-1-3-oxo-3-(TRANS-2,6,6-trimethyl-3-cyclohexen-1-yl)propyl-2-methacrylate and methacrylic acid (CA. 1:5) (3A):

Trifurcation acid (TFA, 15 ml) is added to a solution of 2A (0,90 g of 0.91 mmol) in CH2Cl2(15 ml) and the reaction mixture was stirred at room temperature for 1 hour. The environment becomes orange. Precipitation in cold diethyl give 0.55 g (86%) of a white solid.

IR (neat): 3700-2400w (br.), 2982m, 2969m, 2956m, 2935m, 2900m, 2838m, 1697s, 1474m, 1449m, 1387m, 1369m, 1252m, 1151s, 1065m, 1029w, 999w, 961m, 933m, 832w, 793w, 750w, 700w, 683w, 668w, 632w, 625w, 617w, 605w.

1H-NMR (MeOD): 5.58 (m, 1H); 5.49 (m, 1H); 5.11 (m, 1H); 3.14 (m, 1H); 2.90 (m, 1H); 2.67 (m, 1H); 2.50 (m, 1H); 2.32 (m, 1H); 2.20-1.78 (m, 19H); 1.75 (m, 2H); 1.52 (m, 2H); 1.45 (m, 4H); 1.30 (m, 7H); 1.11-0,73 (m, 32H).

13C-NMR (MeOD): 213.50 (s, br.); 183.69 (s, br.); 182.53 (s, br.); 182.24 (s, br.); 181.34 (s, br.); 179.15 (s, br.); 132.81 (d, br.); 125.50 (d, br); 69.33 (d, br.); 64.03 (d, br.); 55.69 (t, br.); 54.18 (t, br.); At 53.20 (t, br.); 52.90 (t, br.); 47.53 (s, br.); 46.32 (s, br.); 45.94 ('s. br.); 42,81 (t); 34.19 (s, br.); 32.92 (d. br.); At 30.51 (q. br.); 28.24 (q, br.); 21.50 (q, br.); 20.33 (q, br.); 19.93 (q, br.); 19.28 (q, br.); At 30.51 (q, br.); 17.36 (q, br.); 17.02 (q.br.).

1. Flavouring composition containing as an active ingredient, at least a compound of the formula

where w is an integer from 1 to 10000;

m is an integer from 1 to 4;

R represents a hydrogen atom or a radical of qualifying education fragrant α,β-unsaturated ketone, aldehyde or ester of carboxylic acid represented by the formula

in which the wavy line indicates the position relationship between P and X;

R1represents a hydrogen atom, a C1-C6CNS radical or a C1-C15linear, cyclic or branched alkyl, alkanniny or akadeemiline radical, possibly substituted C1-C4alkyl groups;

R2, R3and R4represent and what Ohm hydrogen, aromatic ring or a C1-C15linear, cyclic or branched alkyl, alkanniny or akadeemiline radical, possibly substituted C1-C4alkyl groups; or two or three, R1-R4groups are linked together to form a saturated or unsaturated ring having from 6 to 20 carbon atoms including the carbon atom to which these R1, R2, R3or R4groups are attached, the ring may be substituted C1-C8linear, branched or cyclic alkyl or alkenylamine groups; and provided that at least one R group has the formula (II) as defined above;

e) X is a functional group selected from the group comprising formulas (i)-(vi) and (viii-x):

where the wavy line are as defined above, and the bold lines show the position relationship between X and G, provided that X may be absent when R represents a hydrogen atom;

G is a polyvalent radical (m+1 valence) aryl radical, possibly substituted, or a divalent cyclic, linear or branched alkyl, alkanniny hydrocarbon radical having from 6 to 22 carbon atoms, or three, four or patev the build-cyclic, linear or branched alkyl hydrocarbon radical having from 1 to 22 carbon atoms specified hydrocarbon radical may be substituted, containing from 1 to 10 functional groups selected from the group including a simple ether; the possible substituents G are NO2, OR6, NR62, COOR6or R6group, R6represents a C1-C15alkyl or alkenylphenol group;

Q represents a hydrogen atom (in this case w=1 and n=1) or is a group of [[P-X]m[G]n]where R, X, G and m are as defined above (in this case w=1, a n=0 or 1) or a polymer skeleton of the Monomeric units of the formula (A) (in this case n=1 or 0);

where the dashed lines show the position relationship between the specified monomer link and G;

n is 1 or 0;

R7represent simultaneously or independently a hydrogen atom;

Z represents a functional group selected from the group comprising formulas (2) and 5):

where the dashed lines defined above, the dotted arrows show the position relationship between the specified Z and the rest of the unit link, and this composition contains as the active ingredient, by at least one compound of formula (I) and one or more aromatic cogredient.

2. Flavouring composition according to claim 1, wherein in the formula (I)

w is an integer from 1 to 10000; m is 1 or 2; R represents a hydrogen atom or a radical of the formulae (P-1) to (P-11), in the form of any one of its isomers:

where the wavy line have the meanings indicated above, and the dotted lines represent a single or double bond, R9denotes a methyl or ethyl group, and R10represents a C6-C9linear or branched alkyl, alkenylphenol or akadeemiline group; and provided that at least one R group has the formula (P-1) to (P-11)as defined above;

X represents a functional group selected from the group comprising the formula:

where values in bold or wavy lines have the meanings indicated above; and provided that X may be absent when R represents a hydrogen atom;

G represents a divalent or trivalent radical, aryl radical, possibly substituted, or a divalent cyclic, linear or branched alkyl, alkanniny hydrocarbon radical having from 8 to 22 carbon atoms or trivalent cyclic, linear or once lvlany alkyl hydrocarbon radical, having from 1 to 22 carbon atoms specified hydrocarbon radical may be substituted, containing from 1 to 5 functional groups selected from the group including a simple ether; and the possible substituents G are, NO2, OR6, NR62, COOR6or R6group, R6represents a C1-C15alkyl or alkenylphenol group; and

Q represents a hydrogen atom (in this case w=1 and n=1) or is a group of [[P-X]m[G]n]where R, X, G, and m are as defined above (in this case w=1 and n=0 or 1), or a polymer skeleton, derived from the Monomeric level, of the formula:

where the dashed lines and n are as defined above in claim 1;

R7represent simultaneously or independently a hydrogen atom;

Z represents a functional group selected from the group comprising formulas (2) and 5);

where the dashed lines, dotted arrows and the arrows are defined above in claim 1.

3. Flavouring composition according to claim 1, characterized in that the active ingredient is represented by the formula

where m has a value of 1 or 2;

Q represents a hydrogen atom;

R is the fight radical of the formulae (P-1) to (P-7), in the form of any one of its isomers:

where the wavy line and dotted line are as defined above; X represents a functional group selected from the group consisting of formulas

where oily or wavy lines are defined above; G is a divalent or trivalent arene radical, possibly substituted with NO2, OR6, NR62, COOR6and R6group, R6represents a C1-C6alkyl or alkenylphenol group.

4. Flavouring composition according to claim 1, characterized in that the active ingredient is represented by the formula

where R, m and Q are as defined in claim 3;

X represents a functional group of the formula, including iii) or x), as defined in claim 1,and

G represents a divalent radical derived from a linear or branched alkyl or alkenylphenol, hydrocarbon radical having from 8 to 15 carbon atoms; or G represents a trivalent radical derived from a linear or branched alkyl hydrocarbon radical having from 2 to 10 carbon atoms.

5. Flavouring composition according to claim 1, the call is connected with the fact, the active ingredient is represented by the formula

where R, m and Q are as defined in claim 3;

X represents a functional group selected from the group comprising formulas (ii), (viii) or (ix)as defined above;

G represents a divalent or trivalent radical derived from a linear or branched alkyl or alkenylphenol hydrocarbon radical having from 8 to 15 carbon atoms.

6. Flavouring composition according to claim 1, characterized in that the active ingredient is represented by the formula (I")

where Q and R have the meanings given in claim 3;

G represents a trivalent radical derived from a linear or branched alkyl or alkenylphenol, hydrocarbon radical having from 3 to 6 carbon atoms,

7. The way to improve, enhance or modify the odor of perfumed products or fragrance composition, comprising adding to the specified product or composition is effective to impart odor quantities of the compounds of formula (I)as defined in any one of claims 1 to 6.

8. The way of aromatization surface, characterized in that the specified surface is treated in the presence of the compounds of formula (I)as defined in any which one of claims 1 to 6.

9. Method of enhancing or prolonging the diffusion effect of the ingredient that gives the smell on the surface, characterized in that the specified surface is treated in the presence of the compounds of formula (I)as defined in any one of claims 1 to 6.

10. The compound of formula (I) as defined in any one of claims 1 to 6, provided that 3-(phenylmethoxy)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1-butanone, 4-(phenylsulfonyl)-4-(2,6,6-trimethyl-1,3-cyclohexadiene-1-yl)-2-butanone, 4-(phenylthio)-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butanone, 4-(phenylsulfonyl)-4-(2,6,6-trimethyl-1 or 2-cyclohexen-1-yl)-2-butanone, 2-methyl-5-(1-methylethenyl)-3-[(4-were) sulfonyl]-cyclohexanone, 2-methyl-5-(1-methylethenyl)-3-(phenylmethoxy)-cyclohexanone, 2-methyl-5-(1-methylethenyl)-3-(octylthio)-cyclohexanone, 3,3'-THIOBIS[2-methyl-5-(1-methylethenyl)-cyclohexanone, 2-methyl-5-(1-methylethenyl)-3-(phenylthio)-cyclohexanone and its optical isomers, 4-(phenylsulfonyl)-4-(2,5,6,6-tetramethyl-1 or 2-cyclohexen-1-yl)-2-butanone and its optical isomers, beta-[(4-were)thio]-benzoylpropionate, beta-[4-(trifluoromethyl)phenoxy]-benzoylpropionate, beta(phenylsulfonyl)-benzopyranyl, beta(phenylmethoxy)-benzopyranyl, beta-[[[3,5-bis(1,1-dimethylethyl)-4-hydroxy-phenyl]methyl]thio]-benzoylpropionate, beta-[(4-bromo-3-were)thio]-benzoylpropionate, beta-[(4-chlorophenyl)thio]-benzoylpropionate, beta-[(4-were)sulfonyl]-benzoylpropionate and Beth is-(phenylthio)-benzopyranyl excluded.

11. Flavouring composition according to claim 1, characterized in that it contains a solvent commonly used in perfumery.

12. Flavored product containing as an active ingredient, at least a compound of formula (I)as defined in claims 1 to 6, or flavoring composition according to claims 1-6.

13. Flavoured product according to item 12 in the form of a solid or liquid detergent, fabric softener, perfume, Cologne or aftershaves, perfumed Soaps, scented gel for the bath or shower, foam, oil or salt or hygiene or care products hair care products, body, deodorant or antiperspirant, an air freshener, as well as a cosmetic preparation, a refreshing means for cloth, water for iron, paper, toilet or bleach.



 

Same patents:

FIELD: organic chemistry, cosmetics.

SUBSTANCE: invention relates to novel compounds of the formula (I) , wherein a dotted line means a bond or it absent and wherein R1 means: -when a dotted line as a bond is absent: -CHCH3OH or -CHCH3OCOR or -CHCH3XCH2CHOHR' or -CHCH3OCHR'CH2OH or ; -when a dotted line is absent: , -CHCH3OH, -CHCH3OCOR, -COCH3, -CHCH3XCH2CHOHR', -CH2CH2XCH2CHOHR', -CHCH3OCHR'CH2OH, -CHCHCOR', -CHCH2CHR'OH, -CH2CHCHR'OCOR, -CHCHCHOHR' or -CHCHCHR'OCOR wherein R means H, Me, Et, Pr, isoPr, But, isoBut, -CH3(CH2)4, -(CH3)2CHCH2, -CH2=CH or -(CH3)2C=CH; R' means H, Me or Et; X means O, N or S atoms. Owing to their odor proposed compounds can be used in perfume industry, cosmetics and care substances and can be used as aromatizing components for preparing atomatized composition or aromatized article.

EFFECT: valuable properties of compounds.

11 cl, 14 ex

FIELD: textile industry.

SUBSTANCE: textile conditioning agents contain 0.01 to 35% cationic softeners and at least 0.001% specific polymeric thickener, which is prepared by polymerization of 5 to 100 mol % vinyl-addition cationic monomer, 0 to 95 mol % acrylamide, and 70 to 300 ppm cross-linking agent based vinyl-addition bifunctional monomer. When compared to similar compositions containing analogous product obtained via polymerization but utilizing 5 to 45 ppm of cross-linking agent, considerable advantages are achieved.

EFFECT: facilitated transport of odorant contained in softener composition to textiles.

20 cl, 17 dwg, 11 ex

FIELD: organic chemistry.

SUBSTANCE: invention relates to synthetic fragrant substances, namely to 4-acetyl-4-methylpentanone-2 of the formula (I): . This substance is prepared by condensation of mesityl oxide with thioacetic acid. This substance elicits acute garlic-"sulfurous" odor but in large dilution it shows natural odor of black currant buds and leaves with tints of flowers, greens and herbs. Compound can be used as fragrant and taste-aromatic principle in perfume, cosmetic, liqueur and vodka, food, pharmaceutical, tobacco industry, in wine-making industry, domestic chemistry and others fields.

EFFECT: valuable properties of substance.

3 ex

The invention relates to compositions and method of providing additional cosmetic properties of the main composition for softening fabrics in the final phase of its manufacture
The invention relates to detergents and cleaning agents, in particular to means for washing and cleaning of utensils, sanitary ware, as well as for washing clothes

The invention relates to the chemical industry, in particular to the compounds of household chemicals for cleaning hard surfaces (baths, sinks, tiles, ceramic floor tiles, kitchen tiles)

FIELD: organic chemistry, cosmetics.

SUBSTANCE: invention relates to novel compounds of the formula (I) , wherein a dotted line means a bond or it absent and wherein R1 means: -when a dotted line as a bond is absent: -CHCH3OH or -CHCH3OCOR or -CHCH3XCH2CHOHR' or -CHCH3OCHR'CH2OH or ; -when a dotted line is absent: , -CHCH3OH, -CHCH3OCOR, -COCH3, -CHCH3XCH2CHOHR', -CH2CH2XCH2CHOHR', -CHCH3OCHR'CH2OH, -CHCHCOR', -CHCH2CHR'OH, -CH2CHCHR'OCOR, -CHCHCHOHR' or -CHCHCHR'OCOR wherein R means H, Me, Et, Pr, isoPr, But, isoBut, -CH3(CH2)4, -(CH3)2CHCH2, -CH2=CH or -(CH3)2C=CH; R' means H, Me or Et; X means O, N or S atoms. Owing to their odor proposed compounds can be used in perfume industry, cosmetics and care substances and can be used as aromatizing components for preparing atomatized composition or aromatized article.

EFFECT: valuable properties of compounds.

11 cl, 14 ex

FIELD: engineering of devices for producing ethereal oils, sterilization of canned meat, fruit and vegetable goods, caking silicate materials.

SUBSTANCE: autoclave steam transformer includes hermetic tank of autoclave, in which steam generator is mounted, consisting of liquid sprayer, heat energy accumulator and heat energy emitter. Heat energy emitter has convex shape being part of autoclave tank. Between autoclave tank and steam generator a wall with aperture is mounted. Heat energy accumulator is positioned between heat energy emitter and the wall.

EFFECT: more efficient use of heat energy due to effect of steam bath, prevented intensive wear of equipment during operation.

2 dwg

FIELD: engineering of devices for producing ethereal oils, sterilization of canned meat, fruit and vegetable goods, caking silicate materials.

SUBSTANCE: autoclave steam transformer includes hermetic tank of autoclave, in which steam generator is mounted, consisting of liquid sprayer, heat energy accumulator and heat energy emitter. Heat energy emitter has convex shape being part of autoclave tank. Between autoclave tank and steam generator a wall with aperture is mounted. Heat energy accumulator is positioned between heat energy emitter and the wall.

EFFECT: more efficient use of heat energy due to effect of steam bath, prevented intensive wear of equipment during operation.

2 dwg

FIELD: food industry.

SUBSTANCE: method comprises contacting the coffee flavor with volatile organic liquid agent at a temperature when it is in the liquid phase and any moisture is frozen and collecting the volatile organic liquid agent. The freezing temperature of the volatile organic liquid agent should be lower than the temperature of treatment, and its boiling temperature should be higher than treatment temperature. The steam pressure is at least 0.01 mm Hg at 25°C and atmospheric pressure, and water solubility is no more than 10 %, in mass.

EFFECT: enhanced efficiency and stability of aromatizing.

21 cl, 7 tbl, 8 ex

FIELD: food industry.

SUBSTANCE: method comprises contacting the coffee flavor with volatile organic liquid agent at a temperature when it is in the liquid phase and any moisture is frozen and collecting the volatile organic liquid agent. The freezing temperature of the volatile organic liquid agent should be lower than the temperature of treatment, and its boiling temperature should be higher than treatment temperature. The steam pressure is at least 0.01 mm Hg at 25°C and atmospheric pressure, and water solubility is no more than 10 %, in mass.

EFFECT: enhanced efficiency and stability of aromatizing.

21 cl, 7 tbl, 8 ex

FIELD: wood-chemical industry; equipment for the vegetable raw complex processing.

SUBSTANCE: the invention is pertaining to the equipment for wood-chemical industry and may be used by the small enterprises for processing of any essential oil raw, including the wood foliage and the bark of coniferous trees. The pilot installation contains the vegetable raw material distillation chamber having the common wall with the steam generator. The steam generator contains the burner, the chimney of which is located in the steam preheater. The steam generator is connected with the steam distributor. The steam distributor is made in the form of the equidistant steam- conducting bars with the holes uniformly located along the whole its length. The steam distributor is mounted in the distillation chamber. The distillation chamber contains the cartridges for stacking the vegetable raw material. The installation also contains the cooling system connected to the steam generator by the pipeline for its supply with the hot water. In the upper part of the distillation chamber there is a branch-pipe connected to the steam conduit coming out of the steam generator. In the steam generator there is the tank for collection of the still condensate. The collector of the phloretin waters and the cooling system are connected to the steam generator for its additional supply with the water containing the dissolved fraction of the essential oil. The technical result of the invention allows to produce the superfine natural essential oil.

EFFECT: the invention ensures production of the superfine natural essential oil.

1 dwg

FIELD: essential oil industry.

SUBSTANCE: proposed method includes mixing of citric fruit peel with reagent and hydraulic distillation for obtaining essential oil. Used as reagent is aqueous solution of hydrochloric acid and hydrogen peroxide at the following ratio of components: hydrochloric acid : water (in vol-%) : 0.4-0.6:0.7-1.2:98.9:98.2. Material is preliminarily ground before hydraulic distillation to 1-5 mm in size and subjected to standing at room temperature for 3-5 h at volume ratio of material to reagent ranging from 1:1.5 and 1:1.7.

EFFECT: reduction of time required for extraction of target product; increased yield of product; improved quality of product.

2 cl, 8 ex

FIELD: essential oil industry.

SUBSTANCE: proposed method includes mixing of citric fruit peel with reagent and hydraulic distillation for obtaining essential oil. Used as reagent is aqueous solution of hydrochloric acid and hydrogen peroxide at the following ratio of components: hydrochloric acid : water (in vol-%) : 0.4-0.6:0.7-1.2:98.9:98.2. Material is preliminarily ground before hydraulic distillation to 1-5 mm in size and subjected to standing at room temperature for 3-5 h at volume ratio of material to reagent ranging from 1:1.5 and 1:1.7.

EFFECT: reduction of time required for extraction of target product; increased yield of product; improved quality of product.

2 cl, 8 ex

FIELD: fat-and-oil industry; ether-and-oil industry; production of the laboratory installations for distillation of ethereal oil.

SUBSTANCE: the invention is pertaining to the field of fat-and-oil industry and ether-and-oil industry, in particular, to production of the laboratory installations for distillation of ethereal oil. The laboratory installation for distillation of ethereal oil contains the steam generator, the distillation chamber with nets, the cooler and the separating flask. At that the distillation chamber is placed above the steam generator, and the cooler is mounted above the distillation chamber. The cooler is joined to the turning gear used for the cooler lifting and turning, and the separating flask is placed inside the cooler. At that the lid of the distillation chamber and the cooler are joined tightly. The invention allows to raise the production of the qualitative ethereal oil, to simplify the installation design having made its compact.

EFFECT: the invention ensures to raise production of the qualitative ethereal oil, to simplify the installation design having made its compact.

1 dwg

FIELD: fat-and-oil industry; ether-and-oil industry; production of the laboratory installations for distillation of ethereal oil.

SUBSTANCE: the invention is pertaining to the field of fat-and-oil industry and ether-and-oil industry, in particular, to production of the laboratory installations for distillation of ethereal oil. The laboratory installation for distillation of ethereal oil contains the steam generator, the distillation chamber with nets, the cooler and the separating flask. At that the distillation chamber is placed above the steam generator, and the cooler is mounted above the distillation chamber. The cooler is joined to the turning gear used for the cooler lifting and turning, and the separating flask is placed inside the cooler. At that the lid of the distillation chamber and the cooler are joined tightly. The invention allows to raise the production of the qualitative ethereal oil, to simplify the installation design having made its compact.

EFFECT: the invention ensures to raise production of the qualitative ethereal oil, to simplify the installation design having made its compact.

1 dwg

FIELD: polymer materials.

SUBSTANCE: invention provides biodegradable anionic polymers including recurring polymeric subunits preferably formed from dicarboxylic monomers such as maleic anhydride, itaconic anhydride, and cytraconic anhydride. Polymer synthetic is accomplished via free radical polymerization. Polymers can form complexes with ions and/or are appropriate to be mixed with fertilizers or seeds to produce agriculture-acceptable compositions. Preferred industry products can be placed into leaves or introduced into ground in the vicinity of growing plants.

EFFECT: improved assimilation of nutrients by plants.

122 cl, 2 dwg, 3 tbl, 20 ex

FIELD: organic chemistry, medicine, pharmacy.

SUBSTANCE: invention relates to new derivatives of glucopyranosyloxybenzylbenzene represented by the formula (I): wherein R1 represents hydrogen atom or hydroxy(lower)alkyl; R2 represents lower alkyl group, lower alkoxy-group and lower alkylthio-group being each group is substituted optionally with hydroxy- or (lower)alkoxy-group, or to its pharmaceutically acceptable salts. Also, invention relates to pharmaceutical composition eliciting hypoglycemic activity and to a method for treatment and prophylaxis of hyperglycemia-associated diseases, such as diabetes mellitus, obesity and others, and to their intermediate compounds. Invention provides preparing new derivatives of glucopyranosyloxybenzylbenzene that elicit the excellent inhibitory activity with respect to human SGLT2.

EFFECT: valuable medicinal properties of compounds.

13 cl, 2 tbl, 2 ex

The invention relates to an improved process for the preparation of esters of carboxylic acids of General formula (I) esterification of the corresponding acids or anhydrides with alcohols in a molar ratio acid:ethanol=1: 0.35 to 2.2 in the presence of hydrocarbons as solvent and aromatic sulfonic acids or acidic sulfate as a catalyst at the boiling temperature of the reaction mixture by distillation of the formed water, followed by washing of the reaction mixture and neutralizing it with an alkaline solution, taken from 5-20 wt

The invention relates to the synthesis of biologically active chemical compounds and can be implemented in pharmacology, medicine and agriculture
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