# US 12,595,338 B2 · Process for preparing a hydroxy group functionalized thioether > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,595,338 B2 - Document ID: US12595338B2 - Status: Granted - Kind: B2 - Application number: 18/018,534 - Filed: 2021-07-23 - Published: 2023-10-26 - Granted: 2026-04-07 - Earliest claimed: 2020-07-30 - Assignees: BASF SE - Applicants: BASF SE - Inventors: Bernd Bruchmann; Peter Rudolf; Markus Meise; Elliot Christ; Juergen Ruehe; Tassilo Gleede - Web page: https://patentgrep.com/patent/US12595338B2 ## CPC - C08G 75/04: from mercapto compounds or metallic derivatives thereof (C08G75/0204 takes precedence) - C08G 75/045: from mercapto compounds and unsaturated compounds - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS ## Abstract A process can be used for preparing a compound A having n groups of formula In Formula (I), X is C2-C12-alkylene or C2-C12-alkylene substituted with C1-C4-alkoxy, C1-C4-alkylthio, and/or interrupted with O or S; R1, R2, and R3 are independently of one another hydrogen or C1-C4-alkyl; and n is an integer of 1, 2, 3, 4, 5, or 6. The process involves reacting a compound B having n —SH groups with a compound C of formula in the presence of a free radical generator. ## Claims ### Claim 1 A process for preparing a compound A having n groups of formula (I) wherein X is C2-C12-alkylene or C2-C12-alkylene substituted with C1-C4alkoxy, C1-C4-alkylthio, and/or interrupted with O or S; R1, R2, and R3 are independently of one another hydrogen or C1-C4-alkyl; n is an integer of 1, 2, 3, 4, 5, or 6; the process comprising: reacting a compound B having n —SH groups with a compound C of formula (II) in the presence of a free radical generator, to obtain the compound A having n groups of formula (I). ### Claim 2 (depends on 1) The process according to claim 1, wherein R1 and R2 are hydrogen, R3 is hydrogen or C1-C4-alkyl; and X is C2-C6-alkylene or C2-C6-alkylene interrupted with O or S. ### Claim 3 (depends on 1) The process according to claim 1, wherein the process is conducted at a temperature of from 30 to 130° C., and wherein the free radical generator is a radical initiator. ### Claim 4 (depends on 1) The process according to claim 1, wherein the compound A having n groups of formula (I) is a compound of formula (III) or (IV) wherein Y1 is C1-C18-alkyl; C1-C18-alkyl substituted with OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen, NR6R7, C3-C18-cycloalkyl, C6-C18-aryl, or C2-C18-heteroaryl, and/or interrupted with O, S, —SO—, —SO2, —COO—, —OCOO—, —CO—, C3-C18-cycloalkylene, C6-C18-arylene- or C2-C18-heteroarylene; C3-C18-cycloalkyl; C3-C18-cycloalkyl substituted with OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen, or NR8R9, and/or interrupted by O or S; C6-C18-aryl; C6-C12-aryl substituted with C1-C12-alkyl, OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen, or NR10R11; C2-C18-heteroaryl, or C2-C18-heteroaryl substituted with C1-C12-alkyl, OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen, or NR12R13; R4 and R5 are independently of one another and at each occurrence hydrogen, C1-C18-alkyl, C1-C18-alkyl substituted with halogen or interrupted with O or S; C6-C18-aryl or C6-C12-aryl substituted with C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, or halogen; R6, R7, R8, R9, R10, R11, R12, and R13 are independently of one another and at each occurrence C1-C4-alkyl, C1-C4-alkyl substituted with OH, C1-C4-alkoxy, C1-C4-alkylthio, or halogen; C6-C10-aryl or C6-C10-aryl substituted with OH, C1-C4-alkoxy, C1-C4-alkylthio, or halogen; or R6 and R7, R8 and R9, R10 and R11, or R12 and R13 together are C4-C6-alkylene or C4-C6-alkylene interrupted by O, S, and/or NR14; R14 is C1-C4-alkyl; m is at each occurrence 0 to 12; Y2 is a n-valent linking group; and n is an integer of 2, 3, 4, 5, or 6. ### Claim 5 (depends on 4) The process according to claim 4, wherein R4 and R5 are independently of one another and at each occurrence hydrogen, C1-C4-alkyl, C1-C4-alkyl substituted with halogen or interrupted with O or S; C6-C12-aryl or C6-C12-aryl substituted with C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, or halogen; and m is 1 to 10. ### Claim 6 (depends on 4) The process according to claim 4, wherein Y1 is C1-C12-alkyl; C1-C12-alkyl substituted with OH, C1-C4-alkoxy, C1-C4-alkylthio, C5-C6-cycloalkyl, C6-C12-aryl, or C2-C10-heteroaryl, and/or interrupted with O, S, —SO—, —SO2, —COO—, —OCOO—, —CO—, C6-C8-cycloalkylene, C6-C12-arylene, or C4-C10-heteroarylene; C5-C8-cycloalkyl; C5-C8-cycloalkyl substituted with OH, C1-C4-alkoxy, C1-C4-alkylthio, and/or interrupted by O or S; C6-C12-aryl; C6-C10-aryl substituted with C1-C6-alkyl, OH, C1-C4-alkoxy, or C1-C4-alkylthio; C2-C10-heteroaryl, or C2-C10-heteroaryl substituted with C1-C6-alkyl, OH, C1-C4-alkoxy, or C1-C4-alkylthio; and m is 0. ### Claim 7 (depends on 4) The process according to claim 4, wherein Y1 is C2-C12-alkyl substituted with OH and optionally interrupted with O or S; R4 is hydrogen and R5 is at each occurrence hydrogen, C1-C4alkyl, C1-C4-alkyl substituted with halogen or interrupted with O or S; or phenyl; and m is 1 to 10. ### Claim 8 (depends on 4) The process according to claim 4, wherein Y2 is a n-valent linking group comprising an aliphatic unit, a cycloaliphatic unit, an aromatic unit, and/or a heteroaromatic unit, and optionally comprising a functional group containing a heteroatom; and n is an integer of 2, 3, 4, or 6. ### Claim 9 (depends on 4) The process according to claim 4, wherein Y2 is a divalent linking group, wherein said divalent linking group comprises at least one group selected from the group consisting of C1-C18-alkylene; C1-C18-alkylene substituted with C1-C4-alkoxy, C1-C4-alkylthio, halogen, NR15R16, C5-C12-cycloalkyl, C6-C12-aryl, or C2-C12-heteroaryl; C5-C12-cycloalkylene; C5-C12-cycloalkylene substituted with C1-C4-alkoxy, C1-C4-alkylthio, halogen or NR17R18, and/or interrupted with O or S; C6-C12-arylene; C6-C12-arylene substituted with C1-C12-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, halogen, or NR19R20; C2-C12-heteroarylene; and C2-C12-heteroarylene substituted with C1-C12-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, halogen, or NR21R22; and wherein said divalent linking group optionally comprises at least one hetero-functional group selected from the group consisting of —O—, —S—, —SO—, —SO2, —COO—, —OCOO—, and —CO—; and R15, R16, R17, R18, R19, R20, R21, and R22 are independently of one another and at each occurrence C1-C4-alkyl, C1-C4-alkyl substituted with OH, C1-C4-alkoxy, C1-C4-alkylthio, or halogen; C6-C10-aryl or C6-C10-aryl substituted with OH, C1-C4-alkoxy, C1-C4-alkylthio, or halogen; and n is 2. ### Claim 10 (depends on 4) The process according to claim 4, wherein Y2 is a divalent linking group, wherein said divalent linking group comprises at least one group selected from the group consisting of C1-C12-alkylene; C5-C8-cycloalkylene; C5-C8-cycloalkylene interrupted with O or S; C6-C12-arylene; C6-C12-arylene substituted with C1-C4-alkyl; C2-C12-heteroarylene; and C2-C12-heteroarylene substituted with C1-C4-alkyl, and wherein said divalent linking group optionally comprises at least one group selected from the group consisting of —O—, —S—, and —COO—. ### Claim 11 (depends on 4) The process according to claim 4, wherein Y2 is a trivalent linking group selected from the group consisting of benzenetriyl, triazinetriyl, and methylidyne, or Y2 is a trivalent linking group composed of either benzenetriyl, methylidyne, or nitrogen, and a divalent group, or Y2 is a tetravalent linking group derived from methane or benzene, or a tetravalent linking group composed of the tetravalent linking group derived from methane or benzene and the divalent group, or Y2 is a hexavalent group of formula and optionally the divalent group, wherein said divalent group is at each occurrence a C1-C12-alkylene and optionally comprises at least one group selected from the group consisting of —O—, —S—, and —COO—. ### Claim 12 (depends on 4) The process according to claim 4, wherein Y2 is a divalent linking group, wherein said divalent linking group comprises at least one group selected from the group consisting of C1-C18-alkylene, —CH2—O—CH2, —CH2—S—CH2—, —(CH2CH2O)p—CH2CH2—, —(CH2CH2S)p—CH2CH2— with p being an integer of 2 to 10, —(C3H7O)q—C3H7—, —(C3H7S)q—C3H7— with q being an integer of 1 to 10, o-phenylene, m-phenylene, p-phenylene, ### Claim 13 A compound A of formula (III) or (IV) wherein Y1 is C1-C18-alkyl substituted with OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen, NR6R7, C3-C18-cycloalkyl, C6-C18-aryl, or C2-C18-heteroaryl, and/or interrupted with —O—, —S—, —SO—, —SO2—, —COO—, —OCOO—, —CO—, C3-C18-cycloalkylene, C6-C18-arylene, or C2-C18-heteroarylene; C3-C18-cycloalkyl; C3-C18-cycloalkyl substituted with OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen, or NR8R9, and/or interrupted by O or S; C6-C18-aryl; C6-C12-aryl substituted with C1-C12-alkyl, OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen, or NR10R11; C2-C18-heteroaryl, or C2-C18-heteroaryl substituted with C1-C12-alkyl, OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen, or NR12R13; X is C2-C12-alkylene or C2-C12-alkylene substituted with C1-C4-alkoxy, C1-C4-alkylthio, and/or interrupted with O or S; R1, R2, and R3 are independently of one another hydrogen or C1-C4-alkyl; R4 and R5 are independently of one another and at each occurrence hydrogen, C1-C18-alkyl, C1-C18-alkyl substituted with halogen or interrupted with O or S; C6-C18-aryl or C6-C12-aryl substituted with C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, or halogen; R6, R7, R8, R9, R10, R11, R12, and R13 are independently of one another and at each occurrence C1-C4-alkyl, C1-C4-alkyl substituted with OH, C1-C4-alkoxy, C1-C4-alkylthio, or halogen; C6-C10-aryl or C6-C10-aryl substituted with OH, C1-C4-alkoxy, C1-C4-alkylthio, or halogen; or R6 and R7, R8 and R9, R10 and R11, or R12 and R13 together are C4-C6-alkylene or C4-C6-alkylene interrupted by O, S, and/or NR14; R14 is C1-C4-alkyl; m is at each occurrence 1 to 12; Y2 is a n-valent linking group; and n is an integer of 2, 3, 4, 5, or 6, provided that R4 and R5 are not simultaneously H. ### Claim 14 (depends on 13) The compound A according to claim 13, obtainable by a process comprising: a) reacting a thiol of formula (V) or (VI) Y1—SH (V), or (Y2)n—SH (VI), with a cyclic monothiocarbonate of formula (VII) to form a compound B; and b) reacting compound B with a compound C of formula (II) in the presence of a free radical generator. ### Claim 15 A compound A of formula (IV) wherein R1 and R2 are hydrogen, and R3 is hydrogen or C1-C4-alkyl; and X is C2-C6-alkylene or C2-C6-alkylene interrupted with O or S; R4 is hydrogen and R5 is at each occurrence hydrogen, C1-C4-alkyl, C1-C4-alkyl substituted with halogen or interrupted with O or S; or phenyl; Y2 is a n-valent linking group; m is 2 to 6, and n is an integer of 2, 3, 4, 5, or 6. ### Claim 16 (depends on 13) A chain extender or cross-linking agent, comprising: the compound of formula (IV) as defined in claim 13. ### Claim 17 (depends on 3) The process according to claim 3, wherein the radical initiator is an azo compound. ### Claim 18 (depends on 8) The process according to claim 8, wherein n is an integer of 2, 3, or 4. ### Claim 19 (depends on 10) The process according to claim 10, wherein the divalent linking group comprises at least one selected from the group consisting of —O— and —S—. ### Claim 20 (depends on 13) The compound A according to claim 13, wherein m is at each occurrence 1 to 10.