TECHNICAL FIELD

The technical field generally relates to processes for the preparation of sulfamic acids derivatives, for instance, halogenated derivatives and their salts, including ionic liquids. The technical field also relate to these sulfamic acid derivatives and to their use in electrolytes for electrochemical applications.

BACKGROUND

Some sulfamic acid derivatives, due to their unique properties, gained importance in electrochemical applications. Examples of such compounds include bis(fluorosulfonyl)amide, N-fluorosulfonyl(trifluoromethanesulfonyl)amide and their salts, especially their lithium salts (commonly called LiFSI and LiFTFSI). 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 U.S. Pat. Nos. 6,365,301, 5,874,616, and US 2011/007086).

Known methods for their preparation include the reaction of halosulfuric acids with isocyanates, sulfinylamines and phosphazenes. However, these methods are time consuming, typically requiring reaction times over 20 hours to ensure a good conversion.

The reaction of various amides with phosphorus pentachloride yielding trichlorophosphazenes, which can in turn be reacted with various acids to produce new disubstituted amides, especially bis(fluorosulfonyl)amide and N-fluorosulfonyl-(trifluoromethanesulfonyl)amide have been previously described (see R. Appel et al.,Chem. Ber.1962, 95, 625-626; W. Haubold et al.,Z. Anorg. Alig. Chem1967, 352, 113-121; V. H. W. Roesky et al.,Inorg. Nucl. Chem. Lett.1971, 7, 171-175; and K. Xu et al.,Inorg. Chem. Comm.1999, 2, 261-264). The main disadvantage of these is the use of highly corrosive and toxic phosphorus compounds and the required separation of desired products from their by-products.

R. Appel et al., Chem. Ber. 1962, 95, 1753-1755; R. Appel et al.,Chem. Ber.1964, 97, 849-851; and U.S. Pat. No. 8,134,027, described reactions of acids with chlorosulfonyl isocyanate. The products obtained are chlorosulfonyl substituted amides. However, prolonged reaction times, i.e. over 24 h in some cases, are needed to complete the reactions.

The reaction of amides with SO2Cl2and chlorosulfonic acid typically generates amides substituted with chlorosulfonyl groups, and this, also after 24 h hours under reflux (see see M. Beran et al.,Z. Anorg. Allg. Chem.,2005, 631, 55-59; M. Beran et al.,Polyhedron2010, 29, 991-994; and Chinese patent application No. 10174724).

US application published under No. 2011/0070486 describes the preparation of N-fluorosulfonyl(trifluoromethanesulfonyl)amide by acylation of potassium trifluoromethanesulfonimide with non-commercially available fluorosulfonic anhydride. U.S. Pat. No 5,874,616 describes the preparation, at low temperatures, of N-fluorosulfonyl-(trifluoromethanesulfonyl)amide by acylation of trifluoromethanesulfonylamide using highly toxic sulfuryl fluoride, which makes the method inappropriate when a larger scale production is contemplated.

On the other hand, acylation of sulfamic acid was also used to prepare various N-sulfonyl sulfamic acids (see Scozzafava, A. et al.,J. Enz. Inhib.,2000, 15(5), 443-453). However, the publication only reports the preparation of substituted sulfamic acid and some salts.

All of the aforementioned methods require long reaction times, and are thus not adapted for cost efficient production.

Sulfonation of non-halogenated (more reactive) amides with the pyridinium-sulfur trioxide complex were also described in P. Baumgarten, et al.,Berichte d. D. Chem. Gesellschaft(A and B Series) 1931, 64, 1582-1588. Other sulfur trioxide complexes were also prepared and used in sulfonations, such as those reviewed in Gilbert, E. E.,Chem. Rev.,1962. 62(6): p. 549-589.

A group also studied the preparation of various sulfamic acid derivatives by sulfonation of amines and amidosulfates using sulfur trioxide complexes (see Kanetani, F. et al., Yuki Gosei Kagaku Kyokaishi (J. Synth. Org. Chem. (Japan)), 1974. 32, p. 460-466, and Kanetani, F. et al,Bull. Chem. Soc. Jap.,1974. 47(11), p. 2713-2716). The further transformation of these derivatives into halogenated sulfamic acid derivatives was not described.

Preparation of sulfonyl chlorides from sulfonic acid salts is known to organic chemists (e.g., see Bögemann, M. et al., eds.Schwefel-,Selen-,Tellur-Verbindungen. Methoden der organischen Chemie(Houben-Weyl), 4. Auflage, ed. E. Müller. Vol. IX. 1955, Georg Thieme: Stuttgart, pp 391-394, 561-597; Vogel, A.,Vogel's Textbook of Practical Organic Chemistry.5thed 1989, London: Longman Group, Ltd., pp 1284; and Blotny, G.,Tetrahedron Letters,2003. 44(7): p. 1499-1501).

Preparation of sulfonyl fluorides was also described in Olah, G. et al.,J. Org. Chem.,1961. 26(1): p. 237-238.; Olah, G. A. et al.,Synthesis,1973: p. 487-488.; Oláh, G. et al.,Chem. Ber.,1956. 89(4): p. 862-864; and Olah, G. A., et al.,J. Org. Chem.,1979. 44(22): p. 3872-3881. Several compounds were also prepared from sulfur fluorides (see Hudlicky, M.,Org. Reactions,1988. 35: p. 513-637).

Therefore, it is highly desirable to develop an improved process for the production of sulfamic acid derivatives.

SUMMARY

According to one aspect, here is described a process for the preparation of a sulfamic acid derivative, or a salt thereof with one or more metallic or organic cations. For instance, the sulfamic acid derivative is defined according to Formula I:


wherein,

R1is selected from hydrogen and a linear or branched C1-C24alkyl, a C6-C10aryl or a C5-C10heteroaryl group, the alkyl, aryl and heteroaryl groups being optionally halogenated, or R1and the adjacent nitrogen atom together form a salt wherein the nitrogen atom is negatively charged (anion) and R1is (Mn+)1/nor X+;

R2is selected from hydrogen, cyano, sulfonyl, chlorosulfonyl, fluorosulfonyl, chlorocarbonyl, fluorocarbonyl, optionally halogenated linear or branched C1-C24alkanoyl, optionally halogenated aryloyl, optionally halogenated heteroaryloyl, optionally halogenated linear or branched C1-C24alkanesulfonyl, optionally halogenated arylsulfonyl, and optionally halogenated heteroarylsulfonyl;

R3is selected from OH, F, Cl, O−(Mn+)1/n, O−X+, and optionally halogenated linear or branched C1-C24alkoxy;

(Mn+)1/nis a metal cation, wherein M is a metal and n is an integer selected from 1 to 4, for instance, M is Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, Zn, Cu, Sc, 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, Sc, and Ti, for instance M is an alkali metal, 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 instance, selected from ammonium, alkylammonium, dialkylammonium, trialkylammonium, tetraalkylammonium, 1,3-dialkylimidazolium, N-alkylpyrrolidinium, N-alkylpiperidinium, trialkyloxonium, trialkylsulfonium, tetraalkylphosphonium, and the like;

the process comprising the steps of:

i) contacting a compound of the formula:


with a sulfur trioxide source and a tertiary amine and heating at a temperature comprised between about 50° C. and about 300° C.; andii) optionally converting the product obtained in step (i) to produce a compound of Formula I.

When the above compound, or any other compound described in the present document, is in the form of a salt, then the ratio of anion to cation is understood as aiming for the electroneutrality of the compound (for example, two sulfamic acid derivatives of a −1 charge may be required when a magnesium Mg2+cation is used, similarly, two lithium (+1) cations may be combined to a dianion of a sulfamic acid derivative).

According to one embodiment, the sulfur trioxide source 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; ClSO3H (chlorosulfonic acid) and its salts; FSO3H (fluorosulfonic acid) and its salts; SO3-ammonia complex (sulfamic acid); complexes of sulfur trioxide with organic amines; complexes of sulfur trioxide with other organic compounds such as dioxane, thioxane, dimethylformamide; and acylsulfates, which are generated by introduction of SO3into dry carboxylic acids, for example, acetyl sulfate (CH3C(O)OSO3H).

In another embodiment, the sulfur trioxide source and the tertiary amine are added together as a complex, and the tertiary amine is selected from the following compounds: trimethylamine, triethylamine, tripropylamine, tributylamine, diisopropylethylamine, N-alkyl substituted pyrrolidines and morpholines, pyridine, picoline, lutidine, quinoline, N,N-dimethylaniline, and other amines. For instance, the complex is selected from pyridine-sulfur trioxide, trimethylamine-sulfur trioxide and triethylamine-sulfur trioxide complexes.

In another embodiment, step (i) comprises heating at a temperature of between about 100° C. and about 250° C., or between about 150° C. and about 220° C., for instance, for 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 a solvent.

According to a further embodiment, the process comprises step (ii) which includes contacting the product obtained in step (i) with a metallic base. For example, the metallic base is selected from metal hydroxides, metal alkoxides, organometallics and Grignard reagents, said metal being selected from alkali metals, alkaline earth metals, and aluminum, for instance, the metallic base is a metal hydroxide.

In another embodiment, the process further comprises a step of treating the product of step (i) or of step (ii) with a strong acid or passing a solution thereof through an acidic ion exchange resin. For instance, the strong acid is selected from hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, and trifluoromethanesulfonic acid.

In a further embodiment, the process comprises step (ii) which includes contacting the product obtained in step (i) with a chlorinating agent. For example, the chlorinating agent is selected from inorganic and organic acid chlorides, such as PCl5, POCl3, SOCl2, ClSO3H, COCl2, ClCOCOCl, sulfur chlorides, cyanuric chloride, acetyl chloride, trifluoroacetyl chloride, methanesulfonyl chloride, trifluoromethanesulfonyl chloride, benzoyl chloride, (trichloromethyl)benzene, benzenesulfonyl chloride, toluenesulfonyl chloride and the like, for instance, the chlorinating agent is SOCl2, COCl2, or ClCOCOCl. In yet another embodiment, the process further comprises a step of contacting the product obtained in step (ii), after chlorination, with a fluorinating agent. For instance, the fluorinating agent is selected from fluoride or hydrogen difluoride salts (such as an ammonium, sodium, potassium, or cesium salt, e.g. KF or KHF2), and a complex salt of amines and hydrofluoric acid (like pyridinium or triethylammonium polyhydrofluorides).

In a further embodiment, the process comprises step (ii) which includes contacting the product obtained in step (i) with a strong fluorinating agent. In another embodiment, the fluorinating agent is selected from reactive inorganic and organic acid fluorides, such as PF5, POF3, SOF2, FSO3H, COF2, FCOCOF, organic and inorganic hexafluorophosphates, hexafluorosilicates, tetrafluoroborates, sulfur tetrafluoride and organic derivatives (like diethylaminosulfur trifluoride (DAST) and morpholinosulfur trifluoride), cyanuric fluoride, acetyl fluoride, trifluoroacetyl fluoride, methanesulfonyl fluoride, trifluoromethanesulfonyl fluoride, benzoyl fluoride, (trifluoromethyl)benzene, benzenesulfonyl fluoride, toluenesulfonyl fluoride and the like.

According to another aspect, this relates to a sulfamic acid derivative prepared by a process as herein described. In one embodiment, the sulfamic acid derivative is defined by Formula I:


wherein,

R1is selected from hydrogen and linear or branched C1-C24alkyl, C6-C10aryl or C5-C10heteroaryl groups, the alkyl, aryl and heteroaryl groups being optionally halogenated, or R1and the adjacent nitrogen atom together form a salt wherein the nitrogen atom is negatively charged (anion) and R1is (Mn+)1/nor X+;

R2is selected from hydrogen, cyano, sulfonyl, chlorosulfonyl, fluorosulfonyl, chlorocarbonyl, fluorocarbonyl, optionally halogenated linear or branched C1-C24alkanoyl, optionally halogenated aryloyl, optionally halogenated heteroaryloyl, optionally halogenated linear or branched C1-C24alkanesulfonyl, optionally halogenated arylsulfonyl, and optionally halogenated heteroarylsulfonyl;

R3is selected from OH, F, Cl, O−(Mn+)1/n, O−Z+, and an optionally halogenated linear or branched C1-C24alkoxy;

(Mn+)1/nis a metal cation, wherein M is a metal and n is an integer selected from 1 to 4, for instance, M is Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, Zn, Cu, Sc, 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, Sc, and Ti, for instance M is an alkali metal, 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 instance, selected from ammonium, alkylammonium, dialkylammonium, trialkylammonium, tetraalkylammonium, 1,3-dialkylimidazolium, N-alkylpyrrolidinium, N-alkylpiperidinium, trialkyloxonium, trialkylsulfonium, tetraalkylphosphonium and the like.

In one embodiment, R1is (Mn+)1/nwhere M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, Zn, Cu, Sc, Y, Fe, Co, Ni, Ti, Sn, V, Cr, and Mn. In another embodiment, M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, Zn, Sc, and Ti, or M is Li, Na or K.

In another embodiment, R1is X+and is selected from ammonium, alkylammonium, dialkylammonium, trialkylammonium, tetraalkylammonium, 1,3-dialkylimidazolium, N-alkylpyrrolidinium, N-alkylpiperidinium, trialkyloxonium, trialkylsulfonium, tetraalkylphosphonium ions and other similar ions. In some cases, a salt including an organic cation may be liquid at room temperature, thereby forming an ionic liquid.

In one embodiment, R2is selected from the groups chlorosulfonyl, fluorosulfonyl, chlorocarbonyl, fluorocarbonyl, linear or branched C1-C24alkanoyl, perfluorinated linear or branched C1-C24alkanoyl, linear or branched C1-C24alkanesulfonyl, and perfluorinated linear or branched C1-C24alkanesulfonyl, all other groups being as herein defined.

In a further embodiment, the sulfamic acid derivative is a compound of Formula II:


wherein R1and R3are as previously defined; and

R4is selected from hydrogen, cyano, fluorine, chlorine, and a linear or branched C1-C24alkyl, C6-C10aryl or C5-C10heteroaryl group, each being optionally halogenated.

In another embodiment, the sulfamic acid derivative is a compound of Formula III:


wherein R1, R3, and R4are as previously defined.

In one embodiment, R4in Formula II or III is selected from fluorine, chlorine, and a linear or branched C1-C24alkyl, all other groups being as herein defined. In another embodiment, R4is a perfluorinated linear or branched C1-C24alkyl, perfluorinated C6-C10aryl, or perfluorinated C5-C10heteroaryl group, for instance, a perfluorinated linear C1-C24alkyl group, all other groups being as herein defined.

In another embodiment, according to any one of the above formulae, R1is Mn+1/nwherein M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, and Al, all other groups being as herein defined. Alternatively, R1is selected from a linear or branched C1-C24alkyl, a C6-C10aryl and a C5-C10heteroaryl, each being an optionally perhalogenated, for instance, R1is a perhalogenated linear or branched C1-C24alkyl, such as a perfluorinated linear or branched C1-C24alkyl, all other groups being as herein defined.

In yet another embodiment, R1is (Mn+)1/nand R3is O−(Mn+)1/n, wherein M and n are the same in each instance and are as herein defined, for instance, 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 herein defined. In a further embodiment, R3is F or Cl, the other groups being as herein defined.

This document also refers to a sulfamic acid derivative selected 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 further relates to an electrolyte or electrolyte composition comprising a sulfamic acid derivative prepared by a process of the present document, or as defined herein. For instance, the electrolyte may further comprise a solvent or solvating polymer suitable for preparing polymer electrolytes. The electrolyte may be in liquid or gel form, optionally including a separator (membrane), or in solid form.

Also contemplated are electrochemical cells comprising an electrolyte as defined herein, an electrode and a counter-electrode, for example, a battery, an electrochromic device, or a capacitor. According to one example, the battery is a lithium or lithium-ion battery. The use of these electrochemical cells in electric or hybrid vehicles, or in computing and/or telecommunications devices is also contemplated.

Although the above compounds may be useful in electrochemistry, other uses, such as chemical catalysis, may also be contemplated.

Other features of the present technology will be better understood upon reading the herein below description.

