Method for producing thioether
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- FIRMENICH SA
- Filing Date
- 2026-02-27
- Publication Date
- 2026-06-09
Smart Images
Figure 2026094302000001 
Figure 2026094302000002 
Figure 2026094302000003
Abstract
Claims
1. Formula R-SH [wherein R represents a linear or branched alkyl group having 8 to 15 carbon atoms, and the group is a carboxylic acid or C that is not directly bonded to a sulfur atom] １ ~C ８ A method for measuring the amount of thiols or thioether compounds having fewer than 6 carbon atoms in a thiol [which may contain a carboxylic acid ester functional group] by gas chromatography-mass spectrometry (GC-MS) combined with solid-phase microextraction (SPME), wherein the SPME is performed with the sample cooled to a temperature of -100°C to -50°C.
2. The method according to claim 1, wherein the thiol or thioether compound having fewer than six carbon atoms is selected from the group consisting of 1-propantheol, 2-propantheol, 2-methyl-1-propantheol, 2-methyl-2-propantheol, 1-butanethiol, and tetrahydrothiophene.
3. The method according to claim 1 or 2, wherein the MS of the GC / MS is a triple quadrupole, quadrupole time of flight (Q-TOF), or quadrupole orbit trap type.
4. The method according to any one of claims 1 to 3, wherein the GC-MS data acquisition mode is selected ion monitoring (SIM) or selected reaction monitoring (SRM).
5. formula 【Chemistry 1】 [In the formula, The dashed line indicates the position of the bond between P and the sulfur atom; P represents a group capable of producing aromatic α,β-unsaturated ketones, aldehydes, or carboxylic acid esters, and the formula 【Chemistry 2】 [During the ceremony, The wavy line indicates the location of the connection between P and S; R １ represents a hydrogen atom, C １ to C ６ alkoxyl group, or a linear, cyclic or branched alkyl, alkenyl or alkadienyl group of C １ to C １５ , and the group may be substituted with 1 to 4 C １ to C ４ alkyl groups; R ２ , R ３ and R ４ These are, independently of each other, a hydrogen atom, an aromatic ring, or C １ ~C １５ This represents a linear, cyclic, or branched alkyl, alkenyl, or alkadienyl group, wherein the group is C １ ~C ４ It may be substituted with an alkyl group; or the base R １ ~R ４ Two or three of these are bonded together to form a saturated or unsaturated ring, the ring having 5 to 20 carbon atoms, and the R １ , R ２ , R ３ Or R ４ The ring contains carbon atoms to which the group is bonded, and the ring is C １ ~C ８ It is represented as [which may be substituted with linear, branched, or cyclic alkyl or alkenyl groups]; R represents a linear or branched alkyl group having 8 to 15 carbon atoms, and the group is a carboxylic acid or C that is not directly bonded to a sulfur atom. １ ~C ８ [May contain carboxylic acid ester functional groups] A method for producing the compound, The above method is, 【Transformation 3】 [In the formula, R １ , R ２ , R ３ and R ４ The process includes the step of reacting a compound of the formula R-SH [wherein R has the same meaning as defined above] with a thiol of the formula R-SH [wherein R has the same meaning as defined above], A method characterized in that the thiol contains no more than 50 μg / kg of thiols or thioether compounds having fewer than 6 carbon atoms.
6. The thiol in the above formula R-SH is a) A maximum of 5 μg / kg of 1-propanethol b) A maximum of 5 μg / kg of 2-propanethol c) A maximum of 5 μg / kg of 2-methyl-1-propanethol d) 2-methyl-2-propantheol at a maximum of 20 μg / kg e) A maximum of 5 μg / kg of 1-butanethiol, and f) Tetrahydrothiophene at a maximum of 10 μg / kg The method according to claim 5, which includes only the following.
7. The method according to claim 5 or 6, wherein the thiol of formula R-SH does not contain trace amounts of 1-propantheol, 2-propantheol, 2-methyl-1-propantheol, 2-methyl-2-propantheol, 1-butanethiol, or tetrahydrothiophene.
8. The method according to any one of claims 5 to 7, wherein the thiol of formula R-SH is purified by distillation before being reacted with the compound of formula (III).
9. The method according to any one of claims 5 to 8, wherein R may be a linear alkyl group having 10 to 14 carbon atoms.
10. The method according to any one of claims 5 to 9, wherein the thiol in the formula R-SH is 1-dodecanethiol.
11. The above P is given by equations (P-1) to (P-14): 【Chemistry 4】 [In the formula, the dashed line has the meaning shown above, and the dotted line represents a single bond or a double bond. R ａ R is a hydrogen atom or a methyl group, ｂ is a hydrogen atom, a hydroxyl group or a methoxy group or C １ ~C ４ R represents a linear or branched alkyl group. ｃ is a hydrogen atom or C １ ~C ４ The method according to any one of claims 5 to 10, wherein the group is selected from the group consisting of [representing a linear or branched alkyl group], and is one form of any of the isomers thereof.
12. The method according to any one of claims 5 to 11, wherein P is (P-1), (P-2), (P-3), (P-7), (P-13), or (P-14).
13. The method according to any one of claims 5 to 12, wherein the compound of formula (I) is selected from the group consisting of 3-(dodecylthio)-1-(2,6,6-trimethylcyclohexa-3-en-1-yl)butan-1-one, 2-(dodecylthio)-4-octanone, 3-(dodecylthio)-1-(2,6,6-trimethylcyclohexa-2-en-1-yl)butan-1-one, 4-(dodecylthio)-4-(2,6,6-trimethylcyclohexa-2-en-1-yl)butan-2-one, and 4-(dodecylthio)-4-methylpentan-2-one.
14. The method according to any one of claims 5 to 13, wherein the reaction between the compound of formula (III) and the thiol of formula R-SH is carried out in the presence of a base.
15. It contains a compound of formula (I), and contains no more than 50 μg / kg of thiol or thioether compounds with fewer than 6 carbon atoms, and formula 【Transformation 5】 A material composition containing at most 1 ppm of the compound [wherein the formula, the dashed line indicates the position of the bond between P and the sulfur atom; P has the same meaning as defined in claims 5 to 14, and R' represents an alkyl group having 1 to 5 carbon atoms].