# US 11,440,873 B1 · Method of electrochemical substitution of azides for hydrogen on tertiary carbons > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,440,873 B1 - Document ID: US11440873B1 - Status: Granted - Kind: B1 - Application number: 16/873,402 - Filed: 2020-04-07 - Granted: 2022-09-13 - Earliest claimed: 2020-04-07 - Assignees: The United States of America as represented by the Secretary of the Navy - Applicants: The United States of America as Represented by the Secretary of the Navy - Inventors: Farhad Forohar; Victor Bellitto - Web page: https://patentgrep.com/patent/US11440873B1 ## CPC - C07C 247/14: with azido groups bound to carbon atoms of rings other than six-membered aromatic rings - B01J 19/088: {giving rise to electric discharges (for heating purposes H05B7/00; for the production of ozone C01B13/11, H01T19/00)} - C25B 3/00: Electrolytic production of organic compounds - C25B 3/09: Nitrogen containing compounds - C25B 11/057: consisting of a single element or compound - C25B 15/00: Operating or servicing cells - C25B 15/02: Process control or regulation - B01J 2219/0809: employing two or more electrodes - B01J 2219/0839: Carbon - B01J 2219/0841: Metal - B01J 2219/0877: Liquid - C25B 11/042: Electrodes formed of a single material - C25B 11/043: Carbon, e.g. diamond or graphene - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - C25B: ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR (anodic or cathodic protection C23F13/00; single-crystal growth C30B) ## Abstract A method of substituting an azide for hydrogen bonded to a tertiary carbon atom is provided. A liquid mixture in an oxygen-free environment has spaced-apart carbon and platinum electrodes disposed therein. The liquid mixture includes a solvent, ammonium azide, and a base material having at least one tertiary carbon atom with hydrogen bonded thereto. An electric current is applied to the electrodes where the liquid mixture undergoes a reaction. The electrochemically-induced reaction yields a liquid product and a solid product. The liquid product includes the solvent and a constituent having at least one tertiary carbon atom with an azide bonded thereto. ## Claims ### Claim 1 A method of substituting an azide for hydrogen bonded to at least one tertiary carbon atom, comprising: providing a liquid mixture in an oxygen-free environment with a carbon electrode and a platinum electrode disposed in said liquid mixture in a spaced-apart fashion, said liquid mixture includes a solvent, ammonium azide, and a base material having said at least one tertiary carbon atom with the hydrogen bonded thereto; and applying an electric current to said carbon electrode and said platinum electrode wherein said liquid mixture undergoes a reaction to yield a liquid product and a solid product, said liquid product includes said solvent and a constituent having said at least one tertiary carbon atom with an azide bonded thereto. ### Claim 2 (depends on 1) The method according to claim 1, wherein said base material comprises adamantane. ### Claim 3 (depends on 1) The method according to claim 1, further comprising stirring said liquid mixture at room temperature during said step of applying. ### Claim 4 (depends on 1) The method according to claim 1, wherein said base material comprises adamantane, wherein said solvent comprises lithium percholate dissolved in anhydrous acetonitrile, and wherein said liquid mixture further includes acetic acid and a catalytic quantity of manganese (II) bromide tetrahydrate. ### Claim 5 (depends on 1) The method according to claim 1, wherein said base material comprises 250 milligrams of adamantane, wherein said solvent comprises 90 milliliters of 0.1 mole of lithium percholate dissolved in anhydrous acetonitrile, wherein said liquid mixture includes 2.7 grams of said ammonium azide, and wherein said liquid mixture further includes 10 milliliters of acetic acid and 100 milligrams of manganese (II) bromide tetrahydrate. ### Claim 6 (depends on 5) The method according to claim 5, further comprising stirring said liquid mixture at room temperature during said step of applying. ### Claim 7 (depends on 1) The method according to claim 1, further comprising removing said solvent from said liquid product wherein a paste is generated; mixing ethyl ether with said paste wherein an ethereal solution is generated that includes said constituent; and evaporating said ethyl ether from said ethereal solution to yield said constituent in a solid state. ### Claim 8 A method of substituting an azide for hydrogen bonded to at least one tertiary carbon atom, comprising: providing a liquid mixture that includes a solvent, ammonium azide, and a base material having said at least one tertiary carbon atom with the hydrogen bonded thereto; disposing said liquid mixture in an oxygen-free environment; positioning a carbon electrode and a platinum electrode in a spaced-apart fashion in said liquid mixture; and applying an electric current to said carbon electrode and said platinum electrode wherein said liquid mixture undergoes a reaction to yield a liquid product and a solid product, said liquid product includes said solvent and a constituent having said at least one tertiary carbon atom with an azide bonded thereto. ### Claim 9 (depends on 8) The method according to claim 8, wherein said base material comprises adamantane. ### Claim 10 (depends on 8) The method according to claim 8, further comprising stirring said liquid mixture at room temperature during said step of applying. ### Claim 11 (depends on 8) The method according to claim 8, wherein said base material comprises adamantane, wherein said solvent comprises lithium percholate dissolved in anhydrous acetonitrile, and wherein said liquid mixture further includes acetic acid and a catalytic quantity of manganese (II) bromide tetrahydrate. ### Claim 12 (depends on 8) The method according to claim 8, wherein said base material comprises 250 milligrams of adamantane, wherein said solvent comprises 90 milliliters of 0.1 mole of lithium percholate dissolved in anhydrous acetonitrile, wherein said liquid mixture includes 2.7 grams of said ammonium azide, and wherein said liquid mixture further includes 10 milliliters of acetic acid and 100 milligrams of manganese (II) bromide tetrahydrate. ### Claim 13 (depends on 12) The method according to claim 12, further comprising stirring said liquid mixture at room temperature during said step of applying. ### Claim 14 (depends on 8) The method according to claim 8, further comprising removing said solvent from said liquid product wherein a paste is generated; mixing ethyl ether with said paste wherein an ethereal solution is generated that includes said constituent; and evaporating said ethyl ether from said ethereal solution to yield said consistent in a solid state. ### Claim 15 (depends on 8) The method according to claim 8, wherein said step of disposing includes the steps of: partially filling a container with said liquid mixture; sealing said container wherein a gaseous volume is defined in said container; and filling said gaseous volume with an oxygen-free gas. ### Claim 16 A method of substituting an azide for hydrogen bonded to at least one tertiary carbon atom, comprising: providing a liquid mixture in an oxygen-free environment with a carbon electrode and a platinum electrode disposed in said liquid mixture in a spaced-apart fashion, said liquid mixture includes a solvent, ammonium azide, and a base material having said at least one tertiary carbon atom with the hydrogen bonded thereto; stirring said liquid mixture at room temperature; applying, during said step of stirring, an electric current to said carbon electrode and said platinum electrode wherein said liquid mixture undergoes a reaction to yield a liquid product and a solid product, said liquid product including said solvent and a constituent having said at least one tertiary carbon atom with an azide bonded thereto; removing said solvent from said liquid product wherein a paste is generated; mixing ethyl ether with said paste wherein an ethereal solution is generated that includes said constituent; and evaporating said ethyl ether from said ethereal solution to yield said constituent in a solid state. ### Claim 17 (depends on 16) The method according to claim 16, wherein said base material comprises adamantane. ### Claim 18 (depends on 16) The method according to claim 16, wherein said base material comprises adamantane, wherein said solvent comprises lithium percholate dissolved in anhydrous acetonitrile, and wherein said liquid mixture further includes acetic acid and a catalytic quantity of manganese (II) bromide tetrahydrate. ### Claim 19 (depends on 16) The method according to claim 16, wherein said base material comprises 250 milligrams of adamantane, wherein said solvent comprises 90 milliliters of 0.1 mole of lithium percholate dissolved in anhydrous acetonitrile, wherein said liquid mixture includes 2.7 grams of said ammonium azide, and wherein said liquid mixture further includes 10 milliliters of acetic acid and 100 milligrams of manganese (II) bromide tetrahydrate.