Method for preparing hydroxyl group-functionalized thioethers

Abstract

n of formula (I) (wherein X is C2 to C 12 -alkylene; or C2-C substituted with C1-C4-alkoxy, C1-C4-alkylthio and / or interrupted by O or S 12 - alkylene; R 1 , R 2 and R 3 are, independently of one another, hydrogen or C1-C4-alkyl; and n is an integer of 1, 2, 3, 4, 5 or 6), which comprises reacting a compound B having n —SH groups with a compound C of formula (II) in the presence of a free radical generator. [Formula 1] TIFF2023535606000053.tif25163 [2] TIFF2023535606000054.tif18163

Description

[Technical Field]

[0001] The present invention relates to a method for preparing compound A containing a thioether group and a hydroxyl group by reacting a thiol with an alkenyl group-containing thioether-alcohol in the presence of a free radical generator. Furthermore, the present invention relates to a compound having one or more groups derived from an alkenyl group-containing thioether-alcohol, and to the use of polyfunctional compound A as a chain extender or crosslinking agent. [Background technology]

[0002] Structures having two or more hydroxyl functional groups can be suitably used as building blocks in the field of polyaddition or polycondensation reactions, particularly for polyether, polyester, polycarbonate, and polyurethane-based plastics or resins.

[0003] Bifunctional compounds may be used as linear structural blocks, for example, as chain extenders, either as part of a hard segment or as part of a soft segment. Compounds with higher functionality can generally be used as crosslinking agents.

[0004] Sulfur-containing compounds, particularly sulfur-containing oligomers and polymers, are of great interest in many technical applications. For example, introducing sulfur atoms in the form of thioether groups into bifunctional and higher functional alcohols increases the attractiveness of hydroxyl-containing structural blocks due to the favorable properties of the sulfur atoms. For instance, this makes it possible to prepare polymers with improved chemical and thermal stability, or with increased refractive index, which is particularly advantageous in the field of optical applications. Furthermore, thioether groups allow for chemical modifications that fine-tune the properties of the polymer, such as polarity and solubility.

[0005] Thiadiazole can generally be prepared by treating dithiol with sodium metal and subsequently adding 2-chloroethanol. Such a method is described, for example, for the synthesis of 3,6-dithiaoctane-1,8-diol by R.A. Odhiambo et al., RSC Adv., 2018, 8, pp. 3663 - 3672, or by R.E. Wolf et al., J. Am. Chem. Soc. 1987, 109, pp. 4328 - 4335.

[0006] [Chemical formula]

[0007] 3,6,9-Trithioundecane-1,11-diol can be prepared similarly to the procedure using 3-thiapentane-1,5-dithiol instead of ethan-1,2-dithiol.

[0008] To prepare 3,6,9,12-tetrathiatetradecane-1,14-diol, 3,6-dithiaoctane-1,8-diol is first converted to the corresponding dithiol using thiourea and subsequently by the addition of 2-chloroethanol, which has been described previously herein (R.A. Odhiambo et al., RSC Adv., 2018, 8, pp. 3663 - 3672; M. Tanaka et al., J. Org. Chem. 2001, 66, pp. 7008 - 7012). The said thiadiazole is described to be used for thiacrown ether.

[0009] These procedures are elaborate, and the use of sodium metal or chlorine-containing materials that involve the release of chlorine-containing compounds and salt formation should be avoided due to aspects related to safety and environmental regulations.

[0010] JP 2009-203416 A discloses a thermally conductive resin composition containing 3,6,9-trithioundecane-1,11-diol.

[0011] The glycols of the following formulas, where v=3, 5, and 7, can also be prepared by the reaction of divinyl sulfide with 2-mercaptoethanol or the corresponding mercapto-alcohol, as described by ADB Sloan in Chemistry and Industry, 1967, p. 666.

[0012] [ka]

[0013] 3,6-Dithiaoctane-1,8- Geo The synthesis of 3,6-dithiooctane-1,8- is also described in H. Naarmann, Pure Appl. Chem., 1973, 36(1-2), p. 267, where 2-mercaptoethanol is reacted with vinyl hydroxyethyl thioether. However, the melting point of 122°C indicates that a different compound is formed. Geo The molten metal has a melting point of 64°C.

[0014] The need for readily available synthetic routes to mono-, di-, and polyhydroxy-containing polythioethers starting from thiols remains. The introduction of additional thioether groups into alcohols allows for greater stability of such compounds because the initial terminal -SH functional group is replaced by a more stable -OH functional group. Thus, the tendency of the -SH functional group to oxidatively dimerize is eliminated.

[0015] Furthermore, there is a need for methods for preparing mono-, di-, and polyhydroxy-containing polythioethers that can avoid toxicological problems, for example, enabling simpler and faster achievement. [Prior art documents] [Patent Documents]

[0016] [Patent Document 1] JP 2009-203416 A [Non-patent literature]

[0017] [Non-Patent Document 1] RA Odhiambo et al., RSC Adv., 2018, 8, pp. 3663-3672. [Non-Patent Document 2] RE Wolf et al., J. Am. Chem. Soc. 1987, 109, pp. 4328-4335. [Non-Patent Document 3] RA Odhiambo et al., RSC Adv., 2018, 8, pp. 3663-3672. [Non-Patent Document 4] M. Tanaka et al., J. Org. Chem. 2001, 66, pp. 7008-7012. [Non-Patent Document 5] ADB Sloan, Chemistry and Industry, 1967, 666 pages [Non-Patent Document 6] H. Naarmann, Pure Appl. Chem., 1973, 36(1-2), p. 267. [Overview of the Initiative] [Problems that the invention aims to solve]

[0018] Therefore, one object of the present invention is to provide an economical and flexible method for preparing hydroxyl-containing polythioethers.

[0019] Furthermore, one objective of the present invention is to provide a hydroxyl-containing polythioether that will be used as a building block in the preparation of various polymers.

[0020] Furthermore, one objective of the present invention is to provide a hydroxyl-containing polythioether that exhibits improved storage stability in the presence of air, for example, enabling easy and safe handling. [Means for solving the problem]

[0021] It has now been discovered that hydroxyl-containing polythioethers can be easily prepared by reacting thiols with alkenyl group-containing thioether-alcohols. In particular, the method for preparing di- or polyhydroxyl-containing polythioethers provides easy access to the constituent blocks, making them suitable for use in the preparation of a variety of polymers with improved properties such as increased chemical stability and / or elevated refractive index.

[0022] Therefore, in the first aspect, the present invention relates to n formulas [ka] (In the formula, X is C2~C 12 -Alkylene; or C1-C4-alkoxy, C1-C4-alkylthio substituted and / or C2-C1-C4-interrupted with O or S 12 -It is alkylene; R 1 , R 2 and R 3 These are, independently of each other, hydrogen or C1-C4 alkyl; n is an integer, either 1, 2, 3, 4, 5, or 6. A method for preparing compound A having the group, Compound B having n -SH groups is subjected to the formula in the presence of a free radical generator. [ka] The present invention relates to a method comprising the step of reacting with compound C.

[0023] In a further embodiment, the present invention relates to the formula [ka] TIFF0007848180000006.tif33160(in the formula, Y 1 C1~C 18 -alkyl;OH, C1~C4-alkoxy, C1~C4-alkylthio, halogen, NR 6R 7 ~C3, C 18 - cycloalkyl, C6 ~ C 18 - aryl or C2 ~ C 18 - heteroaryl substituted and / or -O-, -S-, -SO-, -SO2-, -COO-, -OCOO- or -CO-, C3 ~ C 18 - cycloalkylene, C6 ~ C 18 - arylene or C2 ~ C 18 - heteroarylene interrupted C1 ~ C 18 - alkyl; C3 ~ C 18 - cycloalkyl; OH, C1 - C4 alkoxy, C1 - C4 alkylthio, halogen or NR 8 R 9 substituted and / or interrupted by O or S C3 ~ C 18 - cycloalkyl; C6 ~ C 18 - aryl; C1 ~ C 12 - alkyl, OH, C1 - C4 alkoxy, C1 - C4 alkylthio, halogen or NR 10 R 11 substituted C6 ~ C 12 - aryl; C2 ~ C 18 - heteroaryl; C1 ~ C 12 - alkyl, OH, C1 - C4 alkoxy, C1 - C4 alkylthio, halogen or NR 12 R 13 substituted C2 ~ C 18 - heteroaryl; X is C2 ~ C 12 - alkylene; or C1 - C4 alkoxy, C1 - C4 alkylthio substituted and / or interrupted by O or S C2 ~ C 12 - alkylene; R 1 R 2 and R 3 are, independently of one another, hydrogen or C1 - C4 alkyl; R 4 and R 5These are, independently of each other and in each instance, hydrogen, C1~C 18 -Alkyl; C1-C substituted with halogen or interrupted with O or S 18 -alkyl; C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or C6-C substituted with halogen 18 - Aryl or C6~C 12 -Aryl; R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 These are C1-C4-alkyl;C6-C, which are substituted with C1-C4-alkyl;OH, C1-C4-alkoxy, C1-C4-alkylthio, or halogen, independently of each other and in each instance. 10 -aryl; or C6-C4 substituted with OH, C1-C4-alkoxy, C1-C4-alkylthio or halogen. 10 -Is it an allele? or R 6 and R 7 , R 8 and R 9 , R 10 and R 11 , or R 12 and R 13 These together are C4-C6 alkylenes; or O, S and / or NR 14 It is a C4-C6 alkylene that is interrupted by, R 14 It is a C1-C4 alkyl group; m is 1 to 12, preferably 1 to 10, for each occurrence; Y 2 is an n-valent bonding group, n is an integer of 2, 3, 4, 5, or 6. However, R 4 and R 5 (Assuming that H cannot be the same for both) Regarding compound A.

[0024] In a further embodiment, the present invention is R 1 and R 2 is hydrogen, R 3 is hydrogen or C1-C4 alkyl; X is a C2-C6 alkylene; or a C2-C6 alkylene interrupted by O or S; R 4 is hydrogen, R 5 However, each occurrence is hydrogen, a C1-C4 alkyl substituted with a halogen or interspersed with O or S, or a phenyl; Y 2 is an n-valent bonding group; m is between 2 and 6, n is an integer of 2, 3, 4, 5, or 6. This concerns compound A of formula (IV).

[0025] In a further embodiment, the present invention relates to the use of a compound of formula (IV), which can be obtained by a method specified in any embodiment herein, as a chain extender or a crosslinking agent. [Modes for carrying out the invention]

[0026] The terms alkyl, alkylene, cycloalkyl, alkoxy, aryl, heteroaryl, and halogen are known in the art and generally have the following meanings when the group is further specified in the particular embodiments listed below.

[0027] Alkyl, for example, C1-C 18 -Alkyl, C1~C 12 -alkyl, C1-C4-alkyl, C1-C6-alkyl or C2-C 12-Alkyl atoms may, where possible, be within a given limit of linear or branched carbon atoms. Examples include methyl (Me), ethyl (Et), n-propyl, isopropyl, n-butyl, 1-methylpropyl, 2-methylpropyl, t-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, 1-methylhexyl, n-heptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, and the constituent isomers of the aforementioned n-alkyl groups.

[0028] Alkylenes, for example, C1~C 12 -Alkylene, C2~C6-Alkylene, C2~C4-Alkylene, C2~C 12 -Alkylenes or C4-C6-alkylenes can be derived from the alkyls defined above by removing a hydrogen atom from any terminal carbon atom of the alkyl. Examples include methylene, 1,2-ethanediyl, 1,1-ethanediyl, 1,1-propanediyl, 1,2-propanediyl, 2,2-propanediyl, 1,3-propanediyl, 2-methyl-2,3-propanediyl, 1,1-butanediyl, 1,2-butanediyl, 2,2-butanediyl, 2,3-butanediyl, 1,3-butanediyl, 1,4-butanediyl, 1,5-pentanediyl, 1,6-hexanediyl, 1,8-octanediyl, 1,10-decanediyl, and 1,12-dodecanediyl.

[0029] Any alkyl or alkylene group having one or more carbon atoms, particularly two or more carbon atoms, or any alkyl moiety that is part of another, can be intercepted by heterofunctional groups such as -O-, -S-, -SO-, -SO2, -COO-, -OCOO-, or -CO-. They may be intercepted by one or more of these heterofunctional groups, one of which is generally inserted into the CC- bond of one of the alkyl or alkylene groups. If the intercepted group is further substituted, the substituent is generally not at the heteroatom. If two or more intercepting groups of type -O- or -S- occur within a single group, they are often identical.

[0030] Cycloalkyl, for example, C3-C 18 -Cycloalkyl, C5~C 12 -Cycloalkyl, C5-C8-cycloalkyl, and C5-C6-cycloalkyl include cycloalkyl groups that may be unsubstituted or substituted with alkyl groups. Examples include cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl, butylcyclohexyl, hexylcyclohexyl, dodecylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, or cyclododecyl. Cyclohexyl and cyclopentyl are preferred, and cyclohexyl is more preferred. Cycloalkyl groups, for example, C3-C6 groups that are interspersed by one or more oxygen or sulfur atoms, preferably one oxygen atom. 18 -Cycloalkyls include, for example, tetrahydropyranyl.

[0031] Cycloalkylenes, for example, C3-C 18 -Cycloalkylene, C6~C8-Cycloalkylene, C5~C 12 -Cycloalkylenes, C5-C8-cycloalkylenes, can be derived from the cycloalkyls defined above by removing a hydrogen atom from any ring carbon atom.

[0032] Alkoxy groups, such as C1-C4 alkoxy groups, are alkyl-O groups.

[0033] Alkylthio, for example, C1-C4-alkylthio, is alkyl-S.

[0034] Aryl, for example, C6~C 18 -Aaryl, C6~C 10 - Aryl or C6~C 12 -The aryl may be within a given limit of carbon atoms, and may be phenyl, fluorenyl, biphenylyl, terphenylyl, or naphthyl, for example, having a fused ring in the indanyl. Preferred examples are phenyl, 1-naphthyl, 2-naphthyl, 3- or 4-biphenylyl. Each aryl may be unsubstituted or one or more times substituted.

[0035] Arrinene, for example, C6~C 18 -Ariren, C6~C 12 -Arylenes can be derived from the aryls defined above by removing a hydrogen atom from any ring carbon atom. Examples include o-phenylene, m-phenylene, p-phenylene, 1,4-naphthylene, or 2,6-naphthylene.

[0036] Heteroaryls are C2-C 18 - Heteroaryl, C2~C 10 - Heteroaryl or C2~C 12- Heteroaryl, which may be a ring having 5 to 7 ring atoms, where nitrogen, oxygen or sulfur are possible heteroatoms. Examples are within the given limitations of carbon atoms and include thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, pyridyl, triazinyl, pyrimidinyl, benzofuranyl, isobenzofuranyl, xanthenyl, dibenzofuranyl, bipyridyl, triazinyl, isoindolyl, indolyl, 3H - indolyl, quinoxalinyl, indazolyl, quinolyl, isoquinolyl, phthalazinyl, naphthyridinyl, carbazolyl, benzoxazolyl, benzothiazolyl, benzisothiazolyl, benzimidazolyl, phenazinyl, phenothiazinyl or phenoxazinyl. Each heteroaryl may be unsubstituted or may be substituted one or more times. The term "heteroaryl" also includes combinations of heteroaryl groups and arylene groups such as 1,3 - phenylene, 1,4 - phenylene, 1,8 - naphthylene, 1,4 - naphthylene or 2,6 - naphthylene as listed above.

[0037] Heteroarylene, for example C2 - C 18 - Heteroarylene, C4 - C 10 - Heteroarylene, C2 - C 12 - Heteroarylene can be derived from the heteroaryl defined above by removing a hydrogen atom from any ring carbon atom of the heteroaryl.

[0038] Halogen (Hal) means I, Br, Cl or F, preferably Cl carried on alkyl and Cl or Br carried on aryl.

[0039] An amine group, for example NR 6 R 7 (wherein R 6 and R 7 together are C4 - C6 - alkylene interrupted by O, S and / or NR 14 ) and the amine group represented by is a cyclic amine, wherein R 6 and R 7In this way, together with the nitrogen atoms to which they are bonded, they form aliphatic N-heterocyclic residues containing 4 to 6 ring atoms, which may be substituted by alkyl groups. Examples include morpholinyl, thiomorpholinyl, piperidinyl, pyrrolidinyl, [ka] or variants thereof substituted with C1-C4 alkyl groups.

[0040] As used herein, the term "aliphatic unit" means a group derived from a linear hydrocarbon, which may be branched.

[0041] As used herein, the term "alicyclic unit" means a group derived from a cyclic hydrocarbon, which may be substituted with an alkyl group.

[0042] As used herein, the term "aromatic unit" refers to a group derived from an aromatic compound.

[0043] As used herein, the term “heteroaromatic unit” refers to a group derived from a heteroaromatic compound.

[0044] The term "substituted" means "one or more substitutions," i.e., 1 to 3 substitutions where possible, preferably 1 to 2, and more preferably 1. If more than one substituent occurs in the group, it may differ with each occurrence.

[0045] As used herein, the singular articles "a," "an," and "the" encompass the plural unless the context clearly indicates otherwise.

[0046] This method is, [ka] The present invention provides compound A having one or more of the groups.

[0047] Preferably, X is C2~C 12 -Alkylene; or C2~C interrupted by O or S 12 - is an alkylene. More preferably, X is a C2-C6 alkylene; or a C2-C6 alkylene interspersed with O or S, and most preferably, X is a C2-C4 alkylene; or a C2-C4 alkylene interspersed with O or S, particularly an S interspersed C2-C4 alkylene.

[0048] In a particularly preferred embodiment, X is ethylene or propylene, and especially ethylene.

[0049] Preferably, R 1 and R 2 is hydrogen, R 3 R is hydrogen or a C1-C4 alkyl group, preferably hydrogen or methyl. Specifically, R 1 , R 2 and R 3 It is hydrogen.

[0050] Therefore, in one preferred embodiment, the present invention is R 1 and R 2 is hydrogen, R 3 is hydrogen or C1-C4 alkyl; X is a C2-C6 alkylene; or a C2-C6 alkylene interrupted with O or S, preferably an S-interrupted C2-C6 alkylene. Regarding the method.

[0051] This method preferably involves n formulas [ka] (In the formula, R 3 is hydrogen or CH3; X is a C2-C4 alkylene; or a C2-C4 alkylene interrupted with O or S, preferably a C2-C4 alkylene; or a C2-C4 alkylene interrupted with S. n is an integer, either 1, 2, 3, 4, 5, or 6. The present invention provides compound A having the group.

[0052] More preferably, X is ethylene or propylene, most preferably ethylene.

[0053] What is particularly preferable is, R 1 and R 2 is hydrogen, R 3 is hydrogen or methyl, and especially R 1 , R 2 and R 3 is hydrogen; X is ethylene or propylene, especially ethylene. It is a method.

[0054] What is particularly preferable is, R 1 , R 2 and R 3 is hydrogen; X is ethylene. It is a method.

[0055] Preferably, the present invention relates to a compound A having n groups of formula (I), [ka] (In the formula, Y 1 C1~C 18 -alkyl;OH, C1~C4-alkoxy, C1~C4-alkylthio, halogen, NR 6 R 7 , C3~C 18 -Cycloalkyl, C6~C 18 - Aryl or C2~C 18 - Substituted with heteroaryls and / or -O-, -S-, -SO-, -SO2, -COO-, -OCOO-, C3~C 18 -Cycloalkylene, C6~C 18 - Arirene or C2~C 18 -C1~C is interrupted by heteroarrene 18-alkyl; C3~C 18 -Cycloalkyl;OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen or NR 8 R 9 C3~C which are replaced and / or interrupted by O or S 18 -Cycloalkyl; C6~C 18 -Aryl; C1~C 12 -alkyl, OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen or NR 10 R 11 C6~C which are replaced by 12 -Aryl; C2~C 18 - Heteroaryl; C1~C 12 -alkyl, OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen or NR 12 R 13 C2~C which are replaced by 18 - is heteroaryl; R 4 and R 5 These are, independently of each other and in each instance, hydrogen, C1~C 18 -Alkyl; C1-C substituted with halogen or interrupted with O or S 18 -alkyl; C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or C6-C substituted with halogen 18 - Aryl or C6~C 12 -Aryl; R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 These are C1-C4-alkyl;C6-C, which are substituted with C1-C4-alkyl;OH, C1-C4-alkoxy, C1-C4-alkylthio, or halogen, independently of each other and in each instance. 10-aryl; or C6-C4 substituted with OH, C1-C4-alkoxy, C1-C4-alkylthio or halogen. 10 -Is it an allele? or R 6 and R 7 , R 8 and R 9 , R 10 and R 11 , or R 12 and R 13 These together are C4-C6 alkylenes; or O, S and / or NR 14 It is a C4-C6 alkylene that is interrupted by, R 14 It is a C1-C4 alkyl group; m is between 0 and 12 for each occurrence; Y 2 is an n-valent bonding group; n is an integer of 2, 3, 4, 5, or 6. This relates to a compound and a method.

[0056] If m is greater than 1, then m is the -S-CHR present in one chain. 4 -CHR 5 - This refers to the average number of units.

[0057] -S-CHR 5 -CHR 4 Structural isomers of compounds of formula (III) or (IV) containing the - group can also be obtained, but only in small amounts. For example, when m is greater than 1, -S-CHR 4 -CHR 5 -Base and -S-CHR 5 -CHR 4 - A mixture of compounds of formula (III) or (IV) containing the group can be obtained, where the latter is usually present only in small amounts.

[0058] Preferably, Y 1 C1~C 12 -alkyl;OH, C1~C4-alkoxy, C1~C4-alkylthio, halogen, NR 6 R 7, C5~C6-cycloalkyl, C6~C 12 - Aryl or C2~C 10 - Substituted with heteroaryls and / or O, S, -SO-, -SO2, -COO-, -OCOO-, -CO-, C6~C8-cycloalkylenes, C6~C 12 - Arirene or C4~C 10 -C1~C is interrupted by heteroarrene 12 -alkyl; C5-C8 cycloalkyl;OH, C1-C4 alkoxy, C1-C4 alkylthio, halogen or NR 8 R 9 C5-C8 cycloalkyl groups that are substituted and / or interrupted by O or S; C6~C 12 -aryl; C1-C6-alkyl, OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen or NR 10 R 11 C6~C which are replaced by 10 -Aryl; C2~C 10 - Heteroaryl; C1-C6-alkyl, OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen or NR 12 R 13 C2~C which are replaced by 10 - is heteroaryl; R 4 and R 5 These are, independently of each other and in each instance, hydrogen, C1~C 18 - Alkyl; halogen-substituted and / or interposed with O or S C1~C 18 -alkyl; C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or C6-C substituted with halogen 18 - Aryl or C6~C 12 -Aryl; R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R13 These are C1-C4 alkyl groups that are independently and, in each instance, substituted with C1-C4 alkyl;OH or phenyl.

[0059] Comfortable, R 6 and R 7 , R 8 and R 9 , R 10 and R 11 , and R 12 and R 13 These are identical and are C1-C4 alkyl groups; or C1-C4 alkyl groups substituted with OH.

[0060] Most preferably, Y 1 C1~C 12 -alkyl;OH, C1-C4-alkoxy, C1-C4-alkylthio, C5-C6-cycloalkyl, C6-C 12 -aryl or C2~C 10 - Heteroaryl substituted and / or O, S, C6-C8-cycloalkylene, C6-C 12 - Arirene or C4~C 10 -C1~C is interrupted by heteroarrene 12 -alkyl; C5-C8 cycloalkyl; C5-C8 cycloalkyl substituted with OH, C1-C4 alkoxy, or C1-C4 alkylthio and / or interposed by O or S; C6~C 12 -aryl; C1-C6-alkyl, OH, C1-C4-alkoxy or C1-C4-alkylthio substituted C6-C 10 -Aryl; C2~C 10 - Heteroaryl; C2-C substituted with C1-C6-alkyl, OH, C1-C4-alkoxy or C1-C4-alkylthio 10 -It is a heteroaryl compound.

[0061] In particular, Y 1 These are C1~C which are substituted with OH and interrupted with O or S, specifically interrupted with S.12 -It is alkyl.

[0062] A preferred method for preparing compound A of formula (III) is one in which m is 1 to 10, i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, more preferably 1 to 8, and particularly 2 to 6.

[0063] In particular, R 4 is hydrogen, R 5 Each instance of appearance is hydrogen, C1~C 18 - Alkyl; halogen-substituted and / or interposed with O or S C1~C 18 -alkyl; C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or C6-C substituted with halogen 18 - Aryl or C6~C 12 - It is Ariel.

[0064] Alternatively, R 4 and R 5 These are C1-C4 alkyl groups that are substituted with hydrogen, C1-C4 alkyl groups that are halogenated, or C1-C4 alkyl groups that are interspersed with O or S, and C6-C6 alkyl groups. 12 -aryl; or C6-C4 substituted with C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or halogen 12 - It is Ariel.

[0065] therefore, R 4 and R 5 However, each instance is independent of the others and each instance is substituted with hydrogen, C1-C4 alkyl; halogen, or interspersed with O or S, C1-C4 alkyl; C6-C 12 -aryl; or C6-C4 substituted with C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or halogen. 12 -Aryl; m is 1 to 10, preferably 1 to 8, and particularly 2 to 6. A method for preparing compound A of formula (III) or (IV) is preferred.

[0066] In particular, R 4 is hydrogen, R 5 Each occurrence is either hydrogen, C1-C4 alkyl; halogen-substituted or interspersed with O or S, or C1-C4 alkyl; C6-C 12 -aryl; or C6-C4 substituted with C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or halogen 12 - is aryl; m is 1 to 10, preferably 1 to 8, i.e., 1, 2, 3, 4, 5, 6, 7, or 8, particularly 2 to 6.

[0067] R 4 is hydrogen, R 5 Each occurrence is, for each instance, hydrogen, a C1-C4 alkyl; a C1-C4 alkyl substituted with a halogen or interspersed with O or S; or phenyl; m is between 1 and 8, especially between 2 and 6. A method for preparing compound A of formula (III) or (IV) is more preferred.

[0068] especially, R 4 is hydrogen, R 5 However, each occurrence is either hydrogen or a C1-C4 alkyl group; m is between 1 and 8, and if specified, m is between 1 and 6, or between 2 and 6. A method for preparing compound A of formula (III) or (IV) is preferred.

[0069] therefore, Y 1 However, C1~C 12 -alkyl;OH, C1-C4-alkoxy, C1-C4-alkylthio, C5-C6-cycloalkyl, C6-C 12 - Aryl or C2~C 10 - Heteroaryl substituted and / or O, S, C6-C8-cycloalkylene, C6-C 12 - Arirene or C4~C 10 -C1~C is interrupted by heteroarrene12 -alkyl; C5-C8 cycloalkyl; C5-C8 cycloalkyl substituted with OH, C1-C4 alkoxy, or C1-C4 alkylthio and / or interposed by O or S; C6~C 12 -aryl; C1-C6-alkyl, OH, C1-C4-alkoxy or C1-C4-alkylthio substituted C6-C 10 -Aryl; C2~C 10 - Heteroaryl; C2-C substituted with C1-C6-alkyl, OH, C1-C4-alkoxy or C1-C4-alkylthio 10 - is heteroaryl; R 4 is hydrogen, R 5 However, each occurrence is either hydrogen, C1-C4 alkyl; halogen substituted or interspersed with O or S, or C1-C4 alkyl; C6-C 12 -aryl; or C6-C4 substituted with C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or halogen 12 -Aryl; m is 1-8, especially m is 1-6, or 2-6. A method for preparing compound A of formula (III) is even more preferred.

[0070] Alternatively, a preferred method is to prepare compound A of formula (III) where m is 0.

[0071] therefore, Y 1 However, C1~C 12 -alkyl;OH, C1-C4-alkoxy, C1-C4-alkylthio, C5-C6-cycloalkyl, C6-C 12 - Aryl or C2~C 10 - Heteroaryl substituted and / or O, S, C6-C8-cycloalkylene, C6-C 12 - Arirene or C4~C 10 -C1~C is interrupted by heteroarrene12 -alkyl; C5-C8 cycloalkyl; C5-C8 cycloalkyl substituted with OH, C1-C4 alkoxy, or C1-C4 alkylthio and / or interposed by O or S; C6~C 12 -aryl; C1-C6-alkyl, OH, C1-C4-alkoxy or C1-C4-alkylthio substituted C6-C 10 -Aryl; C2~C 10 - Heteroaryl; C2-C substituted with C1-C6-alkyl, OH, C1-C4-alkoxy or C1-C4-alkylthio 10 - is heteroaryl; m is 0, A method for preparing compound A of formula (III) is preferred.

[0072] Even better is, Y 1 However, C1~C which are substituted with OH and interrupted with O or S, especially those interrupted with S 12 -It is alkyl; R 4 is hydrogen, R 5 However, each occurrence is hydrogen, a C1-C4 alkyl substituted with a halogen or interspersed with O or S, or a phenyl; m is 1 to 10, preferably 1 to 8, and particularly 2 to 6. This is a method for preparing compound A of formula (III).

[0073] R is particularly preferable. 4 is hydrogen, R 5 However, this is a method for preparing compound A of formula (III), which is the same each time it appears and is either hydrogen or a C1-C4 alkyl group.

[0074] The method can also provide compound A having more groups of formula (I).

[0075] Therefore, in one preferred embodiment, the present invention is formula [ka] (In the ceremony Y 2 is an n-valent bonding group, X is a C2-C6 alkylene, or a C2-C6 alkylene interrupted by O or S; R 1 , R 2 and R 3 These are, independently of each other, hydrogen or C1-C4 alkyl; n is an integer of 2, 3, 4, 5, or 6. This relates to a method for preparing compound A.

[0076] A more preferable option is, R 1 and R 2 is hydrogen, R 3 is hydrogen or C1-C4 alkyl; X is a C2-C6 alkylene; or a C2-C6 alkylene that is interrupted by O or S. This is a method for preparing compound A of formula (IV).

[0077] The most preferable is, R 1 and R 2 is hydrogen, R 3 is hydrogen or CH3; X is a C2-C4 alkylene; or a C2-C4 alkylene interrupted with O or S, preferably a C2-C4 alkylene; or a C2-C4 alkylene interrupted with S. This is a method for preparing the compound of formula (IV).

[0078] The n-valence is preferably an integer of 2, 3, 4, or 6, more preferably 2, 3, or 4, most preferably 2 or 3, and particularly 2.

[0079] Therefore, in one preferred embodiment, the present invention is Y 2is an n-valent bonding group; n is an integer of 2, 3, 4, or 6, especially 2, 3, or 4. This relates to a method for preparing the compound of formula (IV).

[0080] The n-valent bonding group may include an aliphatic unit, an alicyclic unit, an aromatic unit and / or a heteroaromatic unit, and optionally a functional group containing a heteroatom.

[0081] Therefore, in a further preferred embodiment, the present invention is Y 2 However, it is an n-valent bond group comprising an aliphatic unit, an alicyclic unit, an aromatic unit and / or a heteroaromatic unit, and optionally a functional group containing a heteroatom; n is an integer of 2, 3, 4, or 6, preferably 2, 3, or 4. This relates to a method for preparing the compound of formula (IV).

[0082] The heteroatom-containing functional group is a heterofunctional group selected from -O-, -S-, -SO-, -SO2-, -COO-, -OCOO-, or -CO-. The heteroatom-containing functional group may be part of the aliphatic unit, alicyclic unit, aromatic unit and / or heteroaromatic unit of the n-valent bonded group, and may optionally be located between at least one of the aforementioned units.

[0083] If n is 2, Y 2 Y is a divalent bonding group. 2 It may include an alkylene group, a cycloalkylene group, an arylene group and / or a heteroarylene group, and optionally at least one heterofunctional group selected from -O-, -S-, -SO-, -SO2-, -COO-, -OCOO- or -CO-.

[0084] Preferably, a divalent bond group Y 2 C1~C 18 -Alkylene; C1-C4-alkoxy, C1-C4-alkylthio, halogen, NR 15 R 16 , C5~C 12-Cycloalkyl, C6~C 12 -aryl or C2~C 12 - Heteroaryl-substituted C1~C 18 -Alkilen; C5~C 12 -Cycloalkylene; C1-C4-alkoxy, C1-C4-alkylthio, halogen or NR 17 R 18 C5~C which are replaced and / or interrupted by O or S 12 -Cycloalkylene; C6~C 12 -Ariren; C1~C 12 -alkyl, C1-C4-alkoxy, C1-C4-alkylthio, halogen or NR 19 R 20 C6~C which are replaced by 12 -Ariren; C2~C 12 -Heteroarrene; C1~C 12 -alkyl, C1-C4-alkoxy, C1-C4-alkylthio, halogen or NR 21 R 22 C2~C which are replaced by 12 - comprising at least one group selected from heteroarylenes and optionally at least one heterofunctional group selected from -O-, -S-, -SO-, -SO2-, -COO-, -OCOO-, or -CO-; R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 and R 22 These are C1-C4-alkyl;C6-C, which are substituted with C1-C4-alkyl;OH, C1-C4-alkoxy, C1-C4-alkylthio, or halogen, independently of each other and in each instance. 10 -aryl; or C6-C4 substituted with OH, C1-C4-alkoxy, C1-C4-alkylthio or halogen. 10 - Containing at least one base selected from aryl groups.

[0085] It is understood that the heterofunctional group selected from -O-, -S-, -SO-, -SO2-, -COO-, -OCOO-, or -CO- is not part of an alkylene group, cycloalkylene group, arylene group, and / or heteroarylene group.

[0086] The heterofunctional group is preferably selected from -O-, -S-, or -COO-, and more preferably selected from -O- or -S-.

[0087] more preferably, a divalent bond group Y 2 C1~C 18 -Alkylene; C5~C 12 -Cycloalkylene; C5~C interrupted with O or S 12 -Cycloalkylene; C6~C 12 -Arylene; C6-C4 substituted with alkyl 12 -Ariren; C2~C 12 -Heteroarylene; or C2-C4-alkyl substituted 12 - comprises at least one group selected from heteroarylenes and optionally at least one group selected from -O-, -S-, or -COO-.

[0088] Most preferably, a divalent bond group Y 2 C1~C 12 -Alkylene; C5~C8-Cycloalkylene; C5~C8-Cycloalkylene interrupted by O or S; C6~C 12 -Arylene; C6-C4 substituted with alkyl 12 -Ariren; C2~C 12 -Heteroarylene; or C2-C4-alkyl substituted 12 - comprises at least one group selected from heteroarylenes and optionally at least one heterofunctional group selected from -O-, -S-, or -COO-, particularly -O or -S-.

[0089] Therefore, in one preferred embodiment, the present invention is Y 2is a divalent bonding group, and the divalent bonding group is C1~C 12 -Alkylene; C5~C8-Cycloalkylene; C5~C8-Cycloalkylene interrupted by O or S; C6~C 12 -Arylene; C1~C4-alkyl, C2~C 12 -C6~C substituted with heteroarylene 12 -Arylene; or C2-C4-alkyl substituted 12 - comprising at least one group selected from heteroarylenes and optionally at least one group selected from -O-, -S-, or -COO-, particularly -O- or -S-, This relates to a method for preparing the compound of formula (IV).

[0090] divalent bond group Y 2 C1~C of various lengths 18 - May contain one or more alkylene groups.

[0091] C1~C 18 Examples of alkylenes include methylene, ethylene, -CHCH3-, -C(CH3)2-, 1,2-propylene, 1,3-propylene, 2,2-dimethyl-1,3-propylene, 2-butyl-2-ethyl-1,3-propylene, 1,4-butylene, 1,6-hexylene, 1,12-dodecylene, and 1,16-hexadecylene.

[0092] Divalent group Y 2 Examples include C1~C 18 -Alkylene, -CH2-O-CH2-, -CH2-S-CH2-, -(CH2CH2O) p -CH2CH2-, -(CH2CH2S) p -CH2CH2-(wherein p is an integer between 1 and 10, preferably between 2 and 10, more preferably between 2 and 4), -(C3H7O) q -C3H7-, -(C3H7S) q -C3H7- (wherein q is an integer from 1 to 10, preferably from 1 to 4, or from 2 to 4), o-phenylene, m-phenylene, p-phenylene, 4,4'-isopropylidene-diphenylene, [ka] ,for example [ka] These are some examples.

[0093] If n is 3, Y 2 This is a trivalent bonding group preferably derived from benzene (i.e., benzenetriyl), triazinetriyl, or methylidene, or a trivalent bonding group consisting of benzenetriyl, methylidene, or nitrogen, and at least one of the divalent groups previously described herein.

[0094] more, Y 2 This is a trivalent bonding group selected from benzenetriyl, triazinetriyl, or methylidene, or one of benzenetriyl, triazinetriyl, or methylidene and C1-C 12 -A trivalent bonding group comprising an alkylene and at least one divalent group selected from at least one heterofunctional group selected from -O-, -S-, or -COO-.

[0095] Examples of trivalent bonding groups are: [ka] The file is TIFF0007848180000015.tif127162.

[0096] If n is 4, Y 2 This is a tetravalent bonding group preferably derived from methane or benzene, or a tetravalent bonding group composed of one derived from methane or benzene and at least one divalent bonding group as previously described herein.

[0097] more, Y 2This is a tetravalent bonding group derived from methane or benzene, or a C1-C bond derived from methane or benzene. 12 -A tetravalent bonding group consisting of an alkylene and, optionally, at least one divalent group selected from at least one group selected from -O-, -S-, or -COO-.

[0098] Examples of tetravalent bonding groups are: [ka] That is the case.

[0099] Pentavalent or hexavalent bonding groups can be derived from penta- or hexa-sugar alcohols, such as xylitol, ribitol, sorbitol, mannitol, or galacticol.

[0100] Further examples of hexavalent bonding groups are: [ka] That is the case.

[0101] In a further preferred embodiment, the present invention is Y 2 However, it is a trivalent bond group selected from benzenetriyl, triazinetriyl, or methylidine, or a trivalent bond group composed of benzenetriyl, methylidene, or nitrogen and at least one divalent group, Y 2 However, it is a tetravalent bond group derived from methane or benzene, or a tetravalent bond group composed of something derived from methane or benzene and at least one divalent group, Y 2 However, the formula [ka] And in some cases, it is a hexavalent group with at least one divalent group. Each of the divalent groups, C1~C 12- at least one group selected from alkylene and optionally from -O-, -S-, or -COO-, This relates to a method for preparing the compound of formula (IV).

[0102] In a further preferred embodiment, the present invention is Y 2 However, it is a divalent bonding group, and the said divalent bonding group is C1~C 18 -Alkylene, -CH2-O-CH2-, -CH2-S-CH2-, -(CH2CH2O) p -CH2CH2-, -(CH2CH2S) p -CH2CH2-(wherein p is an integer between 1 and 10, preferably between 2 and 10), -(C3H7O) q -C3H7-, -(C3H7S) q -C3H7- (where q is an integer from 1 to 10), o-phenylene, m-phenylene, p-phenylene, 4,4'-isopropylidene-diphenylene, [ka] Includes at least one base selected from, This relates to a method for preparing the compound of formula (IV).

[0103] In a further preferred embodiment, the present invention is R 4 is hydrogen, R 5 However, each occurrence is hydrogen, a C1-C4 alkyl substituted with a halogen or interspersed with O or S, or a phenyl; m is 1 to 10, preferably 1 to 8, and particularly 2 to 6. This relates to a method for preparing the compound of formula (IV).

[0104] Monothiol compounds or polythiol compounds that can be used in practice of the present invention are commercially available or can be prepared by methods generally known in the art.

[0105] For example, a compound having an alcohol group may be reacted with thiourea in a mineral acid, followed by alkaline hydrolysis to convert it to the corresponding thiol compound, as described, for example, in EP0378895 A1.

[0106] The preparation of isothiouronium salts by the direct action of thiourea and halogenated acids on alcohols is described, for example, by RL Frank et al. in J. Am. Chem. Soc., 1946, 68, 10, pp. 2103-2104. Accessing an alkyl alcohol, thiourea, and 48% hydrobromic acid or hydrochloric acid under reflux for 9 hours, followed by neutralization with NaOH, yields alkylthiols. The thiols can be extracted from the acidified mixture using ether.

[0107] The rapid one-pot synthesis of thiols from alcohols under mild conditions is generally possible using triphenylphosphine, N-bromo-succinimide (NBS), and polymer-supported hydrosulfides, as described, for example, by BP Bandgar et al., Synlett 2000, 6, pp. 908-910. Dialkyl sulfide formation does not occur under these conditions, and yields of approximately 85% are possible.

[0108] Mercaptans can also be obtained from alcohols with H2S in moderate yield (44%) by using dicobalt octacarbonyl as a catalyst (CO, 60 bar, 150°C), as described, for example, by H. Alper et al. in J. Org. Chem. 1988, 53, pp. 3306-3309.

[0109] Monothiol compound B1 for the method of preparing the compound of formula (III) is, in general formula [ka] It may also be something else.

[0110] The preferred compound B1 of formula (VIII) is (In the formula, Y 1 C1~C 18 -alkyl;OH, C1~C4-alkoxy, C1~C4-alkylthio, halogen, NR 6 R 7 , C3~C 18 -Cycloalkyl, C6~C 18 - Aryl or C2~C 18 - Substituted with heteroaryls and / or -O-, -S-, -SO-, -SO2-, -COO-, -OCOO-, -CO-, C3~C 18 -Cycloalkylene, C6~C 18 - Arirene or C2~C 18 -C1~C is interrupted by heteroarrene 18 -alkyl; C3~C 18 -Cycloalkyl;OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen or NR 8 R 9 C3~C which are replaced and / or interrupted by O or S 18 -Cycloalkyl; C6~C 18 -Aryl; C1~C 12 -alkyl, OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen or NR 10 R 11 C6~C which are replaced by 12 -Aryl; C2~C 18 - Heteroaryl; C1~C 12 -alkyl, OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen or NR 12 R 13 C2~C which are replaced by 18 - is heteroaryl; R 4 and R 5 These are, independently of each other and in each instance, hydrogen, C1~C 18 - Alkyl; halogen-substituted and / or interposed with O or S C1~C 18-alkyl; C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or C6-C substituted with halogen 18 - Aryl or C6~C 12 -Aryl; R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 These are C1-C4-alkyl;C6-C, which are substituted with C1-C4-alkyl;OH, C1-C4-alkoxy, C1-C4-alkylthio, or halogen, independently of each other and in each instance. 10 -aryl; or C6-C4 substituted with OH, C1-C4-alkoxy, C1-C4-alkylthio or halogen. 10 -Is it an allele? or R 6 and R 7 , R 8 and R 9 , R 10 and R 11 , or R 12 and R 13 These together are C4-C6 alkylenes; or O, S and / or NR 14 It is a C4-C6 alkylene that is interrupted by; R 14 It is a C1-C4 alkyl group; m is between 0 and 12. It is a compound of [the compound].

[0111] A more preferable formula is Y 1 -SH (V) (In the formula, Y 1 C1~C 12 -alkyl;OH, C1-C4-alkoxy, C1-C4-alkylthio, C5-C6-cycloalkyl, C6-C 12 - Aryl or C2~C 10 - Heteroaryl substituted and / or O, S, C6-C8-cycloalkylene, C6-C12 - Arirene or C4~C 10 -C1~C is interrupted by heteroarrene 12 -alkyl; C5-C8 cycloalkyl; C5-C8 cycloalkyl substituted with OH, C1-C4 alkoxy, or C1-C4 alkylthio and / or interposed by O or S; C6~C 12 -aryl; C1-C6-alkyl, OH, C1-C4-alkoxy or C1-C4-alkylthio substituted C6-C 10 -Aryl; C2~C 10 - Heteroaryl; C2-C substituted with C1-C6-alkyl, OH, C1-C4-alkoxy or C1-C4-alkylthio 10 - (It is a heteroaryl) This is compound B1.

[0112] The most preferable is, Y 1 However, C1~C which are substituted with OH and interrupted with O or S, especially those interrupted with S 12 -It is alkyl, This is compound B1 of formula (V).

[0113] Examples of suitable compounds include alkyl mercaptans such as methyl mercaptan or ethyl mercaptan, aryl mercaptans such as thiophenol, and mercapto alcohols such as mercaptoethanol, mercaptoglycol, or mercaptophenol.

[0114] A preferable alternative is, Y 1 However, C1~C 12 -alkyl;OH, C1-C4-alkoxy, C1-C4-alkylthio, C5-C6-cycloalkyl, C6-C 12 - Aryl or C2~C 10 - Heteroaryl substituted and / or O, S, C6-C8-cycloalkylene, C6-C 12- Arirene or C4~C 10 -C1~C is interrupted by heteroarrene 12 -alkyl; C5-C8 cycloalkyl; C5-C8 cycloalkyl substituted with OH, C1-C4 alkoxy, or C1-C4 alkylthio and / or interposed by O or S; C6~C 12 -aryl; C1-C6-alkyl, OH, C1-C4-alkoxy or C1-C4-alkylthio substituted C6-C 10 -Aryl; C2~C 10 - Heteroaryl; C2-C substituted with C1-C6-alkyl, OH, C1-C4-alkoxy or C1-C4-alkylthio 10 - is heteroaryl; R 4 and R 5 However, each instance is independent of the others and each instance is substituted with hydrogen, C1-C4 alkyl; halogen, or interspersed with O or S, C1-C4 alkyl; C6-C 12 -aryl; or C6-C4 substituted with C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or halogen. 12 -Aryl; m is between 1 and 10. This is compound B1 of formula (VIII).

[0115] What is particularly preferable is, Y 1 However, C1~C which are substituted with OH and interrupted with O or S, especially those interrupted with S 12 -It is alkyl; R 4 is hydrogen, R 5 However, each occurrence is hydrogen, a C1-C4 alkyl substituted with a halogen or interspersed with O or S, or a phenyl; m is between 1 and 8, especially between 1 and 6. This is compound B1 of formula (VIII).

[0116] Even better is, Y 1 However, C1~C which are substituted with OH and interrupted with O or S, especially those interrupted with S 12 -It is alkyl; R 4 is hydrogen, R 5 However, each occurrence is the same, and is either hydrogen or a C1-C4 alkyl group; m is between 1 and 8, especially between 1 and 6. This is compound B1 of formula (VIII).

[0117] For a method of preparing the compound of formula (IV), polythiol compound B2 having at least two mercapto groups is a general formula [ka] (In the formula, Y 2 This is an n-valent bond group comprising an aliphatic unit, an alicyclic unit, an aromatic unit and / or a heteroaromatic unit, and optionally a functional group containing a heteroatom; R 4 and R 5 These are, independently of each other and in each instance, hydrogen, C1~C 18 - Alkyl; halogen-substituted and / or interposed with O or S C1~C 18 -alkyl; C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or C6-C substituted with halogen 18 - Aryl or C6~C 12 -Aryl; m is between 0 and 12; n is 2, 3, 4, 5, or 6, preferably n is 2, 3, or 4, more preferably n is 2 or 3. It may also be something else.

[0118] The preferred compound B2 of formula (IX) is, Y 2However, it is an n-valent bond group comprising an aliphatic unit, an alicyclic unit, an aromatic unit and / or a heteroaromatic unit, and optionally a functional group containing a heteroatom; R 4 and R 5 However, each instance is independent of the others and each instance is substituted with hydrogen, C1-C4 alkyl; halogen, or interspersed with O or S, C1-C4 alkyl; C6-C 12 -aryl: or C6-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or halogen-substituted C6-C 12 -Aryl; m is between 0 and 10; n is an integer of 2, 3, 4, or 6, preferably 2, 3, or 4, more preferably n is an integer of 2 or 3. It is a compound.

[0119] A more preferable option is, Y 2 However, it is a divalent bonding group, and the said divalent bonding group is C1~C 12 -Alkylene; C5~C8-Cycloalkylene; C5~C8-Cycloalkylene interrupted by O or S; C6~C 12 -Arylene; C1~C4-alkyl, C2~C 12 -C6~C substituted with heteroarylene 12 -Arylene; or C2-C4 alkyl and optionally C2-C4 alkyl and at least one group selected from -O-, -S-, or -COO-, particularly -O- or -S-. 12 -It is a heteroarrene. This is compound B2 of formula (IX).

[0120] Furthermore, a more preferable option is, Y 2 However, it is a trivalent bond group selected from benzenetriyl, triazinetriyl, or methylidene, or a trivalent bond group composed of benzenetriyl, methylidene, or nitrogen, and at least one divalent group. or a tetravalent bond group derived from methane or benzene, or a tetravalent bond group composed of a derivative from methane or benzene and at least one divalent group, Each of the divalent groups, C1~C 12 -Selected from alkylene and optionally at least one group selected from -O-, -S-, or -COO-, This is compound B2 of formula (IX).

[0121] Furthermore, a more preferable option is, Y 2 However, it is a trivalent bond group selected from benzenetriyl, triazinetriyl, or methylidene, or a trivalent bond group composed of benzenetriyl, methylidene, or nitrogen and at least one divalent group, Y 2 However, it is a tetravalent bond group derived from methane or benzene, or a tetravalent bond group composed of something derived from methane or benzene and at least one divalent group, Y 2 However, the formula [ka] And in some cases, it is a hexavalent group with at least one divalent group. Each of the divalent groups, C1~C 12 -Selected from alkylene and optionally at least one group selected from -O-, -S-, or -COO-, This is compound B2 of formula (IX).

[0122] Examples of suitable dithiol compounds B2 include 1,2-dimercaptoethane, 2,2-dimercaptopropane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, 1,6-dimercaptohexane, tetra(ethylene glycol)dithiol, 3,6-dioxa-1,8-octane-dithiol, 2,2'-thiodiethanethiol, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5, 7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 1,1,3,3-Tetrakis(mercaptomethylthio)propane, 1,2-Bis(2-mercaptoethylthio)ethane, 1,5-Dimercapto-3-Oxapentane, 2,2-Dimethylpropane-1,3-Dithiol, 2-Mercaptomethyl-1,3-Dimercaptopropane, Benzene dimethanethiol (isomer), (1,1'-Bihenyl)-4,4'Dimethanethiol, 2-Mercaptoethyl ether, Dimercaptobenzene (isomer) ), terphenyldithiol, 1,4-bis(mercaptomethyl)cyclohexane, 1,4-dimercaptocyclohexane, 2,5-dimercaptothiophene, 2,5-dimercapto-1,3,4-thiadiazole, 2,4-dimercapto-s-triazolo-[4,3-b]-1,3-4-thiadiazole (C3H2N4S3), dithiocyanuric acid, bis(4-mercaptophenyl) sulfide, bis(4-mercaptophenyl) ether, 2-mercaptomethyl-1,4-dimercaptopropane, 2-(2-mercaptoethyl Thio)-1,3-dimercaptopropane, 1,2-bis(2-mercaptoethyl-thio)-3-mercaptopropane, ethylene glycol dithioglycolate, ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), 1,4-butanediol bis(2-mercaptoacetate), 1,4-butanediol bis(3-mercaptopropionate), 2,5-bis(mercaptomethyl)-1,4-dithiane, 2,5-bis(mercaptoethyl)-1,4-dithiane, 2,Examples include 2-bis(4-mercaptophenyl)propane, bis(4-mercaptomethylphenyl)sulfide, bis(4-mercaptomethylphenyl)ether, or 2,2-bis(4-mercaptomethylphenyl)propane.

[0123] Suitable examples of trithiol compounds include 1,3,5-trimercaptobenzene, 1,3,5-tris(mercaptomethyl)benzene, trimethylolpropane tri(3-mercaptopropionate), trimethylolpropane tris-(thioglycolate), 1,2,3-trimercaptopropane, trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), trithiocyanuric acid (TMT) = 1,3,5-triazine-2,4,6-trithiol; or 1,1,1-tris(mercaptomethyl)propane.

[0124] Examples of tetrathiol compounds include pentaerythritol tetrakis-(thioglycolate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 1,1,3,3-tetrakis(mercaptomethylthio)propane, or tetrakis(mercaptomethyl)methane.

[0125] Compound C of formula (II) is commercially available or can be obtained by methods known in the art. For example, vinyl mercaptoethanol is commercially available.

[0126] Generally, vinyl thioethers can be obtained by the Reppe process, which involves reacting a compound having a thiol group with acetylene in the presence of a basic catalyst, as described, for example, in U.S. Patent No. 2003 / 0,105,353 A1.

[0127] Vinyl thioethers can also be obtained by the conversion of mercaptoethanol using bromoethane in ethanol or tetrahydrofuran (THF) with sodium methoxide as a basic catalyst, as described, for example, by A. Gubu et al. in Chem. Eur. J., 2018, 24, pp. 5895-5900.

[0128] Vinyl thioethers can also be obtained by ring-opening of 1,4-octathian in dry THF using lithium diisopropylamine (LDA), as described, for example, by Y.-Y. Wang et al., J. Am. Chem. Soc. 2019, 141, 24, pp. 9739-9745.

[0129] This method is typically carried out in an organic solvent, under an inert atmosphere, and in the presence of a free radical generator, by increasing the temperature.

[0130] Compounds B and C of formula (II) are generally dissolved in an appropriate amount of organic solvent or water. The same solvent or different solvents may be used, but preferably the same solvent is used.

[0131] Examples of suitable organic solvents include aprotic solvents such as butanone, 2-pentanone, 2-heptanone, 3-heptanone, cyclohexanone, or ketones like methyl isobutyl ketone; aromatic solvents such as toluene or xylene; ethers such as tetrahydrofuran; esters such as ethyl acetate or butyl acetate; or amides such as dimethylformamide (DMF), dimethylacetamide, or N-methylpyrrolidone (NMP). Of these, ketones, ethers, and esters are preferred.

[0132] Further examples of suitable solvents may be protic solvents, preferably alcohols such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, or water.

[0133] The solvents may be used individually or in combination of two or more of them.

[0134] If at least one of the reactants is a liquid under the reaction conditions, the method may be carried out without a solvent, provided that the reaction mixture is converted into a suspension or homogeneous solution during the process.

[0135] This method is typically carried out in the presence of a free radical generator. Essentially, any type of free radical generator may be used to initiate the reaction. For example, free radical-generating chemical compounds, ultraviolet light, or irradiation may be used. The radical initiator is generally used as a solution in an organic solvent.

[0136] Any radical initiator may be used, for example, an azo compound or a peroxygen compound. An azo compound is preferred.

[0137] Suitable azo compounds include 2,2'-azobisisobutyronitrile (AIBN), 1,1'-azobis(cyclohexanecarbonitride), 2,2'-azobis(2-methylbutyronitrile), dimethylazodiisobutyrate, and 2-tert-butylazo-2-cyanopropane. Suitable peroxygen compounds include potassium peroxide, ammonium peroxide, benzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, lauryl peroxide, and cumene hydroperoxide.

[0138] The organic solvent may be the same as the one used for one of compounds B and C, and preferably is the same.

[0139] The radical initiator can be used in a catalytically effective amount, for example, 0.0008 to 0.005 equivalents per thiol functional group to be reacted, preferably 0.001 to 0.004 equivalents.

[0140] This method is typically carried out under an inert atmosphere, for example, under a nitrogen or argon atmosphere. If oxygen is present in the reaction mixture, the amount of radical initiator should be increased to obtain a suitable radical yield. For example, the catalytic effective amount of radical initiator should be increased up to 500% when 0.5–21% oxygen is present, up to 300% when 0.5–10% oxygen is present, and up to 100% when 0.5–5% oxygen is present.

[0141] Depending on the radical generator, the method is generally carried out at room temperature (20-23°C) or at a higher temperature, for example, 30-130°C, preferably 40-120°C, and / or by irradiation with UV light. The reaction time is usually 15 minutes to 40 hours, preferably 1 to 12 hours.

[0142] The reaction is preferably carried out under an inert atmosphere, with compound B supplied to a suitable solvent at room temperature. The solution / suspension may then be heated to a temperature of 40–130°C. Typically, compound B of formula (II), dissolved in the solvent, is slowly added at this temperature, preferably dropwise over a period of 30 minutes to 8 hours. Typically, the solution of the radical initiator is added slowly and simultaneously. Generally, the resulting mixture is stirred at increasing temperature for several hours.

[0143] After cooling to room temperature, the product can be separated by conventional methods, for example, by filtration or evaporation.

[0144] Therefore, in a preferred embodiment, the present invention relates to a method for preparing compound A, wherein the method is carried out at a temperature of 30 to 130°C and in the presence of a radical initiator.

[0145] The molar ratio of compound B, which has one -SH group, to compound C of formula (II) is usually, The ratio is 0.8:1.2 to 1.2:0.8, preferably 0.85:1.15 to 1.15:0.85, more preferably 0.9:1.1 to 1.1:0.9, and most preferably 0.95:1.05 to 1.05:0.95.

[0146] When reacting compound B having n -SH groups (wherein n is an integer of 2, 3, 4, 5, or 6), compound C of formula (II) is usually used in an amount of (0.85 ≤ n ≤ 1.15) equivalents, preferably (0.9 ≤ n ≤ 1.1), and more preferably (0.95 ≤ n ≤ 1.05), based on one equivalent of compound B.

[0147] For example, when reacting compound B having two -SH groups, compound C of formula (II) is used in an amount of 1.7 to 2.3 equivalents, preferably 1.8 to 2.2, and more preferably 1.9 to 2.1.

[0148] In a further embodiment, the present invention relates to the formula [ka] (In the formula, Y 1 C1~C 18 -alkyl;OH, C1~C4-alkoxy, C1~C4-alkylthio, halogen, NR 6 R 7 , C3~C 18 -Cycloalkyl, C6~C 18 - Aryl or C2~C 18 - Substituted with heteroaryls and / or -O-, -S-, -SO-, -SO2-, -COO-, -OCOO- or -CO-, C3~C 18 -Cycloalkylene, C6~C 18 - Arirene or C2~C 18 -C1~C is interrupted by heteroarrene 18 -alkyl; C3~C 18 -Cycloalkyl;OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen or NR 8 R 9C3~C which are replaced and / or interrupted by O or S 18 -Cycloalkyl; C6~C 18 -Aryl; C1~C 12 -alkyl, OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen or NR 10 R 11 C6~C which are replaced by 12 -Aryl; C2~C 18 - Heteroaryl; C1~C 12 -alkyl, OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen or NR 12 R 13 C2~C which are replaced by 18 - is heteroaryl; X is C2~C 12 -Alkylene; or C1-C4-alkoxy, C1-C4-alkylthio substituted and / or C2-C1-C4-interrupted with O or S 12 -It is alkylene; R 1 , R 2 and R 3 These are, independently of each other, hydrogen or C1-C4 alkyl; R 4 and R 5 These are, independently of each other and in each instance, hydrogen, C1~C 18 -Alkyl; C1-C substituted with halogen or interrupted with O or S 18 -alkyl; C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or C6-C substituted with halogen 18 - Aryl or C6~C 12 -Aryl; R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13These are C1-C4-alkyl;C6-C, which are substituted with C1-C4-alkyl;OH, C1-C4-alkoxy, C1-C4-alkylthio, or halogen, independently of each other and in each instance. 10 -aryl; or C6-C4 substituted with OH, C1-C4-alkoxy, C1-C4-alkylthio or halogen. 10 -Is it an allele? or R 6 and R 7 , R 8 and R 9 , R 10 and R 11 , or R 12 and R 13 These together are C4-C6 alkylenes; or O, S and / or NR 14 It is a C4-C6 alkylene that is interrupted by; R 14 It is a C1-C4 alkyl group; m is 1 to 12, preferably 1 to 10, more preferably 1 to 8 for each occurrence; Y 2 is an n-valent bonding group; n is an integer of 2, 3, 4, 5, or 6. However, R 4 and R 5 (Assuming that H cannot be the same for both) Regarding compound A.

[0149] In a further embodiment, the present invention is Y 1 However, C1~C 18 -alkyl;OH, C1~C4-alkoxy, C1~C4-alkylthio, halogen, NR 6 R 7 , C3~C 18 -Cycloalkyl, C6~C 18 - Aryl or C2~C 18 - Substituted with heteroaryls and / or -O-, -S-, -SO-, -SO2-, -COO-, -OCOO- or -CO-, C3~C 18 -Cycloalkylene, C6~C 18- Arirene or C2~C 18 -C1~C is interrupted by heteroarrene 18 -alkyl; C3~C 18 -Cycloalkyl;OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen or NR 8 R 9 C3~C which are replaced and / or interrupted by O or S 18 -Cycloalkyl; C6~C 18 -Aryl; C1~C 12 -alkyl, OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen or NR 10 R 11 C6~C which are replaced by 12 -Aryl; C2~C 18 - Heteroaryl; C1~C 12 -alkyl, OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen or NR 12 R 13 C2~C which are replaced by 18 - is heteroaryl; X is C2~C 12 -Alkylene; or C1-C4-alkoxy, C1-C4-alkylthio substituted and / or C2-C1-C4-interrupted with O or S 12 -It is alkylene; R 1 , R 2 and R 3 However, they are independently hydrogen or C1-C4 alkyl; R 4 and R 5 However, they appear independently of each other, and each time they appear, hydrogen, C1~C 18 -Alkyl; C1-C substituted with halogen or interrupted with O or S 18 -alkyl; C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or C6-C substituted with halogen 18 - Aryl or C6~C 12 -Aryl; R6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 However, each instance is independently and each instance is substituted with C1-C4-alkyl;OH, C1-C4-alkoxy, C1-C4-alkylthio, or halogen C1-C4-alkyl;C6-C 10 -aryl; or C6-C4 substituted with OH, C1-C4-alkoxy, C1-C4-alkylthio or halogen. 10 -Is it an allele? or R 6 and R 7 , R 8 and R 9 , R 10 and R 11 , or R 12 and R 13 Together, they are C4-C6 alkylenes; O, S and / or NR 14 It is a C4-C6 alkylene that is interrupted by; R 14 It is a C1-C4 alkyl group; For each occurrence, m is 1 to 12, preferably 1 to 10, more preferably 1 to 8. This concerns compound A of formula (III).

[0150] Preferably, compound A is Y 1 However, C1~C 12 -alkyl;OH, C1-C4-alkoxy, C1-C4-alkylthio, C5-C6-cycloalkyl, C6-C 12 - Aryl or C2~C 10 - Heteroaryl substituted and / or O, S, C6-C8-cycloalkylene, C6-C 12 - Arirene or C4~C 10 -C1~C is interrupted by heteroarrene 12 -alkyl; C5-C8 cycloalkyl; C5-C8 cycloalkyl substituted with OH, C1-C4 alkoxy, or C1-C4 alkylthio and / or interposed by O or S; C6~C 12 -aryl; C1-C6-alkyl, OH, C1-C4-alkoxy or C1-C4-alkylthio substituted C6-C 10 -Aryl; C2~C 10 - Heteroaryl; C2-C substituted with C1-C6-alkyl, OH, C1-C4-alkoxy or C1-C4-alkylthio 10 - is heteroaryl; R 1 and R 2 is hydrogen, R 3 is hydrogen or C1-C4 alkyl; X is a C2-C6 alkylene; or a C2-C6 alkylene interrupted by O or S; R 4 and R 5 However, each instance is independent of the others and each instance is substituted with hydrogen, C1-C4 alkyl; halogen, or interspersed with O or S, C1-C4 alkyl; C6-C 12 -aryl; or C6-C4 substituted with C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or halogen 12 -Aryl; m is between 1 and 10, specifically between 1 and 8, and more specifically between 2 and 6. However, R 4 and R 5 The condition is that H cannot exist at the same time. It is of formula (III) or (IV).

[0151] Preferably, compound A is Y 1 However, C1~C 12 -alkyl; C1~C4-alkoxy, C1~C4-alkylthio, C5~C6-cycloalkyl, C6~C 12 - Aryl or C2~C 10- Heteroaryl substituted and / or O, S, C6-C8-cycloalkylene, C6-C 12 - Arirene or C4~C 10 -C1~C interrupted by heteroalile 12 -alkyl; C5-C8 cycloalkyl; C5-C8 cycloalkyl substituted with OH, C1-C4 alkoxy, or C1-C4 alkylthio and / or interposed by O or S; C6~C 12 -aryl; C1-C6-alkyl, OH, C1-C4-alkoxy or C1-C4-alkylthio substituted C6-C 10 -Aryl; C2~C 10 - Heteroaryl; C2-C substituted with C1-C6-alkyl, OH, C1-C4-alkoxy or C1-C4-alkylthio 10 - is heteroaryl; R 1 and R 2 is hydrogen, R 3 is hydrogen or C1-C4 alkyl; X is a C2-C6 alkylene; or a C2-C6 alkylene interrupted by O or S; R 4 and R 5 However, each instance is independent of the others and each instance is substituted with hydrogen, C1-C4 alkyl; halogen, or interspersed with O or S, C1-C4 alkyl; C6-C 12 -aryl; or C6-C4 substituted with C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or halogen. 12 -Aryl; m is between 1 and 10. It is of formula (III).

[0152] More preferably, compound A is Y 1 However, C1~C which are substituted with OH and interrupted with O or S, especially those interrupted with S 12 -It is alkyl; R 1 and R 2 is hydrogen, R 3 is hydrogen or C1-C4 alkyl; X is a C2-C6 alkylene; or a C2-C6 alkylene interrupted by O or S; R 4 is hydrogen, R 5 However, each occurrence is hydrogen, a C1-C4 alkyl substituted with a halogen or interspersed with O or S, or a phenyl; m is between 1 and 10, specifically between 1 and 8, and more specifically between 2 and 6. However, R 4 and R 5 The condition is that H cannot exist at the same time. It is of formula (III) or (IV).

[0153] What is particularly preferable is, Y 1 However, C1~C which are substituted with OH and interrupted with O or S, especially those interrupted with S 12 -It is alkyl; R 1 and R 2 is hydrogen, R 3 is hydrogen or C1-C4 alkyl; X is a C2-C6 alkylene; or a C2-C6 alkylene interrupted by O or S; R 4 is hydrogen, R 5 However, each occurrence is the same, and is either hydrogen or a C1-C4 alkyl group; m is between 1 and 8, specifically 1 to 6, and more specifically 2 to 6. However, R 4 and R 5 The condition is that H cannot exist at the same time. It is compound A of formula (III) or (IV).

[0154] In a further embodiment, the present invention is R 1 and R 2is hydrogen, R 3 is hydrogen or C1-C4 alkyl; X is a C2-C6 alkylene; or a C2-C6 alkylene interrupted by O or S; R 4 is hydrogen, R 5 However, each occurrence is hydrogen, a C1-C4 alkyl substituted with a halogen or interspersed with O or S, or a phenyl; Y 2 is an n-valent bonding group; m is between 2 and 6, n is an integer of 2, 3, 4, 5, or 6. This concerns compound A of formula (IV).

[0155] Compound B1 of formula (VIII) or compound B2 of formula (IX), wherein m is 1 to 10, preferably 1 to 8, more preferably 2 to 6, and n is 2 to 6, preferably 2, 3, or 4, can be prepared according to the method described in PCT / EP2020 / 061400, [ka] (In the formula, R 4 and R 5 (as previously provided in any manner herein) It can be obtained from cyclic monothiocarbonate compounds.

[0156] therefore, a) Formula Y 1 -SH (V) The thiol of formula [ka] Reacting with the cyclic monothiocarbonate, formula [ka] The step of forming compound B1, b) The step of reacting compound B1 in a manner previously defined in any embodiment herein. Includes, However, R 4 and R 5 A method that is conditional on the fact that H cannot be the same as H. Compound A of formula (III), which can be obtained by the above method, is preferred, in which m is 1 to 10, preferably 1 to 8.

[0157] Compound B2 of formula (IX) is formula (Y 2 ) n -SH (VI) The thiol can be prepared by reacting it with the cyclic monothiocarbonate of formula (VII).

[0158] therefore, a) Formula (Y 2 ) n -SH (VI) The thiol reacts with the thiol, formula [ka] The step of forming compound B2, b) The step of reacting compound B2 by a method previously defined in any embodiment herein. Includes, However, R 4 and R 5 A method that is conditional on the fact that H cannot be the same as H. Compound A of formula (IV), which can be obtained by the above method, is preferred, in which m is 1 to 10, preferably 1 to 8.

[0159] What is preferable is, a) Formula Y 1 -SH (V), or (Y 2 ) n -SH (VI) The thiol of formula [ka] The step of reacting with a cyclic monothiocarbonate to form compound B, b) The step of reacting compound B by a method specified in any embodiment herein. Includes, However, R 4 and R 5 A method that is conditional on the fact that H cannot be the same as H. Compound A of formula (III) or (IV) can be obtained by [method].

[0160] Therefore, in one preferred embodiment, the present invention is a) Formula Y 1 -SH (V), or (Y 2 ) n -SH (VI) The thiol of formula [ka] Reacting with the cyclic monothiocarbonate, formula [ka] Compound B1, or formula [ka] The step of forming compound B2, b) The step of reacting compound B1 or B2 by a method specified in any embodiment herein, Includes, However, R 4 and R 5 A method that is conditional on the fact that H cannot be the same as H. This relates to compound A of formula (III) or (IV), which can be obtained by the following method.

[0161] Cyclic monothiocarbonates are typically added in amounts of approximately (n × m) equivalents, based on one equivalent of the thiol of formula (VI).

[0162] The reaction can be carried out in the presence of a basic catalyst. Suitable catalysts include compounds having a tertiary amino group, a guanidino group, an amidine group, or a phosphone group, or basic metal salts such as metal hydroxides, metal alkoxides from titanium or tin, such as tetraalkylates or dialkyltin alkanoates, or metal sulfides.

[0163] Cyclic monothiocarbonates are typically added in an amount of approximately m equivalents to one equivalent of the thiol of formula (V).

[0164] Suitable cyclic monothiocarbonate compounds are: R 4 and R 5 However, hydrogen, C1~C4-alkyl, CH2Cl, CH2O-nC4H9, CH2O-C 12 / C 14 Alternatively, phenyl, preferably hydrogen or C1-C4 alkyl, most preferably hydrogen or methyl, It is a compound of formula (VI). Substituent "C 12 / C 14 " is C 12 / C 14 This refers to substituents derived from fatty alcohols.

[0165] Preferred cyclic monothiocarbonates are R 4 and R 5 One of them is H, and the others are hydrogen, C1~C4-alkyl, CH2Cl, CH2O-nC4H9, CH2O-C 12 / C 14 It is a compound that is either phenyl or phenyl.

[0166] Comfortable, R 5 This is hydrogen or a C1-C4 alkyl group, most preferably hydrogen or methyl.

[0167] Cyclic monothiocarbonates can be prepared according to the methods described in U.S. Patent No. 3,072,676, U.S. Patent No. 3,201,416, or WO2019 / 034469 A1.

[0168] In a further embodiment, the present invention can be obtained by a method specified in any embodiment herein, formula (IV) [ka] (In the formula, X is C2~C 12 -Alkylene; or C1-C4-alkoxy, C1-C4-alkylthio substituted and / or C2-C1-C4-interrupted with O or S 12 -It is alkylene; R 1 , R 2 and R 3 These are, independently of each other, hydrogen or C1-C4 alkyl; R 4 and R 5 These are, independently of each other and in each instance, hydrogen, C1~C 18 -Alkyl; C1-C substituted with halogen or interrupted with O or S 18 -alkyl; C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or C6-C substituted with halogen 18 - Aryl or C6~C 12 -Aryl; m is between 0 and 12 for each occurrence; Y 2 is a trivalent bond group selected from benzenetriyl, triazinetriyl, or methylidene, or a trivalent bond group composed of benzenetriyl, methylidene, or nitrogen and a divalent group; or Y 2 This is a tetravalent bonding group derived from methane or benzene, or a tetravalent bonding group composed of a component derived from methane or benzene and a divalent group. Each of the divalent groups, C1~C 12 -Selected from alkylene and optionally at least one group selected from -O-, -S- or -COO-; or Y 2 is a divalent bonding group, and the said divalent bonding group is C1~C18 -Alkylene, -CH2-O-CH2-, -CH2-S-CH2-, -(CH2CH2O) p -CH2CH2-, -(CH2CH2S) p -CH2CH2-(where p is an integer between 2 and 10), -(C3H7O) q -C3H7-, -(C3H7S) q -C3H7- (where q is an integer from 1 to 10), o-phenylene, m-phenylene, p-phenylene, 4,4'-isopropylidene-diphenylene, [ka] (Includes at least one base selected from TIFF0007848180000034.tif60164) Compound A of, or Y 2 is an n-valent bonding group, However, R 4 and R 5 The condition is that H cannot exist at the same time. m is between 1 and 12 for each occurrence, and n is 2, 3, or 4. The compound of formula (IV), Regarding its use as a chain extender or crosslinking agent.

[0169] Furthermore, the present invention is R 1 and R 2 is hydrogen, R 3 is hydrogen or C1-C4 alkyl; X is a C2-C6 alkylene; or a C2-C6 alkylene interrupted by O or S; R 4 is hydrogen, R 5 However, each occurrence is hydrogen, a C1-C4 alkyl substituted with a halogen or interspersed with O or S, or a phenyl; Y 2 is an n-valent bonding group; m is between 2 and 6, n is an integer of 2, 3, 4, 5, or 6. Compound A of formula (IV), Regarding its use as a chain extender or crosslinking agent.

[0170] Compound A of formula (IV) with n=2 is typically used as a chain extender, and compound A of formula (IV) with n=3, 4, 5, or 6, preferably n=3 or 4, is typically used as a crosslinking agent.

[0171] The method of the present invention enables readily available synthetic routes to mono-, di-, and polyhydroxy-containing polythioethers starting from thiol-containing compounds. The introduction of additional thioether groups in these compounds allows for greater stability of such compounds because the -SH functional group starting compound is converted to an -S functional group, while the chain ends of the resulting compound exhibit OH groups, which allow for greater stability against oxidation.

[0172] Furthermore, this method provides access to hydroxy-containing polythioethers, which will be used as structural blocks in the preparation of a variety of polymers, particularly as chain extenders or crosslinking agents. These structural blocks are suitably used in the preparation of a variety of polymers having improved properties such as increased chemical stability and / or an elevated refractive index.

[0173] This hydroxyl-containing polythioether exhibits improved storage stability, for example, in the presence of air, enabling easy and safe handling.

[0174] Furthermore, the hydroxyl-containing polythioether exhibits reduced odor compared to the starting compound and enables more environmentally friendly implementation conditions.

[0175] The definitions and priorities given in this specification to the methods previously mentioned apply in any combination and in any combination of other aspects of the present invention.

[0176] The present invention will now be described in more detail with reference to the following embodiments. These embodiments should not be construed as limiting. Unless otherwise stated, "%" always refers to weight percent (wt%). [Examples]

[0177] [Example 1] Synthesis of 3,6-Dithiaoctane-1,8-diol

[0178] [ka] A solution of 2-mercaptoethanol (46.8 g; 0.6 mol) and methyl isobutyl ketone (90 g) was supplied to a 500 ml reactor at room temperature (approximately 20-25°C) and degassed with dry nitrogen for no more than 15 minutes. The solution was heated to 80°C and then stirred. Solution 1, consisting of vinyl mercaptoethanol (62.55 g; 0.6 mol) and methyl isobutyl ketone (90 g), and Solution 2, consisting of Wako V59 ((2,2'-azobis(isobutyronitrile), AIBN, Wako Specialty Chemicals) (117 mg, 0.71 mmol, 0.0012 equivalents) and methyl isobutyl ketone (75 g), were added dropwise simultaneously. Solution 1 was added within 2 hours, and Solution 2 was added within 4 hours. The resulting mixture was then stirred at 90°C for 8 hours. After cooling to room temperature, the product was obtained by precipitation. The product of formula (X) was removed by filtration, and the mixture was recrystallized in toluene to obtain a white powder (87% yield, melting point 65°C).

[0179] [Example 2] Synthesis of 3,6,9-Tritiaundecane-1,11-diol 2a) Synthesis of 3-thia-5-mercapto-1-pentanol Vinyl mercaptoethanol (30 g, 288 mmol, 1 equivalent) was placed in a round-bottom flask and diluted with MeOH (100 mL). Thioacetic acid (22 g, 288 mmol, 1 equivalent) was added to this solution. A reflux condenser was placed in the flask, and the mixture was stirred at 60°C for 4 hours. After adding 30 mL of aqueous HCl (10%), the mixture was stirred until the reaction was complete. Chloroform and water were added to the reaction mixture. The pH of the aqueous phase was adjusted to pH=7 using potassium carbonate. The chloroform phase was separated, and extraction was repeated twice with chloroform. The combined chloroform phase was dehydrated with calcium chloride. After evaporation of chloroform in vacuum, a colorless oil was produced, which was further subjected to an oil pump vacuum at room temperature to remove trace amounts of solvent and impurities. Yield 17.5 g (44%).

[0180] 2b) Synthesis of 3,6,9-trithiaundecane-1,11-diol

[0181] [ka] In a Schlenk tube, 1.5 g of Example 2a (10.85 mmol, 1 equivalent) was diluted with 20 mL of isobutyl methyl ketone, and the mixture was degassed by bubbling nitrogen through it. Subsequently, vinyl mercaptoethanol (1.25 g, 11.93 mmol, 1.1 equivalents) was added under a nitrogen atmosphere. To initiate the reaction, 5 mg of AIBN (0.03 mmol, 0.003 equivalents) was added to the mixture. The Schlenk tube was sealed with a rubber stopper, heated to 70°C, and the mixture was vigorously stirred. After 10 minutes, the product precipitated as a colorless solid. The solid was removed by filtration and recrystallized in toluene (83% yield, melting point 96°C). NMR 1 H (400 MHz, d6-DMSO): δ [ppm] 2.60 (4H, t, C H 2CH2OH), 2.72 (8H, d, SC H 2C H 2S), 3.52 (4H, dd, C H 2OH), 4.75 (2H, t, H OCH2)

[0182] [Example 3] Synthesis of 3,6,9,12-tetrathiatetradecane-1,14-diol

[0183] [ka] A solution of ethanedithiol (40 g; 0.425 mol) in methyl isobutyl ketone (90 g) was supplied to a 1000 ml reactor at room temperature and degassed with dry nitrogen for no more than 15 minutes. The solution was heated to 80°C and then stirred, and solution 1 of vinyl mercaptoethanol (88.54 g; 0.84 mol) and methyl isobutyl ketone (120 g) and solution 2 of Wako V59 (160 mg, 0.974 mmol) and methyl isobutyl ketone (90 g) were added dropwise simultaneously. Solution 1 was added within 2 hours, and solution 2 was added within 4 hours. The resulting mixture was then stirred at 90°C for 8 hours. After cooling to room temperature, the product was obtained by precipitation. The product was filtered off, and recrystallized in toluene to obtain a white powder (94% yield, melting point 114°C). NMR 1 H (400 MHz, d6-DMSO): δ [ppm] 2.61 (4H, t, C H 2CH2OH), 2.75 (12H, d, SC H 2C H 2S), 3.55 (4H, dd, C H 2OH), 4.79 (2H, t, H OCH2) NMR 13 C (100 MHz, d6-DMSO): δ [ppm] 31.9 ( C H2S C H2 C H2S C H2), 32.3 (HOCH2 C H2), 34.4 (HOCH2CH2S C H2), 61.5 (HO C H2)

[0184] [Example 4]

[0185] [ka] In a Schlenk tube, 2 g of benzene-1,3-dithiol (14 mmol) was diluted with 10 mL of isobutyl methyl ketone, and the mixture was degassed by bubbling nitrogen through it. Vinyl mercaptoethanol (3 g, 28 mmol) was added to the mixture under a nitrogen atmosphere. 23 mg of AIBN (0.14 mmol, 0.01 equivalent) dissolved in isobutyl methyl ketone was added to the mixture. The tube was sealed with a rubber stopper and heated to 80°C, during which the mixture was vigorously stirred. After 1 hour, the reaction was complete, and it was 1 This was confirmed by 1H NMR. The solvent was evaporated to obtain 4.6 g of a yellowish oil (93% crude yield). 1.5 g of the crude product was purified by column chromatography (silica, 80:20 (volume / volume) mixture using ethyl acetate and petroleum ether). After evaporation of the solvent, 2.2 g of a waxy, colorless solid was formed (72% yield). Refractive index (determined by Abbe refractometer at 23°C): 1.6401 Melting point: 42℃ NMR 1 H (300 MHz, CDCl3): δ [ppm] 7.33 - 6.99 (m, 4H), 3.65 (q, J = 5.8 Hz, 4H), 3.20 - 2.89 (m, 4H), 2.82 - 2.50 (m, 8H), 2.42 - 2.18 (t, 2H).

[0186] [Example 5]

[0187] [ka] In a Schlenk tube, 1 g of 4,4'-dimercaptodiphenyl sulfide (4 mmol) was diluted with 10 mL of isobutyl methyl ketone, and the mixture was degassed by bubbling nitrogen through it. 0.85 g of vinyl mercaptoethanol (8 mmol) was added to the mixture under a nitrogen atmosphere. 15 mg of AIBN (0.009 mmol, 0.023 equivalents) dissolved in isobutyl methyl ketone was added to the mixture. The tube was sealed with a rubber stopper and heated to 80°C, during which the mixture was vigorously stirred. After stirring at 80°C for 16 hours, the reaction mixture was cooled to 23°C, and the product precipitated as a colorless crystalline solid. This was removed by filtration and dried in vacuum at 50°C (yield: 83%; melting point 130°C). NMR 1 H (300 MHz, d6-DMSO): δ [ppm] 7.41 - 7.16 (m, 8H), 4.79 (t, J = 5.4 Hz, 2H), 3.64 - 3.42 (q, 4H), 3.25 - 3.09 (m, 4H), 2.83 - 2.68 (m, 4H), 2.62 (t, J = 6.7 Hz, 4H).

[0188] [Example 6] Compound 6a) of formula (XVa) was prepared in a manner similar to that described in EP0378895 A1 and KR20110021371 A.

[0189] [ka] 2-mercaptoethanol (30 g; 384.5 mmol) was added dropwise to a NaOH solution (7.7 g) in 50 ml of water at room temperature over 15 minutes with stirring. Epichlorohydrin (17.8 g; 192.2 mmol) was then added dropwise over 3 hours. HCl (37%, 80 g) and thiourea (54.2 g; 712 mmol) were added, and the resulting mixture was heated to 105°C and stirred for 8 hours. After cooling to 50°C, toluene (90 ml) and aqueous ammonia (25%, 60 g) were added and stirred. The toluene phase was separated, washed with water, and dehydrated with calcium chloride. The solvent was removed by evaporation under vacuum to obtain a clear oil, which was used in step 5b) without further purification. Yield 93%.

[0190] 6b) A solution (50 g; 0.192 mol) of the product from Example 6a) in methyl isobutyl ketone (60 g) was supplied to a 1000 ml reactor at room temperature and degassed with dry nitrogen for no more than 15 minutes. The solution was heated to 80°C and then stirred, and solution 1 of vinyl mercaptoethanol (60 g; 0.577 mol) and methyl isobutyl ketone (90 g) and solution 2 of Wako V59 (100 mg) and methyl isobutyl ketone (60 g) were added dropwise simultaneously. Solution 1 was added within 2 hours, and solution 2 was added within 4 hours. The resulting mixture was then stirred at 80°C for 8 hours, and the solvent was removed by evaporation under vacuum to obtain the product of formula (XVb) as an oil that solidifies into a waxy solid at room temperature. Yield 90%; melting point 47°C. 1 H-NMR (400 MHz, CDCl3): δ [ppm] 2.66-2.92 (31H), 3.68 (6H, t, C H 2OH).

[0191] [ka]

[0192] [Example 7] 7a) Synthesis of oligomacyoalcohols

[0193] [ka] Mercaptoethanol (15 g; 192 mmol) and propylene thiocarbonate (113 g; 960 mmol, 5 equivalents) of formula (XVI) were mixed with stirring and heated to 60°C. Diazabicyclo-undecane (DBU) (1.5 g; 9.65 mmol) was added and the mixture was stirred at 60°C for 8 hours. After cooling to room temperature, the resulting clear oil was used in step 4b) without further purification.

[0194] 7b) Synthesis of oligothioetherdiols

[0195] [ka] The product of Example 7a) (85 g; 0.188 mol) in methyl isobutyl ketone (90 g) was supplied to a 1000 ml reactor at room temperature and degassed with dry nitrogen for 15 minutes. The solution was heated to 80°C and then stirred, and solution 1 of vinyl mercaptoethanol (19.8 g; 0.188 mol) and methyl isobutyl ketone (60 g) and solution 2 of Wako V59 (28 mg) and methyl isobutyl ketone (60 g) were added dropwise simultaneously. Solution 1 was added within 2 hours, and solution 2 was added within 4 hours. The resulting mixture was then stirred at 80°C for 8 hours, and the solvent was removed by evaporation under vacuum to obtain the product as a brownish oil. Refractive index R I Measured at 24.5℃: 1.5550 Molecular weight (SEC, THF as mobile phase, polystyrene standard): Mw=3430Da; Mn=2720, Pd=1.26 The present invention encompasses the following embodiments. (Embodiment 1) n-piece set [ka] (In the formula, X is C 2 ~C 12 -Alkilen; or C 1 ~C 4 -alkoxy, C 1 ~C 4 -C which is substituted with alkylthio and / or interposed with O or S 2 ~C 12 -It is alkylene; R 1 、R 2 and R 3 These are, independently of each other, hydrogen or C 1 ~C 4 -It is alkyl; n is an integer, either 1, 2, 3, 4, 5, or 6. A method for preparing compound A having the group, Compound B having n -SH groups is subjected to the formula in the presence of a free radical generator.

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Claims

1. n-piece set 【Chemistry 1】 (In the formula, X is C 2 ~C 12 -Alkilen; or C 1 ~C 4 -alkoxy, C 1 ~C 4 -C which is substituted with alkylthio and / or interposed with O or S 2 ~C 12 -It is alkylene; R 1 、R 2 and R 3 are, independently of one another, hydrogen or C 1 to C 4 -alkyl; n is an integer, either 1, 2, 3, 4, 5, or 6. A method for preparing compound A having the group, Compound B having n -SH groups is subjected to the formula in the presence of a free radical generator. 【Chemistry 2】 A method comprising the step of reacting compound C with the compound.

2. R 1 and R 2 That is hydrogen, R 3 is hydrogen or C 1 ~C 4 -It is alkyl; X, C 2 ~C 6 -Alkilen; or C interrupted by O or S 2 ~C 6 -The method according to claim 1, wherein the material is alkylene.

3. The method according to claim 1 or 2, carried out at a temperature of 30 to 130°C in the presence of a radical initiator.

4. Compound A having n groups of formula (I) 【Transformation 3】 【change】 (In the formula, Y 1 C 1 ~C 18 -alkyl;OH, C 1 ~C 4 -alkoxy, C 1 ~C 4 -alkylthio, halogen, NR 6 R 7 , C 3 ~C 18 -Cycloalkyl, C 6 ~C 18 -aryl or C 2 ~C 18 - Substituted with heteroaryl and / or O, S, -SO-, -SO 2 -COO-, -OCOO-, -CO-, C 3 ~C 18 -Cycloalkylene, C 6 ~C 18 -Arirene or C 2 ~C 18 -C is interrupted by heteroarrene 1 ~C 18 -alkyl; C 3 ~C 18 -Cycloalkyl;OH, C 1 ~C 4 -alkoxy, C 1 ~C 4 -alkylthio, halogen or NR 8 R 9 C is replaced and / or interrupted by O or S 3 ~C 18 -Cycloalkyl; C 6 ~C 18 -Aryl;C 1 ~C 12 -alkyl, OH, C 1 ~C 4 -alkoxy, C 1 ~C 4 -alkylthio, halogen or NR 10 R 11 C is replaced by 6 ~C 12 -Aryl; C 2 ~C 18 -heteroaryl;C 1 ~C 12 -alkyl, OH, C 1 ~C 4 -alkoxy, C 1 ~C 4 -alkylthio, halogen or NR 12 R 13 C is replaced by 2 ~C 18 - is heteroaryl; R 4 and R 5 are, independently of each other and for each occurrence, hydrogen, C 1 to C 18 -alkyl; C 1 to C 18 -alkyl substituted with halogen or interrupted by O or S; C 1 to C 4 -alkyl, C 1 to C 4 -alkoxy, C 1 to C 4 -alkylthio or C 6 to C 18 -aryl substituted with halogen or C 6 to C 12 -aryl; R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 and R 13 are, independently of each other and for each occurrence, C 1 ~C 4 -alkyl; OH, C 1 ~C 4 -alkoxy, C 1 ~C 4 -alkylthio or halogen-substituted C 1 ~C 4 -alkyl; C 6 ~C 10 -aryl; or OH, C 1 ~C 4 -alkoxy, C 1 ~C 4 -alkylthio or halogen-substituted C 6 ~C 10 -aryl; or or R 6 and R 7 , R 8 and R 9 , R 10 and R 11 , or R 12 and R 13 Together, C 4 ~C 6 -Alkylene; or O, S and / or NR 14 C is interrupted by 4 ~C 6 -It is alkylene; R 14 is C 1 ~C 4 -It is alkyl; m is between 0 and 12 for each occurrence; Y 2 is an n'-valent bonding group; n' is an integer of 2, 3, 4, 5, or 6. The method according to any one of claims 1 to 3, wherein the compound is [the compound].

5. R 4 and R 5 However, independently of each other and in each instance, hydrogen and C 1 ~C 4 -alkyl; C substituted with halogen or interrupted with O or S 1 ~C 4 -alkyl;C 6 ~C 12 -aryl; or C 1 ~C 4 -alkyl, C 1 ~C 4 -alkoxy, C 1 ~C 4 -C substituted with alkylthio or halogen 6 ~C 12 -Aryl; m is between 1 and 10. The method according to claim 4.

6. Y 1 However, C 1 ~C 12 -alkyl;OH, C 1 ~C 4 -alkoxy, C 1 ~C 4 -Alkylthio, C 5 ~C 6 -Cycloalkyl, C 6 ~C 12 -aryl or C 2 ~C 10 - Substituted with heteroaryl and / or O, S, -SO-, -SO 2 -COO-, -OCOO-, -CO-, C 6 ~C 8 -Cycloalkylene, C 6 ~C 12 -Arirene or C 4 ~C 10 -C is interrupted by heteroarrene 1 ~C 12 -alkyl; C 5 ~C 8 -Cycloalkyl;OH, C 1 ~C 4 -alkoxy, C 1 ~C 4 -C which is substituted with alkylthio and / or interposed by O or S 5 ~C 8 -Cycloalkyl; C 6 ~C 12 -Aryl;C 1 ~C 6 -alkyl, OH, C 1 ~C 4 -alkoxy or C 1 ~C 4 -C substituted with alkylthio 6 ~C 10 -Aryl; C 2 ~C 10 -heteroaryl;C 1 ~C 6 -alkyl, OH, C 1 ~C 4 -alkoxy or C 1 ~C 4 -C substituted with alkylthio 2 ~C 10 - is heteroaryl; m is 0, The method according to claim 4.

7. Y 1 However, C is substituted with OH and may be interrupted with O or S. 2 ~C 12 -It is alkyl; R 4 is hydrogen, R 5 However, with each appearance, hydrogen, C 1 ~C 4 -alkyl; C substituted with halogen or interrupted with O or S 1 ~C 4 -alkyl; or phenyl; m is between 1 and 10. The method according to claim 4 or 5.

8. Y 2 However, it is an n'-valent bond group comprising an aliphatic unit, an alicyclic unit, an aromatic unit and / or a heteroaromatic unit, and optionally a functional group containing a heteroatom; n' is an integer of 2, 3, 4, or 6, or is an integer of 2, 3, or 4. The method according to claim 4 or 5.

9. Y 2 is a divalent bonding group, and the divalent bonding group is C 1 ~C 18 -Alkilen;C 1 ~C 4 -alkoxy, C 1 ~C 4 -alkylthio, halogen, NR 15 R 16 , C 5 ~C 12 -Cycloalkyl, C 6 ~C 12 -aryl or C 2 -C 12 - Heteroaryl-substituted C 1 ~C 18 -Alkilen; C 5 ~C 12 -Cycloalkylene; C 1 ~C 4 -alkoxy, C 1 ~C 4 -alkylthio, halogen or NR 17 R 18 C is replaced and / or interrupted by O or S 5 ~C 12 -Cycloalkylene; C 6 ~C 12 -Ariren;C 1 ~C 12 -alkyl, C 1 ~C 4 -alkoxy, C 1 ~C 4 -alkylthio, halogen or NR 19 R 20 C is replaced by 6 ~C 12 -Ariren;C 2 ~C 12 -heterarylene;C 1 ~C 12 -alkyl, C 1 ~C 4 -alkoxy, C 1 ~C 4 -alkylthio, halogen or NR 21 R 22 C is replaced by 2 ~C 12 -At least one group selected from heteroarylenes, and optionally -O-, -S-, -SO-, -SO 2 It comprises at least one heterofunctional group selected from -COO-, -OCOO-, or -CO-; R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 and R 22 However, independently of each other and in each instance, C 1 ~C 4 -alkyl;OH, C 1 ~C 4 -alkoxy, C 1 ~C 4 -C substituted with alkylthio or halogen 1 ~C 4 -alkyl;C 6 ~C 10 -aryl; or OH, C 1 ~C 4 -alkoxy, C 1 ~C 4 -C substituted with alkylthio or halogen 6 ~C 10 -Aryl; n' is 2. The method according to any one of claims 4, 5, or 8.

10. Y 2 is a divalent bonding group, and the divalent bonding group is C 1 ~C 12 -Alkilen;C 5 ~C 8 -Cycloalkylene; C is interrupted by O or S 5 ~C 8 -Cycloalkylene; C 6 ~C 12 -Ariren;C 1 ~C 4 -C substituted with alkyl 6 ~C 12 -Ariren;C 2 ~C 12 -heterarylene; or C 1 ~C 4 -C substituted with alkyl 2 ~C 12 - comprising at least one group selected from heteroarylenes and optionally at least one group selected from -O- or -S-, The method according to any one of claims 4, 5, 8, or 9.

11. Y 2 However, it is a trivalent bond group selected from benzenetriyl, triazinetriyl, or methylidene, or a trivalent bond group composed of benzenetriyl, methylidene, or nitrogen and a divalent group, or Y 2 However, it is either a tetravalent bond group derived from methane or benzene, or a tetravalent bond group composed of a component derived from methane or benzene and a divalent group, or Y 2 However, the formula 【Chemistry 4】 In some cases, it is a hexavalent group with a divalent group. Each time the aforementioned divalent group appears, C 1 ~C 12 -Selected from alkylene and optionally at least one group selected from -O-, -S-, or -COO-, The method according to claim 4, 5, or 8.

12. Y 2 is a divalent bonding group, and the divalent bonding group is C 1 ~C 18 -alkylene, -CH 2 -O-CH 2 -, -CH 2 -S-CH 2 -,-(CH 2 CH 2 O) p -CH 2 CH 2 -,-(CH 2 CH 2 S) p -CH 2 CH 2 -(where p is an integer between 2 and 10), -(C 3 H 7 O) q -C 3 H 7 -,-(C 3 H 7 S) q -C 3 H 7 -(wherein q is an integer from 1 to 10), o-phenylene, m-phenylene, p-phenylene, 4,4'-isopropylidene-diphenylene, 【Transformation 5】 Includes at least one base selected from, The method according to any one of claims 4, 5, 8, 9, or 10.

13. formula 【Transformation 6】 【change】 (In the formula, Y 1 C 1 ~C 12-alkyl;OH, C 1 ~C 4 -alkoxy, C 1 ~C 4 -Alkylthio, C5-C6-cycloalkyl, C 6 ~C12-aryl or C 2 Substituted with ~C10-heteroaryl and / or O-, -S-, C6-C8-cycloalkylene, C 6 C is interrupted by ~C12-arylene or C4~C10-heteroarylene 1 ~C12-alkyl; C5-C8-cycloalkyl;OH, C 1 ~C 4 -alkoxy or C 1 ~C 4 -C5-C8 cycloalkyls substituted with alkylthio and / or interposed by O or S; C 6 ~C 12-aryl;C 1 ~C6-alkyl, OH, C 1 ~C 4 -alkoxy or C 1 ~C 4 -C substituted with alkylthio 6 ~C 10-aryl; C 2 ~C 10-heteroaryl; C 1 ~C6-alkyl, OH, C 1 ~C 4 -alkoxy or C 1 ~C 4 -C substituted with alkylthio 2 It is a ~C 10-heteroaryl; X is C 2 ~C 6-alkylene; or C interrupted by O or S 2 ~C6-alkylene; and R 1 and R 2 is hydrogen, and R 3 is hydrogen or C 1 ~C 4 -It is alkyl; R 4 and R 5 These are, independently of each other and in each instance, hydrogen and C 1 ~C 4-alkyl; C substituted with halogen or interposed with O or S 1 ~C4-alkyl; C6-~C12-aryl or C 1 ~C 4 -alkyl, C 1 ~C 4 -alkoxy, C 1 ~C 4 -C substituted with alkylthio or halogen 6 ~C 12 -Aryl; and m is between 2 and 6; Y 2 is an n'-valent bonding group; n' is an integer of 2, 3, 4, 5, or 6. However, R 4 and R 5 (Assuming that H cannot be the same for both) Compound A.

14. Formula (IV) 【Transformation 7】 Compound A, R 1 and R 2 is hydrogen, R 3 is hydrogen or C 1 ~C 4 -It is alkyl; X, C 2 ~C 6 -Alkilen; or C interrupted by O or S 2 ~C 6 -It is alkylene; R 4 is hydrogen, R 5 However, with each appearance, hydrogen, C 1 ~C 4 -alkyl; C substituted with halogen or interrupted with O or S 1 ~C 4 -alkyl; or phenyl; Y 2 is an n'-valent bonding group; m is between 2 and 6. n' is an integer of 2, 3, 4, 5, or 6. Compound A.

15. Use of a compound of formula (IV) that can be obtained by the method described in any one of claims 11 or 12, or a compound of formula (IV) described in claim 13 or 14, as a chain extender or crosslinking agent.

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