# US 11,267,773 B2 · Hexasubstituted benzenes, surfaces modified therewith, and associated methods > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,267,773 B2 - Document ID: US11267773B2 - Status: Granted - Kind: B2 - Application number: 17/190,694 - Filed: 2021-03-03 - Published: 2021-11-11 - Granted: 2022-03-08 - Earliest claimed: 2019-09-10 - Assignees: Countertrace LLC - Applicants: Countertrace, LLC - Inventors: Robert E. Hanes, Jr.; Richard L. Pettys; David M. Headley; Paul T. Hoopingarner - Web page: https://patentgrep.com/patent/US11267773B2 ## CPC - C07C 22/04: containing six-membered aromatic rings - C07C 219/22: and containing six-membered aromatic rings - C07C 235/60: having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms - C07C 247/10: and containing rings - C07D 249/06: with aryl radicals directly attached to ring atoms - C07D 303/08: with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals - C07D 303/36: with hydrocarbon radicals, substituted by nitrogen atoms (nitro, nitroso radicals C07D303/08) - C07D 405/14: containing three or more hetero rings - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08) ## Abstract Phenyl rings provide a robust scaffold for molecular design, given the limited number of ring carbon atoms and the fixed geometry in between. However, it can be difficult to form highly substituted phenyl rings suitable for covalent attachment of multiple moieties thereto. Moreover, binding phenyl rings to a surface in a fixed geometry may be difficult. Hexasubstituted benzenes having certain structural features may alleviate the foregoing difficulties by providing versatile groups for further functionalization and surface attachment. Such hexasubstituted benzenes may have a structure of in which each X is independently Cl, Br or N3, and each Z is independently —CH(Br)CH3, —CH(N3)CH3, —CH═CH2, —CH2CH3, —CH2CH2SiR′3 (R′=hydrocarbyl), or Alternating groups in the hexasubstituted benzenes may be directed toward opposite faces of the phenyl ring, such that orthogonal reactive groups are directed toward the opposite faces. Certain groups may facilitate surface attachment of the hexasubstituted benzenes. ## Claims ### Claim 1 A hexasubstituted benzene having a structure of wherein each X is independently Cl, Br or N3, and each Z is independently —CH(Br)CH3, —CH═CH2, or; ### Claim 2 (depends on 1) The hexasubstituted benzene of claim 1, wherein each Z is —CH(Br)CH3 and each X is Br or each X is Cl. ### Claim 3 (depends on 1) The hexasubstituted benzene of claim 1, wherein each Z is —CH═CH2 and each X is Br or each X is Cl. ### Claim 4 (depends on 1) The hexasubstituted benzene of claim 1, wherein each Z is —CH═CH2 and each X is N3. ### Claim 5 (depends on 1) The hexasubstituted benzene of claim 1, wherein each Z is and each X is Br or each X is Cl. ### Claim 6 (depends on 1) The hexasubstituted benzene of claim 1, wherein each Z is and each X is N3. ### Claim 7 A hexasubstituted benzene having a structure of wherein Nu1, Nu2 and Nu3 are each nucleophiles, each X is independently Cl, Br, N3 or NH2, and each Y is independently H or OH. ### Claim 8 (depends on 7) The hexasubstituted benzene of claim 7, wherein each X is Br or each X is Cl. ### Claim 9 (depends on 7) The hexasubstituted benzene of claim 7, wherein each X is N3. ### Claim 10 (depends on 7) The hexasubstituted benzene of claim 7, wherein each X is NH2. ### Claim 11 (depends on 7) The hexasubstituted benzene of claim 7, wherein Nu1, Nu2 and Nu3 are each different. ### Claim 12 A modified surface comprising: a base surface having a plurality of functionalities reactive with an amine or an azide; and a reaction product of the base surface and a hexasubstituted benzene bearing an amine or an azide, the reaction product being covalently bonded to the base surface and having a structure of wherein B is the base surface; wherein each A is a vinyl group, a reaction product of a vinyl group, an epoxide, or a reaction product formed from opening of an epoxide with a nucleophile; and wherein each L is a linking group connecting a benzylic carbon of the hexasubstituted benzene to the base surface, each L being formed from a reaction between a functionality located upon the base surface and an azide or an amine located upon the benzylic carbon. ### Claim 13 (depends on 12) The modified surface of claim 12, wherein L comprises a cycloaddition reaction product of a benzylic azide. ### Claim 14 (depends on 13) The modified surface of claim 13, wherein the cycloaddition reaction product is a 1,2,3-triazole. ### Claim 15 (depends on 12) The modified surface of claim 12, wherein L comprises a secondary or tertiary benzylic amine reaction product or a secondary or tertiary benzylic amide reaction product of a primary benzylic amine. ### Claim 16 (depends on 12) The modified surface of claim 12, wherein each A is an epoxide or a reaction product formed from opening of an epoxide with a nucleophile. ### Claim 17 A method comprising: providing a base surface having a plurality of functionalities reactive with an amine or an azide; contacting the base surface with a hexasubstituted benzene having a structure of wherein each A is a vinyl group, a reaction product formed from a vinyl group, an epoxide, or a reaction product formed from opening of an epoxide with a nucleophile; and wherein each T is independently N3 or NH2; and reacting at least a portion of the plurality of functionalities with T to form a modified surface comprising a reaction product covalently bonded to the base surface and having a structure of wherein B is the base surface; and wherein each L is a linking group connecting a benzylic carbon of the hexasubstituted benzene to the base surface, each L being formed from a reaction between a functionality and T. ### Claim 18 (depends on 17) The method of claim 17, wherein the base surface is selected from the group consisting of a polymer surface, a metal surface, a ceramic surface, a glass surface, a cement surface, a wood surface, a geological surface, and any combination thereof. ### Claim 19 (depends on 17) The method of claim 17, wherein each A is an epoxide or a reaction product formed from opening of an epoxide with a nucleophile.