RU2821398C2 - Method of producing sulphur-containing or selenized compound by thiolene reaction - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a compound of formula (I), where X is selected from S, Se, values R₁ R₂, R₃, R₄ and R₅ are defined in the claims. Method involves reaction of a compound of formula (IV), where X is selected from S and Se, m is equal to 1 or 2, R₁ is as defined for compound (I), and if m is 1, R₂₁ is H, if m is 2, R₂₁ is selected from alkyl, aryl and alkylaryl groups, with a compound of formula (V), where R₂, R₃, R₄ and R₅ are as defined for the compound of formula (I), by irradiation with radiation with wavelength from 200 to 800 nm in the presence of at least one compound containing at least one functional group, selected from alcohol, carboxyl, thioether and selenium ether functional groups, which is a compound of formula (VI), where X' is selected from S or Se, p and t independently represent 0 or 1, q, r and s independently represent 0–10, provided that p + r + t is greater than or equal to 1, and if p is not equal to 0, then q + s is not equal to 0, R₂₂ is selected, if p is 0, from H and alkyl, aryl and arylalkyl groups, and if p is 1, from alkyl, aryl and arylalkyl groups, and R₂₃, R₂₄, R₂₅, R₂₆ and R₂₇ are independently selected from H and alkyl, aryl and alkylaryl groups.

EFFECT: present invention provides an alternative to existing methods, wherein the addition of a compound of formula (VI) has a positive effect on conversion, output and selectivity parameters.

16 cl, 4 tbl, 4 ex

Description

The invention relates to a method for producing a sulfur-containing or selenized compound of formula (I)

[Formula I]

(I),

Where

X selected from S, Se;

R ₁ is selected from alkyl, aryl, alkylaryl and heteroaryl groups, optionally containing one or more functional groups selected from

hydroxyl functional group and functional groups derived from it, such as the ether functional group,

carbonyl functional group, such as ketone and aldehyde functional groups, and functional groups derived therefrom, such as hemiacetal and acetal functional groups, and

a carboxyl functional group and functional groups derived therefrom, such as carboxyester functional groups;

R ₂ , R ₃ and R ₄ are independently selected from H and alkyl, aryl and alkylaryl groups; or R ₂ and R ₄ together form a C5-C10 carbon ring;

R ₅ is selected from H and alkyl, aryl and alkylaryl groups,

or R ₅ corresponds to formula (II)

[Formula II]

(II),

Where

n is 0-24,

R ₆ and R ₇ are independently selected from H, alkyl, aryl and alkylaryl groups, OR ₈ , NR ₈ R ₉ , where R ₈ and R ₉ are independently selected from H and alkyl, aryl, alkylaryl and acyl groups ;

R ₁₀ is selected from H, alkyl, aryl and alkylaryl groups, OR ₁₁ and NR ₁₁ R _12, where R ₁₁ and R ₁₂ are independently selected from H, alkyl, aryl, alkylaryl and acyl groups,

or R ₁₀ is selected from CN, COR ₁₃ , COOR ₁₃ and CONR ₁₃ R ₁₄ , where R ₁₃ and R ₁₄ are independently selected from H and alkyl, aryl and alkylaryl groups,

or R ₁₀ represents CH ₂ OR ₁₅ , where R ₁₅ is selected from H and alkyl, aryl, alkylaryl and acyl groups,

or R ₅ corresponds to formula (III)

[Formula III]

(III),

Where

n' equals 0-24,

Y is selected from O and NR ₁₆ , where R ₁₆ is selected from alkyl, aryl, alkylaryl groups, OR ₁₄ , where R ₁₄ is as previously defined,

Z is selected from H, alkyl, aryl, alkylaryl groups, CN,

COR ₁₇ , where R ₁₇ is selected from H, alkyl, aryl and alkylaryl groups and from OR ₁₈ , NR ₁₈ R ₁₉ , where R ₁₈ , R ₁₉ and R ₂₀ are independently selected from H and alkyl, aryl and arylalkyl groups, and CH ₂ OR ₂₀ , where R ₂₀ is selected from H and alkyl, aryl, alkylaryl and acyl groups, and

OR ₁₈ and NR ₁₈ R ₁₉ , where R ₁₈ and R ₁₉ are independently selected from H and alkyl, aryl and arylalkyl groups.

Main examples of these compounds include 2-hydroxy-4-methylthiobutyric acid (HMTBA or MHA) and its analogues, such as its salts, its chelates, in particular metal chelates (Zn, Ca, Mn, Mg, Cu, Na...), its esters such as isopropyl and tert-butyl esters HMTBA, which are widely used in animal feed. Selenized derivatives of these hydroxya analogues of methionine are also important constituents in animal feed.

The preparation of HMTBA is well known and can be carried out in a variety of ways using various synthesis intermediates, in particular acrolein and methanethiol. 2-Hydroxy-4-methylselenobutyric acid is also readily available through similar synthetic routes. The disadvantage of commercial scale processes is that significant quantities of salts are produced by neutralization to give access to the final product, such as ammonium sulfate or sodium sulfate, the separation of which requires intensive purification using large quantities of solvent, and the processing of which remains difficult. presents difficulties.

The fact that most of these processes require intermediates derived only from propylene as a source of acrolein, an essential intermediate, is another major disadvantage.

The present invention provides an alternative to existing methods and, in addition, allows access to a large number of sulfur-containing or selenium compounds, the use of which is, of course, not limited to animal feed. Thus, such compounds can be used in many fields, namely, in the formulation and/or preparation of surfactants, monomers, polymers, plasticizers, adhesives, coatings, varnishes, films, emulsifiers, antioxidants, antimicrobial agents, anticorrosion agents , packaging materials, consumer goods, and in medicine or agriculture.

According to the method of the invention, the compound of formula I above involves the reaction of the compound of formula (IV)

[Formula IV]

R ₁ - (X) _m - R ₂₁

(IV),

Where

X is selected from S and Se;

m is equal to 1 or 2;

R ₁ is as defined above for compound (I), that is, it is selected from alkyl, aryl, alkylaryl and heteroaryl groups, optionally containing one or more functional groups selected from

hydroxyl functional group and functional groups derived from it, such as the ether functional group,

carbonyl functional group, such as ketone and aldehyde functional groups, and functional groups derived therefrom, such as hemiacetal and acetal functional groups, and

a carboxyl functional group and functional groups derived therefrom, such as carboxyester functional groups; And

if m is 1, R ₂₁ represents H;

if m is 2, R ₂₁ is selected from alkyl, aryl and alkylaryl groups,

with a compound of formula (V):

[Formula V]

(V),

where R ₂ , R ₃ , R ₄ and R ₅ are as defined above for the compound of formula (I),

by irradiation with radiation with a wavelength from 200 to 800 nm in the presence of at least one compound containing at least one functional group selected from alcohol, carboxyl, thioether and selenoether functional groups, representing a compound of formula (VI),

[Formula VI]

(VI),

Where

X' is selected from S or Se;

p and t are independently 0 or 1;

q, r and s independently represent 0-10;

provided that p + r + t is greater than or equal to 1, and if p is not equal to 0, then q + s is not equal to 0;

R ₂₂ is selected, if p is 0, from H and alkyl, aryl and arylalkyl groups, and, if p is 1, from alkyl, aryl and arylalkyl groups; And

R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ and R ₂₇ are independently selected from H and alkyl, aryl and alkylaryl groups.

The features, applications and advantages of the invention are described below in more detail with the understanding that these features may be considered independently of each other or in combination, regardless of the combination.

Before this description, definitions of some of the terms used are provided below.

In formulas defining the compounds obtained or involved, the term "alkyl" is to be understood as a linear or branched saturated hydrocarbon monovalent radical containing from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, n-hexyl or a cyclic saturated hydrocarbon monovalent radical containing from 3 to 20 carbon atoms, preferably from 5 to 7 carbon atoms, such as cyclopentyl, cycloheptyl.

By "aryl" group is meant an aromatic hydrocarbon monovalent radical containing from 6 to 22 carbon atoms, which can be functionalized, for example, with methoxy or ester groups, as shown by phenyl, naphthyl, anisole, alkyl benzoate groups, where the term alkyl is defined, given earlier.

By "alkylaryl" group is meant an aryl group containing from 6 to 22 carbon atoms, said aryl group being substituted by at least one alkyl group as defined above, as illustrated by tolyl, mesityl, xylyl groups; the term indifferently refers to an alkyl group as defined above which is substituted by at least one aryl group as defined above as illustrated by benzyl, benzyhydryl, phenethyl, trityl groups.

The term "heteroaryl" defines an aromatic hydrocarbon monovalent radical containing from 3 to 21 carbon atoms and at least one heteroatom, such as O, N, as illustrated by pyrrolyl, pyridyl, indolyl, furyl groups.

The term "acyl" defines a monovalent radical RC(O)-, where R represents an alkyl group as defined above.

The compound of formula (VI) according to the invention is also called an additive. In formula (VI) as defined above, and from the condition that p + r + t must be greater than or equal to 1, it follows that the additive according to the invention is a hydrocarbon compound which contains at least one functional group selected from thioether, selenoether, primary alcohol/hydroxyl, secondary alcohol/hydroxyl, tertiary alcohol/hydroxyl and carboxyl functional groups. It may contain at least two or at least three of these functional groups, or more, and these functional groups are the same or different. According to the invention, the method can be implemented in the presence of a mixture of various compounds of formula (VI); in this embodiment, each of the compounds of formula (VI) may contain one or more of the specified functional groups. Formula (VI) is to be understood as covering compounds for which, if q, r and/or s are greater than 1, the substituents R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ and R ₂₇ may in general represent, respectively, different substituents R ₂₃ ', R ₂₃ '', R ₂₃ '''..., R ₂₄ ', R ₂₄ '', R ₂₄ '''..., R ₂₅ ', R ₂₅ '', R ₂₅ '''..., R ₂₆ ' , R ₂₆ '', R ₂₆ '''..., and R ₂₇ ', R ₂₇ '', R ₂₇ '''...; for example, compound (VI) may consist of 4-methyl-1,2-butanediol.

The method according to the invention should be carried out in the presence of irradiation with radiation with a wavelength of 200 to 800 nm. This sign is significant. Comparing irradiation with wave radiation in the visible light spectrum and irradiation with UV radiation (ultraviolet radiation) with identical compounds involved, although the reaction occurs in both situations, it is observed that its yield is significantly higher when the radiation is UV radiation. Thus, the method according to the invention is advantageously carried out under the influence of radiation with a wavelength of 254 to 400 nm, ideally 365 ± 20 nm. In a preferred embodiment, the exposure to radiation is continuous.

Suitable irradiation conditions, as described above, can be provided by, but not limited to, a light-emitting diode (LED).

Below is a more detailed description of compound (VI).

As stated above, the additive in the method according to the invention is a compound (VI) which contains at least one functional group selected from alcohol, carboxyl, thioether and selenoether functional groups; thus, it may contain 2 or more of these functional groups, the same or different. According to one embodiment, several of these additives can be used in the method according to the invention, which respectively contain one or more of the specified functional groups, the same or different. As an illustration of a multi-additive process, these will include a mixture of a thioether- or selenoether-functional compound and a hydroxyl- and/or carboxyl-functional compound. According to a particular embodiment, which is preferred from the point of view of reaction selectivity, compound (VI) is an α-hydroxy acid. In particular, it was observed that for compound (VI), which contains hydroxyl and carboxyl functional groups, the performance increases when the hydroxyl and carboxyl functional groups are combined. For example, such a hydroxy acid may consist of lactic acid, glycolic acid, 2-hydroxyisobutyric acid. Based on this definition, those skilled in the art have the general knowledge necessary to use one or more compounds (VI) as additive(s) according to the invention.

As non-limiting examples to illustrate formula (VI), the compound is selected from alkyl sulfides, such as alkyl sulfides, such as methyl sulfide and ethyl sulfide, propionic acid, butanoic acid, lactic acid, 3-hydroxypropionic acid, 3-hydroxybutyric acid, 6-hydroxycaproic acid , 3-methylthiopropanoic acid, 4-methylthiobutanol, 2,4-hydroxybutyric (2,4-DHB) acid, 4-methylthio-2-hydroxybutyric acid (MHA) and methylthiobutanediol (MTBDO), these compounds can be used alone or in mixtures of 2, 3 or more.

Compound (VI) is present in the reaction medium in a preferable amount of at least 0.1 equivalent, more preferably at least 0.2 equivalent. per 1 eq. compounds (V). Thus, a significant increase in the selectivity of the reaction is observed when compound (VI) is present in the reaction medium under the conditions of the invention defined above, even in small quantities. Up to an amount of approximately 0.5 eq. compounds (VI) are measured to increase reaction rate and selectivity. Excess of compound (VI), for example, more than 10 equiv. and even more than 5 equiv., does not allow to improve the reaction characteristics and a further decrease in the reaction yield may be noticed. Optimally, the amount of compound (VI) is at least 0.5 eq. and no more than 2 equivalents. per 1 eq. compounds (V).

Below is a more detailed description of compound (IV).

Compound (IV) may be selected from any alkylthiol or alkylselenol such as methanethiol, ethanethiol, n-butanethiol, tert-butanethiol, methaneselenol, as well as any alkylthiol or alkylselenol containing one or more hydroxyl, carbonyl, carboxyl or carboxyester functional groups , such as thioglycolic acid. Said compound may also consist of a disulphide or diselenide, in particular any alkyl disulphide or diselenide such as dimethyl or aryl disulphide, such as diphenyl disulphide and diphenyl diselenide.

It has been noted that the presence in compound (IV) of one or more functional groups that should be present in compound (VI) significantly increases the reactivity. This effect was observed, in particular, with thioglycolic acid.

Preferably, compound (IV) is used in excess compared to compound (V). Typically, the molar ratio of compound (IV) to compound (V) is in the range of 1.1-15:1 or 1.2-10:1. This ratio mainly depends on the compounds (IV) and (V) involved and is determined by those skilled in the art. As a guide, if compound (IV) is a sulfide or selenide, the ratio of compound (IV) to compound (V) is more likely to be in the range of 1.1-2:1; when compound (IV) is a disulfide or diselenide, the excess of compound (IV) is higher and the ratio is in the range of 5-10:1.

Below is a more detailed description of compound (V).

According to formula (V) defined above, compound (V) includes a carbon-carbon double bond, in which compound (IV) will react according to a thiolene reaction. This reaction is known to those skilled in the art, who will be able to select compounds (IV) and (V) according to the target compound (I) respectively, as well as the reactivity of the functional groups contained in the formulas of said compounds (IV) and (V ) in this thiolene reaction. Therefore, all compounds (IV) and (V) that can react by thiolene addition can be used in the method according to the invention. As non-limiting examples, compound (V) is selected from butene, pentene, hexene, 2,3-dimethylbutene, but-3-enoic acid, but-2-enoic acid, but-3-en-2-ol, butenediol, cyclohexene, vinyl glycolic acid (VGA), methyl vinyl glycolate (MVG). VGA and MVG are biomass-derived compounds and therefore represent a natural and abundant source of compound (V), which gives the present invention another advantage for its use on an industrial scale.

The method according to the invention is also interesting in that it can be carried out at temperatures close to room temperature. In particular, it was experimentally established that while a temperature in the range of 32°C ± 5°C is optimal, increasing it to 50°C leads to a comparable kinetic profile, but with a decrease in selectivity. Thus, the temperature range is from -10 to 100°C, more preferably from 0 to 50°C and even more preferably from 20 to 35°C.

According to an embodiment of the invention, the reaction can be carried out in the presence of at least one photoinitiator, which in the context of the invention has the effect of accelerating the reaction. It will be selected from Type I or II photoinitiators and more preferably from Type II photoinitiators. By way of example, as a type I photoinitiator, mention may be made of benzoin and 2,2-dimethoxy-2-phenylacetophenone (DMPA), and as a type II photoinitiator, mention may be made of thioxanthone and its derivatives such as 1-chloro-4-hydroxythioxanthone, 1- chloro-4-propoxythioxanthone or benzophenone and derivatives thereof, in particular selected from 3-alkylbenzophenone and 4-alkylbenzophenone, for example 3-methylbenzophenone. When one or more photoinitiators are/are used, the amount(s) thereof correspond to the amount(s) commonly used and are within the general knowledge of those skilled in the art.

The invention is also interesting in that it can be carried out without any solvent. However, the present invention covers any process in which a solvent is used, for example to dilute compound (VI), in which case the solvent may be polar, protic or aprotic, and in particular selected from methanol and acetonitrile.

The invention and its advantages are further illustrated by examples.

In these examples, the characteristics of the invention are assessed by determining the following parameters:

conversion, that is, the degree of conversion of compound (V), expressed in%,

yield, which determines the ratio in % of compound (I) formed to compound V introduced, and

selectivity, which determines the ratio in % of the formed compound (I) to the actually converted compound V,

for the preparation of compounds of formula (I) by the reaction of a compound of formula (IV) and a compound of formula (V) under irradiation in the presence of an additive of formula (VI) or in the absence of such an additive.

Example 1: Synthesis of (n-butylthio)-cyclohexane in the presence of various additives according to the invention and comparison with the synthesis of the same compound without any additives

In a 20 mL mini-reactor equipped with a magnetic rod, cyclohexene (500 mg), butanethiol (1.5 eq.) and, where indicated, additive (0.5 eq.) are introduced sequentially. The mixture is irradiated with LED (365 nm) at 32 °C for 30 minutes. Reaction characteristics are calculated using ^1H NMR (nuclear magnetic resonance) analysis (compared to 3,5-dimethylanisole used as an internal control and calculated at the 99% level) and are illustrated in Table 1 below.

[Table 1] No. Additive (0.5 eq.) Conversion (%) Exit (%) Selectivity (%) 1 No 85 76 90 2 MeSEt 96 95 99 3 lactic acid 97 96 99 4 1,2-butanediol 100 98 98 5 M.H.A. 99 98 99

It is obvious that all tested additives have an unexpectedly positive effect on all measured parameters.

Example 2: Synthesis of (n-butylthio)-2-butanol in the presence of various additives according to the invention and comparison with the synthesis of the same compound without any additives

But-3-en-2-ol (500 mg), butanethiol (1.5 eq.) and, where indicated, additive (0.5 eq.) were introduced sequentially into a 20 mL mini-reactor equipped with a magnetic rod. The mixture is irradiated with LED (365 nm) at 32°C for 1 hour. Reaction characteristics are calculated using ¹ H NMR analysis (compared to 3,5-dimethylanisole used as an internal control and calculated at the 99% level) and are illustrated in Table 2 below.

[Table 2] No. Additive (0.5 eq.) Conversion (%) Exit (%) Selectivity (%) 1 No 42 31 73 2 Lactic acid 99 98 99 3 Lactic acid + MeSEt (1:1) 90 88 98 4 M.H.A. 100 97 97

It is obvious that all tested additives have an unexpectedly positive effect on all measured parameters. This example also shows that the preparation of compound (I) can be carried out in the presence of several additives, functionalized in different ways.

Example 3: Synthesis of (n-butylthio)-2-hydroxybutanoic acid in the presence of 4-methylthio-2-hydroxybutanoic acid (MHA) as an additive according to the invention and comparison with the synthesis of the same compound without any additives

In a 20 mL mini-reactor equipped with a magnetic bar, 2-hydroxy-3-butenoic acid (500 mg), butanethiol (1.5 eq.) and, where indicated, additive (0.5 eq.) were introduced sequentially. The mixture is irradiated with LED (365 nm) at 32 °C for 1 hour. Reaction characteristics are calculated using ¹ H NMR analysis (compared to 3,5-dimethylanisole used as an internal control and calculated at the 99% level) and are illustrated in Table 3 below.

[Table 3] No. Additive (0.5 eq.) Conversion (%) Exit (%) Selectivity (%) 1 No 63 51 81 2 M.H.A. 98 96 98

This example highlights the interest in MHA as an additive in the synthesis of another compound (I).

Example 4: Synthesis of 4-methylthio-2-hydroxybutanoic acid methyl ester in the presence of MHA as an additive according to the invention and comparison with the synthesis of the same compound without any additive

Methyl 2-hydroxy-3-butenoate (500 mg), dimethyl sulfide (10 eq.) and, where indicated, additive (0.5 eq.) were added sequentially to a 20 mL mini-reactor equipped with a magnetic bar. The mixture is irradiated with LED (365 nm) at 32 °C for 2 hours. Reaction characteristics are calculated using ^1H NMR analysis (compared to 3,5-dimethylanisole used as an internal control and calculated at the 99% level) and are illustrated in Table 4 below.

[Table 4] No. Additive (0.5 eq.) Conversion (%) Exit (%) Selectivity (%) 1 No 68 31 45 2 M.H.A. 72 38 52

Even though the degree is less compared to the previous examples, a positive effect of the additive of formula (V) according to the invention is observed.

Claims (78)

1. Method for preparing the compound of formula (I) [Formula I] Where X selected from S, Se; R ₁ is selected from alkyl, aryl, alkylaryl and heteroaryl groups, optionally containing one or more functional groups selected from hydroxyl functional group and ether functional group, carbonyl functional group, hemiacetal and acetal functional groups, and carboxyl functional group and carboxyester functional groups; R ₂ , R ₃ and R ₄ are independently selected from H and alkyl, aryl and alkylaryl groups and R ₅ is selected from alkyl, aryl and alkylaryl groups; or R ₂ and R ₄ together form a C5-C10 carbon ring and R ₅ is selected from H and alkyl, aryl and alkylaryl groups; or R ₅ corresponds to formula (II) [Formula II] (II), Where n is 0-24, R ₆ and R ₇ are independently selected from H, alkyl, aryl and alkylaryl groups, OR ₈ , NR ₈ R ₉ , where R ₈ and R ₉ are independently selected from H and alkyl, aryl, alkylaryl and acyl groups ; R ₁₀ is selected from H, alkyl, aryl and alkylaryl groups, OR ₁₁ and NR ₁₁ R ₁₂ , where R ₁₁ and R ₁₂ are independently selected from H, alkyl, aryl, alkylaryl and acyl groups, or R ₁₀ is selected from CN, COR ₁₃ , COOR ₁₃ and CONR ₁₃ R ₁₄ , where R ₁₃ and R ₁₄ are independently selected from H and alkyl, aryl and alkylaryl groups, or R ₁₀ represents CH ₂ OR ₁₅ , where R ₁₅ is selected from H and alkyl, aryl, alkylaryl and acyl groups, or R ₅ corresponds to formula (III) [Formula III] (III), Where n' equals 0-24, Y is selected from O and NR ₁₆ , where R ₁₆ is selected from alkyl, aryl, alkylaryl groups, OR ₁₄ , where R ₁₄ is as previously defined, Z is selected from H, alkyl, aryl, alkylaryl groups, CN, COR ₁₇ , where R ₁₇ is selected from H, alkyl, aryl and alkylaryl groups and from the groups OR ₁₈ , NR ₁₈ R ₁₉ , where R ₁₈ , R ₁₉ and R ₂₀ are independently selected from H and alkyl, aryl and arylalkyl groups , and CH ₂ OR ₂₀ , where R ₂₀ is selected from H and alkyl, aryl, alkylaryl and acyl groups, and OR ₁₈ and NR ₁₈ R ₁₉ , where R ₁₈ and R ₁₉ are independently selected from H and alkyl, aryl and arylalkyl groups, wherein the method involves reacting a compound of formula (IV) [Formula IV] R ₁ - (X) _m - R ₂₁ (IV), Where X is selected from S and Se; m is equal to 1 or 2; R ₁ is as defined above for compound (I), that is, it is selected from alkyl, aryl, alkylaryl and heteroaryl groups, optionally containing one or more functional groups selected from hydroxyl functional group and ether functional group, carbonyl functional group, hemiacetal and acetal functional groups, and carboxyl functional group and carboxyester functional groups; And if m is 1, R ₂₁ represents H; if m is 2, R ₂₁ is selected from alkyl, aryl and alkylaryl groups, with a compound of formula (V): [Formula V] where R ₂ , R ₃ , R ₄ and R ₅ are as defined above for the compound of formula (I), by irradiation with radiation with a wavelength from 200 to 800 nm in the presence of at least one compound containing at least one functional group selected from alcohol, carboxyl, thioether and selenoether functional groups, representing a compound of formula (VI), [Formula VI] Where X' is selected from S or Se; p and t are independently 0 or 1; q, r and s independently represent 0-10; provided that p + r + t is greater than or equal to 1, and if p is not equal to 0, then q + s is not equal to 0; R ₂₂ is selected, if p is 0, from H and alkyl, aryl and arylalkyl groups, and, if p is 1, from alkyl, aryl and arylalkyl groups; And R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ and R ₂₇ are independently selected from H and alkyl, aryl and alkylaryl groups, where in the indicated formulas (I)-(VI): the alkyl radical contains from 1 to 20 carbon atoms, or is cyclic and contains from 3 to 20 carbon atoms; the aryl group contains from 6 to 22 carbon atoms and is optionally functionalized with methoxy or ester groups; an alkylaryl group contains from 6 to 22 carbon atoms and includes an aryl group as defined above substituted by at least one alkyl group as defined above, or includes an alkyl group as defined above substituted with at least one aryl group, corresponding to the above definition; a heteroaryl group contains from 3 to 21 carbon atoms and at least one heteroatom selected from O and N; And the acyl group is RC(O)-, where R is an alkyl group as defined above. 2. The method according to claim 1, in which in the specified formulas (I)-(VI) the alkyl radical contains from 1 to 6 carbon atoms. 3. The method according to claim 2, in which the alkyl radical is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl and n-hexyl. 4. The method according to claim 1, in which in the specified formulas (I)-(VI) the alkyl radical is cyclic and contains from 5 to 7 carbon atoms. 5. The method according to claim 4, in which the alkyl radical is selected from cyclopentyl and cycloheptyl. 6. The method according to claim 1, in which in the specified formulas (I)-(VI) the aryl group is selected from phenyl, naphthyl, anisole and alkyl benzoate groups, wherein in the specified alkyl benzoate group the alkyl contains from 1 to 20 carbon atoms and is preferably selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl and n-hexyl, or is cyclic and contains from 3 to 20 carbon atoms and is preferably selected from cyclopentyl and cycloheptyl. 7. The method according to claim 1, in which in the specified formulas (I)-(VI) the alkylaryl group is selected from tolyl, mesityl, xylyl, benzyl, benzyhydryl, phenethyl and trityl groups. 8. The method according to claim 1, in which in the specified formulas (I)-(VI) the heteroaryl group is selected from pyrrolyl, pyridyl, indolyl and furyl groups. 9. Method according to any one of paragraphs. 1-8, characterized in that the radiation has a wavelength from 254 to 400 nm, preferably 365 ± 20 nm. 10. Method according to any one of paragraphs. 1-9, characterized in that compound (VI) includes at least alkyl sulfides such as methyl sulfide and ethyl sulfide, propionic acid, butanoic acid, lactic acid, 3-hydroxypropionic acid, 3-hydroxybutyric acid, 1-hydroxycaproic acid, 3- methylthiopropanoic acid, 4-methylthiobutanol, 2,4-hydroxybutyric (2,4-DHB) acid, methylthiobutyric acid (MHA) and methylthiobutanediol (MTBDO). 11. Method according to any one of paragraphs. 1-10, characterized in that the amount of compound (VI) is at least 0.1 equivalent, preferably at least 0.5 equivalent, and preferably not more than 10 equivalent, more preferably not more than 5 equivalent. and even more preferably no more than 2 eq. per 1 eq. compounds (V). 12. Method according to any one of paragraphs. 1-11, characterized in that the reaction is carried out on a compound (IV) selected from any alkylthiol or alkylselenol, such as methanethiol, ethanethiol, n-butanethiol, tert-butanethiol, methaneselenol, from any alkylthiol or alkylselenol containing one or more hydroxyl, carbonyl, carboxyl or carboxyester functional groups, such as thioglycolic acid, or from disulfides and diselenide, such as alkyl disulfide or diselenide, such as dimethyl or aryl disulfide, such as diphenyl disulfide and diphenyl diselenide. 13. Method according to any one of paragraphs. 1-12, characterized in that a compound (V) selected from butene, pentene, hexene, 2,3-dimethylbutene, but-3-enoic acid, but-2-enoic acid, butene-3-ene-2 is subjected to the reaction -ol, butenediol, cyclohexene, vinyl glycolic acid (VGA) and methyl vinyl glycolate (MVG). 14. The method according to claim 13, characterized in that the compound (I) is selected from 4-methylthio-2-hydroxybutyric acid, 4-methylseleno-2-hydroxybutyric acid and their esters. 15. Method according to any one of paragraphs. 1-14, characterized in that the molar ratio of compound (IV) to compound (V) is 1.1-15:1, preferably 1.2-10:1. 16. Method according to any one of paragraphs. 1-15, characterized in that the reaction is carried out in the presence of a photoinitiator selected from benzoin, 2,2-dimethoxy-2-phenylacetophenone (DMPA), thioxanthone, 1-chloro-4-hydroxythioxanthone, 1-chloro-4-propoxythioxanthone, benzophenone , 3-alkylbenzophenone and 4-alkylbenzophenone.