CN114315727A - Sulfonyl diazoles and N- (fluorosulfonyl) azoles and methods for their preparation - Google Patents

Abstract

The present invention provides a process for the preparation of N- (fluorosulfonyl) azoles, sulfonyldiazoles, or derivatives thereof; and related products, including N- (fluorosulfonyl) azoles, sulfonyldiazoles, and related derivatives. The symmetric or asymmetric sulfonyldiazoles may also be prepared by reacting sulfonyl fluorides with oxazoles, in the presence of metal fluorides, in one vessel or by a two-step reaction.

Description

Sulfonyl diazoles and N- (fluorosulfonyl) azoles and methods for their preparation

Technical Field

The present invention relates generally to the chemical synthesis of azole derivatives. More particularly, the disclosed subject matter relates to methods of making N- (fluorosulfonyl) azoles, sulfonyldiazoles, or related derivatives thereof.

Background

N, N '-sulfonyldiimidazole (or 1,1' -sulfonyldiimidazole) having SO₂Im₂In the structural formula, Im represents an imidazolyl group. SO in the literature₂Im₂For about 150 different reactions. SO (SO)₂Im₂Also as an additive for lithium ion batteries.

SO₂Im₂First in 1966 from imidazole and sulfonyl chloride (SO)₂Cl₂) And (4) preparation. This method is most widely used for producing SO₂Im₂The method of (1). SO (SO)₂Im₂Also from N- (trimethylsilyl) imidazole (Me)₃Siim) and SO₂Cl₂And (4) preparation.

The preparation and use of sulfonylbis (2-methylimidazole) has been reported several times in the literature and sulfonylbis (2-methylimidazole) is prepared by reacting an excess of 2-methylimidazole with SO₂Cl₂Prepared by reaction in dichloromethane. Except for SO₂Im₂And sulfonylbis (2-methylimidazole), other sulfonylbisimidazoles are unknown.

Except for SO₂Im₂And sulfonylbis (2-methylimidazole), other sulfonylbisoxazoles reported in the literature include compounds such as sulfonylbis- (1,2, 4-triazole) and sulfonylbispyrazole. For example, sulfonyl bis- (1,2, 4-triazole) (SO₂Tz₂) And sulfonyl bispyrazole (SO)₂Pz₂) By 1- (trimethylsilyl) -1,2, 4-triazole (Me)₃Sitz) and 1- (trimethylsilyl) pyrazole (Me)₃SiPz) with SO₂Cl₂In pentane. SO (SO)₂Tz₂Also using Me₃SiTz/SO₂Cl₂But prepared in toluene.

Sulfonyldiimidazole (SO)₂Im₂) Is useful but is currently very expensive and its high cost prevents its broader use. One fundamental reason is that all are currently used for the preparation of SO₂Im₂All methods utilize SO₂Cl₂As a reactant. SO (SO)₂Cl₂Are highly corrosive and toxic liquids, adding additional cost to the associated manufacturing process.

Therefore, it would be desirable to have a new safer and cheaper process with a greater ability to produce different types of N- (fluorosulfonyl) azoles, sulfonyldiazoles, or their related derivatives.

Disclosure of Invention

The present invention provides processes for the preparation of N- (fluorosulfonyl) azoles, sulfonyldiazoles, or their related derivatives, and the resulting products.

According to some embodiments, the present invention provides a method of obtaining N- (fluorosulfonyl) azoles by reacting sulfonyl fluorides with azoles, azole anion compounds ("azole salts"), or combinations thereof. The present invention also provides methods for obtaining symmetric and asymmetric sulfonyldiazoles by further reacting N- (fluorosulfonyl) azoles with oxazoles, azolium salts, or combinations thereof. These reactions can be combined in a single vessel to prepare symmetric sulfonyldiazoles such as sulfonyldiimidazole directly from sulfuryl fluoride. These reactions may be carried out in the presence of a metal fluoride and optionally an aprotic solvent. Examples of azoles used include, but are not limited to, imidazole, pyrazole, 1,2, 4-triazole, benzimidazole, benzotriazole, indazole, and substituted derivatives thereof, such as 2-methylimidazole, 2-methylbenzimidazole, and 3, 5-dimethylpyrazole. Examples of metal fluorides as inorganic aprotic bases include sodium fluoride, potassium fluoride, cesium fluoride, and combinations thereof.

In some embodiments, N- (fluorosulfonyl) oxazole (oxazolyl 1-SO) having a first oxazolyl structure (oxazolyl 1) is first prepared₂F) And then reacted with an azole or azole salt having a second oxadiazolyl structure (azolyl 2) to prepare an N, N' -sulfonyldiazole. N- (fluorosulfonyl) azoles (azolyl 1-SO)₂F) Is prepared by reacting SO₂F₂By reaction with azolyl 1. At least one step of the reaction is carried out in the presence of a metal fluoride, and optionally in the presence of an aprotic solvent, to form the N, N' -sulfonyldiazole (azolyl 1-SO)₂-azolyl 2). Can separate out N, N' -sulfonyl diazole (azolyl 1-SO)₂-azolyl 2). The structures of the azoles used in the present invention, including the first azolyl structure and the second azolyl structure, may have any suitable protic azole as described above as the parent structure.

The N, N' -sulfonyldiazoles may be symmetrical or asymmetrical. In some embodiments, the first oxazolyl structure (oxazolyl 1) and the second oxazolyl structure (oxazolyl 2) are the same. The N, N' -sulfonyldiazoles are symmetrical. In some embodiments, the first oxazolyl structure (oxazolyl 1) and the second oxazolyl structure (oxazolyl 2) are different. The N, N' -sulfonyldiazoles are asymmetric.

One or more of the reactions described herein may optionally be carried out in the presence of an aprotic solvent. Examples of suitable aprotic solvents include, but are not limited to, acetonitrile, dichloromethane, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, methylcyclopentyl ether, methyl tert-butyl ether, propionitrile, butyronitrile, toluene, saturated hydrocarbon solvents such as n-hexane, heptane, pentane, and the like, and any combination thereof. In some embodiments, the reactants may be suspended or dissolved in a solvent.

In some embodiments, the azolium salt has a metal cation. Examples of suitable metals include, but are not limited to, lithium, sodium, potassium, cesium, magnesium, and combinations thereof.

In some embodiments, the azolium salt is derived from a protic (azolyl 2) and an aprotic azolyl. The terms "proton" and "aprotic" are defined in the description of the embodiments.

In another aspect, the present invention provides a process for producing a symmetric N, N' -sulfonyldiazole directly in a single container. Sulfuryl fluoride (SO) in the presence of a metal fluoride, and optionally in the presence of an aprotic solvent₂F₂) With an azole or azole salt having a first azole group structure (e.g., azole group 1). Isolation of the N, N' -sulfonyldiazole (azolyl 1-SO)₂-azolyl 1). Examples of suitable azole-based structures include, but are not limited to, imidazole, pyrazole, 1,2, 4-triazole, benzimidazole, benzotriazole, indazole, 2-methylimidazole, 2-methylbenzimidazole, and 3, 5-dimethylpyrazole.

In some embodiments, the azolium salt has a metal cation, which may be lithium, sodium, potassium, cesium, magnesium, or combinations thereof. In some embodiments, the azolium salt is derived from proton azolyl 1 (azolyl 1) and a metal fluoride. Examples of metals in the metal fluoride include sodium, potassium, cesium, and combinations thereof.

Examples of N, N '-sulfonyldiazoles according to the invention include, but are not limited to, N' -Sulfonyldiimidazole (SO)₂Im₂) N, N' -Sulfonyldipyrazoles (SO)₂Pz₂) 1,1' -sulfonylbis (1,2, 4-triazole) (SO)₂Tz₂) 1,1' -sulfonylbis (2-methyl-1H-imidazole), 1' -sulfonylbis (benzimidazole), 1' -sulfonylbis (benzotriazole)1- (1H-imidazole-1-sulfonyl) -1H-pyrazole (ImSO)₂Pz) and 1,1' -sulfonylbis (3, 5-dimethylpyrazole).

Detailed Description

For the purposes of the following description, it is to be understood that the embodiments described below may assume alternative variations and embodiments. It should also be understood that the specific articles, compositions, and/or methods described herein are exemplary and should not be considered as limiting.

In the present invention, the singular forms "a", "an" and "the" include plural references, and reference to a particular numerical value includes at least that particular value, unless the context clearly dictates otherwise. Thus, for example, reference to a "ring structure" is a reference to one or more of such structures and equivalents thereof known to those skilled in the art, and so forth. When values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another embodiment. As used herein, "about X" (wherein X is a numerical value) preferably means. + -. 10% of the cited value, inclusive. For example, the phrase "about 8" preferably refers to a value of 7.2 to 8.8, inclusive; as another example, the phrase "about 8%" preferably (but not always) refers to a value of 7.2% to 8.8%, inclusive. When present, all ranges are inclusive and combinable. For example, when a range of "1 to 5" is recited, the recited range should be interpreted to include the ranges "1 to 4", "1 to 3", "1-2 and 4-5", "1-3 and 5", "2-5", and the like. Additionally, when a list of alternatives is provided with certainty, such list may be construed to mean that any alternatives may be excluded, for example, by a negative limitation in the claims. For example, when a range of "1 to 5" is recited, the recited range can be interpreted as including the case where any one of 1,2, 3, 4, or 5 is negatively excluded; thus, a recitation of "1 to 5" may be interpreted to mean "1 and 3-5, but not 2", or simply "2 is not included therein". It is intended that any component, element, attribute or step specifically referenced herein be explicitly excluded from the claims, whether or not such component, element, attribute or step is listed as a substitute or whether or not it is referenced individually.

The terms "protic" and "aprotic" as used herein refer to the presence or absence of a hydrogen atom bonded to a nitrogen or oxygen atom. The term "proton" is used because the labile hydrogen atom is usually mobile in the form of a proton, but does not necessarily have to be acidic in order to be a proton. For example, diethylamine is both a protic acid and a very weak acid. Its N-H hydrogen can only be removed with butyllithium or the like, but its N-H hydrogen is very unstable in many solvents. Protic hydrogen is primarily bonded to a nitrogen or oxygen atom, while aprotic hydrogen is primarily bonded to a carbon atom. Thus, the term "aprotic solvent" refers to a solvent that has no-OH or-NH moieties. For example, diethyl ether is an aprotic solvent and ethanol is a protic solvent. The base may be protic or aprotic. Certain metal fluorides (e.g., NaF, KF, CsF) can act as aprotic bases. The anion (and cation) may be protic or aprotic. The azoles may also be protic or aprotic. Examples of aprotic oxazoles are thiazole and oxazole. Examples of protic azoles include, but are not limited to, imidazole, pyrazole, 1,2, 4-triazole, benzimidazole, benzotriazole, indazole, 2-methylimidazole, 2-methylbenzimidazole, and 3, 5-dimethylpyrazole. The protic oxazoles may be treated with a base to give the aprotic azolate salt (an aprotic azolate salt). Proton oxazoles are commonly referred to as "free oxazoles," and these terms are interchangeable. The protic azole contains a hydrogen atom bonded to a nitrogen atom. For example, "protic imidazole" and "free imidazole" both refer to the same chemical species, formally designated 1H-imidazole. Unless otherwise indicated, references to "azole" herein are to be understood as including protic, rather than aprotic, azoles.

Unless otherwise indicated, reference to "vessel (pot)" in the present invention means a flask or autoclave for carrying out the reaction or for containing the transferred reaction contents.

Unless otherwise indicated, reference herein to "low pressure" means reaction conditions at or below atmospheric pressure and the term "high pressure" means reaction conditions above atmospheric pressure. The term "under pressure" is also used to describe an unspecified high pressure.

The term "ice cooling (iced)" used in the present invention refers to a process of cooling a container to a temperature range of 0 to +4 ℃ in an ice-water mixture.

The term "GCMS" as used herein refers to gas chromatography-mass spectrometry analysis. The charge to mass ratio is reported as an integer with the term "m/e". Mass spectrometry detection is performed by electron collision.

The present invention provides a process for the preparation of N- (fluorosulfonyl) azoles, sulfonyldiazoles, or derivatives thereof; and related products, including N- (fluorosulfonyl) azoles, sulfonyldiazoles, and related derivatives.

In some embodiments, the present invention is not limited to the elimination of SO from process streams₂Cl₂And, through simplified non-aqueous post-treatment procedures, enables the low-cost manufacture of sulfonyldiazoles such as SO₂Im₂。

The inventors have discovered that protic oxazoles, also known as free oxazoles, when dissolved in a solvent, are reacted with sulfuryl fluoride (SO) in the presence of a stoichiometric amount of certain metal fluorides or combinations₂F₂) Reacting to obtain sulfonyl diazole SO₂(azole)₂And by-product metal hydrogen fluoride MFHF. Preferred metal fluorides are sodium fluoride, potassium fluoride and cesium fluoride. The preferred solvent is acetonitrile. The preferred temperature is 25 ℃ to 50 ℃. The preferred concentration of oxazole in acetonitrile is about 1 mole. The theoretical ratio of metal fluoride to azole is 2: 1. in practice, a molar ratio of 3: 1 is more preferred. For example, FSO₂Im reacts with imidazole to generate SO₂Im₂. SO may be used instead₂F₂Obtaining SO from imidazole in a vessel₂Im₂。

SO₂F₂With an azolium salt in the presence of a solvent. These salts can be suspended in an aprotic solvent or formed in small successive amounts by reaction of the oxazole with a metal fluoride to give the symmetrical sulfonyldiazoles.

Many embodiments of the present invention use liquid-full reactants, or readily form liquid-full vessels, and are suitable for continuous large-scale production in a flow reactor.

In a broader aspect, the inventors have discovered at least two exemplary methods for producing N- (fluorosulfonyl) azoles, sulfonyldiazoles, or related derivatives thereof.

In a first exemplary method, first, N- (fluorosulfonyl) oxazole (oxazolyl 1-SO) having a first oxazolyl structure (oxazolyl 1) is prepared₂F) And then reacted with oxazole or a (oxazolyl 2) oxazole salt having a second oxazole structure to produce an N, N' -sulfonyloxadiazole. The reaction may be carried out in the presence of a basic catalyst (e.g., a metal fluoride) or an aprotic solvent, or both. Reacting N- (fluorosulfonyl) oxazole (azolyl-1-SO)₂F) Reacting with oxazole or oxazole salt having a second oxazolyl structure (oxazolyl 2) to produce N, N' -sulfonyldiazole (oxazolyl 1-SO)₂-azolyl 2). The reaction is optionally carried out in the presence of an aprotic solvent or a basic catalyst (e.g., a metal fluoride) or both. Can separate out N, N' -sulfonyl diazole (azolyl 1-SO)₂-azolyl 2).

The first and second azolyl structures may be derived from any suitable protic azole. Examples include, but are not limited to, imidazole, benzimidazole, pyrazole, 1,2, 4-triazole, benzotriazole, indazole, 2-methylimidazole, 2-methylbenzimidazole, and 3, 5-dimethylpyrazole. This description applies to all azole-based structures in each of the exemplary methods described herein.

The N, N' -sulfonyldiazoles may be symmetrical or asymmetrical. In some embodiments, the first oxazolyl structure (oxazolyl 1) and the second oxazolyl structure (oxazolyl 2) are the same. The N, N' -sulfonyldiazoles are symmetrical. In some embodiments, the first oxazolyl structure (oxazolyl 1) and the second oxazolyl structure (oxazolyl 2) are different. The N, N' -sulfonyldiazoles are asymmetric. For example, the first and second azolyl structures are the same, and sulfuryl fluoride (SO)₂F₂) Reacted directly with the first oxazole in one pot to provide the symmetrical sulfonyldiazole. The N, N' -sulfonyldiazole may be isolated or further purified by crystallization.

One or more of the reactions described herein may optionally be carried out in the presence of an aprotic solvent. Examples of suitable aprotic solvents include, but are not limited to, acetonitrile, dichloromethane, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, methylcyclopentyl ether, methyl tert-butyl ether, propionitrile, butyronitrile, toluene, saturated hydrocarbon solvents such as hexane, heptane, pentane, and the like, and any combination thereof. In some embodiments, the reactants may be suspended or dissolved in a solvent.

In some embodiments, the azolium salt has a metal cation. Examples of suitable metals include, but are not limited to, lithium, sodium, potassium, cesium, magnesium, and combinations thereof.

In some embodiments, the azolium salt is derived from a protic azole (e.g., azolyl 2) and a metal base, such as a metal fluoride. Examples of metals in the metal fluoride include sodium, potassium, cesium, and combinations thereof.

The N- (fluorosulfonyl) azoles are reacted with an azole salt, optionally suspended in an aprotic solvent, or continuously produced in small quantities by reaction of the azoles with a metal fluoride to give symmetrical and unsymmetrical sulfonyldiazoles. The purification of the N- (fluorosulfonyl) azole product of the present invention is best accomplished by distillation. Purification of the sulfonyldiazole product of the present invention is best accomplished by recrystallization.

In a second exemplary process, the symmetric N, N' -sulfonyldiazole is produced directly in a single pot. Reacting sulfuryl fluoride (SO)₂F₂) With an azole or azole salt having a first azole group structure (e.g., azole group 1), optionally in the presence of an aprotic solvent as described herein. Can separate out N, N' -sulfonyl diazole (azolyl 1-SO)₂-azolyl 1). The reaction may be carried out in the presence of a metal fluoride.

As noted above, examples of suitable azole-based structures include, but are not limited to, imidazole, pyrazole, 1,2, 4-triazole, benzimidazole, benzotriazole, indazole, 2-methylimidazole, 2-methylbenzimidazole, and 3, 5-dimethylpyrazole.

In some embodiments, the azole salt is an azole anion salt having a metal ion, which can be lithium, sodium, potassium, cesium, magnesium, or a combination thereof.

In some embodiments, the azolium salt is derived from a protic azole (e.g., azolyl 1) and a metal fluoride. Examples of metals in metal fluorides are described in a first exemplary method. In some embodiments, the azole salt is derived from a protic azole (e.g., azole group 1) and an aprotic base, or a protic azole (e.g., azole group 1) as a base.

As mentioned above, the azole-based structure can have any suitable structure, such as imidazole, pyrazole, 1,2, 4-triazole, benzimidazole, benzotriazole, indazole, 2-methylimidazole, 2-methylbenzimidazole, and 3, 5-dimethylpyrazole. Examples of suitable aprotic solvents are given in the first exemplary method. Examples of suitable basic catalysts are given in the first exemplary process.

Examples of N, N '-sulfonyldiazoles according to the invention include, but are not limited to, N' -Sulfonyldiimidazole (SO)₂Im₂) N, N' -Sulfonyldipyrazoles (SO)₂Pz₂) 1,1' -sulfonylbis (1,2, 4-triazole) (SO)₂Tz₂) 1,1' -sulfonylbis (2-methyl-1H-imidazole), 1' -sulfonylbis (benzimidazole), 1' -sulfonylbis (benzotriazole), 1- (1H-imidazole-1-sulfonyl) -1H-pyrazole (ImSO)₂Pz) and 1,1' -sulfonylbis (3, 5-dimethylpyrazole). The N, N' -sulfonyldiazole may be isolated by crystallization or further purified.

With sulfonyl fluoride (SO)₂F₂) And (4) reacting.

In some embodiments, when SO₂F₂Is a reactant and SO is present when the sulfonyl-bisoxazole is the desired product₂F₂The molar ratio to oxazole or an oxazole containing precursor is preferably close to 1: 2. In some embodiments, when SO₂F₂Is a reactant and the sulfonyl-bisoxazole is the desired product, if SO₂F₂Molar ratios greater than 1:2 with oxazole or an oxazole containing precursor can be found to increase the amount of intermediate N- (fluorosulfonyl) oxazole and result in loss of product, particularly when SO₂F₂The addition is rapid and the intermediate cannot react further in time.

In some embodiments, when SO₂F₂As a reactant, SO₂Im₂To the desired product, SO₂F₂The molar ratio to imidazole is preferably less than 1:2, more preferably about 1: 4.

In some embodiments, when SO₂F₂Is a reactant and SO when N- (fluorosulfonyl) azole is the desired product₂F₂The molar ratio to oxazole or an oxazole containing precursor is preferably 1:1 or greater. In some embodiments, when SO₂F₂When N- (fluorosulfonyl) azole is the desired product for the reactants, the use of a molar ratio greater than 1:1 can increase the yield of N- (fluorosulfonyl) azole.

In some embodiments, when SO₂F₂Is a reactant and N- (fluorosulfonyl) azole is the desired product, lower temperatures may be preferred.

In some embodiments, when SO₂F₂Is a reactant and the desired product is a sulfonyldiazole, higher temperatures may be preferred.

SO₂F₂Reaction with imidazole: sulfonyl diimidazoles (SO)₂Im₂)。

In some embodiments, the SO is added under anhydrous conditions₂F₂Introduced into a sealed vessel containing a suspension of an acetonitrile solution of imidazole and a metal base such as a metal fluoride, at low pressure. The dissolved imidazole exists in equilibrium with its anion, presumably at or near the surface of the solid. Some freely soluble imidazole esters may also be present. Adding SO to a vessel₂F₂An exothermic reaction may result. When potassium fluoride (KF) is used (example 2), the addition is rapid. Theoretically, imidazole: the molar ratio of fluoride is 1:2 respectively. In practice, an excess of fluoride is preferred. The reaction may preferably be carried out at a temperature of +25 ℃ to +50 ℃. Imidazole container charge may be as high as 2 moles or more, although container charges of 2 moles or less in acetonitrile are more preferred because of product SO₂Im₂Remains dissolved and the container is easier to empty. In addition, only at about 20 ℃ or higher, 2 moles of imidazole were completely dissolved in acetonitrile. At the end of the reaction, the insoluble salts are separated and the solvent is removed. Residual salts were eliminated by dissolving the crude solid in dichloromethane, filtering and evaporating the solvent. Recrystallizing in ethanol with concentration of more than or equal to 3mL/g to obtain the product. If the vessel is sufficiently cooled, high pressure may be used; however, the device is not suitable for use in a kitchenThe use of low pressure, however, means better safety and also enables the use of large reactors with the same investment costs as smaller autoclaves. In addition, better temperature control and more accurate end point can be achieved using low pressure to add SO₂F₂Any excess of (c) is minimized.

In some embodiments, the SO is added₂F₂The imidazole was previously fully deprotonated and the resulting imidate salt was used. Suitable imidazolium cations include lithium, sodium, potassium, cesium, and magnesium. Sodium imidazolide is preferred. By heating to 200 ℃ under dynamic vacuum and<imidazole and sodium hydroxide were readily prepared in anhydrous form at 50 Pa. This treatment produced a brittle solid which readily formed a fine suspension in acetonitrile. When SO is added₂F₂The addition takes place rapidly at low pressure when the container has been previously emptied. In some embodiments, the method is performed at low pressure, when a fully deprotonated metal imidazolide is used and with addition of SO₂F₂When the vessel is previously properly degassed, the pressure in the vessel near the endpoint will drop below the vapor pressure of the pure solvent.

In some embodiments, reactors made of metal or plastic are preferred over glass that can corrode in the presence of fluoride.

In some embodiments, where an azole other than imidazole is used, the azole may be reacted with SO₂F₂Reacted to produce the symmetrical bisazole. For example, metal salts of pyrazole, 1,2, 4-triazole, benzimidazole and benzotriazole, respectively, may be used for the production of SO₂Pz₂、SO₂Tz₂Sulfonyl bis (benzimidazole) and sulfonyl bis (benzotriazole). Many other metal salts of oxazol may also be used if available in anhydrous form.

In some embodiments, when the vessel contains an ionic component, such as a metal salt, the crude vessel solids obtained by removing the volatile components of the reaction may be absorbed in a less polar solvent (e.g., dichloromethane) and filtered. This process can remove all traces of metal fluoride and other ionic components, leaving only traces of free oxazole impurity. These oxazoles are generally sufficiently volatile to sublime from the dried filtrate to give the product in pure form as a residue. The process also improves the purity of the recrystallized product.

FSO₂Reaction of oxazoles with oxazoles or azole salts.

In some embodiments, fluorosulfonyl azoles (e.g., FSO)₂Im) reacts with oxazole and oxazole salt to produce symmetrical or unsymmetrical sulfonyldiazoles. When the azole groups are the same, a symmetrical sulfonyldiazole is obtained. When the azole groups are different, an asymmetric sulfonyldiazole is obtained.

In some embodiments, fluorosulfonyl azoles (e.g., FSO)₂Im) is reacted with oxazole to give sulfonylbisoxazoles. In some embodiments, when fluorosulfonyl oxazole is reacted with oxazole and sulfonyl bisoxazole is the product, a stoichiometric amount of a metal fluoride or an aprotic base (e.g., triethylamine) can be used. In some embodiments, when the fluorosulfonyl azole is reacted with an azole, and the sulfonyl diazole is the product, a solvent may be used.

In some embodiments, many different solvents or mixtures of solvents may be used. In acetonitrile, if the product is a solid, it is usually precipitated in high purity from a vessel.

In all embodiments, the best yield is obtained by using anhydrous reactants and solvents throughout the process.

Examples

All reactions were carried out in a fume hood. The low pressure condition is provided using a pressure gate that regulates the pressure of the vessel. When the vessel pressure drops below the set pressure, more gas is added until the set pressure is reached. The pressure gate display also serves as a pressure gauge. In the majority of cases involving SO₂F₂In the examples, mono-and bis-adducts were prepared. In some examples, the two products are separated and yields are given, but generally only the yield of the desired product. The progress of the reaction is typically monitored by GCMS, which determines the identity of each peak in the trace, but only qualitatively its relative amount in the vessel. When a liquid product is obtained, the removal of the more volatile methylene chloride or ethylene glycol is omitted in the examplesNitrile, and only product boiling points are reported.

Example 1: a sulfonyl bis-triazole. A600 mL autoclave was charged with 1,2, 4-triazole (20g, 0.29 mole), potassium fluoride (60.5g, 1.04 mole) and acetonitrile (300mL), sealed, ice-cooled and evacuated to constant static pressure (4.5 kPa). The vessel was stirred vigorously and ice-cooled, and SO was added over 11 minutes at 80kPa₂F₂(16.1g, 0.16 mol). The temperature was slightly raised from +2 to +4 ℃ and then dropped. The vessel was then held at 40 ℃ for two hours with vigorous stirring. The residual gas was evacuated, the vessel was purged with nitrogen, opened, and the solid was isolated by filtration through a coarse frit. The filtrate (slightly cloudy and colorless liquid) was transferred to a rotary evaporator and the solvent was removed at 47 ℃/0.2kPa to give a white residue which was extracted twice with 200mL warm dichloromethane. The extracts were filtered through a fine glass frit, combined, and the clear colorless solution was concentrated to dryness. The solid thus obtained was recrystallized from ethanol (250ml) and the crystals were dried in vacuo to give the needle-like product (19.3g, 0.096 mol, 67%) with a melting point of 138-.

Example 2: a sulfodiimidazole. A600 mL autoclave was charged with imidazole (20.3g, 0.3 mol), potassium fluoride (60g, 1.03 mol), and acetonitrile (300mL), sealed, ice-cooled, and evacuated to constant static pressure (4 kPa). The vessel was stirred vigorously and cooled, and SO was added over ten minutes at 80kPa₂F₂(15.8g, 0.154 mol). The temperature was slightly raised from +2 to +4 ℃ and then dropped. The vessel was then held at 40 ℃ for two hours with vigorous stirring. The residual gas was evacuated, the vessel was charged with nitrogen, opened, and the solid was isolated by filtration through a medium frit. The filtrate was a colorless transparent liquid, which was transferred to a rotary evaporator and the solvent was removed at 55 deg.C/0.2 kPa to give a white residue, which was recrystallized from ethanol (80mL) and the crystals were vacuum dried to give a prismatic product (20.3g, 0.1 mole, 69%) having a melting point of 139-140 deg.C.

Although the subject matter of the present disclosure has been described in terms of exemplary embodiments, the subject matter is not so limited. Rather, the appended claims should be construed broadly, to include other variants and embodiments, which may be made by those skilled in the art.

Claims (12)

1. A method, comprising:

by reacting sulfuryl fluoride (SO) in the presence of metal fluoride₂F₂) With an azole or azole salt having a first azole group structure (azole group 1), wherein the azole group 1 in free form is a protic azole; and

isolation of the N, N' -sulfonyldiazole (azolyl 1-SO)₂-azolyl 1).

2. The method of claim 1, wherein the first azole-based structure is selected from the group consisting of imidazole, pyrazole, 1,2, 4-triazole, benzimidazole, benzotriazole, indazole, 2-methylimidazole, 2-methylbenzimidazole, and 3, 5-dimethylpyrazole.

3. The method of claim 1, wherein the metal fluoride is a fluoride of a metal selected from the group consisting of sodium, potassium, cesium, and combinations thereof.

4. The method of claim 1, wherein the azolium salt is an azole anion salt having a metal ion selected from the group consisting of lithium, sodium, potassium, cesium, magnesium, and combinations thereof.

5. The method of claim 1, wherein SO₂F₂With said oxazole or said oxazole salt in the presence of an aprotic solvent.

6. The method of claim 5, wherein the aprotic solvent is acetonitrile.

7. A method, comprising:

by reacting sulfuryl fluoride (SO) in the presence of metal fluoride₂F₂) Reacting with (azolyl 1) azole or azolium salt having a first azolyl structure to obtain N- (fluorosulfonyl) azole (azolyl 1-SO)₂F) Wherein the azole radical 1 in free form is a protic azole;

reacting N- (fluorosulfonyl) oxazole (azolyl-1-SO)₂F) With a protic azole or azole salt having a second azolyl structure (azolyl 2), wherein the free form of oxazolyl 2 is protic azole; and

isolation of the N, N' -sulfonyldiazole (azolyl 1-SO)₂-azolyl 2).

8. The method of claim 7, wherein SO₂F₂With said oxazole or said oxazole salt in the presence of an aprotic solvent.

9. The process according to claim 7, wherein N- (fluorosulfonyl) azole (azolyl 1-SO) is reacted in the presence of a metal fluoride and optionally an aprotic solvent₂F) With said protic azole or azole salt having a second azolyl structure (azolyl 2).

10. The method of claim 7, wherein the first and second azolyl structures are each independently selected from the group consisting of imidazole, pyrazole, 1,2, 4-triazole, benzimidazole, benzotriazole, indazole, 2-methylimidazole, 2-methylbenzimidazole, and 3, 5-dimethylpyrazole.

11. The method of claim 7, wherein the first azole structure (azole 1) and the second azole structure (azole 2) are different.

12. The method of claim 7 or 9, wherein each metal fluoride is a fluoride of a metal selected from the group consisting of sodium, potassium, cesium, and combinations thereof, and

each aprotic solvent is acetonitrile.