EP3529232A1 - Sulfaminsäurederivate und herstellungsverfahren dafür - Google Patents

Sulfaminsäurederivate und herstellungsverfahren dafür

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Publication number
EP3529232A1
EP3529232A1 EP17861268.5A EP17861268A EP3529232A1 EP 3529232 A1 EP3529232 A1 EP 3529232A1 EP 17861268 A EP17861268 A EP 17861268A EP 3529232 A1 EP3529232 A1 EP 3529232A1
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EP
European Patent Office
Prior art keywords
compound
branched
linear
fluoride
sulfamic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP17861268.5A
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English (en)
French (fr)
Other versions
EP3529232A4 (de
Inventor
Matjaz Kozelj
Catherine Gagnon
Abdelbast Guerfi
Karim Zaghib
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Hydro Quebec
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Hydro Quebec
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Publication of EP3529232A1 publication Critical patent/EP3529232A1/de
Publication of EP3529232A4 publication Critical patent/EP3529232A4/de
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
    • C01B21/093—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more sulfur atoms
    • C01B21/096—Amidosulfonic acid; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/34—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfuric acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
    • C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/035—Liquid electrolytes, e.g. impregnating materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C307/00—Amides of sulfuric acids, i.e. compounds having singly-bound oxygen atoms of sulfate groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C307/02—Monoamides of sulfuric acids or esters thereof, e.g. sulfamic acids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the technical field generally refers to processes for the preparation of sulfamic acid derivatives, for example, of halogenated derivatives and their only ones, including ionic liquids.
  • the technical field also refers to these sulfamic acid derivatives and their use in electrolytes for electrochemistry applications.
  • Some sulfamic acid derivatives because of their unique properties, have gained importance in electrochemical applications.
  • examples of such compounds include bis (fluorosulfonyl) amide, N-fluorosulfonyl (trifluoromethanesulfonyl) amide and their salts, particularly their lithium salts (commonly referred to as LiFSI and LiFTFSI).
  • LiFSI and LiFTFSI lithium salts
  • Their unique properties include good solubility, electrochemical stability and ability to lower the viscosity and melting temperature of ionic liquids, i.e., when these fluorosulfonylamides are used as anions in ionic liquids (see US 6,365,301, US Pat. US 5,874,616, and US 201/0007086).
  • U.S. Patent No. 5,874,616 discloses the preparation, at low temperatures, of N-fluorosulfonyl- (trifluoromethanesulfonyl) amide by the acylation of trifluoromethanesulfonylamide using the highly toxic sulfuryl fluoride, rendering the method unsuitable when larger scale production is required. considered.
  • sulfamic acid derivative or a salt thereof, and one or more metal (s) or organic cation (s).
  • sulfamic acid derivative is defined according to Formula I:
  • R 1 is chosen from hydrogen and linear or branched C 2 -C 6 alkyl groups, G 5 -C 10 aryl or C 5 -C 10 heteroaryl, the alkyl, aryl and heteroaryl groups being optionally halogenated, or R 1 and the adjacent nitrogen atom together form a salt in which the nitrogen atom is negatively charged (anion) and R 1 is (M n + ) i / n or X + ;
  • R 2 is chosen from hydrogen, cyano, sulphonyl, chlorosulfonyl, fluorosulfonyl, chlorocarbonyl, fluorocarbonyl, linear or optionally halogenated branched C2-alkanoyl, optionally halogenated aryloyl, optionally halogenated heteroaryloyl, optionally substituted linear or branched C1-C2 alkanesulfonyl, optionally arylsulphonyl; halogenated, and optionally halogenated heteroarylsulfonyl;
  • R 3 is selected from OH, F, Cl, O " (M n + ) i / n , 0 " X + , and linear or branched, optionally halogenated, alkoxy d-C2;
  • M n + ) i / n is a cation of a metal, wherein M is a metal and n is an integer of 1 to 4, for example, M is Li, Na, K, Rb, Cs, Be, Mg , Ca, Sr, Ba, Al, Zn, Cu, Se, Y, Fe, Co, Ni, Ti, Sn, V, Cr, or Mn, for example, M is selected from Li, Na, K, Rb, Cs , Be, Mg, Ca, Sr, Ba, Al, Zn, Se, and Ti, for example M is an alkali metal, an alkaline earth metal, or aluminum, or M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba, and n is 1 or 2; and
  • X + represents an organic cation, for example, selected from ammonium, alkylammonium, dialkylammonium, trialkylammonium, tetraalkylammonium, 1,3-dialkylimidazolium, N-alkylpyrrolidinium, N-alkylpiperidinium, trialkyloxonium, trialkylsulfonium, tetraalkylphosphonium, and so on;
  • step (i) optionally converting the product obtained in step (i) to produce a compound of Formula I.
  • the ratio of the anion to the cation is understood as aiming at the electroneutrality of the compound (e.g. Sulphamic acid feed-1 derivatives may be needed when a Mg 2+ magnesium cation is used, even two lithium (+1) cations can be combined with a dianion of a sulfamic acid derivative).
  • the source of sulfur trioxide is selected from SO3 (sulfur trioxide itself) and its oligomers and polymers; H2SO4 (sulfuric acid); H2S2O7 (disulfuric acid) and other polysulfuric acids and their salts; CISO3H (chlorosulfonic acid) and its salts; FSO3H (fluorosulfonic acid) and its salts; SO3-ammonia complex (sulfamic acid); sulfur trioxide complexes with organic amines; sulfur trioxide complexes with other organic compounds such as dioxane, thioxane, dimethylformamide; and acylsulfates, the latter being generated by the introduction of SO3 into dry carboxylic acids, for example, acetyl sulfate (CH3C (O) OSO3H).
  • SO3 sulfur trioxide itself
  • H2SO4 sulfuric acid
  • H2S2O7 disulfuric acid
  • the source of sulfur trioxide and the tertiary amine are added together as a complex
  • the tertiary amine is selected from the following compounds: trimethylamine, triethylamine, tripropylamine, tributylamine, diisopropylethylamine, pyrrolidines and morpholines substituted with a V-alkyl, pyridine, picoline, lutidine, quinoline, A, N-dimethylaniline, and other amines.
  • the complex is selected from pyridine-sulfur trioxide, trimethylamine-sulfur trioxide and triethylamine-sulfur trioxide complexes.
  • step (i) comprises heating at a temperature between about 100 ° C and about 250 ° C, or between about 150 ° C and about 220 ° C, for example, over a period of less than 10 hours, less than 4 hours, or less than 1 hour. According to one embodiment, step (i) is carried out without addition of solvent.
  • the method comprises step (ii) which includes contacting the product obtained in step (i) with a metal base.
  • the metal base is chosen from metal hydroxides, metal alkoxides, organometallics and Grignard reagents, said metal being chosen among alkali metals, alkaline earth metals, and aluminum, for example, the metal base is a hydroxide of a metal.
  • the method further comprises a step of treating the product of step (i) or step (ii) with a strong acid or passing a solution thereof through a an acidic ion exchange resin.
  • the strong acid is selected from hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, and trifluoromethanesulfonic acid.
  • the process comprises step (ii) which includes contacting the product obtained in step (i) with a chlorinating agent.
  • the chlorinating agent is chosen from inorganic and organic acid chlorides, such as PCI 5 , POCl 3 , SOCI 2 , CISO 3 H, COCl 2 , CICOCOCI, sulfur chlorides, cyanuric chloride, chlorine chloride and the like.
  • the method further comprises a step of contacting the product obtained in step (ii), after chlorination, with a fluorinating agent.
  • the fluorinating agent is selected from fluoride or hydrogen difluoride salts (such as an ammonium, sodium, potassium, or cesium salt, for example, KF or KHF2), and a salt. complex of amines and hydrofluoric acid (such as polyhydrofluoride pyridinium or triethylammonium).
  • fluoride or hydrogen difluoride salts such as an ammonium, sodium, potassium, or cesium salt, for example, KF or KHF2
  • a salt. complex of amines and hydrofluoric acid such as polyhydrofluoride pyridinium or triethylammonium.
  • the method comprises step (ii) which includes contacting the product obtained in step (i) with a strong fluorinating agent.
  • the fluorinating agent is chosen from reactive inorganic and organic acid fluorides, such as PF 5 , POF 3 , SOF 2 , FSO 3 H, COF 2 , FCOCOF, organic and inorganic hexafluorophosphates, hexafluorosilicates, tetrafluoroborates, sulfur tetrafluoride and organic derivatives (such as diethylaminosulfide trifluoride (DAST) and morpholinosulfide trifluoride), cyanuric fluoride, acetyl fluoride, trifluoroacetyl fluoride, methanesulfonyl fluoride, trifluoromethanesulfonyl fluoride, benzoyl fluoride, ( trifluoromethyl) benzene, benzene
  • DAST die
  • R 1 is chosen from hydrogen and linear or branched C 1 -C 20 alkyl, C 6 -C 10 aryl or C 5 -C 10 heteroaryl groups, the alkyl, aryl and heteroaryl groups being optionally halogenated, or R 1 and the adjacent nitrogen atom; together form a salt in which the nitrogen atom is negatively charged (anion) and R 1 is (M n + ) i / n or X + ;
  • R 2 is chosen from hydrogen, cyano, sulphonyl, chlorosulfonyl, fluorosulfonyl, chlorocarbonyl, fluorocarbonyl, linear or optionally halogenated branched C2-alkanoyl, optionally halogenated aryloyl, optionally halogenated heteroaryloyl, optionally substituted linear or branched C1-C2 alkanesulfonyl, optionally arylsulphonyl; halogenated, and optionally halogenated heteroarylsulfonyl;
  • R 3 is selected from OH, F, Cl, O " (M n + ) i / n , 0 " X + , and linear or branched, optionally halogenated, alkoxy d-C2;
  • M n + ) i / n is a cation of a metal, wherein M is a metal and n is an integer of 1 to 4, for example, M is Li, Na, K, Rb, Cs, Be, Mg , Ca, Sr, Ba, Al, Zn, Cu, Se, Y, Fe, Co, Ni, Ti, Sn, V, Cr, or Mn, for example, M is selected from Li, Na, K, Rb, Cs , Be, Mg, Ca, Sr, Ba, Al, Zn, Se, and Ti, for example M is an alkali metal, an alkaline earth metal, or aluminum, or M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba, and n is 1 or 2; and
  • X + represents an organic cation, for example selected from ammonium, alkylammonium, dialkylammonium, trialkylammonium, tetraalkylammonium, 1,3-dialkylimidazolium, N-alkylpyrrolidinium, N-alkylpiperidinium, trialkyloxonium, trialkylsulfonium, tetraalkylphosphonium, and the like.
  • R 1 is (M n + ) i / n where M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, Zn, Cu, Se, Y , Fe, Co, Ni, Ti, Sn, V, Cr, and Mn.
  • M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, Zn, Se, and Ti, or M is Li, Na or K.
  • R 1 is X + and is chosen from ammonium, alkylammonium, dialkylammonium, trialkylammonium, tetraalkylammonium, 1,3-dialkylimidazolium, N-alkylpyrrolidinium, N-alkylpiperidinium, trialkyloxonium, trialkylsulfonium, tetraalkylphosphonium and other similar ions ions; .
  • a salt including an organic cation may be liquid at room temperature, thereby forming an ionic liquid.
  • R 2 is selected from chlorosulfonyl, fluorosulfonyl, chlorocarbonyl, fluorocarbonyl, linear or branched alkanoyl, linear or branched perfluoroalkanoyl alkanoyl, linear or branched C 1 -C 4 alkanesulfonyl, and C 1 -C 4. linear or branched perfluorinated alkanesulfonyl, all other groups being as defined herein.
  • the sulfamic acid derivative is a compound of Formula II:
  • R 4 is selected from hydrogen, cyano, fluorine, chlorine, and a linear or branched C 1 -C 4 alkyl, C 6 -C 10 aryl or C 5 -C 10 heteroaryl, each optionally halogenated.
  • the sulfamic acid derivative is a compound of Formula III:
  • R 1 , R 3 , and R 4 are as previously defined.
  • R 4 in Formula II or III is selected from fluorine, chlorine, and a linear Ci-C2 branched or 4, all other groups are as defined here.
  • R 4 is a linear or branched perfluorinated C 1 -C 2 4 alkyl, perfluorinated C 6 -C 10 aryl, or perfluorinated C 6 -C 10 heteroaryl, for example a perfluorinated linear C 1 -C 4 alkyl group, all other groups being as defined herein.
  • R 1 is M n + 1 / n wherein M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca , Sr, Ba, and Al, all other groups being as defined herein.
  • R 1 is chosen from a linear or branched C 1 -C 4 alkyl, a C 6 -C 10 aryl and a C 5 -C 10 heteroaryl each optionally perhalogenated, for example R 1 is a linear or branched C 1 -C 4 alkyl perhalogenated , such as linear or branched perfluoroalkyl, all other groups being as defined herein.
  • R 1 is (M n + ) i n and R 3 is 0 " (M n + ) i n , wherein M and n are identical to each instance and are as defined here, for example M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba, and n is 1 or 2, or M is Li and n is 1, the other groups being as here In another embodiment, R 3 is F or Cl, the other groups being as defined herein.
  • the present document also relates to a sulfamic acid derivative chosen from Compounds 1 to 9, Compounds 10 to 18, Compounds 19 to 27, or Compounds 28 to 36, as defined below.
  • the present technology also relates to an electrolyte or electrolyte composition
  • an electrolyte or electrolyte composition comprising a sulfamic acid derivative prepared by a process of this document, or as described herein.
  • the electrolyte may further comprise a solvent or a solvating polymer suitable for the preparation of polymer electrolytes.
  • the electrolyte may be in liquid or gel form, optionally including a separator (membrane), or in solid form.
  • electrochemical cells comprising an electrolyte as defined herein, an electrode and a counter electrode, for example a battery, an electrochromic device or a capacitor.
  • the battery is a lithium or lithium-ion battery.
  • FIG. 1 shows the potential as a function of time at the formation step in a cell or half-cell using a LiFSI-containing electrolyte produced by the present method respectively with (a) LiFePC and (b) graphite as electrode material according to Example 13.
  • Figure 2 shows the discharge capacity as a function of the discharge rate (power capacity) for a cell or half-cell using an electrolyte containing LiFSI produced by the present method respectively with (a) LiFePC and (b) graphite as material. electrode, according to Example 13.
  • Figure 3 shows the results of stability tests, illustrated by the variation of the capacity of the cell as a function of the number of cycles, for a battery or half-cell using an electrolyte containing LiFSI produced by the present method respectively with (a) ) LiFePC and (b) graphite as electrode material, according to Example 13.
  • Figure 4 shows the time potential at the forming step in two identical half-cells using a LiFTFSI-containing electrolyte produced by the present method with a graphite electrode according to Example 14.
  • Figure 5 shows the results of stability tests, illustrated by the change in cell capacity versus number of cycles, for a half-cell using a LiFTFSI-containing electrolyte produced by the present method with a graphite electrode according to Example 14.
  • Figure 6 shows the comparative discharge capacity versus discharge rate (power capacity) data for 3 half-cells using an electrolyte containing LiFSI (triangles), LiFTFSI (diamonds), both being produced by the present method, and LiPF6 (squares) with a graphite electrode according to Example 15.
  • alkyl refers to a saturated hydrocarbon group having from one to twenty-four carbon atoms, including linear or branched groups.
  • alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, tert-butyl, sec-butyl, isobutyl, and so on.
  • C1-C10alkyl refers to an alkyl group having the number "i” to the number "ii" of carbon atom (s).
  • aryl refers to an aromatic group having 4n + 2 electrons ⁇ ( ⁇ ), where n is an integer ranging from 1 to 3, in a monocyclic or polycyclic conjugated system (fused or not) and having from six to fourteen ring atoms.
  • a polycyclic system includes at least one aromatic ring.
  • the group can be linked directly, or connected via a group d-Csalkyl.
  • aryl groups include, but are not limited to, phenyl, benzyl, phenethyl, 1-phenylethyl, tolyl, naphthyl, biphenyl, terphenyl, indenyl, benzocyclooctenyl, benzocycloheptenyl, azulenyl, acenaphthylenyl, fluorenyl, phenanthrenyl, anthracenyl, perylenyl, and so on.
  • aryl includes substituted or unsubstituted groups.
  • C6-C n aryl refers to an aryl group having from 6 to the indicated number "n" of carbon atoms in the ring structure.
  • heteroaryl refers to an aryl group having 4n + 2 electrons ⁇ ( ⁇ ), where n is an integer from 1 to 3, in a monocyclic or polycyclic conjugate system and having from five to fourteen ring atoms, and wherein at least one carbon atom is replaced by a heteroatom such as nitrogen, oxygen or sulfur, or by a group comprising this heteroatom (for example, NH, NR X (R x being alkyl); , acyl, aryl, heteroaryl or cycloalkyl), SO, and the like).
  • a polycyclic system includes at least one heteroaromatic ring.
  • the heteroaryls may be directly connected, or a C1-C3alkyl group.
  • the heteroaryl groups may be connected to the rest of the molecule by a carbon atom or a heteroatom, (such as nitrogen), where possible.
  • the present application relates to a process for the preparation of sulfamic acid derivatives, for example a compound of Formula I:
  • R 1 is chosen from hydrogen and the linear or branched G-C2 alkyl groups, Gs-Cioaryl and Cs-Cioheteroaryl, each optionally halogenated, or R 1 and the adjacent nitrogen atom together form a salt in which l nitrogen atom is negatively charged (anion) and R 1 is (M n + ) i / n or X + ;
  • R 2 is chosen from hydrogen and cyano, sulphonyl, chlorosulfonyl, fluorosulfonyl, chlorocarbonyl, fluorocarbonyl, d-C2 linear or branched optionally halogenated alkanoyl, optionally halogenated aryloyl, optionally halogenated heteroaryloyl, linear or branched optionally halogenated C1-C2 alkanesulfonyl radicals; optionally halogenated arylsulfonyl and optionally halogenated heteroarylsulfonyl;
  • R 3 is selected from OH, F, Cl, O " (M n + ) i / n , 0 " X + , and linear or branched, optionally halogenated, linear or branched alkoxy d-C 2, e.g. optionally halogenated linear or branched d-Csalkoxy;
  • M n + ) i / n is a cation of a metal, wherein M is a metal and n is an integer selected in the range of 1 to 4, for example, M is Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, Zn, Cu, Se, Y, Fe, Co, Ni, Ti, Sn, V, Cr, or Mn, for example, M is chosen from Li, Na, For example, M is an alkali metal, an alkaline earth metal, or aluminum, or M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba, and n is 1 or 2, or M is Li and n is 1; and
  • X + represents an organic cation, for example, selected from ammonium, alkylammonium, dialkylammonium, trialkylammonium, tetraalkylammonium, 1,3-dialkylimidazolium, N-alkylpyrrolidinium, N-alkylpiperidinium, trialkyloxonium, trialkylsulfonium, tetraalkylphosphonium, and other similar organic cations.
  • R 1 , R 2 and R 3 is a halogenated group.
  • R 1 may be chosen from hydrogen and linear or branched d-Csalkyl groups, Cearyl and Cs-Ceheteroaryl, each optionally halogenated.
  • R 1 and the adjacent nitrogen atom together form a salt in which the nitrogen atom is negatively charged (anion) and R 1 is (M n + ) i / n .
  • R 1 and the adjacent nitrogen atom together form a salt in which the nitrogen atom is negatively charged (anion) and R 1 is X + .
  • R 2 is selected from Ci-C2 4 alkanoyl groups perfluorinated linear or branched perfluorinated aryloyl, heteroaryloyl perfluorinated dC ⁇ linear or branched perfluorinated alkanesulfonyl, arylsulfonyl perfluorinated, and heteroarylsulfonyl perfluorinated.
  • the alkanoyl or perfluoroalkylsulfonyl moiety is linear.
  • R 2 is selected from linear or branched perfluoroalkyl-perfluoroalkyl, perfluoroalkyl-perfluoroalkyl, perfluoro-Cs-O-heteroaryloyl, linear or branched perfluoroalkylsulfonyl, perfluoroalkylsulfonyl, and perfluorinated Cs-Ceheteroarylsulfonyl.
  • the group Ci-Csalkanoyie or Ci-Csalkanesulfonyl perfluoro is linear.
  • the sulfamic acid derivative is a compound of Formula II or
  • R 1 and R 3 are as previously defined;
  • R 4 is selected from hydrogen, cyano, fluorine, chlorine, and linear or branched C 1 -C 4 alkyl, C 6 -C 10 aryl or C 5 -C 10 heteroaryl, each optionally halogenated.
  • at least one of R 3 and R 4 is a halogen, that is to say a fluorine or chlorine atom and the other groups are as defined above.
  • R 3 is a halogen, i.e., a fluorine or chlorine atom.
  • R 4 is chosen from linear or branched C 2 -C 4 alkyl groups, Os-Cioaryl or C 5 -C 10 heteroaryl, each optionally being halogenated.
  • R 4 is selected from linear or branched perfluorinated C 1 -C 4 alkyl, perfluorinated C 6 -C 10 aryl, and perfluoro C 6 -C 10 heteroaryl.
  • the group -C 2 perfluoroalkyl 4 is linear.
  • R 4 is chosen from linear or branched d-Csalkyl groups, a Cearyl or a Cs-Ceheteroaryl, each optionally being halogenated.
  • R 4 is selected from linear or branched perfluorinated C 1 -C 6 alkyl groups, perfluorinated Caryl, and perfluorinated C 8 -C 10 heteroaryl.
  • the perfluorinated Ci-Csalkyl group is linear.
  • sulfamic acid derivatives include, without limitation, the following compounds:
  • Compound 35 Compound 36 in which R 1 is as defined above and R 5 is an optionally halogenated linear or branched C 1 -C 4 alkyl group, or OR 5 is 0 " (M n + ) i / n or 0 " X + , where M, X and n are as defined here.
  • R 1 , R 2 , M and n are as previously described.
  • Sources of SO3 include any chemical compound that can generate sulfur trioxide under specific reaction conditions.
  • these compounds may be selected from the following reagents: SO3 (sulfur trioxide itself) and its and its oligomers and polymers; H2SO4 (sulfuric acid); H2S2O7 (disulfuric acid) and other polysulfuric acids and their salts; CISO3H (chlorosulfonic acid) and its salts; FSO3H (fluorosulfonic acid) and its salts; SO3-ammonia complex (sulfamic acid); complexes of sulfur trioxide and organic amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, diisopropylethylamine, pyrrolidines and morpholines substituted with a V-alkyl, pyridine, picoline, lutidine, quinoline, A, N-dimethylaniline, and other amines;
  • the tertiary amines used in the reactions illustrated in Scheme 1 above are amines having three organic substituents (i.e. not having a hydrogen atom covalently bonded to the nitrogen atom). ).
  • Examples of tertiary amines include, but are not limited to, the following amines: trimethylamine, triethylamine, tripropylamine, tributylamine, diisopropylethylamine, pyrrolidines and morpholines substituted with a V-alkyl, quinuclidine, V-methylimidazole, pyridine, picoline, lutidine, quinoline , N, N-dimethylaniline, and other similar amines.
  • the source of sulfur trioxide and the tertiary amine are used as a sulfur trioxide-tertiary amine complex.
  • the chlorinating agents which may be used for the conversion of substituted sulfamic acid and tertiary amine salts to substituted sulfamoyl chlorides may be selected from inorganic and organic acid chlorides, for example, PCI5, POC, SOC, CISO3H, COC, CICOCOCI, sulfur chlorides, cyanuric chloride, acetyl chloride, trifluoroacetyl chloride, methanesulfonyl chloride, trifluoromethanesulfonyl chloride, benzoyl chloride, (trichloromethyl) benzene, benzenesulfonyl chloride, toluenesulfonyl chloride and other compounds which are known to those skilled in the art. In some examples of chlorination, it may be advantageous to add small amounts of / V, / V-dimethylformamide or other ⁇ -disubstituted carboxamides as a catalyst.
  • the fluorinating agents A which can be used for the direct conversion of substituted sulfamic acid and tertiary amine salts to substituted sulfamoyl fluorides may be selected from reactive inorganic and organic acid fluorides, for example, PF 5 , POF 3 , SOF 2 , FSO 3 H, COF 2 , FCOCOF, organic and inorganic hexafluorophosphates, hexafluorosilicates, tetrafluoroborates, sulfur tetrafluoride and its organic derivatives such as DAST (diethylaminosulfide trifluoride) and morpholinosulfide trifluoride; cyanuric fluoride, fluoride acetyl, (trifluoromethyl) benzene, trifluoroacetyl fluoride, methanesulfonyl fluoride, trifluoromethanesulfonyl fluoride, benzoyl
  • the fluorinating agents B which may be used for the conversion of substituted sulfamoyl chlorides to substituted sulfamoyl fluorides include less reactive fluorinating agents such as hydrogen fluoride and fluoride salts, for example, ammonium fluorides. , sodium, potassium, and cesium and their equivalents hydrogen bifluoride (example HN4 + HF2 ”) - complex salts of amines and hydrofluoric acid, such as pyridinium and polyhydrofluorides triethylammonium in addition, all. the fluorinating agents A listed in the preceding paragraph may also be used as fluorinating agents B.
  • fluorinating agents A listed in the preceding paragraph may also be used as fluorinating agents B.
  • the metal base includes any basic compound comprising at least one cation of a metal as a counterion of a basic anion.
  • Known examples include hydroxides, alkoxides and, in some cases, substituted amides of metals, but organometallics and Grignard reagents could also be used as particularly strong bases.
  • Examples of strong acids suitable for conversion of substituted sulfamic acid salts to free sulfamic acids should have a lower pKa than that of the substituted sulfamic acid, or should form an insoluble precipitate with the metal cation.
  • Examples of such acids include hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, and trifluoromethanesulfonic acid.
  • An acidic ion exchange resin could also be used as a source of strong acid.
  • the processes for the preparation of sulfamic acid derivatives defined herein comprise a first step which is the sulfonation of an amine or an amide with sulfur trioxide or a reactive derivative thereof in the presence of a tertiary amine.
  • the product thus obtained is the second compound in Scheme 1 above, for example, a compound of Formula I as defined herein, in which R 3 is 0 " X + , where X + represents a protonated tertiary amine, that is, the compound of Formula I is a tertiary ammonium salt of a substituted sulfamic acid (for example, a substituted ammonium salt of substituted amidosulphonate.)
  • This sulfonation step which results in the formation of a sulfamoyl group, is very rapid, having a significant advantage over the existing processes described above.
  • a first category is the transformation of an amidosulfonate group into a sulfamoyl chloride group.
  • the tertiary ammonium salt of substituted sulfamic acid obtained in the first step is reacted with a chlorinating agent to substitute the oxygen atom with a chlorine atom.
  • the conversion of the amidosulfonate group to the sulfamoyl fluoride group will be accomplished by the reaction of the tertiary ammonium salt of substituted sulfamic acid with a strong fluorinating agent, thereby replacing the oxygen atom with a fluorine atom.
  • sulfamic acid substituted with an acidic ion exchange resin can be converted to sulfamoyl fluoride group by the use of softer fluorinating agents.
  • a metal salt of divalent sulfamic acid such as a substituted azanidosulfonate
  • R 1 is ( M n + ) i / n and R 3 is 0 " (M n + ) i / n )
  • the tertiary ammonium salt of substituted sulfamic acid obtained in the first step is reacted with a metal base so as to substitute
  • These salts can also be used in the preparation of a free substituted sulphamic acid by the reaction of metal salts with a strong acid or by bringing into contact a solution of a sodium salt.
  • sulfamic acid substituted with an acidic ion exchange resin can also be used in the preparation of a free substituted sulphamic acid by the reaction of metal salts with
  • the starting compounds for the preparation of sulfamic acid derivatives are selected from substituted amines, and simple or substituted amides.
  • primary alkylamines can provide N-substituted sulfamic acid derivatives, for example, ⁇ -alkylimidodisulfuric acid salts and other ⁇ -alkylimidodisulfuric acid derivatives, primary carboxamides and the like.
  • Primary sulfonamides can provide mixed secondary amides, and the alkylamides can provide mixed secondary / mixed V-alkylamides.
  • an amine compound or substituted amide (carboxamide or sulfonamide), having at least one hydrogen atom on the nitrogen atom (which can be sulfonated), is inserted into a reactor, and a tertiary amine is then added.
  • the mixture obtained may optionally be diluted in a suitable non-reactive solvent (for example, DMF, dioxane, dichloroethane and the like). The resulting mixture can also be reacted without the addition of solvent.
  • the tertiary amine may be chosen from commercially available products, for example trimethylamine, triethylamine, tripropylamine, tributylamine, pyrrolidines and morpholines substituted with a V-alkyl, N-methylimidazole, pyridine, picoline, lutidine, quinoline, A /, A / -dimethylaniline, diisopropylethylamine, quinuclidine, and others. Then, the sulfonating agent is slowly added to the reaction mixture while monitoring the temperature since the reaction may be exothermic in some cases.
  • the sulfonating agent is selected from SO3 (sulfur trioxide itself) and its oligomers and polymers; H2SO4 (sulfuric acid); H2S2O7 (disulfuric acid) and other polysulfuric acids and their salts; CISO3H (chlorosulfonic acid) and its salts; FSO3H (fluorosulfonic acid) and its salts; S03-ammonia complex (sulfamic acid); sulfur trioxide complexes with organic amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, diisopropylethylamine, pyrrolidines and morpholines substituted with N-alkyl, picoline, lutidine, quinoline, N, N-dimethylaniline, and other amines; sulfur trioxide complexes with other organic compounds such as dioxane, thioxane, dimethylformamide; and
  • the mixture is stirred at a temperature between room temperature and 300 ° C, preferably between 50 ° C and 250 ° C.
  • the product is, in most cases, obtained as a solid ready for further use or in crystalline form, separated by filtration, and optionally purified by recrystallization.
  • the amine or substituted amide is mixed in the solid state with a solid complex of sulfur trioxide and a tertiary amine, preferably sulfur trioxide is a pyridine complex.
  • sulfur trioxide trimethylamine sulfur trioxide or triethylamine sulfur trioxide, which are commercially available.
  • the molar ratio between the amide and the Sulfur trioxide in the mixture is preferably around 1: 1, ie 1 for each sulfonyl group to be introduced into the molecule.
  • the mixture thus obtained is stirred and heated under an inert atmosphere at a temperature in the range of 50 ° C to 300 ° C, preferably in the range of 100 ° C to 250 ° C, to melt the reaction mixture. and allow the reaction to proceed.
  • the reaction time is short, usually ending in less than 10 hours, or less than 4 hours, or even less than 1 hour.
  • the tertiary ammonium salt of the substituted amidosulphonate crystallizes from the melt.
  • the compound can also be recrystallized with an organic solvent, but can be used as such in the subsequent steps.
  • the tertiary ammonium amidosulfonate may be further converted into a sulfamoyl chloride group by reaction with a chlorinating agent selected from inorganic and organic acid chlorides, for example, PCIs, POC, SOC, CISO3H, COC, CICOCOCI , sulfur chlorides, cyanuric chloride, acetyl chloride, trifluoroacetyl chloride, methanesulfonyl chloride, trifluoromethanesulfonyl chloride, benzoyl chloride, (trichloromethyl) benzene, benzenesulfonyl chloride, toluenesulfonyl chloride and other compounds known to the person art.
  • a chlorinating agent selected from inorganic and organic acid chlorides, for example, PCIs, POC, SOC, CISO3H, COC, CICOCOCI , sulfur chlorides, cyanuric chloride, acety
  • dimethylformamide or other N, N-substituted carboxamides may be advantageous to add small amounts of dimethylformamide or other N, N-substituted carboxamides as a catalyst.
  • the selection of the agent of chlorination agent depends on the compounds used during the process and must be adjusted to each specific derivative of sulfamic acid but, in most cases, thionyl chloride (SOCb) can be used as a reagent.
  • SOCb thionyl chloride
  • the molar ratio of tertiary ammonium amidosulfonate to the chlorinating agent is adjusted so that for each mole of amidosulfonate group at least 1 mole of active chloride is used, but excess is often used to accelerate the reaction and ensure its completion.
  • the appropriate chlorinating agent and tertiary ammonium amidosulphonate are mixed pure or diluted in a suitable non-reactive solvent, for example, dichloroethane, and the mixture is heated to a temperature in the range of 30 ° C to 300 ° C, preferably in the range of 40 ° C to 200 ° C, and more particularly at the reflux temperature of the mixture.
  • the reaction time is usually short, typically completing within 24 hours, less than 12 hours. h, or even less than 4 h.
  • the sulfamoyl chloride product can be extracted from the reaction mixture with a low polarity organic solvent.
  • the second step of the process can be accomplished by treating the reaction mixture of the preceding steps, without further purification, with a chlorinating agent, preferably PCI 5 , POCI 3 , SOCI 2 , CISO 3 H, COCI 2 , CICOCOCI , more particularly SOC, COC, CICOCOCI, which form gaseous by-products and thus allow a simpler isolation of the desired product.
  • a chlorinating agent preferably PCI 5 , POCI 3 , SOCI 2 , CISO 3 H, COCI 2 , CICOCOCI , more particularly SOC, COC, CICOCOCI, which form gaseous by-products and thus allow a simpler isolation of the desired product.
  • the reaction mixture of the first step can also be pulverized to increase the reaction rate. The rate can also be accelerated by the addition of about 5 mole% of DM F or other A /, A / -disubstituted carboxamide as a catalyst.
  • the mixture is stirred and heated under an inert atmosphere at a temperature between 50 ° C and 300 ° C, preferably at a temperature between 100 ° C and 250 ° C to melt the reaction mixture and allow the reaction to proceed. .
  • the reaction time is generally short and the reaction is typically completed in less than 24 hours, less than 12 hours, or even less than 4 hours.
  • a complex mixture of tertiary amine hydrochloride, by-products of the chlorinating agent, and substituted sulfamic acid chloride (sulfamoyl chloride compound) is obtained.
  • the mixture is extracted with a solvent which dissolves the desired product and does not dissolve the tertiary amine salts.
  • the substituted sulfamic acid chloride may be distilled or crystallized to obtain the product as a pure or substantially pure compound. If this step is an intermediate step in the preparation of sulfamoyl fluoride compounds, the extract could also be used in a fluorination step without further purification.
  • tertiary ammonium amidosulphonates to sulfamoyl fluorides can be accomplished, inter alia, in two possible ways, either by direct fluorination of the tertiary ammonium salt or by fluorination of the sulphamoyl chloride group obtained in the step described in US Pat. previous paragraphs.
  • the direct fluorination of tertiary ammonium amidosulfonates is carried out by the reaction of the starting material with a strong fluorinating agent, which may be selected from inorganic and organic acid fluorides, including PF5, POF3, SOF2, FSO3H, COF2, FCOCOF, organic and inorganic hexafluorophosphates, hexafluorosilicates, tetrafluoroborates, sulfur tetrafluoride and organic derivatives (such as diethylaminosulfide trifluoride (DAST) and morpholinosulfide trifluoride), cyanuric fluoride, acetyl fluoride, trifluoroacetyl fluoride, methanesulfonyl fluoride, trifluoromethanesulfonyl fluoride, benzoyl fluoride, (trifluoromethyl) benzene, benzenesulfonyl fluoride,
  • the selection of the fluorinating agent depends on the compounds used in the process and must be adjusted to each specific sulfamic acid derivative.
  • the molar ratio of tertiary ammonium amidosulphonate to the fluorinating agent is set so that, for each mole of amidosulfonate group, at least 1 mole of active fluoride is used, but a surplus can also be used to accelerate the reaction and / or to ensure its completion.
  • the appropriate fluorinating agent and tertiary ammonium amidosulfonate are mixed pure or diluted with a suitable non-reactive solvent, for example, dichloroethane.
  • a suitable non-reactive solvent for example, dichloroethane.
  • the mixture is then heated to a temperature in the range of 30 ° C to 300 ° C, preferably in the range of 40 ° C to 200 ° C, and more particularly at the reflux temperature of the mixture.
  • the reaction time is short, it is generally complete in less than 24 hours, less than 12 hours, or even less than 4 hours.
  • the sulfamoyl fluoride can be extracted from the reaction mixture with a low polar organic solvent.
  • the reaction mixture of the first step may be mixed with a fluorinating agent, such as sulfur tetrafluoride or an organic derivative thereof (such as DAST (diethylaminosulfide trifluoride) or morpholinosulfide trifluoride), cyanuric fluoride, acetyl fluoride, trifluoroacetyl fluoride, methanesulfonyl fluoride, trifluoromethanesulfonyl fluoride, benzoyl fluoride, (trifluoromethyl) benzene, benzenesulfonyl fluoride, and toluenesulfonyl fluoride, which are liquid and form less toxic by-products, allowing easier isolation of the desired product.
  • a fluorinating agent such as sulfur tetrafluoride or an organic derivative thereof (such as DAST (diethylaminosulfide trifluoride) or morpholinosulfide trifluoride
  • the reaction mixture of the previous step can also be pulverized prior to use in the present step in order to increase the reaction rate.
  • the mixture is stirred under an inert atmosphere at a temperature in the range of 50 ° C to 300 ° C, preferably in the range of 100 ° C to 250 ° C, to melt the mixture and thereby allow reaction to proceed.
  • the reaction time is short since it is usually complete in less than 24 hours, less than 12 hours, or even less than 4 hours.
  • a complex mixture of amine hydrofluoride tertiary, by-products of the agent fluorinating agent and the desired substituted sulfamic acid fluoride (sulfamoyl fluoride compound) is obtained.
  • the mixture can be extracted with a solvent in which the desired product is soluble and which does not dissolve most or most of the impurities.
  • the substituted sulfamic acid fluoride may also be distilled or crystallized to obtain the product in pure or substantially pure form.
  • a sulfamoyl chloride compound with a reactive fluorinating agent, which may be selected from reactive inorganic and organic fluorides, for example, PF5, POF3, SOF2, FSO3H, COF2, FCOCOF, organic and inorganic hexafluorophosphates, hexafluorosilicates, tetrafluoroborates, sulfur tetrafluoride and organic derivatives (such as DAST or morpholinosulfide trifluoride), cyanuric fluoride, acetyl fluoride, trifluoroacetyl fluoride, methanesulfonyl fluoride, trifluoromethanesulfonyl fluoride, benzoyl fluoride , benzenesulfonyl fluoride, toluenesulfonyl fluoride, hydrogen fluoride and fluoride salts (for example,
  • the selection of a fluorinating agent depends on the compounds used in the process and is tailored to each specific sulfamic acid derivative to be produced.
  • the molar ratio between the sulfamoyl chloride group and the fluorinating agent used is set so that, for each sulfamoyl chloride group, at least 1 mole of active fluoride is used, but preferably a surplus is used to accelerate the reaction and / or to ensure its completion.
  • the conversion may be effected by mixing the appropriate fluorinating agent and sulphamoyl chloride compound, pure or diluted in a suitable non-reactive solvent, for example, dichloromethane, dichloroethane, toluene or combinations thereof, and by heating the mixture at a temperature in the range of 30 ° C to 300 ° C, preferably in the range of 40 ° C to 200 ° C, and more particularly at the reflux temperature of the mixture. In some cases the reaction is very exothermic, so this should be carefully monitored and the fluorinating agent should be added slowly to the chloride or vice versa.
  • the reaction time is generally short and it is typically completed in less than 24 hours, less than 12 hours, or less than 4 hours. After completion, the sulfamoyl fluoride product can be extracted from the reaction mixture using a low polarity solvent.
  • a sulfamoyl chloride compound, extracted in the chlorination step can be mixed, without further purification, with a fluorinating agent, for example, with hydrogen fluoride or a fluoride salt (eg for example, fluoride salt or hydrogen and ammonium bifluoride, sodium, potassium, or cesium), and a complex salt of amine and hydrofluoric acid (such as pyridinium or triethylammonium polyhydrofluorides), which are more easy to obtain and have economic advantages vis-à-vis other fluorinating agents.
  • a fluorinating agent for example, with hydrogen fluoride or a fluoride salt (eg for example, fluoride salt or hydrogen and ammonium bifluoride, sodium, potassium, or cesium), and a complex salt of amine and hydrofluoric acid (such as pyridinium or triethylammonium polyhydrofluorides), which are more easy to obtain and have economic advantages vis-à-vis other fluorinating
  • the mixture is then stirred under an inert atmosphere at a temperature in the range of 30 ° C to 300 ° C, preferably 30 ° C to 150 ° C, to melt the reaction mixture and allow the reaction to proceed. .
  • the reaction time is usually short and the reaction typically ends in less than 24 hours, less than 12 hours, or less than 4 hours.
  • a complex mixture of byproducts, formed of the fluorinating agent, and the desired substituted sulfamic acid fluoride compound is obtained.
  • the mixture can be extracted with a solvent in which the desired product is soluble and which does not dissolve or substantially the majority of the impurities.
  • the substituted sulfamic acid fluoride may be further purified by distillation or crystallization to obtain the product in pure or substantially pure form.
  • salts of divalent sulfamic acids such as substituted azanidosulfonates having a negative charge on the nitrogen atom and on the oxygen atom of the sulfonate
  • primary amines or amides should be used as a product starting at the sulfonation step.
  • the sulfonation step then provides the N-monosubstituted sulfamate of the tertiary amine.
  • These compounds can easily be converted to metal salts by treatment with a suitable metal base.
  • metal bases that can be considered to accomplish this conversion are relatively strong bases, including alkali or alkaline earth metal hydroxides, alkoxides, and substituted amides, organometallics, and Grignard reagents.
  • the appropriate metal base at least 2 equivalents, for example about 2.2 equivalents, of this with respect to the amidosulfonate
  • tertiary ammonium amidosulfonate are mixed and diluted in a non-solvent.
  • suitable reagent for example water and / or a lower aliphatic alcohol (such as alcohols having 1 to 4 carbon atoms), and the mixture is heated to a temperature in the range of 30 ° C to 300 ° C, or in the range of 40 ° C to 200 ° C, or at the reflux temperature of the mixture.
  • the reaction time is quite short, it is generally complete in less than 24 hours, less than 12 hours, or less than 4 hours.
  • the product i.e., azanidosulfonate
  • the product can crystallize directly from the solution, or the mixture can be concentrated and the solid residue recrystallized from a suitable solvent.
  • the reaction mixture (from the first step, without purification) is added to a solution of at least 2 equivalents of an alkaline or alkaline earth base, such as LiOH, NaOH, KOH, RbOH, CsOH, Be ( OH) 2 , Mg (OH) 2 , Ca (OH) 2 , Sr (OH) 2 , Ba (OH) 2 , or the aikoxides of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, or Ba.
  • the solvent used for this reaction is selected from water and lower alcohols such as methanol, ethanol, isopropanol, propanol, and butanol, or a combination thereof.
  • the mixture is then stirred under an inert atmosphere at a temperature in the range of 50 ° C to 300 ° C, or in the range of 100 ° C to 250 ° C.
  • the reaction usually takes place quickly and can be complete in less than 24 hours, less than 12 hours, or even less than 4 hours.
  • a complex mixture of free tertiary amine, sulfonating agent byproducts and the desired metal substituted azanidosulfonate is obtained.
  • the reaction product crystallizes out of the mixture during cooling.
  • the mixture is concentrated to remove volatile compounds and the product is extracted with a solvent and / or recrystallized to give the product in pure or substantially pure form.
  • These salts can be used in the preparation of free substituted sulfamic acids by reacting the metal salts with a strong acid or by contacting the salt solution with an acidic ion exchange resin.
  • These free substituted sulfamic acids can also be used as starting materials for the preparation of other salts which could not be obtained directly by neutralization with the corresponding bases.
  • the desired salts of substituted sulfamic acids can be prepared by cationic metathesis, i.e., cation exchange in an ionic reaction driven by the formation and precipitation of an insoluble compound.
  • lithium bis (fluorosulfonyl) imide could be prepared from lithium perchlorate and potassium bis (fluorosulfonyl) imide in acetonitrile. When mixing a solution of the two reagents, the insoluble potassium perchlorate precipitates while the lithium bis (fluorosulfonyl) imide remains in solution.
  • the sulfamic acid derivatives described herein may, in some embodiments, be used as electrolytes or in electrochemical cell electrolyte compositions such as batteries, electrochromic devices and capacitors.
  • electrochemical cells include an anode, a cathode, and an electrolyte.
  • the sulfamic acid derivatives are in the liquid state at the operating temperature of the electrical apparatus for which they are intended. They may themselves be liquid or may be solubilized in a solvent suitable for use in electrolytes. It may be possible to prepare such electrolytes from sulfamic acid derivatives only or from their mixture with other compounds.
  • compounds for the preparation of electrolytes may be represented by Formula II or III:
  • R 1 is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, and Al
  • R 3 is selected from F and Cl
  • R 4 is selected from fluorine, chlorine, linear or branched C 1 -C 20 alkyl, optionally halogenated C 1 -C 10 aryl or C 8 -C 10 heteroaryl, e.g. linear or branched perfluoro C 2 -C 10 alkyl, perfluorinated C 6 -C 10 aryl, or a perfluorinated C 8 -C 10 heteroaryl.
  • the compounds for the preparation of electrolytes may be represented by Formula IIa or Nia:
  • R 1 , R 4 , M and n are as previously defined, for example, R 1 is (M n + ) i / n and M at each instance is selected from Li, Na, K, Cs, Rb, Be, Mg, Ca, Sr, Ba, and Al, and n is an integer of 1 to 3.
  • the electrolytes are prepared from these sulfamic acid derivatives by dissolving in a suitable electrolyte solvent or a solvating polymer for the preparation of the polymer electrolyte.
  • a suitable electrolyte solvent or a solvating polymer for the preparation of the polymer electrolyte.
  • lithium salts of sulfamic acid derivatives may be dissolved at the appropriate concentration, for example between 0.05 and 3 mol / liter.
  • other salts of sulfamic acid derivatives must be dissolved, for example, sodium salts for sodium batteries, magnesium salts for magnesium cells, etc.
  • Non-limiting examples of electrolyte solvents include dimethyl carbonate, diethyl carbonate, ethyl and methyl carbonate, propylene carbonate, ethylene carbonate, ⁇ -butyrolactone, glyme, diglyme, triglyme, tetraglyme, sulfolane, tetraethylsulfamide, and combinations thereof.
  • Various additives may also be added to the electrolyte composition for improving its properties.
  • Non-limiting examples of polymers include poly (ethylene oxide) and its block copolymers and copolymers, poly (propylene oxide) and its block copolymers and copolymers, poly (dimethylsiloxane) and its block copolymers and copolymers, poly (ethylene oxide) alkylene) and its block copolymers and copolymers, poly (alkylenesulfone) and its block copolymers and copolymers, poly (alkylenesulfonamides) and its block copolymers and copolymers, polyurethanes and its block copolymers and copolymers, poly (vinylalcohol) and its block copolymers and copolymers , as well as their combinations.
  • branched or crosslinked solvating polymers may also be included.
  • Various additives may also be included in the polymer electrolyte composition to improve its properties.
  • (unsaturated) carbonates such as vinylene carbonate, fluoroethylene carbonate and fluorovinylene carbonate, and ethane derivatives (i.e., vinyl compounds) can be added in order to improving the high and / or low voltage stability, for example at a concentration of about 0.1 to about 15 percent by weight, based on the total weight of the electrolyte.
  • the sulfamic acid derivatives may also be used as alkylating agents, for example, the compounds of Formulas II and III above, wherein:
  • R 1 is selected from C1-C2 linear or branched alkyl, aryl and optionally perhalogenated heteroaryl;
  • R 3 is F or Cl
  • R 4 is selected from a fluorine or chlorine atom, and linear or branched C 1 -C 20 alkyl, C 6 -C 10 aryl, C 5 -C 10 heteroaryl, perfluorinated linear C 2 -C alkyl, perfluoro C 6 -C 10 aryl, and C 5 -C 10 heteroaryl groups; perfluorinated.
  • ionic liquids can be obtained directly with hydrophobic anions, which are normally only accessible by alkylations elaborated with haloalkanes followed by anionic metathesis. in a solvent using an alkali metal salt with a hydrophobic anion.
  • This procedure illustrates the rapid sulfonation capacity of a complex ammonia-sulfur trioxide (sulfamic acid).
  • Sulfamic acid (9.7094 g, 0.1 mol) in the form of a fine powder was mixed with ammonium sulphamate (1.14 g, 0.1 mol) powder in a round bottom flask. of 100 ml_ equipped with a condenser and a magnetic bar and brought under dry argon. The mixture was heated and stirred in an oil bath at 150 ° C. The mixture melted and resolidified as a crystalline mass in a few minutes. The mixture was then cooled and the IR analysis gave a spectrum identical to that of an authentic sample.
  • step b) illustrates a rapid sulfonation accomplished with the trimethylamine-sulfur trioxide complex
  • step c) illustrates the reaction of trialkyammonium sulfamate with a metal base to prepare a metal sulfamate.
  • Trimethylammonium Sulfamate Sulfamic acid (19.418 g, 0.2 mol) was dissolved in 30 mL of a 45% aqueous solution of trimethylamine and the mixture was allowed to stand to slowly evaporate.
  • Trimethylammonium sulfamate (3.12 g, 20 mmol) and the trimethylamine-sulfur trioxide complex (2.78 g, 20 mmol) were mixed in a tube with a hot air gun until a mass transparent fondue was obtained (5 min, about 200 ° C). After cooling, the mass resolidified as a glassy solid. The characteristic peaks of the imidodisulfonate anion and the trimethylammonium cation were present in the IR spectrum of the solid.
  • the glassy solid obtained in b) was dissolved in 15 mL of water containing potassium hydroxide (3.4 g, 60 mmol) and the resulting mixture was refluxed for 10 min. No precipitates were formed at this stage, indicating that no or very little K2SO4 (insoluble under these conditions) had been formed, this observation being indicative of a quantitative reaction in step b) .
  • the IR spectrum of the product was identical to that of an authentic sample of potassium imidodisulfonate.
  • Example 3 Preparation of pyridinium N-trifluoromethanesulfonylsulfamate This procedure illustrates the fast and high yielding sulfonation of trifluoromethanesulfonylamide (triflamide) by the pyridine-sulfur trioxide complex.
  • the triflamide (1.49 g, 10 mmol) and the pyridine-sulfur trioxide complex (1.75 g, 11 mmol) were weighed into a 25 mL round bottom flask equipped with a condenser and brought under argon. dry. The mixture was heated with a hot air gun until a transparent, yellowish melt (about 180 ° C) was obtained. The ball was brewed (turned) by hand to ensure proper mixing. After 5 min, the mixture was cooled and a glassy solid was first obtained which crystallized in about 1 h. 19 F NMR analysis of the sample showed that triflamide was converted to the title compound in near quantitative yield.
  • the triflamide (1.49 g, 10 mmol) and the trimethylamine-sulfur trioxide complex (1.39 g, 10 mmol) were weighed into a 25 mL round bottom flask equipped with a condenser and brought under dry argon. .
  • the mixture was heated with a hot air gun until a transparent, yellowish melt (about 180 ° C) was obtained.
  • the ball was brewed (turned) by hand to ensure proper mixing. After 5 min, the mixture was cooled and the product immediately crystallized.
  • NMR analysis of the sample showed that the vast majority of the triflamide was converted to the title compound, i.e., 97% yield, as observed by 19 F NMR.
  • This procedure illustrates the rapid and high yield conversion of a substituted sulfamic acid salt to the substituted sulfamoyl fluoride compound.
  • Step b) of this process illustrates the rapid and high yield conversion of a substituted sulfonamide to the substituted sulfamoyl fluoride compound.
  • Liquid ammonia 120 mL was condensed in a 500 mL round-bottomed Schlenk-type flask equipped with a magnetic bar. At -50 ° C, nonafluorobutanesulfonyl fluoride (84 g, 284 mmol) was added dropwise with stirring to partially frozen ammonia over a period of one hour. The mixture was then allowed to warm to room temperature, which was then stirred overnight. The contents of the flask were washed with cold water in a beaker, acidified with hydrochloric acid to pH ⁇ 1 and extracted with ethyl acetate (4 ⁇ 50 mL). The organic phases were combined, dried with Na 2 SO 4 and concentrated to obtain 80 g (95%) of a colorless oil which solidified on standing to a white waxy solid.
  • the nonafluorobutanesulfonylamide (3.19 g, 10.7 mmol) from step (a) and the pyridine-sulfur trioxide complex (1.95 g, 12.3 mmol) were weighed into a round bottom flask. mL equipped with a condenser and brought under dry argon. The mixture was heated with a hot air gun until a transparent, yellowish melt (about 180 ° C) was obtained. The ball was brewed (turned) by hand to ensure proper mixing. After 15 min, the mixture was cooled and a glassy solid formed. To this cooled mixture, SOC (5 mL) was added and the mixture was stirred at reflux for 1 h to form the intermediate chlorosulfamoylamide.
  • Example 7 Preparation of N-fluorosulfonyltridecafluorohexanesulfonylamide a) Tridecafluorohexanesulfonylamide Liquid ammonia (30 mL) was condensed in a Schlenk-type round bottom 100 mL flask equipped with a magnetic bar. At -50 ° C, tridecafluorohexanesulfonyl fluoride (25 g, 62 mmol) is added to the stirred drop with partially frozen ammonia over a period of one hour. The mixture was allowed to warm to room temperature, which was then stirred overnight.
  • Tridecafluorohexanesulfonyl fluoride 25 g, 62 mmol
  • step (a) The tridecafluorohexanesulfonylamide (1 g, 2.5 mmol) of step (a) and the pyridine-sulfur trioxide complex (0.62 g, 3.9 mmol) were weighed in a round bottom flask. of 25 mL equipped with a condenser and brought under dry argon. The mixture was heated with a hot air gun until a transparent, yellowish melt (about 180 ° C) was obtained. The ball was brewed (turned) by hand to ensure proper mixing. After 15 min, the mixture was cooled and a glassy solid formed. NMR analysis confirmed that all the pyridine was in the pyridinium ion form and that the sulfonation was on the amide group, as indicated by the displacement of the two CF2 groups closest to the sulfonyl group.
  • the 19 F NMR analysis showed a characteristic triplet triplet at +58 ppm, which was assigned to the fluorosulfamoyl group linked to the tridecafluorohexanesulfonimide group (coupled with two CF 2 groups, also confirmed by the 19 F-gCOSY experiment), which demonstrated the presence of tetrabutylammonium N-fluorosulfonyltridecafluorohexanesulfonimide in the extract.
  • the tosylamide (3.42 g, 20 mmol) and the pyridine-sulfur trioxide complex (3.66 g, 23 mmol) were weighed into a 25 mL round bottom flask equipped with a condenser and brought under dry argon.
  • the mixture was heated with a hot air gun until a transparent, yellowish melt (about 200 ° C) was obtained.
  • the ball was brewed (turned) by hand to ensure proper mixing. After 10 min, the mixture was allowed to cool and a crystalline solid was formed. 2 g of this solid was dissolved in cold water (40 mL) and KOH was added to bring the pH to 10. Acetic acid was then added to set the pH at 7, 4.
  • Triflamide (14.9 g, 100 mmol) and the pyridine-sulfur trioxide complex (19.2 g, 120 mmol) were weighed into a 100 ml round bottom flask equipped with a condenser and a bar magnetic, and brought under dry argon. The mixture was stirred and heated in an oil bath (180 ° C) until a clear, yellowish melt (20-25 min) was obtained. The mixture was then cooled to 70 ° C, thionyl chloride (10 mL, 140 mmol) was added through the condenser and gas was monitored using a bubbler.
  • LiFSI Lithium bis (fluorosulfonyl) imide
  • EC ethylene carbonate
  • DEC diethyl
  • a LiFePC electrode (LFP) was prepared using a mixture of LiFePC, carbon black and polyvinylidene fluoride (PVDF) in a ratio 84: 3: 3: 10 (wt%) in N-methylpyrrolidone (NMP). This mixture was then spread on an aluminum current collector. The electrode material was dried at 120 ° C in a vacuum oven for 12 hours before use.
  • PVDF polyvinylidene fluoride
  • a graphite electrode (OMAC, Osaka, Japan) was prepared by mixing the graphite, black of carbon and PVDF in a ratio of 92: 2: 6 (wt%) in NMP, which was then applied to a copper current collector.
  • the electrode material was dried at 120 ° C in a vacuum oven for 12 hours before use.
  • the electrodes were cut (punched) to a size that fitted the button cell type assembly.
  • the above-mentioned electrolyte was used in these button-type cells using the graphite or LFP electrode, a polypropylene separator and metallic lithium as the opposite polarity electrode.
  • the cells were also subjected to stability tests using a C / 4 loading rate and a 1 C discharge rate (results shown in Figures 3 (a) and (b)).
  • Cells including the LFP showed excellent retention capacity with 146 mAh / g at the 195th cycle. With graphite, a slight expected reduction in capacity was observed, however, the capacity still being 322 mAh / g after 200 cycles.
  • LiFSi produced by the present method is suitable for use as an electrolyte salt in lithium or lithium-ion batteries.
  • Lithium N- (fluorosulfonyl) trifluoromethansulfonimide (LiFTFSI) prepared as in Example 12 was dissolved in a 3: 7 (vol: vol) mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) to give obtaining a concentration electrolyte 1 M.
  • a graphite electrode (OMAC, Osaka, Japan) was prepared as in Example 13.
  • the electrolyte was used in button cells with the graphite electrode, a polypropylene separator and metallic lithium as the opposite polarity electrode.
  • the cell was cycled between 2.5 and 0.01 V vs Li metal.
  • the formation of the button cell was first performed at a C / 24 rate (results shown in Figure 4).
  • the cells were also subjected to stability tests with a C / 4 feed ratio and a 1 C discharge rate (results for graphite shown in Figure 5). As expected, the cell containing graphite literallynré a slight drop in capacity but the capacity attegnait still 310 mAh / g at 60th cycle.
  • Example 15 Comparison of capacity levels for LiPF 6 , LiFSI and LiFTFSI used with a graphite electrode 1M solutions of LiPF6, LiFSI and LiFTFSI were prepared by dissolving the salts in a 3: 7 (vol / vol) mixture of ethylene carbonate (EC) and diethyl carbonate (DEC). The LiPF6 solution also contained 2% by weight of vinylene carbonate.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • Button cell cells were prepared using metal lithium and graphite electrodes as described in Example 13, a polypropylene separator, and the above solutions as electrolytes. The cells were cycled between 2.5 and 0.01 V vs Li metal. All cells were subjected to two C / 24 formation cycles and capacity levels were examined by measuring discharge capacity versus discharge rate (see Figure 6).
  • the LiFSI and LiFTFSI salts demonstrated nearly identical power capacity characteristics, which were approximately 50 mAh / g higher than that for LiPF6 over the entire power range. This indicates that the SEI layer formed on the graphite with the electrolytes LiFSI and LiFTFSI is higher quality than that formed when LiPF6 is used.
  • the two salts prepared according to the present method are therefore very suitable for use in electrolytes of lithium or lithium-ion batteries, for example, using a graphite anode.

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